JP2010004869A - Apparatus and method for raising organism - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an apparatus for efficiently raising organisms at low cost. <P>SOLUTION: This apparatus for raising organisms 70 by irradiating the organisms 70 with light is composed of: a solar battery 10 which receives light and generates electricity; a light source 40 which emits light by being supplied with electricity generated with the solar battery 10, and irradiates the organisms 70 with light; and a light emission control means 50 which changes with time, the intensity and/or wavelength of light to be irradiated to the organisms 70 from the light source 40. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a biological growth apparatus and a growth method.

  Conventionally, when producing agricultural products indoors, the indoors may be illuminated with artificial light instead of sunlight. For example, when performing hydroponics, house cultivation, greenhouse cultivation, etc. of a plant, the technique which irradiates a plant with artificial light, controlling the irradiation time and irradiation intensity is known. If the example of such a technique is given, the technique etc. of patent documents 1-3 will be mentioned, for example.

JP-A-7-8113 JP-A-9-322661 JP 2005-31444 A

However, in the conventional technique, since electric power is required to generate artificial light, the cost required for producing agricultural products tends to increase. In addition, using fossil fuels for the generation of electric power has been problematic from an environmental point of view.
In this regard, in the techniques described in Patent Documents 1 to 3, it is proposed to use a solar cell as a power generation source in order to solve the cost and environmental problems. However, improvement is not satisfactory only by using solar cells, and further improvement has been desired. This is an issue that should be improved not only for agricultural products but also for the overall growth of organisms.

  The present invention has been made in view of the above-described problems, and an object thereof is to provide a growing apparatus and a growing method capable of growing an organism more efficiently and at a lower cost than before.

  The inventor of the present invention has intensively studied to solve the above problems, and as a result, when the organism is bred by irradiating the organism with the light generated using the power generated by the solar cell, the intensity of light is changed over time. The present invention was completed by discovering that it is possible to grow a living organism more efficiently at a lower cost than before by irradiating while changing the wavelength or changing the wavelength with time.

That is, the gist of the present invention is a growing apparatus for irradiating a living organism with light to grow the living organism, and receives a light to generate power by receiving light, and the power generated by the solar cell is supplied to emit light. And a light source that irradiates the organism with light, and a light emission control means that changes the intensity and / or wavelength of the light emitted to the organism from the light source over time. Claim 1).
Another aspect of the present invention is a growing device for irradiating a plant with light to grow the plant, receiving a light to generate power by receiving light, and being supplied with electric power generated by the solar cell. A growth apparatus comprising: a light source that emits light and irradiates the plant with light; and a light emission control unit that changes the intensity and / or wavelength of light emitted from the light source to the plant over time. (Claim 2).

At this time, it is preferable that the growing device of the present invention is provided with a secondary battery that is charged to supply power to the light source while being charged by the power generated by the solar battery. Furthermore, it is more preferable to provide a charge / discharge control device for controlling charge / discharge of the secondary battery.
Moreover, it is also preferable that the growing apparatus of the present invention includes a controller that changes the control content of the light emission control means (Claim 5).

Further, it is preferable that the light source is selected from the group consisting of a light emitting diode, a laser diode, an inorganic electroluminescence element, and an organic electroluminescence element.
Further, it is preferable that the light source emits light at two or more wavelengths.
Furthermore, the intensity of the light emitted from the light source is 150 μmol ⁻² s ⁻¹ or more and 800 μmol ⁻² s ⁻¹ or less, and the wavelength of the light emitted from the light source is 150 nm or more and 800 nm or less. It is preferable to control light emission with a pulse width of 10 microseconds or more and 400 microseconds or less.

Moreover, it is preferable that the growing apparatus of this invention is equipped with the container which accommodates the said living organism and a light source (Claim 9).
Furthermore, it is more preferable that the container includes a heat insulating material selected from any one of urethane foam and polystyrene.

  Still another subject matter of the present invention is a growing method for growing a living organism by irradiating light to a living organism from a light source that is supplied with power generated by a solar cell and emits light. The growth method is characterized in that the intensity and / or the wavelength of the water is changed over time (claim 11).

  According to the organism growing apparatus and the growing method of the present invention, it is possible to grow an organism efficiently at a lower cost than in the past.

  Hereinafter, the present invention will be described with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples shown below, and may be arbitrarily modified without departing from the scope of the present invention. Can be implemented.

[First embodiment]
[Overview]
1 and 2 schematically show a growing apparatus as a first embodiment of the present invention, FIG. 1 is a functional block diagram thereof, and FIG. 2 is a schematic diagram thereof.
The growing apparatus 1 of the present embodiment grows a living organism by irradiating light to the living organism. As shown in FIG. 1, the solar cell 10, the secondary battery 20, and charging / discharging as charging / discharging control means. A control device 30, a light emitting device 40 as a light source, a light emission control device 50 as a light emission control means, and a controller 60 are provided. In the growing device 1, the electric power generated by the solar cell 10 is supplied to the light emitting device 40, and the light emitting device 40 emits light by the supplied electric power, and this light emission is irradiated to the living organism 70 to grow the living organism 70. It has become. At this time, the light-emitting device 40 can change at least the intensity and / or wavelength of light emission with time by the light-emission control device 50.

[Solar cell 10]
The solar cell 10 receives light (light received by the solar cell to generate power; also referred to as received light) and generates power. Usually, natural light is received, so it is installed outdoors. In the present embodiment, as shown in FIG. 2, the solar cell 10 is connected to the secondary battery 20 via the charge / discharge control device 30, while the light emitting device via the charge / discharge control device 30 and the light emission control device 50. 40. Thereby, the electric power generated in the solar cell 10 is stored in the secondary battery 20 or supplied to the light emitting device 40 according to the control of the charge / discharge control device 30.

The solar cell 10 is usually formed by arranging a plurality of photoelectric conversion elements (solar cell elements) 11 in an array. At this time, the number and type of the photoelectric conversion elements 11 are not limited, and one type may be used alone or a plurality of types may be used, and two or more types may be used in any combination and ratio. Further, the solar cell 10 may include a member other than the photoelectric conversion element 11.
Hereinafter, the photoelectric conversion element 11 will be described with an example. However, the solar cell 10 is not limited to what is comprised by the photoelectric conversion element demonstrated below.

  FIG. 3 is a cross-sectional view schematically showing a configuration of a solar cell as one embodiment of the present invention. As shown in FIG. 3, the solar cell 10 of this embodiment includes a weather-resistant protective film 101, an ultraviolet cut film 102, a gas barrier film 103, a getter material film 104, a sealing material 105, and a photoelectric conversion element 11. A sealing material 106, a getter material film 107, a gas barrier film 108, and a back sheet 109 in this order, and further, a weather resistance protective film 101 and a sealing material 110 that seals the edge of the back sheet 109. ing. And the light is irradiated from the side (lower side in the figure) where the weather-resistant protective film 101 is formed, and the photoelectric conversion element 11 generates power. In addition, when using a highly waterproof sheet such as a sheet in which a fluororesin film is bonded to both sides of an aluminum foil as the back sheet 109 described later, the getter material film 107 and / or the gas barrier film 108 may not be used depending on the application. .

[Weather-resistant protective film 101]
The weather-resistant protective film 101 is a film that protects the photoelectric conversion element 11 from weather changes.
Some components of the photoelectric conversion element 11 deteriorate due to temperature change, humidity change, natural light, erosion caused by wind and rain, and the like. Therefore, by covering the photoelectric conversion element 11 with a weather-resistant protective film 101, the photoelectric conversion element 11 and the like are protected from weather changes and the power generation capacity is kept high.

  Since the weather-resistant protective film 101 is located on the outermost layer of the solar cell 10, it is suitable as a surface covering material for the solar cell 10, such as weather resistance, heat resistance, transparency, water repellency, contamination resistance, and mechanical strength. And has the property of maintaining it for a long time in outdoor exposure.

  Moreover, the weather-resistant protective film 101 is preferably one that transmits visible light from the viewpoint of not preventing the photoelectric conversion element 11 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more.

  Furthermore, since the solar cell 10 is often heated by receiving light, it is preferable that the weather-resistant protective film 101 also has heat resistance. From this viewpoint, the melting point of the constituent material of the weather-resistant protective film 101 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower. Preferably it is 300 degrees C or less. By increasing the melting point, it is possible to reduce the possibility that the weather-resistant protective film 101 is melted and deteriorated when the solar cell 10 is used.

The material which comprises the weather-resistant protective film 101 is arbitrary as long as it can protect the photoelectric conversion element 11 from a weather change. Examples of the material include polyethylene resin, polypropylene resin, cyclic polyolefin resin, AS (acrylonitrile-styrene) resin, ABS (acrylonitrile-butadiene-styrene) resin, polyvinyl chloride resin, fluorine resin, polyethylene terephthalate, polyethylene Examples thereof include polyester resins such as naphthalate, phenol resins, polyacrylic resins, polyamide resins such as various nylons, polyimide resins, polyamide-imide resins, polyurethane resins, cellulose resins, silicone resins, and polycarbonate resins.
Among them, fluorine resin is preferable, and specific examples thereof include polytetrafluoroethylene (PTFE), 4-fluoroethylene-perchloroalkoxy copolymer (PFA), 4-fluoroethylene-6-fluoride. Propylene copolymer (FEP), 2-ethylene-4-fluoroethylene copolymer (ETFE), poly-3-fluoroethylene chloride (PCTFE), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), etc. Can be mentioned.
In addition, the weather-resistant protective film 101 may be formed with 1 type of material, and may be formed with 2 or more types of materials. Moreover, although the weather-resistant protective film 101 may be formed with the single layer film, the laminated | multilayer film provided with the film of two or more layers may be sufficient as it.

  The thickness of the weather-resistant protective film 101 is not particularly defined, but is usually 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, and usually 200 μm or less, preferably 180 μm or less, more preferably 150 μm or less. Increasing the thickness tends to increase mechanical strength, and decreasing the thickness tends to increase flexibility.

The weather-resistant protective film 101 may be subjected to surface treatment such as corona treatment or plasma treatment in order to improve adhesion with other films.
The weatherproof protective film 101 is preferably provided on the outer side of the solar cell 10 as much as possible. This is because more of the constituent members of the solar cell 10 can be protected.

[UV cut film 102]
The ultraviolet cut film 102 is a film that prevents transmission of ultraviolet rays.
Some components of the solar cell 10 are deteriorated by ultraviolet rays. Some of the gas barrier films 103, 108 and the like are deteriorated by ultraviolet rays depending on the type. Therefore, the ultraviolet cut film 102 is provided in the light receiving portion of the solar cell 10 and the light receiving surface 11a of the photoelectric conversion element 11 is covered with the ultraviolet cut film 102, so that the photoelectric conversion element 11 and, if necessary, the gas barrier films 103 and 108 are provided. It is protected from ultraviolet rays and can maintain high power generation capacity.

  The degree of the ability to suppress the transmission of ultraviolet rays required for the ultraviolet cut film 102 is such that the transmittance of ultraviolet rays (for example, wavelength 300 nm) is preferably 50% or less, more preferably 30% or less, and particularly preferably. 10% or less.

  In addition, the ultraviolet cut film 102 is preferably one that transmits visible light from the viewpoint of not hindering the light absorption of the photoelectric conversion element 11. For example, the transmittance of visible light (wavelength 360 to 830 nm) is preferably 80% or more, more preferably 90% or more, and particularly preferably 95% or more.

  Furthermore, since the solar cell 10 is often heated by receiving light, the ultraviolet cut film 102 preferably has resistance to heat. From this viewpoint, the melting point of the constituent material of the ultraviolet cut film 102 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably. Is 300 ° C. or lower. If the melting point is too low, the ultraviolet cut film 102 may melt when the solar cell 10 is used.

  Further, the ultraviolet cut film 102 is preferably a film having high flexibility, good adhesion to an adjacent film, and capable of cutting water vapor and oxygen.

  The material constituting the ultraviolet cut film 102 is arbitrary as long as the intensity of ultraviolet rays can be weakened. Examples of the material include films formed by blending an ultraviolet absorber with an epoxy, acrylic, urethane, or ester resin. Further, a film in which a layer of an ultraviolet absorbent dispersed or dissolved in a resin (hereinafter referred to as “ultraviolet absorbing layer” as appropriate) is formed on a base film may be used.

  As the ultraviolet absorber, for example, a salicylic acid-based, benzophenone-based, benzotriazole-based, or cyanoacrylate-based one can be used. Of these, benzophenone and benzotriazole are preferable. Examples of this include various aromatic organic compounds such as benzophenone and benzotriazole.

  Examples of benzophenone-based UV absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2, 2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy-5- Benzophenone) methane and the like.

  Examples of benzotriazole ultraviolet absorbers include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-tert-butylphenyl) benzotriazole. 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5-methylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) ) Benzotriazole, 2- {2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-me Butylphenyl} benzotriazole, 2,2- methylenebis {4- (1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl) phenol}, and the like. In addition, a ultraviolet absorber may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  As described above, a film in which an ultraviolet absorbing layer is formed on a base film can be used as the ultraviolet absorbing film. Such a film can be produced, for example, by applying a coating solution containing an ultraviolet absorber on a substrate film and drying it.

Although the material of a base film is not specifically limited, For example, polyester is mentioned at the point from which the balance of heat resistance and a softness | flexibility is obtained.
Application | coating can be performed by arbitrary methods. Examples include reverse roll coating, gravure coating, kiss coating, roll brushing, spray coating, air knife coating, wire barber coating, pipe doctor method, impregnation / coating method, curtain coating method and the like. In addition, these methods may be performed alone or in any combination of two or more.

The solvent used in the coating solution is not particularly limited as long as it can uniformly dissolve or disperse the UV absorber. For example, a liquid resin can be used as a solvent, and examples thereof include polyester, acrylic, polyamide, polyurethane, polyolefin, polycarbonate, polystyrene, and other synthetic resins. It is done. Further, for example, natural polymers such as gelatin and cellulose derivatives; water, alcohol mixed solutions of water and ethanol, and the like can also be used as the solvent.
Further, an organic solvent may be used as the solvent. If an organic solvent is used, it becomes possible to dissolve or disperse the pigment and the resin, and to improve the coatability. Examples of the organic solvent include alcohols such as methanol and ethanol; glycols such as ethylene glycol and diethylene glycol; esters such as ethyl acetate, isopropyl acetate and n-butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclohexane Examples thereof include ketones such as pentanone, isophorone and diacetone alcohol.
In addition, 1 type may be used for a solvent and it may use 2 or more types together by arbitrary combinations and a ratio.

The coating solution may further contain a surfactant. Use of the surfactant improves the dispersibility of the ultraviolet absorbing dye in the resin. Thereby, in an ultraviolet absorption layer, generation | occurrence | production of the dent by adhesion of foreign matters etc. by a micro bubble, the repelling in a drying process, etc. are suppressed.
Known surfactants (cationic surfactants, anionic surfactants, nonionic surfactants) can be used as the surfactant. Among these, a silicon-based surfactant or a fluorine-based surfactant is preferable. Specific examples thereof include silicon surfactants such as silane compounds such as aminosilane, acrylic silane, and vinylbenzyl silane; siloxane compounds such as polydimethylsiloxane and polyalkoxysiloxane. On the other hand, examples of the fluorine-based surfactant include tetrafluoroethylene; perfluoroalkyl compounds such as perfluoroalkylammonium salt and perfluoroalkylsulfonic acid amide. In addition, 1 type may be used for surfactant and it may use 2 or more types together by arbitrary combinations and a ratio.

  In addition, the drying after apply | coating a coating liquid to a base film can employ | adopt well-known drying methods, such as hot air drying and drying by an infrared heater, for example. Among these, hot air drying with a high drying speed is preferable.

Examples of specific products of the ultraviolet cut film 102 include Cut Ace (MKV Plastic Co., Ltd.).
Note that the ultraviolet cut film 102 may be formed of one kind of material or may be formed of two or more kinds of materials. Moreover, the ultraviolet cut film 102 may be formed of a single layer film, but may be a laminated film including two or more layers.

  The thickness of the ultraviolet cut film 102 is not particularly defined, but is usually 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and is usually 200 μm or less, preferably 180 μm or less, more preferably 150 μm or less. Increasing the thickness tends to increase the absorption of ultraviolet rays, and decreasing the thickness tends to increase the transmittance of visible light.

Although the ultraviolet cut film 102 should just be provided in the position which covers at least one part of the light-receiving surface 11a of the photoelectric conversion element 11, Preferably it is provided in the position which covers all the light-receiving surfaces 11a of the photoelectric conversion element 11.
However, the ultraviolet cut film 102 may be provided at a position other than the position covering the light receiving surface 11 a of the photoelectric conversion element 11.

[Gas barrier film 103]
The gas barrier film 103 is a film that prevents permeation of water and oxygen.
The photoelectric conversion element 11 tends to be sensitive to moisture and oxygen. In particular, a transparent electrode such as ZnO: Al, a compound semiconductor photoelectric conversion element, and an organic photoelectric conversion element may be deteriorated by moisture and oxygen. Therefore, by covering the photoelectric conversion element 11 with the gas barrier film 103, the photoelectric conversion element 11 can be protected from water and oxygen, and the power generation capacity can be kept high.

The degree of moisture resistance required for the gas barrier film 103 varies depending on the type of the photoelectric conversion element 11 and the like. For example, when the photoelectric conversion element 11 is a compound semiconductor photoelectric conversion element, the water vapor transmission rate per unit area (1 m ² ) per day is 1 × 10 ⁻¹ g / m ² / day or less. Is preferably 1 × 10 ⁻² g / m ² / day or less, more preferably 1 × 10 ⁻³ g / m ² / day or less, and further preferably 1 × 10 ⁻⁴ g / m ^2. / Day or less is particularly preferable, 1 × 10 ⁻⁵ g / m ² / day or less is particularly preferable, and 1 × 10 ⁻⁶ g / m ² / day or less is particularly preferable. In addition, when the photoelectric conversion element 11 is an organic photoelectric conversion device, the water vapor permeability per day unit area (1 m ²⁾ of preferably not more than ^{1 × 10 -1 g / m 2} / day It is more preferably 1 × 10 ⁻² g / m ² / day or less, further preferably 1 × 10 ⁻³ g / m ² / day or less, and further preferably 1 × 10 ⁻⁴ g / m ² / day. Among them, the following is particularly preferable, and it is particularly preferably 1 × 10 ⁻⁵ g / m ² / day or less, and particularly preferably 1 × 10 ⁻⁶ g / m ² / day or less. The more water vapor has to pass through, the lower the degradation caused by the reaction of the photoelectric conversion element 11 and the transparent electrode such as ZnO: Al of the element 11 with moisture, thereby increasing the power generation efficiency and extending the life.

The degree of oxygen permeability required for the gas barrier film 103 varies depending on the type of the photoelectric conversion element 11 and the like. For example, when the photoelectric conversion element 11 is a compound semiconductor photoelectric conversion element, the oxygen permeability per day of the unit area (1 m ² ) is 1 × 10 ⁻¹ cc / m ² / day / atm or less. Preferably, it is 1 × 10 ⁻² cc / m ² / day / atm or less, more preferably 1 × 10 ⁻³ cc / m ² / day / atm or less, and further preferably 1 × 10 2. ⁻⁴ cc / m ² / day / atm or less is particularly preferable, and 1 × 10 ⁻⁵ cc / m ² / day / atm or less is particularly preferable, and 1 × 10 ⁻⁶ cc / m ² / day. / Atm or less is particularly preferable. In addition, for example, when the photoelectric conversion element 11 is an organic photoelectric conversion element, the oxygen permeability per unit area (1 m ² ) per day is 1 × 10 ⁻¹ cc / m ² / day / atm or less. Preferably, it is 1 × 10 ⁻² cc / m ² / day / atm or less, more preferably 1 × 10 ⁻³ cc / m ² / day / atm or less, and further preferably 1 × 10 2. ⁻⁴ cc / m ² / day / atm or less is particularly preferable, and 1 × 10 ⁻⁵ cc / m ² / day / atm or less is particularly preferable, and 1 × 10 ⁻⁶ cc / m ² / day. / Atm or less is particularly preferable. The deterioration of the photoelectric conversion element 11 and the transparent electrode such as ZnO: Al due to oxidation of the photoelectric conversion element 11 due to oxidation is suppressed as the oxygen does not pass therethrough.

  Conventionally, it has been difficult to mount the gas barrier film 103 having such a high moisture-proof and oxygen-blocking capability, so that a solar cell including an excellent photoelectric conversion element such as a compound semiconductor photoelectric conversion element and an organic photoelectric conversion element is realized. Although it was difficult to apply, the application of such a gas barrier film 103 facilitates the implementation of the solar cell 10 utilizing the excellent properties of the compound semiconductor photoelectric conversion element and the organic photoelectric conversion element.

  Further, the gas barrier film 103 is preferably one that transmits visible light from the viewpoint of not preventing the photoelectric conversion element 11 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is usually 60% or more, preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 85% or more. Preferably it is 90% or more, Especially preferably, it is 95% or more, Especially preferably, it is 97% or more. This is to convert more sunlight into electrical energy.

  Furthermore, since the solar cell 10 is often heated by receiving light, it is preferable that the gas barrier film 103 also has heat resistance. From this viewpoint, the melting point of the constituent material of the gas barrier film 103 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably. It is 300 degrees C or less. By increasing the melting point, the possibility that the gas barrier film 103 is melted and deteriorated when the solar cell 10 is used can be reduced.

The specific configuration of the gas barrier film 103 is arbitrary as long as the photoelectric conversion element 11 can be protected from water. However, since the manufacturing cost increases as the amount of water vapor or oxygen that can permeate the gas barrier film 103 increases, it is preferable to use an appropriate film considering these points comprehensively.
Hereinafter, the configuration of the gas barrier film 103 will be described with examples.

Two examples are preferable as the configuration of the gas barrier film 103.
The first example is a film in which an inorganic barrier layer is disposed on a plastic film substrate. In this case, the inorganic barrier layer may be formed only on one side of the plastic film substrate, or may be formed on both sides of the plastic film substrate. When forming on both surfaces, the number of inorganic barrier layers formed on both surfaces may be the same or different.

  The second example is a film in which a unit layer composed of two layers in which an inorganic barrier layer and a polymer layer are arranged adjacent to each other is formed on a plastic film substrate. At this time, a unit layer composed of two layers in which an inorganic barrier layer and a polymer layer are arranged adjacent to each other is regarded as one unit, and this unit layer is composed of one unit (one inorganic barrier layer and one polymer layer are combined into one unit). (Meaning of unit) may be formed, but two or more units may be formed. For example, 2 to 5 units may be laminated.

  The unit layer may be formed only on one side of the plastic film substrate, or may be formed on both sides of the plastic film substrate. When forming on both surfaces, the numbers of inorganic barrier layers and polymer layers formed on both surfaces may be the same or different. In addition, when forming a unit layer on a plastic film substrate, an inorganic barrier layer may be formed and then a polymer layer may be formed thereon, or after forming a polymer layer and forming an inorganic barrier layer. Also good.

(Plastic film substrate)
The plastic film substrate used for the gas barrier film 103 is not particularly limited as long as it is a film that can hold the above-described inorganic barrier layer and polymer layer, and can be appropriately selected depending on the purpose of use of the gas barrier film 103.

  Examples of plastic film base materials include polyester resin, methacrylic resin, methacrylic acid-maleic acid copolymer, polystyrene, transparent fluororesin, polyimide resin, fluorinated polyimide resin, polyamide resin, polyvinyl alcohol resin, polyamideimide. Resin, polyetherimide resin, cellulose acylate resin, polyurethane resin, polyether ether ketone resin, polycarbonate resin, alicyclic polyolefin resin, polyarylate resin, polyether sulfone resin, polysulfone resin, cycloolefin copolymer, fluorene ring modified polycarbonate Examples thereof include thermoplastic resins such as resins, alicyclic modified polycarbonate resins, and acryloyl compounds.

Among these resins, preferred examples include polyester resins, polyarylate resins, polyethersulfone resins, fluorene ring-modified polycarbonate resins, alicyclic modified polycarbonate resins, and acryloyl compounds. It is also preferable to use a condensation polymer containing spirobiindane or spirobichroman. Among the polyester resins, biaxially stretched polyethylene terephthalate (PET) and biaxially stretched polyethylene naphthalate (PEN) are preferably used as a plastic film substrate because they are excellent in thermal dimensional stability.
In addition, 1 type may be used for the material of a plastic film base material, and 2 or more types may be used together by arbitrary combinations and a ratio.

  The thickness of the plastic film substrate is not particularly defined, but is usually 10 μm or more, preferably 15 μm or more, more preferably 20 μm or more, and usually 200 μm or less, preferably 180 μm or less, more preferably 150 μm or less. Increasing the thickness tends to increase mechanical strength, and decreasing the thickness tends to increase flexibility.

  The plastic film substrate is preferably one that transmits visible light from the viewpoint of not preventing the photoelectric conversion element 11 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is usually 60% or more, preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 85% or more. Preferably it is 90% or more, Especially preferably, it is 95% or more, Especially preferably, it is 97% or more. This is to convert more sunlight into electrical energy.

  An anchor coat agent layer (anchor coat layer) may be formed on the plastic film substrate in order to improve adhesion to the inorganic barrier layer. Usually, the anchor coat layer is formed by applying an anchor coat agent. Examples of the anchor coating agent include polyester resins, urethane resins, acrylic resins, oxazoline group-containing resins, carbodiimide group-containing resins, epoxy group-containing resins, isocyanate-containing resins, and copolymers thereof. Among these, a combination of at least one of a polyester resin, a urethane resin, and an acrylic resin and at least one of an oxazoline group-containing resin, a carbodiimide group-containing resin, an epoxy group-containing resin, and an isocyanate group-containing resin is preferable. In addition, an anchor coat agent may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

The thickness of the anchor coat layer is usually 0.005 μm or more, preferably 0.01 μm or more, and usually 5 μm or less, preferably 1 μm or less. If the thickness is less than or equal to the upper limit of this range, the slipperiness is good, and there is almost no peeling from the plastic film substrate due to the internal stress of the anchor coat layer itself. Moreover, if it is the thickness more than the lower limit of this range, a uniform thickness can be maintained and it is preferable.
Also, in order to improve the applicability and adhesion of the anchor coating agent to the plastic film substrate, the plastic film substrate may be subjected to a surface treatment such as normal chemical treatment or electric discharge treatment before application of the anchor coating agent. Good.

(Inorganic barrier layer)
The inorganic barrier layer is usually a layer formed of a metal oxide, nitride or oxynitride. In addition, the metal oxide, nitride, and oxynitride which form an inorganic barrier layer may be 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
Examples of the metal oxide include oxides such as Si, Al, Mg, In, Ni, Sn, Zn, Ti, Cu, Ce, and Ta, nitrides, and oxynitrides. Among these, in order to achieve both high barrier properties and high transparency, it is preferable to include aluminum oxide or silicon oxide, and it is particularly preferable to include silicon oxide from the viewpoint of moisture permeability and light transmittance.

The ratio of each metal atom to oxygen atom is also arbitrary, but in order to improve the transparency of the inorganic barrier layer and prevent coloring, the oxygen atom ratio should be extremely small from the stoichiometric ratio of the oxide. Is desirable. On the other hand, in order to improve the denseness of the inorganic barrier layer and increase the barrier property, it is desirable to reduce oxygen atoms. From this viewpoint, for example, when SiO _x is used as the metal oxide, the value of x is particularly preferably 1.5 to 1.8. For example, when AlO _x is used as the metal oxide, the value of x is particularly preferably 1.0 to 1.4.

  Moreover, when an inorganic barrier layer is comprised from 2 or more types of metal oxides, it is desirable to contain aluminum oxide and silicon oxide as a metal oxide. Among them, when the inorganic barrier layer is made of aluminum oxide and silicon oxide, the ratio of aluminum to silicon in the inorganic barrier layer can be arbitrarily set, but the ratio of Si / Al is usually 1/9 or more, preferably 2/8 or more, and usually 9/1 or less, preferably 8/2 or less.

  When the thickness of the inorganic barrier layer is increased, the barrier property tends to be increased. However, it is desirable to reduce the thickness in order to prevent cracking and prevent cracking when bent. Therefore, the appropriate thickness of the inorganic barrier layer is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably 200 nm or less.

  Although there is no restriction | limiting in the film-forming method of an inorganic barrier layer, Generally, it can carry out by sputtering method, a vacuum evaporation method, an ion plating method, plasma CVD method etc. For example, the sputtering method can be formed by a reactive sputtering method using plasma using one or more metal targets and oxygen gas as raw materials.

(Polymer layer)
Any polymer can be used for the polymer layer, and for example, a film that can be formed in a vacuum chamber can be used. In addition, the polymer which comprises a polymer layer may use 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

A wide variety of compounds can be used as the compound that gives the polymer, and examples include the following (i) to (vii). In addition, 1 type may be used for a monomer and it may use 2 or more types together by arbitrary combinations and a ratio.

(I) Examples include siloxanes such as hexamethyldisiloxane. An example of a method for forming a polymer layer in the case of using hexamethyldisiloxane is to introduce hexamethyldisiloxane as a vapor into a parallel plate type plasma apparatus using an RF electrode, to cause a polymerization reaction in the plasma, The polymer layer can be formed as a polysiloxane thin film by being deposited on a plastic film substrate.

(Ii) Examples include paraxylylene such as diparaxylylene. As an example of a method for forming a polymer layer in the case of using diparaxylylene, first, the vapor of diparaxylylene is heated at 650 ° C. to 700 ° C. in a high vacuum to generate thermal radicals. And the polymer layer can be formed by guiding the radical monomer vapor into the chamber and adsorbing it on the plastic film substrate, and at the same time proceeding radical polymerization reaction to deposit polyparaxylylene.

(Iii) For example, a monomer capable of alternately repeating addition polymerization of two kinds of monomers can be mentioned. The polymer thus obtained is a polyaddition polymer. Examples of the polyaddition polymer include polyurethane (diisocyanate / glycol), polyurea (diisocyanate / diamine), polythiourea (dithioisocyanate / diamine), polythioether urethane (bisethyleneurethane / dithiol), polyimine ( Bisepoxy / primary amine), polypeptide amide (bisazolactone / diamine), polyamide (diolefin / diamide) and the like.

(Iv) For example, an acrylate monomer can be mentioned. The acrylate monomer includes monofunctional, bifunctional, and polyfunctional acrylate monomers, and any of them may be used. However, in order to obtain an appropriate evaporation rate, degree of cure, cure rate, and the like, it is preferable to use a combination of two or more of the above acrylate monomers.
Examples of monofunctional acrylate monomers include aliphatic acrylate monomers, alicyclic acrylate monomers, ether acrylate monomers, cyclic ether acrylate monomers, aromatic acrylate monomers, hydroxyl group-containing acrylate monomers, carboxy group-containing acrylate monomers, and the like. There are, but any can be used.

(V) Monomers capable of obtaining a photocationically cured polymer, such as epoxy and oxetane, are exemplified. As an epoxy-type monomer, an alicyclic epoxy-type monomer, a bifunctional monomer, a polyfunctional oligomer etc. are mentioned, for example. Examples of the oxetane monomer include monofunctional oxetane, bifunctional oxetane, and oxetane having a silsesquioxane structure.

(Vi) An example is vinyl acetate. When vinyl acetate is used as a monomer, polyvinyl alcohol is obtained by saponifying the polymer, and this polyvinyl alcohol can be used as a polymer.

(Vii) Examples thereof include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monoethyl maleate, maleic anhydride and itaconic anhydride. These constitute a copolymer with ethylene, and the copolymer can be used as a polymer. Furthermore, a mixture thereof, a mixture obtained by mixing glycidyl ether compounds, and a mixture with an epoxy compound can also be used as the polymer.

  There is no restriction | limiting in the polymerization method of a monomer when superposing | polymerizing the said monomer and producing | generating a polymer. However, the polymerization is usually carried out after a composition containing a monomer is applied or deposited to form a film. As an example of the polymerization method, when a thermal polymerization initiator is used, the polymerization is started by contact heating with a heater or the like; radiation heating with infrared rays, microwaves or the like; Moreover, when a photoinitiator is used, an active energy ray is irradiated and polymerization is started. Various light sources can be used when irradiating active energy rays, such as mercury arc lamps, xenon arc lamps, fluorescent lamps, carbon arc lamps, tungsten-halogen radiation lamps, and sunlight irradiation light. Can do. Further, electron beam irradiation or atmospheric pressure plasma treatment can also be performed.

Examples of the method for forming the polymer layer include a coating method and a vacuum film forming method.
When the polymer layer is formed by a coating method, for example, methods such as roll coating, gravure coating, knife coating, dip coating, curtain flow coating, spray coating, and bar coating can be used. Moreover, you may make it apply | coat the coating liquid for polymer layer formation in mist form. In this case, the average particle size of the droplets may be adjusted to an appropriate range. For example, when forming a coating liquid containing a polymerizable monomer in the form of a mist on a plastic film substrate, the droplets The average particle size of is 5 μm or less, preferably 1 μm or less.
On the other hand, when forming a polymer layer by a vacuum film-forming method, film-forming methods, such as vapor deposition and plasma CVD, are mentioned, for example.

  The thickness of the polymer layer is not particularly limited, but is usually 10 nm or more, and is usually 5000 nm or less, preferably 2000 nm or less, more preferably 1000 nm or less. By increasing the thickness of the polymer layer, the uniformity of the thickness can be easily obtained, and structural defects of the inorganic barrier layer can be efficiently filled with the polymer layer, and the barrier property tends to be improved. In addition, by reducing the thickness of the polymer layer, the barrier property can be improved because the polymer layer itself is less likely to crack due to an external force such as bending.

Particularly suitable gas barrier film 103 includes, for example, a film obtained by vacuum-depositing SiO _x on a base film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN).
Note that the gas barrier film 103 may be formed of one kind of material or two or more kinds of materials. The gas barrier film 103 may be formed of a single layer film, but may be a laminated film including two or more layers.

  The thickness of the gas barrier film 103 is not particularly defined, but is usually 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and is usually 200 μm or less, preferably 180 μm or less, more preferably 150 μm or less. Increasing the thickness tends to increase gas barrier properties, and decreasing the thickness tends to increase flexibility and improve visible light transmittance.

  As long as the gas barrier film 103 can cover the photoelectric conversion element 11 and protect it from moisture and oxygen, the formation position is not limited, but the front surface of the photoelectric conversion element 11 (the surface on the light receiving surface side, the lower surface in FIG. 3) and It is preferable to cover the back surface (surface opposite to the light receiving surface; upper surface in FIG. 3). This is because the front and back surfaces of the solar cell 10 are often formed in a larger area than the other surfaces. In this embodiment, the gas barrier film 103 covers the front surface of the photoelectric conversion element 11, and a gas barrier film 108 described later covers the back surface of the photoelectric conversion element 11. Then, the edges of the gas barrier films 103 and 108 are sealed with a sealing material 110, and the photoelectric conversion element 11 is placed in a space surrounded by the gas barrier films 103 and 108 and the sealing material 110, whereby moisture and It can be protected from oxygen. In addition, when using a highly waterproof sheet such as a sheet in which a fluororesin film is bonded to both sides of an aluminum foil as the back sheet 109 described later, the getter material film 107 and / or the gas barrier film 108 may not be used depending on the application. .

[Getter material film 104]
The getter material film 104 is a film that absorbs moisture and / or oxygen. Some components of the photoelectric conversion element 11 are deteriorated by moisture as described above, and some are deteriorated by oxygen. Therefore, by covering the photoelectric conversion element 11 with the getter material film 104, the photoelectric conversion element 11 and the like are protected from moisture and / or oxygen, and the power generation capacity is kept high.

Here, unlike the gas barrier film 103 as described above, the getter material film 104 does not prevent moisture permeation but absorbs moisture. By using a film that absorbs moisture, when the photoelectric conversion element 11 is covered with the gas barrier film 103 or the like, the getter material film 104 absorbs moisture that slightly enters the space formed by the gas barrier films 103 and 108 and the sealing material 110. Can be captured and the influence of moisture on the photoelectric conversion element 11 can be eliminated.
The degree of water absorption capacity of the getter material film 104 is usually 0.1 mg / cm ² or more, preferably 0.5 mg / cm ² or more, more preferably 1 mg / cm ² or more. The higher the numerical value, the higher the water absorption capacity, and the deterioration of the photoelectric conversion element 11 can be suppressed. Moreover, although there is no restriction | limiting in an upper limit, it is usually 10 mg / cm < ² > or less.

  Further, when the photoelectric conversion element 11 is covered with the gas barrier films 103 and 108 by absorbing the oxygen by the getter material film 104, the getter material film 104 slightly enters the space formed by the gas barrier films 103 and 108 and the sealing material 110. The getter material film 104 captures oxygen, and the influence of the oxygen on the photoelectric conversion element 11 can be eliminated.

  Furthermore, the getter material film 104 is preferably one that transmits visible light from the viewpoint of not preventing the photoelectric conversion element 11 from absorbing light. For example, the transmittance of visible light (wavelength 360 to 830 nm) is usually 60% or more, preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 85% or more. Preferably it is 90% or more, Especially preferably, it is 95% or more, Especially preferably, it is 97% or more. This is to convert more sunlight into electrical energy.

  Furthermore, since the solar cell 10 is often heated by receiving light, it is preferable that the getter material film 104 also has heat resistance. From this viewpoint, the melting point of the constituent material of the getter material film 104 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably. Is 300 ° C. or lower. By increasing the melting point, the possibility that the getter material film 104 is melted and deteriorated when the solar cell 10 is used can be reduced.

The material constituting the getter material film 104 is arbitrary as long as it can absorb moisture and / or oxygen. Examples of the material include alkali metal, alkaline earth metal, alkaline earth metal oxide, alkali metal or alkaline earth metal hydroxide, silica gel, zeolite compound, magnesium sulfate as a substance that absorbs moisture. And sulfates such as sodium sulfate and nickel sulfate, and organometallic compounds such as aluminum metal complexes and aluminum oxide octylates. Specifically, examples of the alkaline earth metal include Ca, Sr, and Ba. Examples of the alkaline earth metal oxide include CaO, SrO, and BaO. In addition, Zr-Al-BaO, an aluminum metal complex, etc. are also mentioned. Specific product names include, for example, OleDry (Futaba Electronics).
Examples of the substance that absorbs oxygen include activated carbon, silica gel, activated alumina, molecular sieve, magnesium oxide, and iron oxide. In addition, Fe, Mn, Zn, and inorganic salts such as sulfates, chlorides, and nitrates of these metals are also included.
Note that the getter material film 104 may be formed of one kind of material or two or more kinds of materials. The getter material film 104 may be formed of a single layer film, but may be a laminated film including two or more layers.

  The thickness of the getter material film 104 is not particularly defined, but is usually 5 μm or more, preferably 10 μm or more, more preferably 15 μm or more, and usually 200 μm or less, preferably 180 μm or less, more preferably 150 μm or less. Increasing the thickness tends to increase mechanical strength, and decreasing the thickness tends to increase flexibility.

  The getter material film 104 is not limited in its formation position as long as it is in the space formed by the gas barrier films 103 and 108 and the sealing material 110, but the front surface of the photoelectric conversion element 11 (the surface on the light receiving surface side; lower in FIG. 3). Side surface) and the back surface (surface opposite to the light receiving surface; upper surface in FIG. 3) are preferably covered. This is because in the solar cell 10, the front surface and the back surface are often formed in a larger area than the other surfaces, and therefore moisture and oxygen tend to enter through these surfaces. From this viewpoint, the getter material film 104 is preferably provided between the gas barrier film 103 and the photoelectric conversion element 11. In this embodiment, the getter material film 104 covers the front surface of the photoelectric conversion element 11, the getter material film 107 described later covers the back surface of the photoelectric conversion element 11, and the getter material films 104 and 107 are the photoelectric conversion element 11 and the gas barrier film 103, respectively. , 108. In addition, when using a highly waterproof sheet such as a sheet in which a fluororesin film is bonded to both sides of an aluminum foil as the back sheet 109 described later, the getter material film 107 and / or the gas barrier film 108 may not be used depending on the application. .

  The getter material film 104 can be formed by any method depending on the type of the water-absorbing agent or desiccant. For example, a method of attaching a film in which the water-absorbing agent or desiccant is dispersed with an adhesive, water-absorbing agent or desiccant A method of applying the solution by a spin coating method, an inkjet method, a dispenser method, or the like can be used. A film forming method such as a vacuum evaporation method or a sputtering method may be used.

  Examples of the film for the water absorbing agent or the drying agent include polyethylene resins, polypropylene resins, cyclic polyolefin resins, polystyrene resins, acrylonitrile-styrene copolymers (AS resins), and acrylonitrile-butadiene-styrene copolymers. (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, and the like can be used. Among these, films of polyethylene resin, fluorine resin, cyclic polyolefin resin, and polycarbonate resin are preferable. In addition, the said resin may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

[Encapsulant 105]
The sealing material 105 is a film that reinforces the photoelectric conversion element 11. Since the photoelectric conversion element 11 is thin, the strength is usually weak, and thus the strength of the solar cell tends to be weak. However, the strength can be maintained high by the sealing material 105.

Further, the sealing material 105 preferably has a high strength from the viewpoint of maintaining the strength of the solar cell 10.
The specific strength is related to the strength of the weather-resistant protective film 101 other than the sealing material 105 and the strength of the back sheet 109, and is generally difficult to define, but the entire solar cell 10 has good bending workability. It is desirable to have a strength that does not cause peeling of the bent portion.

  Further, the sealing material 105 is preferably one that transmits visible light from the viewpoint of not hindering light absorption of the photoelectric conversion element 11. For example, the transmittance of visible light (wavelength 360 to 830 nm) is usually 60% or more, preferably 70% or more, more preferably 75% or more, still more preferably 80% or more, and particularly preferably 85% or more. Preferably it is 90% or more, Especially preferably, it is 95% or more, Especially preferably, it is 97% or more. This is to convert more sunlight into electrical energy.

  Furthermore, since the solar cell 10 is often heated by receiving light, it is preferable that the sealing material 105 also has heat resistance. From this viewpoint, the melting point of the constituent material of the sealing material 105 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 350 ° C. or lower, preferably 320 ° C. or lower, more preferably. Is 300 ° C. or lower. By increasing the melting point, it is possible to reduce the possibility that the sealing material 105 melts and deteriorates when the solar cell 10 is used.

  The thickness of the sealing material 105 is not particularly defined, but is usually 100 μm or more, preferably 150 μm or more, more preferably 200 μm or more, and usually 700 μm or less, preferably 600 μm or less, more preferably 500 μm or less. Increasing the thickness tends to increase the strength of the entire solar cell 10, and decreasing the thickness tends to increase flexibility and improve visible light transmittance.

  As a material constituting the sealing material 105, for example, an ethylene-vinyl acetate copolymer (EVA) resin composition film (EVA film) or the like can be used. In order to improve weather resistance, the EVA film is usually blended with a crosslinking agent to form a crosslinked structure. As the crosslinking agent, an organic peroxide that generates radicals at 100 ° C. or higher is generally used. Examples of such an organic peroxide include 2,5-dimethylhexane; 2,5-dihydroperoxide; 2,5-dimethyl-2,5-di (t-butylperoxy) hexane; Di-t-butyl peroxide or the like can be used. The compounding amount of these organic peroxides is usually 5 parts by weight or less, preferably 3 parts by weight or less, and usually 1 part by weight or more with respect to 100 parts by weight of the EVA resin. In addition, 1 type may be used for a crosslinking agent and it may use 2 or more types together by arbitrary combinations and a ratio.

  This EVA resin composition may contain a silane coupling agent for the purpose of improving the adhesive strength. Examples of silane coupling agents used for this purpose include γ-chloropropyltrimethoxysilane; vinyltrichlorosilane; vinyltriethoxysilane; vinyl-tris- (β-methoxyethoxy) silane; γ-methacryloxypropyltri Methoxysilane; β- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned. The compounding amount of these silane coupling agents is usually 5 parts by weight or less, preferably 2 parts by weight or less, and usually 0.1 parts by weight or more with respect to 100 parts by weight of the EVA resin. In addition, 1 type may be used for a silane coupling agent and it may use 2 or more types together by arbitrary combinations and a ratio.

  Furthermore, in order to improve the gel fraction of the EVA resin and improve the durability, a crosslinking aid may be included in the EVA resin composition. Examples of the crosslinking aid provided for this purpose include monofunctional crosslinking aids such as trifunctional crosslinking aids such as triallyl isocyanurate and triallyl isocyanate. The amount of these crosslinking aids is usually 10 parts by weight or less, preferably 5 parts by weight or less, and usually 1 part by weight or more with respect to 100 parts by weight of the EVA resin. In addition, 1 type may be used for a crosslinking adjuvant, and 2 or more types may be used together by arbitrary combinations and a ratio.

  Furthermore, for the purpose of improving the stability of the EVA resin, the EVA resin composition may contain, for example, hydroquinone; hydroquinone monomethyl ether; p-benzoquinone; methyl hydroquinone. These compounding quantities are normally 5 weight part or less with respect to 100 weight part of EVA resin.

  However, since the EVA resin cross-linking process requires a relatively long time of about 1 to 2 hours, it may cause a reduction in the production rate and production efficiency of the solar cell 10. In addition, when used for a long time, the decomposition gas (acetic acid gas) of the EVA resin composition or the vinyl acetate group of the EVA resin itself may adversely affect the photoelectric conversion element 11 and reduce the power generation efficiency. Therefore, as the sealing material 105, a copolymer film made of a propylene / ethylene / α-olefin copolymer can be used in addition to the EVA film. As this copolymer, the thermoplastic resin composition with which the following component 1 and the component 2 were mix | blended is mentioned, for example.

Component 1: The propylene polymer is usually 0 part by weight or more, preferably 10 parts by weight or more, and usually 70 parts by weight or less, preferably 50 parts by weight or less.
Component 2: The soft propylene copolymer is 30 parts by weight or more, preferably 50 parts by weight or more, and is usually 100 parts by weight or less, preferably 90 parts by weight or less.
The total amount of component 1 and component 2 is 100 parts by weight. As described above, when component 1 and component 2 are in the preferred range, the moldability of sealing material 105 into a sheet is good, and the resulting sealing material 105 has good heat resistance, transparency, and flexibility. Therefore, it is suitable for the solar cell 10.
Hereinafter, component 1 and component 2 will be described in detail.

[Component 1]
Component 1 is a propylene-based polymer, and examples thereof include a propylene homopolymer; a copolymer of propylene and at least one α-olefin having 2 to 20 carbon atoms other than propylene. Here, as the α-olefin having 2 to 20 carbon atoms other than propylene, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-octene, Examples include decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene. Among these, ethylene or an α-olefin having 4 to 10 carbon atoms is preferable. In addition, alpha-olefin may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  These α-olefins may form a random copolymer with propylene or a block copolymer. The proportion of the constituent units derived from these α-olefins is usually 35 mol% or less, preferably 30 mol% or less in the polypropylene.

  Component 1 has a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg in accordance with ASTM D 1238, usually 0.01 g / 10 min or more, preferably 0.05 g / 10 min or more. Usually, it is 1000 g / 10 min or less, preferably 100 g / 10 min or less.

  The melting point observed by the differential scanning calorimeter of component 1 is usually 100 ° C. or higher, preferably 110 ° C. or higher, and is usually 160 ° C. or lower, preferably 150 ° C. or lower.

Component 1 can use either an isotactic structure or a syndiotactic structure, but the isotactic structure is preferred in view of heat resistance and the like.
Further, as the component 1, a plurality of propylene polymers can be used in combination as necessary, and for example, two or more types of components having different melting points and rigidity can be used.

[Component 2]
Component 2 is a soft propylene-based copolymer, and examples thereof include a copolymer of propylene and at least one α-olefin having 2 to 20 carbon atoms other than propylene.
Component 2 has a Shore A hardness of usually 30 or more, preferably 35 or more, and usually 80 or less, preferably 70 or less.
Furthermore, the melting point observed with the differential scanning calorimeter DSC of component 2 is less than 100 ° C. or no melting point is observed. Here, that the melting point is not observed means that a crystal melting peak having a heat of crystal melting of 1 J / g or more is not observed in the range of −150 to 200 ° C.

In Component 2, the α-olefin used as a comonomer is preferably, for example, ethylene and / or an α-olefin having 4 to 20 carbon atoms. In addition, alpha-olefin may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.
Component 2 contains propylene-derived units usually 45 mol% or more, preferably 56 mol% or more, and usually 92 mol% or less, preferably 90 mol% or less, and usually contains α-olefin-derived units used as a comonomer. 8 mol% or more, preferably 10 mol% or more, and usually 55 mol% or less, preferably 44 mol% or less.

  Component 2 has a melt flow rate (MFR) measured at 230 ° C. and a load of 2.16 kg, usually 0.01 g / 10 min or more, preferably 0.05 g / 10 min or more, in accordance with ASTM D 1238. In addition, it is usually 100 g / 10 min or less, preferably 50 g / 10 min or less.

  Component 2 is based on JIS K6301, using a JIS No. 3 dumbbell, span: 30 mm, tensile speed: 30 mm / min, measured at 23 ° C., stress at 100% strain (M100) is usually 4 MPa. Hereinafter, it is preferably 3 MPa or less, more preferably 2 MPa or less. When the soft propylene copolymer is in such a range, the flexibility, transparency, and rubber elasticity are excellent.

Component 2 has a crystallinity measured by X-ray diffraction of usually 20% or less, preferably 15% or less, and usually 0% or more.
Component 2 has a single glass transition temperature Tg, and the glass transition temperature Tg measured by a differential scanning calorimeter (DSC) is usually in the range of −10 ° C. or lower, preferably −15 ° C. or lower. Is desirable. When the glass transition temperature Tg of Component 2 is within the above range, the cold resistance and low temperature characteristics are excellent.

  The molecular weight distribution (Mw / Mn, polystyrene conversion, Mw: weight average molecular weight, Mn: number average molecular weight) measured by GPC of Component 2 is preferably 4.0 or less, more preferably 3.0 or less, and further Preferably it is 2.5 or less.

Component 2 usually has a heat of fusion ΔH of 30 J / g or less and a C3 (propylene) content when a melting point (Tm, ° C.) exists in an endothermic curve in a differential scanning calorimeter (DSC). It is preferable that the following relational expression holds for the relationship between (mol%) and the heat of fusion ΔH (J / g).
ΔH <345Ln (C3 content mol%)-1492,
(However, in this case, 76 ≦ C3 content (mol%) ≦ 90)

  Preferred specific examples of component 2 include the following propylene / ethylene / α-olefin copolymers. By using such a propylene / ethylene / α-olefin copolymer, a sealing material 105 having good flexibility, heat resistance, mechanical strength, photoelectric conversion element sealing property and transparency can be obtained. Here, the photoelectric conversion element sealing property means that the cracking rate of the element when the photoelectric conversion element 11 is filled can be reduced with good flexibility.

  As propylene / ethylene / α-olefin copolymer, propylene-derived structural units are usually 45 mol% or more, preferably 56 mol% or more, more preferably 61 mol% or more, and usually 92 mol% or less, preferably 90 mol% or less, more preferably 86 mol% or less, and further ethylene-derived structural units are usually 5 mol% or more, preferably 8 mol% or more, and usually 25 mol% or less, preferably 14 mol% or less, more Preferably, it contains 14 mol% or less, and the structural unit derived from an α-olefin having 4 to 20 carbon atoms is usually 3 mol% or more, preferably 5 mol% or more, more preferably 6 mol% or more, and usually 30 mol% or less. , Preferably those containing 25 mol% or less. With regard to α-olefins, 1-butene is particularly preferred.

  A propylene / ethylene / α-olefin copolymer (component 2) containing a propylene-derived structural unit, an ethylene-derived structural unit, and a structural unit derived from an α-olefin having 4 to 20 carbon atoms in the above amount is propylene. The compatibility with the system polymer (component 1) is improved, and the obtained sealing material 105 exhibits sufficient transparency, flexibility, heat resistance, and scratch resistance.

The thermoplastic resin composition in which the above component 1 and component 2 are blended has a melt flow rate (ASTM D 1238, 230 degrees, load 2.16 kg) of usually 0.0001 g / 10 min or more. It is 1000 g / 10 min or less, preferably 900 g / 10 min or less, more preferably 800 g / 10 min or less.
The melting point of the thermoplastic resin composition containing component 1 and component 2 is usually 100 ° C. or higher, preferably 110 ° C. or higher. Moreover, it is 140 degrees C or less normally, Preferably it is 135 degrees C or less.
Density of The thermoplastic resin composition Components 1 and 2 were compounded is preferably from 0.98 g / cm ³ or less, more preferably 0.95 g / cm ³ or less, more preferably 0.94 g / cm ³ or less .

  In the sealing material 105, a coupling agent can be blended into the component 1 and the component 2 as an adhesion promoter for plastics and the like. As the coupling agent, silane, titanate, and chromium coupling agents are preferably used, and a silane coupling agent (silane coupling agent) is particularly preferably used.

  Known silane coupling agents can be used and are not particularly limited. For example, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris (β-methoxy-ethoxysilane), γ-glycidoxypropyl-tri Examples include piltrimethoxysilane and γ-aminopropyltriethoxysilane. In addition, 1 type may be used for a coupling agent and it may use 2 or more types together by arbitrary combinations and a ratio.

  These are usually 0.1 parts by weight or more, usually 5 parts by weight or less, preferably 100 parts by weight of the silane coupling agent, based on 100 parts by weight of the thermoplastic resin composition (total amount of Component 1 and Component 2). It is desirable to contain 3 parts by weight or less.

The coupling agent may be grafted to the thermoplastic resin composition using an organic peroxide. In this case, it is desirable that 0.1 to 5 parts by weight of the coupling agent is included with respect to 100 parts by weight of the thermoplastic resin composition (total amount of Component 1 and Component 2). Even if a silane-grafted thermoplastic resin composition is used, the same or better adhesion to glass and plastic as the silane coupling agent blend can be obtained.
When the organic peroxide is used, the organic peroxide is usually 0.001 part by weight or more, preferably 0.01 part by weight with respect to 100 parts by weight of the thermoplastic resin composition (total amount of Component 1 and Component 2). Part or more, and usually 5 parts by weight or less, preferably 3 parts by weight or less.

  Known organic peroxides can be used and are not particularly limited. Examples thereof include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and dibenzoylperoxide. Examples thereof include oxide, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, and t-butylperoxymaleic acid. In addition, an organic peroxide may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

Further, a copolymer made of an ethylene / α-olefin copolymer can be used as the sealing material 105. As this copolymer, a laminate film having a hot tack property of 5 to 25 ° C., which is formed by laminating a resin composition for a sealing material comprising the following components A and B and a substrate, is exemplified.
Component A: ethylene resin.
Component B: a copolymer of ethylene and an α-olefin having the following properties (a) to (d).
(A) The density is 0.86 to 0.935 g / cm ³ .
(B) Melt flow rate (MFR) is 1 to 50 g / 10 min.
(C) There is one peak in the elution curve obtained by temperature rising elution fractionation (TREF); the peak temperature is 100 ° C. or lower.
(D) The integrated elution amount by temperature rising elution fractionation (TREF) is 90% or more at 90 ° C.

(A) Component A (ethylene-based resin)
Examples of the ethylene-based resin as the component A constituting the resin composition for a sealing material include high-pressure low-density polyethylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer produced by a so-called radical polymerization method. Examples thereof include an ethylene / acrylic acid ester copolymer and an ethylene / vinyl fluoride copolymer. Moreover, the polymer or copolymer which has ethylene as a main component, such as what is called linear low density polyethylene and high density polyethylene manufactured by the ionic polymerization method, is also mentioned. Among these, ethylene / vinyl acetate copolymer and high pressure method low density polyethylene are preferable. In addition, these may use 1 type and may use 2 or more types together by arbitrary combinations and ratios.

When the ethylene resin as component A constituting the resin composition for a sealing material is an ethylene / vinyl acetate copolymer, those having the following properties are suitable.
(I) Melt flow rate (MFR)
The MFR (melt flow rate: melt flow rate) according to JIS K7210 of the ethylene / vinyl acetate copolymer as component A constituting the resin composition for a sealing material is usually 1 g / 10 min or more, preferably 2 g. / 10 min or more, more preferably 3 g / 10 min or more, and usually 50 g / 10 min or less, preferably 30 g / 10 min or less, more preferably 20 g / 10 min or less. Increasing the MFR tends to increase transparency when blended with the component B, and decreasing the MFR tends to facilitate molding.

(Ii) Vinyl acetate content The vinyl acetate content of the ethylene / vinyl acetate copolymer as component A constituting the resin composition for a sealing material is usually 3% by weight or more, preferably 4% by weight or more, more preferably 5%. It is usually not more than 30% by weight, preferably not more than 20% by weight, more preferably not more than 15% by weight. Increasing the vinyl acetate content tends to increase heat sealability, and reducing the vinyl acetate content can suppress stickiness of the sealing material 105.

When the ethylene-based resin as component A constituting the resin composition for a sealing material is a high-pressure method low-density polyethylene, those having the following properties are suitable.
(I) Melt flow rate (MFR)
The MFR (melt flow rate: melt flow rate) according to JIS K7210 of the high-pressure low-density polyethylene as component A constituting the resin composition for a sealing material is usually 1 g / 10 min or more, preferably 2 g / 10. Min. Or more, more preferably 3 g / 10 min or more, and usually 50 g / 10 min or less, preferably 30 g / 10 min or less, more preferably 20 g / 10 min or less. It tends to be easy to extrude by increasing the MFR, and by reducing the MFR, the film becomes too soft and does not easily sag, and the moldability increases.

(Ii) Density by JIS K7112 of high-pressure low-density polyethylene as component A constituting the density encapsulant resin composition is usually 0.915 g / cm ³ or more, preferably 0.916 g / cm ³ or more, more preferably at 0.917 g / cm ³ or more and usually 0.93 g / cm ³ or less, preferably 0.925 g / cm ³ or less, more preferably 0.923 g / cm ³ or less. By increasing the density, stickiness of the sealing material 105 tends to be suppressed, and by decreasing the density, heat sealability tends to increase.

  As the high-pressure method low-density polyethylene as component A constituting the resin composition for a sealing material, those exhibiting the above physical properties can be appropriately selected from commercially available products.

(B) Component B (ethylene / α-olefin copolymer)
Component B constituting the resin composition for a sealing material is an ethylene / α-olefin copolymer other than Component A. Component B preferably has the following properties.

(I) Density The density according to JlS K7112 of the ethylene / α-olefin copolymer as component B constituting the resin composition for a sealing material is usually 0.86 g / cm ³ or more, preferably 0.87 g / cm ^3. or more, more preferably 0.88 g / cm ³ or more and usually 0.935 g / cm ³ or less, preferably 0.915 g / cm ³ or less, more preferably 0.91 g / cm ³ or less. By increasing the density, stickiness when used as a film tends to be suppressed, and by decreasing the density, heat sealability tends to increase.

(Ii) Melt flow rate (MFR)
The MFR (melt flow rate: melt flow rate) according to JLS K7210 of the ethylene / α-olefin copolymer as component B constituting the resin composition for a sealing material is usually 1 g / 10 min or more, preferably It is 2 g / 10 min or more, more preferably 3 g / 10 min or more, and is usually 50 g / 10 min or less, preferably 30 g / 10 min or less, more preferably 20 g / 10 min or less. It tends to be easy to extrude by increasing the MFR, and by reducing the MFR, the film becomes too soft and does not easily sag, and the moldability increases.

  Here, the α-olefin is preferably an α-olefin having 4 to 40 carbon atoms. Among them, among α-olefins, those having usually 4 or more, preferably 6 or more, and usually 12 or less, preferably 10 or less are desirable. For example, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-heptene, 4-methylpentene-1, 4-methylhexene-1, 4,4-dimethylpentene-1, etc. Is mentioned. In addition, alpha-olefin may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  The ratio of α-olefin to ethylene is usually 2% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 60% by weight or less, preferably 50% by weight or less. More preferably 30 wt% or less, ethylene is usually 40 wt% or more, preferably 50 wt% or more, more preferably 70 wt% or more, and usually 98 wt% or less, preferably 95 wt% or less, more preferably It is desirable that the content be 90% by weight or less.

  The blending ratio (component A / component B) of component A and component B is usually 50/50 or more, preferably 55/45 or more, more preferably 60/40 or more, and usually 99 / 1 or less, preferably 90/10 or less, more preferably 85/15 or less. Increasing the amount of component B tends to increase transparency and heat sealability, and decreasing the amount of component B tends to increase the workability of the film.

  The melt flow rate (MFR) of the resin composition for a sealing material produced by blending component A and component B is usually 2 g / 10 minutes or more, preferably 3 g / 10 minutes or more, and usually 50 g / 10 minutes. Hereinafter, it is preferably 40 g / 10 min or less. In addition, the measurement and evaluation of MFR can be implemented by the method based on JISK7210 (190 degreeC, 2.16kg load).

  The melting point of the encapsulant resin composition is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and is usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 200 ° C. or lower. By increasing the melting point, the possibility of melting and deterioration during use of the solar cell 10 can be reduced.

The density of the resin composition for a sealing material is preferably 0.80 g / cm ³ or more, more preferably 0.85 g / cm ³ or more, and preferably 0.98 g / cm ³ or less, 0.95 g / cm ^3. The following is more preferable, and 0.94 g / cm ³ or less is more preferable. The measurement and evaluation of density can be performed by a method based on JIS K7112.

  Further, in the encapsulant 105 using the ethylene / α-olefin copolymer, a coupling agent can be used as in the case of using the propylene / ethylene / α-olefin copolymer.

  Since the sealing material 105 described above does not generate a decomposition gas derived from the material, there is no adverse effect on the photoelectric conversion element 11, and good heat resistance, mechanical strength, flexibility (photoelectric conversion element sealing property) and It has transparency. In addition, since a material cross-linking step is not required, the time for forming the sheet and the manufacturing time of the solar cell 10 can be greatly shortened, and the solar cell 10 after use can be easily recycled.

  Note that the sealing material 105 may be formed of one kind of material or two or more kinds of materials. Further, the sealing material 105 may be formed of a single layer film, but may be a laminated film including two or more layers.

  The thickness of the sealing material 105 is usually 2 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and usually 500 μm or less, preferably 300 μm or less, more preferably 100 μm or less. Increasing the thickness tends to increase mechanical strength, and decreasing the thickness tends to increase flexibility and light transmittance.

  Although there is no restriction | limiting in the position which provides the sealing material 105, Usually, it provides so that the photoelectric conversion element 11 may be inserted | pinched. This is for reliably protecting the photoelectric conversion element 11. In this embodiment, the sealing material 105 and the sealing material 106 are provided on the front surface and the back surface of the photoelectric conversion element 11, respectively.

[Photoelectric conversion element 11]
The photoelectric conversion element 11 is an element that receives light and generates power. There is no restriction | limiting in the kind of the photoelectric conversion element 11, For example, a thin film polycrystalline silicon type photoelectric conversion element, an amorphous silicon type photoelectric conversion element, a compound semiconductor type photoelectric conversion element, an organic photoelectric conversion element etc. can be used.

  However, the thin film polycrystalline silicon photoelectric conversion element is a type of photoelectric conversion element utilizing indirect optical transition. For this reason, in a thin film polycrystalline silicon photoelectric conversion element, it is required to provide a sufficient light confinement structure such as forming an uneven structure on the substrate or the surface to increase light absorption. Furthermore, in thin-film polycrystalline silicon-based photoelectric conversion elements, for example, in order to enable thin film growth on low-cost substrates such as parallel glass and polymer thin films, it is possible to lower the temperature of the high-quality thin film manufacturing process. Required. For this reason, the thin film polycrystalline silicon photoelectric conversion element has room for improvement in terms of cost and the like for practical use.

  On the other hand, in the amorphous silicon photoelectric conversion element, the indirect optical transition in crystalline silicon is a direct transition due to structural disorder, and the optical absorption coefficient in the visible region is large, and even a thin film having a thickness of about 1 μm is sunlight. Has the advantage that it can be absorbed sufficiently. For this reason, if an amorphous silicon photoelectric conversion element is used as the photoelectric conversion element 11, a lightweight solar cell panel can be realized. Further, since amorphous silicon is an amorphous material, it is resistant to deformation of slats.

  However, the amorphous silicon photoelectric conversion element has a low mobility of carriers such as electrons and holes generated by light absorption due to structural disorder. In addition, although the dangling bonds of silicon serve as recombination centers of carriers, the amorphous silicon-based photoelectric conversion element has a high density of dangling bonds and thus has a short carrier life. Furthermore, the amorphous silicon photoelectric conversion element may be deteriorated by long-term light irradiation. Specifically, since the amorphous silicon photoelectric conversion element exhibits a phenomenon in which the density of the defects is further increased by light irradiation (that is, a photodegradation phenomenon), the initial photoelectric conversion efficiency is about 10%. In addition to being less efficient, the photoelectric conversion efficiency tends to be reduced to about 8% by light irradiation (although saturation occurs).

Therefore, in the solar cell 10 of the present embodiment, it is preferable to use a compound semiconductor photoelectric conversion element or an organic photoelectric conversion element as the photoelectric conversion element 11. Moreover, among the compound semiconductor-based photoelectric conversion element, e.g. S, Se, preferably a chalcogenide based photoelectric conversion device comprising a chalcogen element such as Te, inter alia I-III-VI ₂ group semiconductor system (chalcopyrite) photoelectric conversion element In particular, a Cu-III-VI group ₂ semiconductor-based photoelectric conversion element using Cu as a group I element is preferable because it has a theoretically higher photoelectric conversion efficiency than a Si crystal solar cell.

[Cu-III-VI group ₂ semiconductor photoelectric conversion element]
A Cu-III-VI group ₂ semiconductor-based photoelectric conversion element refers to a photoelectric conversion element having a Cu-III-VI group ₂ semiconductor as a constituent material. The Cu-III-VI group ₂ semiconductor refers to a semiconductor composed of a compound containing Cu, a group III element, and a group VI element at a ratio of 1: 1: 2, for example, CuInSe ₂ , CuGaSe ₂ , Cu (In _{1− x Ga x) Se 2, CuInS} 2, CuGaS 2, Cu (In 1-x Ga x) S 2, CuInTe 2, CuGaTe 2, Cu (In 1-x Ga x) Te 2 and the like. A mixture of two or more of these may be used. Especially, a CIS type photoelectric conversion element and a CIGS type photoelectric conversion element are preferable.

The CIS-based photoelectric conversion element refers to a photoelectric conversion device having a CIS-based semiconductor as a constituent material, and the CIS-based semiconductor refers to a _{CuIn (Se 1-y S y} ) 2. Note that y represents a number from 0 to 1. That is, it refers to CuInSe ₂ , CuInS ₂ , or those in a mixed state. Use of S instead of Se is preferable because safety is increased.
The CIGS photoelectric conversion element refers to a photoelectric conversion element having a CIGS semiconductor as a constituent material. Here, the CIGS-based semiconductor _refers to a _{Cu (In 1-x Ga x} ) (Se 1-y S y) 2. X represents a number greater than 0 and less than 1, and y represents a number from 0 to 1. The _{Cu (In 1-x Ga x} ) Se 2 is usually a mixed crystal of CuInSe ₂ and CuGaSe _2. The range of x is usually greater than 0, preferably greater than 0.05, more preferably greater than 0.1, and usually less than 0.8, preferably less than 0.5, more preferably 0. Less than 4.

The Cu-III-VI Group ₂ semiconductor usually functions as a p-type semiconductor. Here, p-type and n-type semiconductors will be described. In semiconductors, there are two types of carriers that transport charges, electrons and holes, and the larger the density, the more carriers are called. Majority carriers are usually determined by the type of semiconductor and the doping state. As the semiconductor type, those in which majority carriers are electrons are called n-type, those in which holes are holes are called p-type, and those in which the majority carriers are balanced are called i-type.
However, the p-type and n-type are not absolutely determined by the type of semiconductor. For example, even when semiconductors of the same type are combined, one may operate as a p-type and the other as an n-type due to the relationship between energy levels (HOMO levels, LUMO levels, Fermi levels) and doping states. is there.

The degree of semiconductor characteristics exhibited by the semiconductor is usually 10 ⁻⁷ cm ² / Vs or more, preferably 10 ⁻⁵ cm ² / Vs or more in terms of carrier mobility. Since electrical conductivity is defined by carrier mobility x carrier density, any material having a certain level of carrier mobility may have carriers present in the material, for example, by heat, doping, or injection from an electrode. For example, the material can transport charges. Note that the higher the carrier mobility of the semiconductor, the better.

The Cu-III-VI group ₂ semiconductor is usually contained in at least one of the layers constituting the photoelectric conversion element 11, and the photoelectric conversion element 11 absorbs light in the layer containing the semiconductor to generate electricity. Is supposed to occur. A specific configuration of the photoelectric conversion element 11 will be described below with an example. However, the photoelectric conversion element 11 according to the present invention is not limited to the example described below.

For example, the Cu-III-VI group ₂ semiconductor-based photoelectric conversion element includes at least a light absorption layer and a buffer layer between a pair of electrodes. In the photoelectric conversion element having such a configuration, light is absorbed in the light absorption layer to generate electricity, and the generated electricity is extracted from the electrode.

-Electrode An electrode can be formed with the arbitrary materials which have electroconductivity. Examples of electrode materials include metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, barium, sodium, and alloys thereof; metal oxides such as indium oxide and tin oxide. Or alloys thereof (ITO); conductive polymers such as polyaniline, polypyrrole, polythiophene and polyacetylene; acids such as hydrochloric acid, sulfuric acid and sulfonic acid, Lewis acids such as FeCl ₃ and halogens such as iodine Materials containing a dopant such as metal atoms such as atoms, sodium and potassium; conductive composite materials in which conductive particles such as metal particles, carbon black, fullerene and carbon nanotubes are dispersed in a matrix such as a polymer binder It is done. In addition, the material of an electrode may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  In the photoelectric conversion element 11, at least a pair (two) of electrodes are provided. At this time, it is preferable that at least the electrode on the light receiving surface side of the pair of electrodes is transparent in order to transmit light for power generation. However, if the electrode is not transparent, such as the area of the electrode is smaller than the area of the power generation layer, it does not necessarily need to be transparent if the power generation performance is not adversely affected. Examples of transparent electrode materials include oxides such as ITO and indium zinc oxide (IZO); and metal thin films. At this time, the specific range of the light transmittance is not limited, but 80% or more is preferable in consideration of the power generation efficiency of the photoelectric conversion element 11. The light transmittance can be measured with a normal spectrophotometer.

  The electrode has a function of collecting holes and electrons generated by light absorption. Therefore, it is preferable to use an electrode material suitable for collecting holes and electrons for the electrode. Examples of the electrode material suitable for collecting holes include materials having a high work function such as Au and ITO. On the other hand, an electrode material suitable for collecting electrons includes a material having a low work function such as Al.

In addition, there is no restriction | limiting in the formation method of an electrode. For example, it can be formed by a dry process such as vacuum deposition or sputtering. Further, for example, it can be formed by a wet process using a conductive ink or the like. At this time, any conductive ink can be used. For example, a conductive polymer, a metal particle dispersion, or the like can be used.
Furthermore, two or more electrodes may be laminated, and characteristics (electric characteristics, wetting characteristics, etc.) due to surface treatment may be improved.

-Light absorption layer A light absorption layer is a layer containing the Cu-III-VI ₂ group semiconductor mentioned above. Usually, since a Cu-III-VI group ₂ semiconductor functions as a p-type semiconductor, it is possible to generate electricity by absorbing light by forming a buffer layer described later with an n-type semiconductor. Note that each of the Cu-III-VI group ₂ semiconductors may be formed of one kind, or two or more kinds may be used in any combination and ratio. Also, a CIS semiconductor and a CIGS semiconductor may be combined.

Usually, the light absorption layer is formed of only a Cu-III-VI group ₂ semiconductor, but may contain other components as long as the effects of the present invention are not significantly impaired. Examples thereof include additives such as Ag. In addition, the other component may contain 1 type and may contain 2 or more types by arbitrary combinations and ratios.

There is no restriction | limiting in the formation method of a light absorption layer. For example, it can be formed by vacuum deposition, sputtering, or the like.
Furthermore, although the light absorption layer usually forms only one layer, two or more layers may be laminated.

Buffer layer The buffer layer is a layer that is laminated so as to be in contact with the light absorption layer. If the semiconductor that the light absorption layer has is p-type, it is formed of an n-type semiconductor, and the semiconductor that the light absorption layer has is n-type. If present, it is formed of a p-type semiconductor. Usually, the Cu-III-VI ₂ group semiconductor because it is p-type semiconductor, the buffer layer in the Cu-III-VI ₂ group semiconductor-based photoelectric conversion device is formed by n-type semiconductor.

Specific examples of the semiconductor forming the buffer layer include CdS, Zn _1-x Mg _x O (0 <x <0.8), ZnS (O, OH), InS, and the like. In addition, since the above-described CuInS ₂ can be formed as an n-type semiconductor layer by setting it to a composition deviating from the stoichiometric ratio depending on manufacturing conditions, it may be used as a buffer layer. In addition, the semiconductor which forms a buffer layer may be 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

There is no restriction | limiting in the formation method of a buffer layer. For example, it can be formed by vacuum deposition, sputtering, or the like.
Furthermore, the buffer layer usually forms only one layer, but two or more layers may be laminated.

[Organic photoelectric conversion element]
An organic photoelectric conversion element refers to a photoelectric conversion element having an organic semiconductor as a constituent material. Examples of the organic semiconductor include naphthalene (or perylene) tetracarboxylic acid diimide, fullerene (C ₆₀ ), and derivatives thereof.
Moreover, for example, conjugated polymers such as polythiophene, polyfluorene, polythienylene vinylene, polyacetylene, and polyaniline; and polymer semiconductors such as alkyl-substituted oligothiophene are also included. These are semiconductors that are soluble in an organic solvent, and are preferable because a coating method can be used in the manufacturing process of the organic photoelectric conversion element.
Furthermore, for example, condensed aromatic hydrocarbons such as naphthacene, pentacene, pyrene, fullerene; oligothiophenes containing 4 or more thiophene rings such as α-sexithiophene; thiophene ring, benzene ring, fluorene ring, naphthalene ring, anthracene Rings, thiazole rings, thiadiazole rings, benzothiazole rings in total of 4 or more; aromatics such as naphthalene tetracarboxylic acid anhydride, naphthalene tetracarboxylic acid diimide, perylene tetracarboxylic acid anhydride, perylene tetracarboxylic acid diimide Examples thereof include carboxylic acid anhydrides and imidized products thereof; phthalocyanine compounds such as copper phthalocyanine and perfluorocopper phthalocyanine; porphyrin compounds such as tetrabenzoporphyrin and macrocyclic compounds such as metal salts thereof.
In addition, those described in International Publication No. 2007/126102 pamphlet can be used.

The organic semiconductor functions as any of p-type, n-type, and i-type depending on the type and usage state.
Moreover, it is preferable that the grade of the semiconductor characteristic which an organic semiconductor shows is the same grade as a Cu-III-VI ₂ group semiconductor.

  The organic semiconductor is usually contained in at least one of the layers constituting the photoelectric conversion element 11, and the photoelectric conversion element 11 absorbs light in the layer containing the semiconductor to generate electricity. ing. A specific configuration of the photoelectric conversion element 11 will be described below with an example. However, the photoelectric conversion element 11 is not limited to the example described below.

  For example, the organic photoelectric conversion element includes at least an active layer between a pair of electrodes. In the photoelectric conversion element having such a configuration, light is absorbed in the active layer to generate electricity, and the generated electricity is extracted from the electrode.

-Electrode Also in an organic photoelectric conversion element, an electrode is the same as that of a Cu-III-VI ₂ group semiconductor type photoelectric conversion element.

Active layer The active layer is a layer containing a semiconductor and is a layer that absorbs light and separates charges. This active layer may be composed of only a single layer film or may be composed of two or more laminated films. In the organic photoelectric conversion element, an organic semiconductor is used as at least one of the above semiconductors, preferably all.

  The specific configuration of the active layer is arbitrary as long as at least a p-type semiconductor and an n-type semiconductor are contained. For example, an n-type semiconductor and a p-type semiconductor may be contained in separate films, or an n-type semiconductor and a p-type semiconductor may be contained in the same film. In addition, each of the n-type semiconductor and the p-type semiconductor may be used alone or in combination of two or more in any combination and ratio.

  Furthermore, the organic semiconductor is usually present in an aggregated state such as in the form of particles or fibers. At this time, the particle size of the semiconductor is usually 2 nm or more, preferably 5 nm or more, and usually 10 μm or less, preferably 1 μm or less. In the organic photoelectric conversion element, it is possible to satisfactorily disperse particles having such a small particle diameter in the active layer. In particular, as described in the pamphlet of International Publication No. 2007/126102, a latent pigment is used. In the organic photoelectric conversion element manufactured using it, it is possible to disperse particularly well.

A latent pigment refers to precursors having different chemical structures of pigments. By applying an external stimulus such as heating or light irradiation to the latent pigment, the chemical structure of the latent pigment is changed and converted into the pigment.
The latent pigment is preferably excellent in film formability. This is because even if the pigment has poor film formability, the cost during film formation can be reduced by forming the film in the state of a latent pigment and then converting it to a pigment. In particular, in order to be able to apply the coating process, it is preferable that the latent pigment itself can be applied in a liquid state, or the latent pigment can be applied as a solution with high solubility in some solvent. If the suitable range of solubility is mentioned, the solubility with respect to the solvent of a latent pigment is 0.1 weight% or more normally, Preferably it is 0.5 weight% or more, More preferably, it is 1 weight% or more.
Furthermore, it is preferable that the latent pigment can be easily converted into a pigment. In the process of converting the latent pigment to the pigment, what kind of external stimulus is given to the latent pigment is arbitrary, but usually heat treatment, light irradiation, etc. are performed.
Moreover, it is preferable that a latent pigment is converted into a pigment with a high yield through a conversion process. Under the present circumstances, the yield of the pigment obtained by converting from a latent pigment is arbitrary unless the performance of an organic photoelectric conversion element is impaired remarkably. If the suitable range of a yield is mentioned, the yield of the pigment obtained from a latent pigment is so preferable that it is high, and is 90% or more normally, Preferably it is 95% or more, More preferably, it is 99% or more.
An organic semiconductor obtained by converting a latent pigment is a compound having a low solubility in a general solvent. Here, the low solubility in a general solvent means, for example, that the solubility in toluene is usually 1% or less, preferably 0.1% or less.

  In the active layer, it is preferable that the p-type semiconductor and the n-type semiconductor are phase-separated and the active layer has a phase-separated structure. If the active layer has a phase separation structure, carrier separation occurs due to light irradiation, and after holes and electrons are generated, the probability of reaching the electrodes without recombination can be increased. Because it can be expected. Such a phase separation structure can be suitably realized when an organic semiconductor and an inorganic semiconductor are used in combination as semiconductors.

  A phase separation structure is a structure in which materials constituting a phase (for example, semiconductors) are not uniformly mixed at the molecular level, and each material is in an aggregated state, and between the aggregated states. Have an interface. This phase-separated structure can be observed by a method of examining a local structure such as an optical microscope, an electron microscope, or an atomic force microscope (AFM), or by diffracting from an aggregated portion by X-ray diffraction. Can be confirmed.

  The specific configuration of the active layer varies depending on the type of the organic photoelectric conversion element. Examples of the configuration of the active layer include a bulk heterojunction type, a stacked type (hetero pn junction type), and a Schottky type.

The bulk heterojunction type includes a p-type semiconductor and an n-type semiconductor in a single active layer. And it has a phase separation structure in which a p-type semiconductor and an n-type semiconductor are phase-separated, carrier separation occurs at the interface of the phase, and positive charges (holes) and negative charges (electrons) in each phase Are separated and transported.
In the bulk heterojunction type active layer, the phase separation structure has an influence on the light absorption process, the exciton diffusion process, the exciton dissociation (carrier separation) process, the carrier transport process, and the like. Therefore, it is considered that good photoelectric conversion efficiency can be realized by optimizing the phase separation structure.

  In the stacked type (hetero pn junction type), the active layer is composed of two or more films, at least one film is formed containing a p-type semiconductor, and the other film contains an n-type semiconductor. Is formed. A phase interface between the p-type semiconductor and the n-type semiconductor is formed at the boundary between the film containing the p-type semiconductor and the film containing the n-type semiconductor, and carrier separation occurs at the phase interface. It is supposed to happen.

  It is also possible to combine a bulk heterojunction type and a laminated type. For example, the active layer is composed of two or more films, and at least one of these films contains both p-type and n-type semiconductors, and the p-type semiconductor and the n-type semiconductor are phase-separated. It is constituted as follows. In this case, carrier separation occurs at both the phase interface formed between the stacked films and the phase interface between the p-type semiconductor and the n-type semiconductor in the film containing both the p-type and n-type semiconductors. It has come to occur. Alternatively, in this case, for example, it is expected that one carrier is blocked between the laminated films to improve the electric extraction efficiency.

  In the Schottky type, a Schottky barrier is formed in the vicinity of an electrode, and carrier separation is performed by an internal electric field in this portion. If an electrode that forms a Schottky barrier is used as the electrode, the structure of the active layer is not limited. As the specific configuration of the active layer in the Schottky type, any of the above-described bulk heterojunction type, stacked type, and a combination type of both can be adopted, and particularly high characteristics (for example, conversion efficiency) are expected. it can.

In the organic photoelectric conversion element, at least one kind of organic semiconductor is used for the active layer, but an inorganic substance may be included in addition to this (hereinafter referred to as a hybrid type).
In the hybrid type, the active layer is formed by containing both an inorganic substance and an organic substance. At this time, the inorganic substance and the organic substance contained in the hybrid active layer may have no semiconductor characteristics except that they contain at least one kind of organic semiconductor, but those having semiconductor characteristics ( That is, it is preferable to use an inorganic semiconductor and an organic semiconductor. For example, perylene pigments, quinacridone pigments, phthalocyanine pigments, porphyrin pigments and the like are listed as organic semiconductors used in the hybrid type, and titania and zinc oxide are listed as inorganic semiconductors.

  A specific example of the layer structure of the hybrid type active layer is as follows. In the bulk heterojunction type active layer, when an inorganic substance is used as one of the p-type and n-type semiconductors and an organic substance is used as the other, the p-type is used. And the case where an inorganic substance and an organic substance are used as one or both of the n-type semiconductor and the like. Thereby, an active layer is comprised as a mixed film of an inorganic semiconductor and an organic semiconductor, and improvement in the efficiency of an organic photoelectric conversion element can be expected.

[Other matters]
Other layers The Cu-III-VI group ₂ semiconductor-based photoelectric conversion element and organic photoelectric conversion element shown in the above example include other layers in addition to the above-described electrode, light absorption layer, buffer layer, and active layer. May be. The positions where other layers are formed are arbitrary as long as the power generation of the photoelectric conversion element 11 is not hindered. An example of such a layer is an electrode interface layer.

  The electrode interface layer is a layer provided for improving electrical characteristics between the light absorbing layer, the buffer layer or the active layer and the electrode. Normally, a layer (p-type semiconductor layer) that blocks electrons and conducts only holes is formed between the electrode that collects holes and the light absorption layer, buffer layer, or active layer, and collects electrons. A layer that blocks holes and conducts only electrons (n-type semiconductor layer) is formed between the electrode to be formed and the light absorption layer, buffer layer, or active layer.

As a material of the p-type semiconductor layer (p-type semiconductor), a material that can efficiently transport generated holes to the positive electrode is preferable. For this purpose, the p-type semiconductor has a high hole mobility, a high conductivity, a small hole injection barrier with the positive electrode, a light absorption layer, a buffer layer, or an active layer to a p-type semiconductor layer. It is preferable to have properties such as a small hole-injection barrier.
Furthermore, when taking light into the light absorption layer or the active layer through the p-type semiconductor layer, it is preferable to use a transparent material as the p-type semiconductor. Usually, visible light will be taken into the light absorption layer or active layer among the light, and as a transparent p-type semiconductor, the transmittance of visible light transmitted through the p-type semiconductor layer is usually 60% or more, Among them, it is preferable to use those that are 80% or more. In order to realize this, a material that does not absorb visible light is used, or the p-type semiconductor layer may be formed as a thin film that is thin enough to satisfy the transmittance even if there is absorption.
Furthermore, in order to reduce the manufacturing cost and increase the area of the photoelectric conversion element 11, it is preferable to use an organic semiconductor as the p-type semiconductor and form the p-type semiconductor layer as a p-type organic semiconductor layer.

  From this point of view, a suitable example of a p-type semiconductor includes a porphyrin compound or a phthalocyanine compound. These compounds may have a central metal or may be metal-free. Specific examples thereof include 29H, 31H-phthalocyanine, copper (II) phthalocyanine, zinc (II) phthalocyanine, titanium phthalocyanine oxide, copper (II) 4,4 ′, 4 ″, 4 ′ ″-tetraaza-29H. , 31H-phthalocyanine and the like; and porphyrin compounds such as tetrabenzoporphyrin, tetrabenzocopper porphyrin, and tetrabenzozinc porphyrin;

Examples of preferable p-type semiconductors other than porphyrin compounds and phthalocyanine compounds include a system in which a dopant is mixed with a hole transporting polymer. In this case, examples of the hole transporting polymer include poly (ethylenedioxythiophene), polythiophene, polyaniline, polypyrrole, and the like. On the other hand, examples of the dopant include iodine; acids such as poly (styrene sulfonic acid) and camphor sulfonic acid; Lewis acids such as PF ₅ , AsF ₅ and FeCl ₃ ; In addition, a p-type semiconductor may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio. Moreover, the semiconductor illustrated here can also be contained in a light absorption layer, a buffer layer, or an active layer.

Although there is no restriction | limiting in the thickness of a p-type semiconductor layer, For example, in an organic photoelectric conversion element, it is 3 nm or more normally, Especially 10 nm or more, Furthermore, it is preferable to set it as 200 nm or less especially 100 nm or less. Increasing the thickness of the p-type semiconductor layer tends to increase the uniformity of the film, and decreasing the thickness of the p-type semiconductor layer tends to improve the transmittance and decrease the series resistance.
For example, in a Cu-III-VI group ₂ semiconductor-based photoelectric conversion element, it is usually 0.5 μm or more, preferably 1 μm or more, and usually 10 μm or less, preferably 5 μm or less. When the p-type semiconductor layer is thinned, the power generation efficiency tends to decrease. When the p-type semiconductor layer is thickened, cracks are easily generated when the p-type semiconductor layer is bent, or the Mo layer is easily separated.

On the other hand, the role required for the n-type semiconductor layer is to block holes separated from the light absorption layer or the active layer and transport only electrons to the negative electrode. As a material of the n-type semiconductor layer (n-type semiconductor), a material that can efficiently transport the generated electrons to the negative electrode is preferable. For this purpose, the n-type semiconductor has high electron mobility, high conductivity, a small electron injection barrier between the negative electrode, and electrons from the light absorption layer, buffer layer, or active layer to the n-type semiconductor. It is preferable to have properties such as a small injection wall.
Furthermore, when taking light into the light absorption layer or the active layer through the n-type semiconductor layer, it is preferable to use a transparent material as the n-type semiconductor. Usually, visible light will be taken into the light absorption layer or active layer among the light, and as a transparent n-type semiconductor, the transmittance of visible light transmitted through the n-type semiconductor layer is usually 60% or more, Among them, it is preferable to use those that are 80% or more. In order to realize this, a material that does not absorb visible light may be used, or the n-type semiconductor layer may be formed as a thin film that is thin enough to satisfy the transmittance even if there is absorption.
The role required for the n-type semiconductor layer is also to prevent the exciton (exciton) generated by absorbing light in the light absorption layer or active layer from being quenched by the negative electrode. For this purpose, the n-type semiconductor preferably has an optical gap larger than that of the electron donor and the electron acceptor.

From this point of view, preferable examples of n-type semiconductors include organic compounds exhibiting electron transport properties such as phenanthroline derivatives and silole derivatives; inorganic semiconductors such as TiO ₂ . In addition, an n-type semiconductor may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios. Moreover, the semiconductor illustrated here can also be contained in a light absorption layer, a buffer layer, or an active layer.

  Although there is no restriction | limiting in the thickness of an n-type semiconductor layer, For example, in an organic photoelectric conversion element, it is usually 2 nm or more, Especially 5 nm or more, Furthermore, it is preferable to set it as 200 nm or less especially 100 nm or less. By forming the n-type semiconductor layer in such a thickness range, when light incident from the positive electrode is transmitted without being absorbed by the light absorption layer or active layer, it is reflected by the negative electrode and is again reflected by the light absorption layer or active layer. It is possible to make use of the optical interference effect by returning to step (b).

-Connection between photoelectric conversion elements Although only one photoelectric conversion element 11 may be provided per one solar cell 10, usually two or more photoelectric conversion elements 11 are provided. The specific number of photoelectric conversion elements 11 may be arbitrarily set. When a plurality of photoelectric conversion elements 11 are provided, the photoelectric conversion elements 11 are often provided in an array.

  When a plurality of photoelectric conversion elements 11 are provided, the photoelectric conversion elements 11 are usually electrically connected to each other, and electricity generated from the group of connected photoelectric conversion elements 11 is taken out from a terminal (not shown). At this time, in order to increase the voltage, the photoelectric conversion elements are usually connected in series.

  Thus, when connecting the photoelectric conversion elements 11, it is preferable that the distance between the photoelectric conversion elements 11 is small, and by extension, the gap between the photoelectric conversion elements 11 and the photoelectric conversion elements 11 is preferably narrow. This is because the light receiving area of the photoelectric conversion element 11 is widened to increase the amount of light received and the power generation amount of the solar cell 10 is increased.

[Encapsulant 106]
The sealing material 106 is a film similar to the sealing material 105 described above, and the same material as the sealing material 106 can be used in the same manner except that the arrangement position is different.
In addition, the constituent member on the back side of the photoelectric conversion element 11 does not necessarily need to transmit visible light, and therefore, a member that does not transmit visible light can be used.

[Getter material film 107]
The getter material film 107 is the same as the getter material film 104 described above, and the same material as the getter material film 104 can be used as necessary except that the arrangement position is different.
In addition, the constituent member on the back side of the photoelectric conversion element 11 does not necessarily need to transmit visible light, and therefore, a member that does not transmit visible light can be used. It is also possible to use a film containing a larger amount of moisture or oxygen absorbent than the getter material film 104. Examples of such absorbents include CaO, BaO, Zr-Al-BaO as moisture absorbents, and activated carbon, molecular sieves and the like as oxygen absorbents.

[Gas barrier film 108]
The gas barrier film 108 is a film similar to the gas barrier film 103 described above, and the same film barrier film 108 can be used as necessary except that the arrangement position is different.
In addition, the constituent member on the back side of the photoelectric conversion element 11 does not necessarily need to transmit visible light, and therefore, a member that does not transmit visible light can be used.

[Back sheet 109]
The back sheet 109 is the same film as the weather-resistant protective film 101 described above, and the same material as the weather-resistant protective film 101 can be used in the same manner except that the arrangement position is different. Further, if the back sheet 109 is difficult to permeate water and oxygen, the back sheet 109 can function as a gas barrier layer.
In addition, the constituent member on the back side of the photoelectric conversion element 11 does not necessarily need to transmit visible light, and therefore, a member that does not transmit visible light can be used. For this reason, as the back sheet 109, it is particularly preferable to use the following (i) to (iv).

(I) As the back sheet 109, various resin films or sheets having excellent strength, weather resistance, heat resistance, water resistance, and light resistance can be used. For example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine Resins, poly (meth) acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate or polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, polyamideimide resins, polyaryl phthalate resins Sheet of various resins such as silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin, etc. It is possible to use. Among these resin sheets, it is preferable to use a fluorine resin, a cyclic polyolefin resin, a polycarbonate resin, a poly (meth) acrylic resin, a polyamide resin, or a polyester resin sheet. In addition, these may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

(Ii) As the back sheet 109, a metal thin film can also be used. For example, corrosion-resistant aluminum metal foil, stainless steel thin film, and the like can be mentioned. In addition, the said metal may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

(Iii) As the back sheet 109, for example, a highly waterproof sheet in which a fluorine resin film is bonded to both surfaces of an aluminum foil may be used. Examples of the fluorine resin include ethylene monofluoride (trade name: Tedlar, manufactured by DuPont), polytetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene and ethylene or propylene (ETFE), and vinylidene fluoride resin. (PVDF), vinyl fluoride resin (PVF) and the like. In addition, 1 type may be used for fluororesin and it may use 2 or more types together by arbitrary combinations and a ratio.

(Iv) As the back sheet 109, for example, an inorganic oxide vapor-deposited film is provided on one side or both sides of the base film, and further, on both sides of the base film provided with the inorganic oxide vapor-deposited film, You may use what laminated | stacked the heat resistant polypropylene resin film. Usually, when a polypropylene resin film is laminated on the base film, the lamination is performed by laminating with a laminating adhesive. By providing a vapor-deposited film of an inorganic oxide, it can be used as a back sheet 109 having excellent moisture resistance that prevents intrusion of moisture, oxygen and the like.

・ Base film Basically, the base film is excellent in close adhesion with inorganic oxide vapor deposition film, etc., excellent in strength, weather resistance, heat resistance, water resistance, and light resistance. Resin films can be used. For example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine Resin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate or polyethylene naphthalate, various polyamide resins such as nylon, polyimide resin, polyamideimide resin, polyaryl phthalate resin Silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin, etc. It is possible to use. Among these, it is preferable to use a film of a fluorine resin, a cyclic polyolefin resin, a polycarbonate resin, a poly (meth) acrylic resin, a polyamide resin, or a polyester resin.

  Among the various resin films described above, for example, a film of a fluorine resin such as polytetrafluoroethylene (PTFE), vinylidene fluoride resin (PVDF), or vinyl fluoride resin (PVF) is used. More preferably it is used. Further, among these fluororesin films, in particular, a fluororesin film (PVF); a fluororesin film made of a copolymer of tetrafluoroethylene and ethylene or propylene (ETFE) is particularly preferable from the viewpoint of strength and the like. preferable. In addition, the said resin may use 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

  Of the various resin films as described above, it is more preferable to use a film of a cyclic polyolefin resin such as cyclopentadiene and a derivative thereof, cyclohexadiene and a derivative thereof.

  The film thickness of the base film is usually 12 μm or more, preferably 20 μm or more, and is usually 300 μm or less, preferably 200 μm or less.

-Vapor deposition film of an inorganic oxide As a vapor deposition film of an inorganic oxide, basically any thin film on which a metal oxide is deposited can be used. For example, a deposited film of an oxide of silicon (Si) or aluminum (Al) can be used. At this time, for example, SiO _x (x = 1.0 to 2.0) can be used as silicon oxide, and for example, AlO _x (x = 0.5 to 1.5) can be used as aluminum oxide. .
In addition, the kind of metal and inorganic oxide to be used may be 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

  The film thickness of the inorganic oxide vapor deposition film is usually 50 mm or more, preferably 100 mm or more, and is usually 4000 mm or less, preferably 1000 mm or less.

  As a method for forming the deposited film, a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a plasma chemical vapor deposition method, a thermal chemical vapor deposition method, or a photochemical vapor deposition method can be used. As a specific example, on one surface of the base film, a monomer gas for vapor deposition such as an organosilicon compound is used as a raw material, an inert gas such as argon gas or helium gas is used as a carrier gas, and oxygen is supplied. An oxygen oxide vapor or the like can be used as a gas, and a vapor deposition film of an inorganic oxide such as silicon oxide can be formed using a low temperature plasma chemical vapor deposition method using a low temperature plasma generator or the like.

-Polypropylene resin film As a polypropylene resin, the homopolymer of propylene; for example, the copolymer of propylene and another monomer (for example, alpha olefin etc.) can be used. Moreover, an isotactic polymer can also be used as a polypropylene resin.

The melting point of the polypropylene resin is usually from 164 ° C to 170 ° C, the specific gravity is usually from 0.90 to 0.91, and the molecular weight is usually from 100,000 to 200,000.
Polypropylene resins are largely controlled by their crystallinity, but high isotactic polymers have excellent tensile strength and impact strength, good heat resistance and bending fatigue strength, and workability. Is very good.

-Adhesive When laminating a polypropylene resin film on a base film, an adhesive for laminating is usually used. Thereby, a base film and a polypropylene resin film are laminated | stacked via the adhesive bond layer for lamination.
Examples of the adhesive constituting the adhesive layer for laminating include, for example, polyvinyl acetate adhesive, polyacrylate adhesive, cyanoacrylate adhesive, ethylene copolymer adhesive, cellulose adhesive, and polyester adhesive. Adhesives, polyamide adhesives, polyimide adhesives, amino resin adhesives, phenol resin adhesives, epoxy adhesives, polyurethane adhesives, reactive (meth) acrylic adhesives, silicone adhesives, etc. Is mentioned. In addition, 1 type may be used for an adhesive agent and it may use 2 or more types together by arbitrary combinations and a ratio.

The composition system of the adhesive may be any composition form such as an aqueous type, a solution type, an emulsion type, and a dispersion type. Moreover, the form may be any form such as a film / sheet form, a powder form, or a solid form. Furthermore, the bonding mechanism may be any form such as a chemical reaction type, a solvent volatilization type, a heat melting type, and a hot pressure type.
The adhesive can be applied by a coating method such as a roll coating method, a gravure roll coating method, a kiss coating method, or the like, or a printing method. As the amount of ^{coating, 0.1g / m 2 ~10g / m} 2 is desirable in the dry state.

[Sealant 110]
The sealing material 110 includes the above-described weather-resistant protective film 101, ultraviolet cut film 102, gas barrier film 103, getter material film 104, sealing material 105, sealing material 106, getter material film 107, gas barrier film 108, and backsheet 109. It is a member that seals the edges to prevent moisture and oxygen from entering the space covered with these films.

The degree of moisture capacity required for the sealing member 110 is preferably water vapor transmission rate per day unit area (1 m ²⁾ is not more than ^{0.1g / m 2 / day, 0.05g} / m 2 / More preferably, it is not more than day. Conventionally, since it has been difficult to mount the sealing material 110 having such a high moisture-proof capability, it is possible to realize a solar cell including an excellent photoelectric conversion element such as a compound semiconductor photoelectric conversion element and an organic photoelectric conversion element. Although it was difficult, application of such a sealing material 110 facilitates the implementation of the solar cell 10 utilizing the excellent properties of the compound semiconductor photoelectric conversion element and the organic photoelectric conversion element.

  Furthermore, since the solar cell 10 is often heated by receiving light, it is preferable that the sealing material 110 also has heat resistance. From this viewpoint, the melting point of the constituent material of the sealing material 110 is usually 100 ° C. or higher, preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 180 ° C. or lower. If the melting point is too low, the sealing material 110 may melt when the solar cell 10 is used.

Examples of the material constituting the sealing material 110 include polymers such as a fluorine resin, a silicone resin, and an acrylic resin.
Note that the sealing material 110 may be formed of one kind of material or may be formed of two or more kinds of materials.

  The sealing material 110 is provided at a position where at least the edges of the gas barrier films 103 and 108 can be sealed. Thereby, the space surrounded by at least the gas barrier films 103 and 108 and the sealing material 110 can be sealed, and moisture and oxygen can be prevented from entering the space.

Although there is no restriction | limiting in the method of forming this sealing material 110, For example, it can form by inject | pouring material between the weather-resistant protective film 101 and the back sheet | seat 109, for example. Specific examples of the forming method include the following methods.
That is, for example, while the curing of the encapsulating material 105 proceeds, the semi-cured solar cell 10 is taken out from the laminating apparatus, and is the outer peripheral portion of the photoelectric conversion element 11 between the weather-resistant protective film 101 and the back sheet 109. What is necessary is just to inject | pour a liquid polymer in the part between and to harden this polymer with the sealing material 105. FIG. Alternatively, after the sealing material 105 has been cured, it may be removed from the laminating apparatus and cured alone. The temperature range for crosslinking and curing the polymer is usually 130 ° C. or higher, preferably 140 ° C. or higher, and is usually 180 ° C. or lower, preferably 170 ° C. or lower.

[Dimensions]
The solar cell 10 of the present embodiment is usually a thin film member. By forming the solar cell 10 as a film-like member in this way, the solar cell 10 can be easily installed in building materials, automobiles, interiors, and the like. The solar cell 10 is light and difficult to break, and thus a highly safe solar cell can be obtained, and can also be applied to curved surfaces, so that it can be used for more applications. Since it is thin and light, it is preferable in terms of distribution such as transportation and storage. Furthermore, since it is in the form of a film, it can be manufactured in a roll-to-roll manner, and a significant cost cut can be achieved.
Although there is no restriction | limiting in the specific dimension of the solar cell 10, The thickness is 300 micrometers or more normally, Preferably it is 500 micrometers or more, More preferably, it is 700 micrometers or more, Usually, 3000 micrometers or less, Preferably it is 2000 micrometers or less, More preferably, it is 1500 micrometers. It is as follows.

[Production method]
Although there is no restriction | limiting in the manufacturing method of the solar cell 10 of this embodiment, For example, what connected the 1 or 2 or more photoelectric conversion element 11 in series or in parallel between the weather-resistant protective film 101 and the back seat | sheet 109 Can be produced by laminating together with the ultraviolet cut film 102, the gas barrier films 103 and 108, the getter material films 104 and 107, and the sealing materials 105 and 106 with a general vacuum laminating apparatus. Under the present circumstances, heating temperature is 130 degreeC or more normally, Preferably it is 140 degreeC or more, and is 180 degrees C or less normally, Preferably it is 170 degrees C or less. The heating time is usually 10 minutes or longer, preferably 20 minutes or longer, usually 100 minutes or shorter, preferably 90 minutes or shorter. The pressure is usually 0.001 MPa or more, preferably 0.01 MPa or more, and usually 0.2 MPa or less, preferably 0.1 MPa or less. By setting the pressure within this range, sealing can be surely performed, and the sealing materials 105 and 106 from the end can be prevented from protruding or reduced in film thickness due to over-pressurization, thereby ensuring dimensional stability.

[advantage]
Since the solar cell 10 of this embodiment is configured as described above, when the light receiving surface is irradiated with light, the photoelectric conversion element 11 that has absorbed the light generates power.
At this time, the solar cell 10 of the present embodiment can be used even in an environment with high humidity because the photoelectric conversion element 11 can be protected from moisture by the gas barrier films 103 and 108 and the sealing material 110. In addition, since the solar cell of this embodiment includes the ultraviolet cut film 102, the gas barrier films 103 and 108, the photoelectric conversion element 11 and the like are not deteriorated by ultraviolet rays, and power generation can be performed with high efficiency over a long period of time. Thus, according to this embodiment, a practical solar cell resistant to moisture and ultraviolet rays can be newly realized.

Moreover, if the solar cell 10 of this embodiment is provided with a compound semiconductor type photoelectric conversion element such as a Cu-III-VI group ₂ semiconductor and / or an organic photoelectric conversion element as the photoelectric conversion element 11, high power generation efficiency. Can generate electricity.
Furthermore, since the solar cell 10 of the present embodiment includes the getter material films 104 and 107, the photoelectric conversion element 11 can be more reliably protected from moisture and oxygen.
Moreover, since the solar cell 10 of the present embodiment includes the weather-resistant protective film 101 and the back sheet 109, the solar cell 10 is resistant to weather changes and can generate power stably over a longer period of time.
Furthermore, since the solar cell 10 of this embodiment includes the sealing materials 105 and 106, the strength is high and the handleability is good.

  Furthermore, the solar cell 10 of the present embodiment can secure a sufficient amount of power generation even when exposed to the outside for a long period of time, and has sufficient flexibility and strength so that it can be curved to a curved surface that could not be installed. Installation is possible.

[Secondary battery 20]
As shown in FIGS. 1 and 2, the secondary battery 20 is connected to the solar battery 10 via the charge / discharge control device 30 and stores the electric power generated by the solar battery 10. Since the amount of power generated by the solar cell 10 varies depending on the weather or the like, the solar cell 10 may generate more power than is necessary for the light emitting device 40 to emit light. The secondary battery 20 stores this surplus power. The power stored in the secondary battery 20 is supplied to the light emitting device 40 when the solar battery 10 cannot sufficiently generate power, such as at night.

  Although there is no restriction | limiting in the kind of secondary battery 20, It is preferable to use a lithium secondary battery from the point which is excellent in energy density, and the nonaqueous lithium secondary battery using a nonaqueous electrolyte solution is more preferable. Hereinafter, an example of the non-aqueous lithium secondary battery will be described. However, the secondary battery is not limited to the examples described below.

  The non-aqueous lithium secondary battery includes at least a negative electrode and a positive electrode that can occlude and release lithium ions, and a non-aqueous electrolyte solution. Usually, a positive electrode and a negative electrode are laminated via a porous film (separator) impregnated with a non-aqueous electrolyte solution, and these are housed in a case (exterior body).

[Non-aqueous electrolyte]
The nonaqueous electrolytic solution contains at least a nonaqueous solvent and an electrolyte.
Examples of commonly used non-aqueous solvents include cyclic carbonates, chain carbonates, chain and cyclic carboxylic acid esters, chain and cyclic ethers, phosphorus-containing organic solvents, sulfur-containing organic solvents, and the like. In addition, a non-aqueous solvent may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Although there is no restriction | limiting in particular in the kind of cyclic carbonate, As an example of what is normally used, ethylene carbonate, propylene carbonate, butylene carbonate, etc. are mentioned. Among these, ethylene carbonate and propylene carbonate are preferable in that they have a high dielectric constant, so that the solute is easily dissolved, and the cycle characteristics are good when a non-aqueous lithium secondary battery is obtained.

  The type of chain carbonate is not particularly limited, but examples of commonly used ones include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl n-propyl carbonate, ethyl n-propyl carbonate, di- and n-propyl carbonate. Among these, diethyl carbonate, methyl-n-propyl carbonate, and ethyl-n-propyl carbonate are preferable. Particularly, diethyl carbonate is preferable in terms of good cycle characteristics when a non-aqueous lithium secondary battery is used.

  Furthermore, the type of chain carboxylic acid ester is not particularly limited, but examples of commonly used ones include methyl acetate, ethyl acetate, acetic acid-n-propyl, acetic acid-i-propyl, acetic acid-n-butyl, -I-butyl acetate, t-butyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, i-propyl propionate, n-butyl propionate, i-butyl propionate, propionic acid -T-butyl and the like. Among these, ethyl acetate, methyl propionate, and ethyl propionate are more preferable.

  Moreover, although there is no restriction | limiting in particular also in the kind of cyclic carboxylic acid ester, As an example of what is used normally, (gamma) -butyrolactone, (gamma) -valerolactone, (delta) -valerolactone, etc. are mentioned. Among these, γ-butyrolactone is more preferable.

  Furthermore, the type of chain ether is not particularly limited, but examples of commonly used ones include dimethoxymethane, dimethoxyethane, diethoxymethane, diethoxyethane, ethoxymethoxymethane, ethoxymethoxyethane, and the like. . Among these, dimethoxyethane and diethoxyethane are more preferable.

  Moreover, although there is no restriction | limiting in particular also in the kind of cyclic ether, Tetrahydrofuran, 2-methyltetrahydrofuran, etc. are mentioned as an example of what is used normally.

  Furthermore, the type of the phosphorus-containing organic solvent is not particularly limited. Examples of commonly used organic solvents include phosphate esters such as trimethyl phosphate, triethyl phosphate, and triphenyl phosphate; trimethyl phosphite, Phosphites such as triethyl phosphite and triphenyl phosphite; phosphine oxides such as trimethyl phosphine oxide, triethyl phosphine oxide and triphenyl phosphine oxide; and the like.

  Further, the kind of the sulfur-containing organic solvent is not particularly limited. Examples of those usually used include ethylene sulfite, 1,3-propane sultone, 1,4-butane sultone, methyl methanesulfonate, busulfan, and sulfolane. , Sulfolene, dimethylsulfone, diphenylsulfone, methylphenylsulfone, dibutyldisulfide, dicyclohexyldisulfide, tetramethylthiurammonosulfide, N, N-dimethylmethanesulfonamide, N, N-diethylmethanesulfonamide, and the like.

  Among these, it is preferable to use ethylene carbonate and / or propylene carbonate, which are cyclic carbonates, and it is preferable to use these in combination with a chain carbonate.

  Thus, when using a cyclic carbonate and a chain carbonate together as a non-aqueous solvent, the suitable content of the chain carbonate in the non-aqueous solvent in the non-aqueous electrolyte is usually 30% by weight or more, preferably 50%. % By weight or more, and usually 95% by weight or less, preferably 90% by weight or less. On the other hand, the suitable content of the cyclic carbonate in the non-aqueous solvent in the non-aqueous electrolyte is usually 5% by weight or more, preferably 10% by weight or more, and usually 50% by weight or less, preferably 40% by weight or less. It is. If the proportion of the chain carbonate is too small, the viscosity of the non-aqueous electrolyte may increase. If the proportion of the chain carbonate is too large, the dissociation degree of the lithium salt, which is an electrolyte, decreases, Conductivity may decrease.

On the other hand, lithium salt is usually used as the electrolyte. Specific examples of the electrolyte include inorganic lithium salts such as LiClO ₄ , LiAsF ₆ , LiPF ₆ , Li ₂ CO ₃ and LiBF ₄ ; LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO _{2) 2,} lithium cyclic 1,3-hexafluoropropane disulfonylimide, lithium cyclic 1,2-tetrafluoroethane _{disulfonylimide, LiN (CF 3 SO 2)} (C 4 F 9 SO 2), LiC (CF ₃ SO ₂ ) ₃ , LiPF ₄ (CF ₃ ) ₂ , LiPF ₄ (C ₂ F ₅ ) ₂ , LiPF ₄ (CF ₃ SO ₂ ) ₂ , LiPF ₄ (C ₂ F ₅ SO ₂ ) ₂ , LiBF ₂ (CF ₃ ) ₂ , LiBF ₂ (C ₂ F ₅ ) ₂ , LiBF ₂ (CF ₃ SO ₂ ) ₂ , LiBF ₂ (C ₂ F ₅ SO ₂ ) ₂ , Fluorine-containing organic lithium salt and the like; lithium bis (oxalato) borate, lithium tris (oxalato) phosphate, lithium difluoro oxalatoborate, containing dicarboxylic acid complex lithium salt and the _{like; KPF 6, NaPF 6, NaBF} 4, NaCF 3 SO ₃ , sodium salt or potassium salt; Among these, LiPF ₆ , LiBF ₄ , LiCF ₃ SO ₃ , LiN (CF ₃ SO ₂ ) ₂ , LiN (C ₂ F ₅ SO ₂ ) ₂ , lithium cyclic 1,2-tetrafluoroethanedisulfonylimide are preferable, In particular, LiPF ₆ and LiBF ₄ are preferable.

Moreover, only 1 type may be used for electrolyte and it may use 2 or more types together by arbitrary combinations and a ratio. In particular, when two types of specific inorganic lithium salts are used in combination, or when inorganic lithium salts and fluorine-containing organic lithium salts are used in combination, gas generation during trickle charging is suppressed, or deterioration after high-temperature storage is suppressed. Therefore, it is preferable. In particular, the combination and the LiPF ₆ and LiBF _4, and an inorganic lithium salt such as _{LiPF 6, LiBF 4, LiCF 3} SO 3, LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) _2, etc. It is preferable to use in combination with a fluorine-containing organic lithium salt.

Furthermore, when LiPF ₆ and LiBF ₄ are used in combination, it is preferable that LiBF ₄ is usually contained at a ratio of 0.01 wt% or more and 20 wt% or less with respect to the entire electrolyte. LiBF ₄ has a low degree of dissociation, and if the ratio is too high, the resistance of the electrolytic solution may be increased.

_Also, LiPF 6, an inorganic lithium salt of LiBF ₄ or the _{like, LiCF 3 SO 3, LiN (} CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) When used in combination with a fluorine-containing organic lithium salt ₂ such as The proportion of the inorganic lithium salt in the entire electrolyte is preferably in the range of usually 70% by weight or more and 99% by weight or less. In general, the fluorine-containing organic lithium salt has a large molecular weight as compared with the inorganic lithium salt, and if the ratio is too high, the ratio of the solvent in the entire electrolytic solution may decrease and the resistance of the electrolytic solution may be increased.

The concentration of the lithium salt in the non-aqueous electrolyte is usually 0.5 mol · dm ⁻³ or more, preferably 0.6 mol · dm ⁻³ or more, more preferably 0.8 mol · dm ⁻³ or more, and usually 3 mol · dm ³ or more. dm ^-3 or less, preferably 2 mol · ^{dm -3} or less, and more preferably 1.5 mol · ^{dm -3} or less of. If this concentration is too low, the electrical conductivity of the non-aqueous electrolyte solution may be insufficient. If the concentration is too high, the electrical conductivity will decrease due to an increase in viscosity, and the performance of the non-aqueous lithium secondary battery will be reduced. May decrease.

Moreover, the non-aqueous electrolyte solution may contain various additives. This additive may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
Examples of the additive include an overcharge inhibitor and an auxiliary agent for improving capacity maintenance characteristics and cycle characteristics after high-temperature storage.

Specific examples of the overcharge inhibitor include aromatic compounds such as biphenyl, alkylbiphenyl, terphenyl, partially hydrogenated terphenyl, cyclohexylbenzene, t-butylbenzene, t-amylbenzene, diphenyl ether, dibenzofuran, etc .; 2 -Partially fluorinated products of the aromatic compounds such as fluorobiphenyl, o-cyclohexylfluorobenzene, p-cyclohexylfluorobenzene; 2,4-difluoroanisole, 2,5-difluoroanisole, 2,6-difluoroaniol, etc. And the like. In addition, these overcharge inhibitors may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
The concentration of the overcharge inhibitor is preferably in the range of usually 0.1 wt% or more and 5 wt% or less with respect to the whole non-aqueous electrolyte solution. By containing an overcharge inhibitor in the nonaqueous electrolytic solution, it is possible to suppress rupture / ignition of the nonaqueous lithium secondary battery due to overcharging, and the safety of the nonaqueous lithium secondary battery is improved, which is preferable.

Specific examples of auxiliaries for improving capacity retention characteristics and cycle characteristics after high-temperature storage include anhydrides of dicarboxylic acids such as succinic acid, maleic acid, and phthalic acid; erythritan carbonate, spirobisdimethylene carbonate Carbonate compounds such as ethylene sulfite, 1,3-propane sultone, 1,4-butane sultone, methyl methanesulfonate, busulfan, sulfolane, sulfolene, dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, dibutyl disulfide, dicyclohexyl disulfide, Sulfur-containing compounds such as tetramethylthiuram monosulfide, N, N-dimethylmethanesulfonamide, N, N-diethylmethanesulfonamide; 1-methyl-2-pyrrolidinone, 1-methyl-2-piperidone, 3- Mechi Nitrogen-containing compounds such as 2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, N-methylsuccinimide, etc .; hydrocarbon compounds such as heptane, octane, cycloheptane, etc .; fluorobenzene, difluorobenzene, benzo Examples thereof include fluorine-containing aromatic compounds such as trifluoride. In addition, these adjuvants may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
The concentration of the auxiliary agent is preferably in the range of usually 0.1 wt% or more and 5 wt% or less with respect to the whole non-aqueous electrolyte solution.

[Negative electrode]
The negative electrode includes a negative electrode active material. The negative electrode active material has at least one atom selected from the group consisting of Si (silicon) atoms, Sn (tin) atoms, and Pb (lead) atoms (these may be referred to as “specific metal elements” hereinafter). It is preferable to use one.

  Examples of the negative electrode active material having at least one atom selected from a specific metal element include a single metal of any one specific metal element, an alloy composed of two or more specific metal elements, one or more specific metals Examples thereof include an alloy composed of an element and other one or more metal elements, and a compound containing one or two or more specific metal elements. By using these simple metals, alloys or metal compounds as the negative electrode active material, the capacity of the battery can be increased.

Examples of compounds containing one or more specific metal elements include composite compounds such as carbides, oxides, nitrides, sulfides, and phosphides containing one or more specific metal elements. .
Moreover, the compound which these complex compounds combined with several elements, such as a metal simple substance, an alloy, or a nonmetallic element, can also be mentioned as an example. More specifically, for example, in Si and Sn, an alloy of these elements and a metal that does not operate as a negative electrode can be used. In addition, for example, in Sn, a complex compound containing 5 to 6 kinds of elements in combination of a metal that acts as a negative electrode other than Sn, Si, Sn, and Pb, a metal that does not operate as a negative electrode, and a nonmetallic element is also included. Can be used.

  Among these negative electrode active materials, since the capacity per unit weight is large when a battery is made, any single element of a specific metal element, an alloy of two or more specific metal elements, an oxide of a specific metal element In particular, Si and / or Sn simple metals, alloys, oxides, carbides, nitrides, and the like are preferable from the viewpoint of capacity per unit weight and environmental load.

In addition, although the capacity per unit weight is inferior to that of using a single metal or an alloy, the following compounds containing Si and / or Sn are also preferable because of excellent cycle characteristics.
-Element ratio of Si and / or Sn and oxygen is usually 0.5 or more, preferably 0.7 or more, more preferably 0.9 or more, usually 1.5 or less, preferably 1.3 or less, More preferably, the oxide of Si and / or Sn is 1.1 or less.
-Element ratio of Si and / or Sn and nitrogen is usually 0.5 or more, preferably 0.7 or more, more preferably 0.9 or more, usually 1.5 or less, preferably 1.3 or less, Si and / or Sn nitride is more preferably 1.1 or less.
-Element ratio of Si and / or Sn and carbon is usually 0.5 or more, preferably 0.7 or more, more preferably 0.9 or more, usually 1.5 or less, preferably 1.3 or less, More preferably, the carbide of Si and / or Sn is 1.1 or less.
In addition, any one of the above-described negative electrode active materials may be used alone, or two or more thereof may be used in any combination and ratio.

  The negative electrode in a non-aqueous lithium secondary battery can be manufactured according to a conventional method. As a specific method for producing the negative electrode, for example, a method in which the above-described negative electrode active material added with a binder or a conductive material is roll-molded as it is to form a sheet electrode, or compression molding to obtain a pellet electrode. A method is also mentioned. In particular, the negative electrode active material is usually contained on a negative electrode current collector (hereinafter also referred to as “negative electrode current collector”) by a method such as a coating method, a vapor deposition method, a sputtering method, or a plating method. A method of forming a thin film layer (negative electrode active material layer) is used. In this case, by adding a binder, a thickener, a conductive material, a solvent, etc. to the above-mentioned negative electrode active material to form a slurry, applying this to the negative electrode current collector, drying, and pressing to increase the density A negative electrode active material layer is formed on the negative electrode current collector.

  Examples of the material of the negative electrode current collector include steel, copper alloy, nickel, nickel alloy, and stainless steel. Of these, copper foil is preferred from the viewpoint of easy processing into a thin film and cost.

  The thickness of the negative electrode current collector is usually 1 μm or more, preferably 5 μm or more, and is usually 100 μm or less, preferably 50 μm or less. If the thickness of the negative electrode current collector is too thick, the capacity of the entire battery may be too low, and conversely, if it is too thin, handling may be difficult.

  In addition, in order to improve the binding effect with the negative electrode active material layer formed on the surface, the surface of these negative electrode current collectors is preferably subjected to a roughening treatment in advance. Surface roughening methods include blasting, rolling with a rough roll, polishing cloth with a fixed abrasive particle, grinder, emery buff, wire brush equipped with steel wire, etc. Examples thereof include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.

  Further, in order to reduce the weight of the negative electrode current collector and improve the energy density per weight of the battery, a perforated negative electrode current collector such as an expanded metal or a punching metal can be used. This type of negative electrode current collector can be freely changed in weight by changing its aperture ratio. Further, when a negative electrode active material layer is formed on both surfaces of this type of negative electrode current collector, the negative electrode active material layer is further less likely to peel due to the rivet effect through the hole. However, when the aperture ratio becomes too high, the contact area between the negative electrode active material layer and the negative electrode current collector becomes small, and thus the adhesive strength may be lowered.

  The slurry for forming the negative electrode active material layer is usually prepared by adding a binder, a thickener and the like to the negative electrode material. The “negative electrode material” refers to a material obtained by combining a negative electrode active material and a conductive material.

  The content of the negative electrode active material in the negative electrode material is usually 70% by weight or more, preferably 75% by weight or more, and usually 97% by weight or less, preferably 95% by weight or less. When the content of the negative electrode active material is too small, the capacity of the secondary battery using the obtained negative electrode tends to be insufficient, and when the content is too large, the content of the binder or the like is relatively insufficient. The strength of the negative electrode tends to be insufficient.

  Examples of the conductive material used for the negative electrode include metal materials such as copper and nickel; carbon materials such as graphite and carbon black. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. In particular, it is preferable to use a carbon material as the conductive material because the carbon material acts as an active material. It is preferable that the content of the conductive material in the negative electrode material is usually 3% by weight or more, particularly 5% by weight or more, and usually 30% by weight or less, particularly 25% by weight or less. When the content of the conductive material is too small, the conductivity tends to be insufficient. When the content is too large, the content of the negative electrode active material and the like is relatively insufficient, and thus the battery capacity and strength tend to decrease.

  As the binder used for the negative electrode, any material can be used as long as it is a material safe with respect to the solvent and the electrolytic solution used at the time of producing the electrode. Examples thereof include polyvinylidene fluoride, polytetrafluoroethylene, polyethylene, polypropylene, styrene / butadiene rubber, isoprene rubber, butadiene rubber, ethylene / acrylic acid copolymer, and ethylene / methacrylic acid copolymer. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. The content of the binder is usually 0.5 parts by weight or more, preferably 1 part by weight or more, and usually 10 parts by weight or less, preferably 8 parts by weight or less with respect to 100 parts by weight of the negative electrode material. When the content of the binder is too small, the strength of the obtained negative electrode tends to be insufficient. When the content is too large, the content of the negative electrode active material and the like is relatively insufficient, and thus the battery capacity and conductivity tend to be insufficient. There is.

  Examples of the thickener used for the negative electrode include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, and casein. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations and a ratio. The thickener may be used as necessary, but when used, the thickener content in the negative electrode active material layer is usually in the range of 0.5 wt% or more and 5 wt% or less. Is preferred.

  The slurry for forming the negative electrode active material layer is prepared by mixing the negative electrode active material with a conductive agent, a binder, or a thickener as necessary, and using an aqueous solvent or an organic solvent as a dispersion medium. The As the aqueous solvent, water is usually used, and an organic solvent such as alcohols such as ethanol and cyclic amides such as N-methylpyrrolidone is used in combination within a range of 30% by weight or less with respect to water. You can also. Examples of the organic solvent include cyclic amides such as N-methylpyrrolidone, linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and aromatic carbonization such as anisole, toluene and xylene. Examples thereof include alcohols such as hydrogens, butanol and cyclohexanol, among which cyclic amides such as N-methylpyrrolidone, linear amides such as N, N-dimethylformamide and N, N-dimethylacetamide are preferable. . Any one of these may be used alone, or two or more may be used in any combination and ratio.

  The obtained slurry is applied onto the above-described negative electrode current collector, dried, and then pressed to form a negative electrode active material layer. The method of application is not particularly limited, and a method known per se can be used. The drying method is not particularly limited, and a known method such as natural drying, heat drying, or reduced pressure drying can be used.

The electrode structure when the negative electrode active material is made into an electrode by the above method is not particularly limited, but the density of the active material present on the current collector is preferably 1 g · cm ⁻³ or more, more preferably 1. 2 g · cm ⁻³ or more, more preferably 1.3 g · cm ⁻³ or more, and the upper limit is usually 2 g · cm ⁻³ or less, preferably 1.9 g · cm ⁻³ or less, more preferably 1.8 g · cm. ^-3 or less, more preferably 1.7 g · cm ^-3 or less. Exceeding this range may destroy active material particles, leading to an increase in initial irreversible capacity and a deterioration in high current density charge / discharge characteristics due to a decrease in the permeability of the non-aqueous electrolyte near the current collector / active material interface. . On the other hand, if it is lower, the conductivity between the active materials is lowered, the battery resistance is increased, and the capacity per unit volume may be lowered.

[Positive electrode]
The positive electrode is configured to contain a positive electrode active material. Examples of the positive electrode active material include transition metal oxides, transition metal and lithium composite oxides (lithium transition metal composite oxides), transition metal sulfides, inorganic compounds such as metal oxides, lithium metal, and lithium An alloy or a composite thereof can be used. Specific examples include transition metal oxides such as MnO, V ₂ O ₅ , V ₆ O ₁₃ , and TiO ₂ ; LiCoO ₂ or lithium cobalt composite oxide whose basic composition is LiCoO ₂ , LiNiO _2, or a basic composition of LiNiO _2. Lithium nickel composite oxide, LiMn ₂ O ₄ or LiMnO ₂ or lithium manganese composite oxide whose basic composition is LiMn ₂ O ₄ or LiMnO ₂ , lithium nickel manganese cobalt composite oxide, lithium nickel cobalt aluminum composite oxide, etc. And lithium transition metal composite oxides; transition metal sulfides such as TiS and FeS; and metal oxides such as SnO ₂ and SiO ₂ . Among them, lithium transition metal composite oxide, specifically, LiCoO ₂ or lithium cobalt composite oxide whose basic composition is LiCoO ₂ , LiNiO ₂ or lithium nickel composite oxide whose basic composition is LiNiO ₂ , LiMn ₂ O ₄ or LiMnO ₂ or a lithium manganese composite oxide, lithium nickel manganese cobalt composite oxide or lithium nickel cobalt aluminum composite oxide having a basic composition of LiMn ₂ O ₄ or LiMnO ₂ achieves both high capacity and high cycle characteristics. Since it is obtained, it is used suitably. In addition, lithium transition metal composite oxide is a part of cobalt, nickel or manganese other than Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, etc. Substitution with metal is preferable because the structure can be stabilized. Any one of these positive electrode active materials may be used alone, or two or more thereof may be used in any combination and ratio.

  The positive electrode can be manufactured according to a conventional method. As a specific method for producing a positive electrode, for example, a method in which a binder or a conductive material added to the positive electrode active material described above is roll-molded as it is to form a sheet electrode, or a method in which compression molding is performed to obtain a pellet electrode , A method (coating method) of forming a positive electrode active material layer by applying an active material on a positive electrode current collector (hereinafter sometimes referred to as “positive electrode current collector”), a vapor deposition method on the positive electrode current collector The method of forming the above-mentioned thin film layer (positive electrode active material layer) containing the positive electrode active material by a method such as sputtering or plating, etc. can be mentioned. Usually, the positive electrode active material layer is formed using a coating method. Form.

  When using the coating method, add a binder, thickener, conductive material, solvent, etc. to the positive electrode active material described above to form a slurry, apply this to the positive electrode current collector, dry it, and press to increase the density. By doing so, a positive electrode active material layer is formed on the positive electrode current collector.

  Examples of the material of the positive electrode current collector include aluminum, titanium, and tantalum, and alloys containing one or more of these. Of these, aluminum and its alloys are preferable.

  The thickness of the positive electrode current collector is usually 1 μm or more, preferably 5 μm or more, and usually 100 μm or less, preferably 50 μm or less. If the thickness of the positive electrode current collector is too thick, the capacity of the entire battery will be too low. Conversely, if it is too thin, handling may be difficult.

  In addition, in order to improve the binding effect with the positive electrode active material layer formed on the surface, it is preferable that the surface of these positive electrode current collectors is roughened in advance. Surface roughening methods include blasting, rolling with a rough roll, polishing cloth with a fixed abrasive particle, grinder, emery buff, wire brush equipped with steel wire, etc. Examples thereof include a mechanical polishing method, an electrolytic polishing method, and a chemical polishing method.

  Further, in order to reduce the weight of the positive electrode current collector and improve the energy density per weight of the battery, a perforated positive electrode current collector such as an expanded metal or a punching metal can be used. This type of positive electrode current collector can be freely changed in weight by changing its aperture ratio. In addition, when a positive electrode active material layer is formed on both surfaces of this type of positive electrode current collector, the positive electrode active material layer is further unlikely to peel due to the rivet effect through this hole. However, when the aperture ratio becomes too high, the contact area between the positive electrode active material layer and the positive electrode current collector becomes small, and thus the adhesive strength may be lowered.

  The positive electrode active material layer usually contains a conductive material in order to increase conductivity. There are no particular restrictions on the type of conductive material, but specific examples include metal materials such as copper and nickel, graphite such as natural graphite and artificial graphite, carbon black such as acetylene black, and amorphous such as needle coke. Examples thereof include carbon materials such as carbon. In addition, these substances may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  The proportion of the conductive material in the positive electrode active material layer is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 1% by weight or more, and usually 50% by weight or less, preferably 30%. % By weight or less, more preferably 15% by weight or less. If the proportion of the conductive material is too low, the conductivity may be insufficient, and conversely if it is too high, the battery capacity may be reduced.

  It does not specifically limit as a binder used for manufacture of a positive electrode active material layer. In particular, in the case of the coating method, any material that is stable with respect to the liquid medium used at the time of electrode production may be used. Specific examples include resin polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, cellulose, nitrocellulose, SBR (styrene butadiene rubber), NBR (acrylonitrile butadiene rubber), fluororubber, Rubber polymers such as isoprene rubber, butadiene rubber, ethylene / propylene rubber, styrene / butadiene / styrene block copolymer and hydrogenated products thereof, EPDM (ethylene / propylene / diene terpolymer), styrene / ethylene / Thermoplastic elastomeric polymers such as butadiene / ethylene copolymer, styrene / isoprene styrene block copolymer and hydrogenated products thereof, syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene Fluorine-based polymers such as vinyl acid copolymers, soft resinous polymers such as propylene / α-olefin copolymers, polyvinylidene fluoride, polytetrafluoroethylene, fluorinated polyvinylidene fluoride, and polytetrafluoroethylene / ethylene copolymers Examples thereof include a polymer and a polymer composition having ion conductivity of alkali metal ions (particularly lithium ions). These substances may be used alone or in combination of two or more in any combination and ratio.

  The ratio of the binder in the positive electrode active material layer is usually 0.1% by weight or more, preferably 1% by weight or more, more preferably 5% by weight or more, and usually 80% by weight or less, preferably 60% by weight or less. More preferably, it is 40% by weight or less, particularly preferably 10% by weight or less. If the proportion of the binder is too low, the positive electrode active material cannot be sufficiently retained and the positive electrode has insufficient mechanical strength, which may deteriorate battery performance such as cycle characteristics. It may lead to a decrease in conductivity.

  The liquid medium for forming the slurry may be any type of solvent that can dissolve or disperse the positive electrode active material, the conductive agent, the binder, and the thickener used as necessary. There is no particular limitation, and either an aqueous solvent or an organic solvent may be used.

  Examples of the aqueous medium include water, a mixed medium of alcohol and water, and the like. Examples of the organic medium include aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; heterocyclic compounds such as quinoline and pyridine; ketones such as acetone, methyl ethyl ketone, and cyclohexanone. Esters such as methyl acetate and methyl acrylate; amines such as diethylenetriamine and NN-dimethylaminopropylamine; ethers such as diethyl ether, propylene oxide and tetrahydrofuran (THF); N-methylpyrrolidone (NMP) Amides such as dimethylformamide and dimethylacetamide; aprotic polar solvents such as hexamethylphosphalamide and dimethylsulfoxide.

  In particular, when an aqueous medium is used, it is preferable to make a slurry using a thickener and a latex such as styrene-butadiene rubber (SBR). A thickener is usually used to adjust the viscosity of the slurry. The thickener is not particularly limited, and specific examples include carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, casein, and salts thereof. These may be used individually by 1 type, or may use 2 or more types together by arbitrary combinations and ratios. Furthermore, when using a thickener, the ratio of the thickener to the active material is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 0.6% by mass or more. The upper limit is usually 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. Below this range, applicability may be significantly reduced. If it exceeds, the ratio of the active material in the positive electrode active material layer may be reduced, and the problem that the battery capacity may be reduced and the resistance between the positive electrode active materials may be increased.

  The viscosity of the slurry is not particularly limited as long as it is a viscosity that can be applied onto the current collector, and may be appropriately adjusted by changing the amount of the solvent used when preparing the slurry so that the viscosity can be applied. .

  The obtained slurry is applied onto the above positive electrode current collector, dried, and then pressed to form a positive electrode active material layer. The method of application is not particularly limited, and a method known per se can be used. The drying method is not particularly limited, and known methods such as natural drying, heat drying, and reduced pressure drying can be used.

The positive electrode active material layer obtained by coating and drying is preferably consolidated by a hand press, a roller press or the like in order to increase the packing density of the positive electrode active material.
Density of the positive electrode active material layer is preferably 1.5 g · ^{cm -3} or more, more preferably 2 g · ^{cm -3} or higher, still more preferably 2.2 g · ^{cm -3} or more, and the upper limit is preferably 3 .5g · ^{cm -3} or less, more preferably 3 g · ^{cm -3} or less, more preferably in the range of 2.8 g · ^{cm -3} or less. If this range is exceeded, the permeability of the non-aqueous electrolyte solution to the vicinity of the current collector / active material interface may decrease, and the charge / discharge characteristics at a high current density may decrease. On the other hand, if it is lower, the conductivity between the active materials may be reduced, and the battery resistance may be increased.

[Separator]
Usually, a separator is interposed between the positive electrode and the negative electrode in order to prevent a short circuit. In this case, the non-aqueous electrolyte is usually used by impregnating the separator.
Although there is no restriction | limiting in particular about the material and shape of a separator, Especially, it is preferable to use the porous sheet | seat or nonwoven fabric etc. which were formed with the material stable with respect to non-aqueous electrolyte solution, and were excellent in the liquid retention property.

  As a material for the separator, for example, polyolefin such as polyethylene and polypropylene, polytetrafluoroethylene, polyethersulfone, glass filter and the like can be used. Of these, glass filters and polyolefins are preferred, and polyolefins are more preferred. These materials may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.

  Although the thickness of a separator is arbitrary, it is 1 micrometer or more normally, Preferably it is 5 micrometers or more, More preferably, it is 10 micrometers or more, and is 50 micrometers or less normally, Preferably it is 40 micrometers or less, More preferably, it is 30 micrometers or less. If the separator is too thin, the insulation and mechanical strength may be reduced. If the separator is too thick, not only the battery performance such as the rate characteristics may be reduced, but the energy density of the entire non-aqueous lithium secondary battery may be reduced. May decrease.

  Furthermore, when a porous material such as a porous sheet or nonwoven fabric is used as the separator, the porosity of the separator is arbitrary, but is usually 20% or more, preferably 35% or more, more preferably 45% or more, Usually, it is 90% or less, preferably 85% or less, more preferably 75% or less. If the porosity is too small, the membrane resistance increases and the rate characteristics tend to deteriorate. On the other hand, if it is too large, the mechanical strength of the separator is lowered and the insulating property tends to be lowered.

  The average pore diameter of the separator is also arbitrary, but is usually 0.5 μm or less, preferably 0.2 μm or less, and usually 0.05 μm or more. If the average pore diameter is too large, a short circuit is likely to occur, and if it is too small, the membrane resistance may increase and the rate characteristics may deteriorate.

[Exterior body]
A non-aqueous lithium secondary battery is usually configured by housing the non-aqueous electrolyte solution, the negative electrode, the positive electrode, the separator and the like in an outer package.
The material of the exterior body is arbitrary, but usually, for example, nickel-plated iron, stainless steel, aluminum or an alloy thereof, nickel, titanium, or the like is used.
The shape of the exterior body is also arbitrary, and may be any of a cylindrical shape, a square shape, a laminate shape, a coin shape, a large size, and the like.

[Charge / Discharge Control Device 30]
The charging / discharging control device 30 is a device that controls charging / discharging of the secondary battery 20. In the present embodiment, the charging / discharging control device 30 is connected to the solar cell 10, the secondary battery 20, and the power generation amount control device 50 as shown in FIGS. Has been. In principle, the electric power generated by the solar cell 10 is supplied to the light emitting device 40 via the charge / discharge control device 30 and the light emission control device 50. At this time, since the power generation amount of the solar cell 10 varies depending on the weather or the like, the charge / discharge control device 30 sends excess power to the secondary battery 20 if the power generation amount in the solar cell 10 becomes excessive. Control is performed to charge the battery. On the other hand, if the amount of power generated by the solar cell 10 is insufficient, the power stored in the secondary battery 20 (this is also the power generated by the solar cell 10) is discharged to extract the power and send it to the light emitting device 40. It is like that.

  In order to realize this, the charge / discharge control device 30 includes a power generation amount sensor that monitors the power generation amount of the solar cell 10, and charge / discharge of the secondary battery according to the power generation amount of the solar cell 10 detected by the power generation amount sensor. Control is to be performed. The solar cell 10 also includes a storage amount sensor that monitors the storage amount of the secondary battery 20, and the storage of the secondary battery 20 detected by the storage amount sensor is detected in order to prevent overcharge of the secondary battery 20. When the amount exceeds the threshold value, the secondary battery 20 is controlled not to be charged even if the amount of power generated by the solar cell 10 is excessive.

  In addition, although there is no restriction | limiting in the hardware constitutions of the charging / discharging control apparatus 30, Usually, it comprises with sensors, such as an ammeter and a voltmeter; Processors, such as CPU, Memory, such as RAM and ROM, Interfaces, such as an input-output terminal. A computer that is configured by an energization circuit having a variable resistor and a switch according to the control of the computer.

[Light Emitting Device 40]
The light emitting device 40 emits light by being supplied with the electric power generated by the solar battery 10, and light emitted from the light emitting device 40 (light emitted from the light emitting device 40 toward the living thing 70. Also referred to as irradiation light). ) Is irradiated to the organism 70. In the present embodiment, as shown in FIG. 2, the light emitting device 40 is connected to the solar cell 10 and the secondary battery 20 via the charge / discharge control device 30 and the light emission control device 50, and is generated by the solar cell 10. Electric power is supplied directly, or after being stored in the secondary battery 20, it can be supplied to emit light.
As the light emitting device 40, a device that emits light only at a certain wavelength may be used, but a device that can change the light emission wavelength into two or more types of wavelengths is preferable. For example, it is preferable to use one that emits light at least at the first wavelength and the second wavelength. Here, the first wavelength and the second wavelength mean that at least a part of the emission wavelength is different. That is, it is preferable to use a light emitting device 40 that can emit at least first light and second light having different emission wavelengths. In addition, since it is sufficient if light can be emitted at at least two wavelengths, a light emitting device 40 that can emit light at three or more wavelengths may be used. Thereby, the wavelength control by the light emission control means 50 can be performed easily.

The emission wavelengths of the light emitting device 40 such as the first wavelength and the second wavelength are not uniform, and are preferably set individually according to the type of the organism 70 and the degree of growth. The light emission wavelength of the light source 40 is usually 150 nm or more, preferably 300 nm or more, and usually 800 nm or less.
However, when a plant is grown as the organism 70, light in the wavelength range of physiologically effective radiation (300 nm to 800 nm) is suitable, and usually a light emitting device 40 that emits red light or blue light is used. To do. In the present embodiment, it is assumed that red light and blue light are used in this way. Note that red light is light having an emission peak in a wavelength range of usually 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less, more preferably 680 nm or less in the emission spectrum. Say. In addition, blue light is a wavelength that is usually greater than 420 nm, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 480 nm or less, more preferably 470 nm or less, and even more preferably 460 nm or less in the emission spectrum. Light having an emission peak in the range.
The light other than red and blue is, for example, a wavelength range of usually 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less in the emission spectrum. Yellow light having an emission peak in the range; usually green light having an emission peak in the wavelength range of greater than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, preferably 542 nm or less, more preferably 535 nm or less. Etc. can also be used.
By selecting an appropriate wavelength in this way, it is possible to improve the growth rate, adjust the nutrient components, adjust the plant shape, and the like. For example, the absorption wavelength region of chlorophyll a is usually from 400 nm to 450 nm for blue light, and is usually from 660 nm to 700 nm for red light, and the absorption wavelength region of chlorophyll b is usually from 430 nm to 500 nm for blue light. Since light is usually 640 nm or more and 670 nm or less, the growth rate of plants can be particularly increased by selecting light emission in these wavelength ranges.

Further, the intensity of the light emitted from the light source 40 is arbitrary as long as the organism 70 can be grown, but is usually 150 μmolm ⁻² s ⁻¹ or more and 800 μmolm ⁻² s ⁻¹ or less. For example, when the organism 70 is a plant, 150 μmol ⁻² s ⁻¹ to 300 μmol ⁻² s ⁻¹ is preferable if the plant is a leaf vegetable, and 300 μmol ⁻² s ⁻¹ to 800 μmol m if the plant is a fruit vegetable. ^-2 s ^-1 or less is preferable.

Further, as the light emitting device 40, one that can emit light continuously (see FIGS. 4D, 4E, and 5A) may be used, but one that can emit light intermittently should be used. Is preferable (see FIGS. 4A to 4C and 4F and FIGS. 5B to 5D). Further, focusing on the spectral waveform of the light emitted by the light emitting device 40, one that emits continuous light (see FIG. 4A) may be used, but pulsed light (FIGS. 4B to 4F), FIG. It is preferable to use those that emit 5 (a) to (d)). Note that the pulse width of the pulsed light is usually 10 to 400 microseconds. This is because, when growing a plant as the organism 70, it is preferable to irradiate light intermittently rather than continuously irradiating light, and it is preferable to irradiate pulsed light rather than irradiating continuous light. This is because the growth rate can be improved, nutritional components can be adjusted, and the shape of the plant can be adjusted.
Further, it is conceivable that the growing apparatus 1 of the present embodiment is not simply used for growing the organism 70 but used for a test for examining the optimum environment for growing the organism 70. In that case, since it is desired to change the irradiation conditions of the light from the light emitting device 40 in various ways, the light emitting device 40 can emit light continuously or intermittently, and can emit both continuous light and pulsed light. It is preferable to use one that can emit light.

  Although only one light emitting device 40 may be provided, a plurality of light emitting devices are usually provided. In this embodiment, as shown in FIG. 2, plants are planted as organisms 70 on each shelf 82 of the rack 81 installed in the room 80, but the light emitting device 40 is sufficient for the plants planted on each shelf 82. It is assumed that a plurality of ceilings of each shelf 82 are installed so that light can be irradiated. However, it goes without saying that the number of installed light emitting devices 40, the installation position, and the like are not limited to those of the present embodiment.

  As an example of the configuration of the light emitting device 40, a configuration having light emitting elements 41 and 42 corresponding to the first wavelength and the second wavelength, respectively, may be mentioned. In the present embodiment, a light emitting element (red light emitting element) 41 that emits red light (light having a first wavelength) and a light emitting element (blue light emitting element) 42 that emits blue light (light having a second wavelength) are respectively provided. In the following description, it is assumed that a light-emitting device installed on a substrate 43 provided with wiring (not shown) for supplying electric power is used. At this time, only one light emitting element 41, 42 may be provided, but a plurality of light emitting elements 41, 42 are usually provided.

  Examples of the light emitting elements 41 and 42 include a light emitting diode (LED), a laser diode (LD), an inorganic electroluminescent element (inorganic EL element), an organic electroluminescent element (organic EL element), and the like. Goods can also be used. Among these, it is preferable to use an LED. This is because LEDs are excellent in luminous efficiency, have a long lifetime, can emit pulsed light, and are inexpensive. Further, since the LED generates little heat due to light emission, there is an advantage that it is possible to avoid complicated control of the growth environment conditions (particularly temperature conditions). However, the light-emitting device 40 may use only 1 type and may use 2 or more types together by arbitrary combinations and ratios.

  For example, the blue LED is preferably a GaN LED using a GaN compound semiconductor. This is because a GaN-based LED has a significantly higher light emission output and external quantum efficiency than SiC-based LEDs that emit light in this region, so that very bright light emission can be obtained with very low power. For example, for a current load of 20 mA, a GaN-based LED usually has a light emission intensity that is 100 times or more that of a SiC-based LED.

The GaN-based LED preferably has an Al _X Ga _Y N light emitting layer, a GaN light emitting layer, or an In _X Ga _Y N light emitting layer. Among the GaN-based LEDs, those having an In _X Ga _Y N light emitting layer are particularly preferable because the light emission intensity is very strong. In the above, the value of X + Y is usually a value in the range of 0.8 to 1.2. In the GaN-based LED, those in which the light emitting layer is doped with Zn or Si or those without a dopant are preferable for adjusting the light emission characteristics.
A GaN-based LED has these light-emitting layer, p-layer, n-layer, electrode, and substrate as basic components, and the light-emitting layer is an n-type and p-type Al _X Ga _Y N layer, GaN layer, or In _X Those having a heterostructure sandwiched between Ga _Y N layers and the like have high luminous efficiency, and those having a heterostructure having a quantum well structure further have high luminous efficiency and are more preferred.

  Further, when the light emitting device 40 having the light emitting elements 41 and 42 is used as in the present embodiment, the light emitting device 40 is preferably provided with a cover 44 for protecting the light emitting elements 41 and 42 and the substrate 43. This is to protect the light emitting elements 41 and 42, the substrate 43, and the like.

  By the way, as the light emitting elements 41 and 42, those having a phosphor can be used. A light emitting element having a phosphor can control the wavelength by using the wavelength conversion function of the phosphor. Hereinafter, a light-emitting element having a phosphor (hereinafter, appropriately referred to as “phosphor light-emitting element”) will be described.

  The phosphor light-emitting element has at least an excitation light source and a phosphor that emits visible light by irradiation with light (excitation light) from the excitation light source, and the fluorescence emitted by the phosphor or the fluorescence and the excitation light. The mixed light is emitted. This phosphor light-emitting element can be a phosphor light-emitting element that emits light in an arbitrary color by adjusting the type and use ratio of the phosphor and arbitrarily adopting a known device configuration. For example, a phosphor that emits near ultraviolet light as an excitation light source, and a phosphor that emits green light (green phosphor), a phosphor that emits red light (red phosphor), and a phosphor that emits blue light If a blue phosphor or a phosphor that emits yellow light (yellow phosphor) is used, a light emitting element that emits green, red, blue, or yellow light can be configured. Also, for example, if an excitation light source that emits blue light is used, and a phosphor that emits a green phosphor, a red phosphor, or a yellow phosphor is used, blue, green, red, or yellow, respectively, A light-emitting element that emits mixed color light can be configured.

Examples of the excitation light source include the above-described light emitting diode (LED), laser diode (LD), inorganic electroluminescent element (inorganic EL element), and organic electroluminescent element (organic EL element). However, the excitation light source preferably has an emission peak wavelength of usually 200 nm or more in the emission spectrum. Among these, when near-ultraviolet light is used as excitation light, it is desirable to use one having a peak emission wavelength of usually 300 nm or more, preferably 330 nm or more, more preferably 360 nm or more, and usually 420 nm or less. When blue light is used as excitation light, it is desirable to use one having a peak emission wavelength of usually 420 nm or more, preferably 430 nm or more, and usually 500 nm or less, preferably 480 nm or less. Both are from the viewpoint of the color purity of the phosphor light emitting element.
Note that only one excitation light source may be used, or two or more excitation light sources may be used in any combination and ratio.

On the other hand, the phosphor is not particularly limited. Examples of the composition include metal oxides represented by Y ₂ O ₃ , YVO ₄ , Zn ₂ SiO ₄ , Y ₃ Al ₅ O ₁₂ , Sr ₂ SiO _{4, and the} like, which are crystal bases, Sr ₂ Si ₅ Metal nitrides typified by N _{8 and the} like, phosphates typified by Ca ₅ (PO ₄ ) ₃ Cl and the like, sulfides typified by ZnS, SrS, CaS and the like, Y ₂ O ₂ S, La ₂ O ₂ Oxysulfides represented by S, etc., ions of rare earth metals such as Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Ag, Cu, Au, Al, A combination of metal ions such as Mn and Sb as an activator element or a coactivator element can be used.

Preferred examples of the crystal matrix include sulfides such as (Zn, Cd) S, SrGa ₂ S ₄ , SrS, and ZnS; oxysulfides such as Y ₂ O ₂ S; (Y, Gd) ₃ Al ₅ O ₁₂ , YAlO ₃ , BaMgAl ₁₀ O ₁₇ , (Ba, Sr) (Mg, Mn) Al ₁₀ O ₁₇ , (Ba, Sr, Ca) (Mg, Zn, Mn) Al ₁₀ O ₁₇ , BaAl ₁₂ O ₁₉ , CeMgAl Aluminates such as ₁₁ O ₁₉ , (Ba, Sr, Mg) O.Al ₂ O ₃ , BaAl ₂ Si ₂ O ₈ , SrAl ₂ O ₄ , Sr ₄ Al ₁₄ O ₂₅ , Y ₃ Al ₅ O ₁₂ ; Y Silicates such as ₂ SiO ₅ and Zn ₂ SiO ₄ ; Oxides such as SnO ₂ and Y ₂ O ₃ ; Borates such as GdMgB ₅ O ₁₀ and (Y, Gd) BO ₃ ; Ca ₁₀ (PO ₄ ) ₆ ( F, Cl _{2, (Sr, Ca, Ba} , Mg) halophosphate such as _{10 (PO 4) 6 Cl 2} ; can be exemplified Sr ₂ P ₂ O 7, the (La, Ce) phosphate PO _4, etc. etc. .

However, the above-mentioned crystal matrix, activator element and coactivator element are not particularly limited in element composition, and can be partially replaced with elements of the same family, and the obtained phosphor is light in the near ultraviolet to visible region. Any material that absorbs and emits visible light can be used.
Specifically, the following phosphors can be used, but these are merely examples, and phosphors that can be used in the present invention are not limited to these. Here, each composition formula is delimited by a punctuation mark (,). In addition, when a plurality of elements are listed by separating them with commas (,), it indicates that one or more of the listed elements may be contained in any combination and composition. For example, the composition formula “(Ca, Sr, Ba) Al ₂ O ₄ : Eu” has “CaAl ₂ O ₄ : Eu”, “SrAl ₂ O ₄ : Eu”, and “BaAl ₂ O ₄ : Eu”. If: the _{"Ca 1-x Sr x Al 2} O 4 Eu ": a _{"Sr 1-x Ba x Al 2} O 4 Eu ": the _{"Ca 1-x Ba x Al 2} O 4 Eu " _{"Ca 1-x-y Sr x} Ba y Al 2 O 4: Eu " and all assumed to generically indicated (in the above formula, 0 <x <1,0 <y <1,0 <X + y <1).

[Green phosphor]
The emission peak wavelength in the emission spectrum of the green phosphor is usually larger than 500 nm, preferably 510 nm or more, more preferably 515 nm or more, and usually 550 nm or less, especially 540 nm or less, further 535 nm or less. Is preferred. If this emission peak wavelength λp is too short, it tends to be bluish, while if it is too long, it tends to be yellowish, and there is a possibility that the characteristics as green light will deteriorate.
In addition, the half-value width of the emission peak of the green phosphor is usually in the range of 40 nm to 80 nm.

As a specific example of the green phosphor, a europium activated alkali represented by (Mg, Ca, Sr, Ba) Si ₂ O ₂ N ₂ : Eu that is composed of fractured particles having a fracture surface and emits light in the green region. Examples include earth silicon oxynitride phosphors.
Examples of the green phosphor include Eu-activated aluminate phosphors such as Sr ₄ Al ₁₄ O ₂₅ : Eu, (Ba, Sr, Ca) Al ₂ O ₄ : Eu, and (Sr, Ba) Al _2. Si ₂ O ₈ : Eu, (Ba, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, (Ba, Sr, Ca) ₂ (Mg, Zn) Si ₂ O ₇ : Eu, (Ba, Ca, Sr, Mg) ₉ (Sc, Y, Lu, Gd) ₂ (Si, Ge) ₆ O ₂₄ : Eu-activated silicate phosphor such as Eu, Y ₂ SiO ₅ : Ce, Ce, Tb-activated silicate phosphors such as Tb, Sr ₂ P ₂ O ₇ —Sr ₂ B ₂ O ₅ : Eu-activated borate phosphate phosphors such as Eu, Sr ₂ Si ₃ O ₈ -2SrCl ₂ : Eu-activated halo silicate phosphor such as _Eu, Zn 2 _SiO 4: M such as Mn Activated silicate _{phosphors, CeMgAl 11 O 19: Tb,} Y 3 Al 5 O 12: Tb -activated aluminate phosphors such as _{Tb, Ca 2 Y 8 (SiO} 4) 6 O 2: Tb, La 3 Ga ₅ SiO ₁₄ : Tb-activated silicate phosphor such as Tb, (Sr, Ba, Ca) Ga ₂ S ₄ : Eu, Tb, Sm-activated thiogallate phosphor such as Eu, Tb, Sm, Y ₃ (Al, Ga) ₅ O ₁₂ : Ce, (Y, Ga, Tb, La, Sm, Pr, Lu) ₃ (Al, Ga) ₅ O ₁₂ : Ce-activated aluminate phosphor such as Ce, Ca ₃ Sc ₂ Si ₃ O ₁₂ : Ce, Ca ₃ (Sc, Mg, Na, Li) ₂ Si ₃ O ₁₂ : Ce activated silicate phosphor such as Ce, Ce activated oxide phosphor such as CaSc ₂ O ₄ : Ce, Eu-activated oxynitride phosphors such as Eu-activated β sialon BaMgAl ₁₀ O _17: Eu, Eu such as Mn, Mn-activated aluminate phosphor, SrAl ₂ O _4: Eu-activated aluminate phosphor such as _{Eu, (La, Gd, Y} ) 2 O 2 S: Tb-activated oxysulfide phosphors such as Tb, LaPO ₄ : Ce, Tb-activated phosphate phosphors such as Ce, Tb, and sulfide phosphors such as ZnS: Cu, Al, ZnS: Cu, Au, Al _{, (Y, Ga, Lu,} Sc, La) BO 3: Ce, Tb, Na 2 Gd 2 B 2 O 7: Ce, Tb, (Ba, Sr) 2 (Ca, Mg, Zn) B 2 O 6: Ce, Tb activated borate phosphors such as K, Ce, Tb, Eu, Mn activated halosilicate phosphors such as Ca ₈ Mg (SiO ₄ ) ₄ Cl ₂ : Eu, Mn, (Sr, Ca, Ba _{) (Al, Ga, in)} 2 S 4: Eu activated thioaluminate such as Eu Light body and thiogallate _{phosphor, (Ca, Sr) 8 (} Mg, Zn) (SiO 4) 4 Cl 2: Eu, Eu such as Mn, Mn-activated halo silicate _{phosphor, M 3 Si 6 O 9 N} 4 : Eu, M ₃ Si ₆ O ₁₂ N ₂ : Eu (where M represents an alkaline earth metal element). It is also possible to use Eu-activated oxynitride phosphors such as
Further, as the green phosphor, for example, a pyridine-phthalimide condensed derivative, a benzoxazinone-based, a quinazolinone-based, a coumarin-based, a quinophthalone-based, a naltalimide-based fluorescent pigment, or an organic phosphor such as a terbium complex may be used. Is possible.

[Orange to red phosphor]
The emission peak wavelength in the emission spectrum of the phosphor emitting orange to red light (orange to red phosphor) is usually 570 nm or more, preferably 580 nm or more, more preferably 585 nm or more, and usually 780 nm or less, preferably 700 nm or less. More preferably, it is in the wavelength range of 680 nm or less.
In addition, the half-value width of the emission peak of the red phosphor is usually in the range of 1 nm to 100 nm.

Examples of such orange to red phosphors include europium represented by (Mg, Ca, Sr, Ba) ₂ Si ₅ N ₈ : Eu that is composed of fractured particles having a red fracture surface and emits light in the red region. The activated alkaline earth silicon nitride phosphor is composed of growing particles having a substantially spherical shape as a regular crystal growth shape, and emits light in the red region (Y, La, Gd, Lu) ₂ O ₂ S: Eu And europium activated rare earth oxychalcogenide phosphors represented by the formula:
Further, as the orange to red phosphor, for example, at least one element selected from the group consisting of Ti, Zr, Hf, Nb, Ta, W, and Mo described in Japanese Patent Application Laid-Open No. 2004-300247 is used. A phosphor containing an oxynitride and / or an oxysulfide containing oxynitride having an alpha sialon structure in which a part or all of Al element is substituted with Ga element, It can be used in the present invention. These are phosphors containing oxynitride and / or oxysulfide.
Furthermore, examples of the red phosphor include Eu-activated oxysulfide phosphors such as (La, Y) ₂ O ₂ S: Eu, Y (V, P) O ₄ : Eu, and Y ₂ O ₃ : Eu. Eu-activated oxide phosphor, (Ba, Mg) ₂ SiO ₄ : Eu, Mn, (Ba, Sr, Ca, Mg) ₂ SiO ₄ : Eu, Mn-activated silicate phosphor such as Eu, Mn, Eu-activated tungstate phosphors such as LiW ₂ O ₈ : Eu, LiW ₂ O ₈ : Eu, Sm, Eu ₂ W ₂ O ₉ , Eu ₂ W ₂ O ₉ : Nb, Eu ₂ W ₂ O ₉ : Sm (Ca, Sr) S: Eu-activated sulfide phosphors such as Eu, YAlO ₃ : Eu-activated aluminate phosphors such as Eu, Ca ₂ Y ₈ (SiO ₄ ) ₆ O ₂ : Eu, LiY _{9 (SiO 4) 6 O 2:} Eu, (Sr, Ba, Ca) 3 SiO 5: Eu, Sr BaSiO _5: Eu-activated silicate phosphors such as _{Eu, (Y, Gd) 3} Al 5 O 12: Ce, (Tb, Gd) 3 Al 5 O 12: Ce -activated aluminate phosphor such as Ce, (Mg, Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Mg, Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Mg, Ca, Sr, Ba) AlSi (N, O) ₃ : Eu activated oxide such as Eu, nitride or oxynitride phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, such as Eu, Mn Mn-activated halophosphate phosphor, Ba ₃ MgSi ₂ O ₈ : Eu, Mn, (Ba, Sr, Ca, Mg) ₃ (Zn, Mg) Si ₂ O ₈ : Eu, Mn-activated silicate _{phosphor, 3.5MgO · 0.5MgF 2 · GeO 2} : Mn such as Mn Tsukekatsuge Man salt phosphor, Eu Tsukekatsusan nitride phosphor such as Eu-activated _{α-sialon, (Gd, Y, Lu,} La) 2 O 3: Eu, Eu Bi, etc., Bi-activated oxide phosphor, (Gd, Y, Lu, La) ₂ O ₂ S: Eu, Bi-activated oxysulfide phosphors such as Eu, Bi, (Gd, Y, Lu, La) VO ₄ : Eu, Bi, such as Eu, Bi Activated vanadate phosphor, SrY ₂ S ₄ : Eu, Ce activated sulfide phosphor such as Eu, Ce, etc., CaLa ₂ S ₄ : Ce activated sulfide phosphor such as Ce, (Ba, Sr, Ca, etc.) _{) MgP 2 O 7: Eu,} Mn, (Sr, Ca, Ba, Mg, Zn) 2 P 2 O 7: Eu, Eu such as Mn, Mn-activated phosphate phosphor, (Y, _Lu) 2 WO _6: Eu, Eu such as Mo, Mo-activated tungstate _{phosphor, (Ba, Sr, Ca)} x Si y N z: u, Ce (provided that, x, y, z are an integer of 1 or more. Eu, Ce-activated nitride phosphors such as (Ca, Sr, Ba, Mg) ₁₀ (PO ₄ ) ₆ (F, Cl, Br, OH): Eu, Mn-activated halophosphoric acid such as Eu, Mn Salt phosphors, ((Y, Lu, Gd, Tb) _1-xy Sc _x Ce _y ) ₂ (Ca, Mg) _1-r (Mg, Zn) _{2 + r} Si _z-q Ge _q O _{12 + δ and} other Ce It is also possible to use an activated silicate phosphor or the like.
In addition, as the red phosphor, for example, a red organic phosphor comprising a rare earth element ion complex having an anion such as β-diketonate, β-diketone, aromatic carboxylic acid, or Bronsted acid as a ligand, a perylene type Pigments (eg, dibenzo {[f, f ′]-4,4 ′, 7,7′-tetraphenyl} diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene), Anthraquinone pigments, lake pigments, azo pigments, quinacridone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments, India Phenol pigments, cyanine pigments, and dioxazine pigments can also be used.

Among these, as red phosphors, (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si (N, O) ₂ : Eu, (Ca, Sr , Ba) AlSi (N, O) ₃ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Ce, (Sr, Ba) ₃ SiO ₅ : Eu, (Ca, Sr) S: Eu, It is preferable to contain (La, Y) ₂ O ₂ S: Eu or Eu complex, more preferably (Ca, Sr, Ba) ₂ Si ₅ (N, O) ₈ : Eu, (Ca, Sr, Ba) Si. (N, O) ₂ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Eu, (Ca, Sr, Ba) AlSi (N, O) ₃ : Ce, (Sr, Ba) ₃ SiO _{5: Eu, (Ca, Sr} ) S: Eu or _{(La, Y) 2 O 2} S: Eu, or Eu ( Preferably comprises a _{dibenzoylmethane)} 3 · 1,10-beta-diketone Eu complex or carboxylic acid Eu complex phenanthroline complex, _{etc., (Ca, Sr, Ba)} 2 Si 5 (N, O) 8: Eu (Sr, Ca) AlSi (N, O): Eu or (La, Y) ₂ O ₂ S: Eu is particularly preferred.
Moreover, among the above examples, (Sr, Ba) ₃ SiO ₅ : Eu is preferable as the orange phosphor.

[Blue phosphor]
The emission peak wavelength in the emission spectrum of the blue phosphor is usually 420 nm or more, preferably 430 nm or more, more preferably 440 nm or more, and usually 490 nm or less, preferably 480 nm or less, more preferably 470 nm or less, still more preferably 460 nm or less. It is preferable to be in the wavelength range.
In addition, the half-value width of the emission peak of the blue phosphor is usually in the range of 20 nm to 80 nm.

Such a blue phosphor is composed of, for example, grown particles having a substantially hexagonal shape as a regular crystal growth shape, and is represented by (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu that emits light in a blue region. Europium-activated barium magnesium aluminate-based phosphor, which is composed of growth particles having a substantially spherical shape as a regular crystal growth shape, and emits light in a blue region (Mg, Ca, Sr, Ba) ₅ (PO ₄ ) ₃ (Cl, F): a europium-activated calcium halophosphate phosphor represented by Eu, composed of growing particles having a substantially cubic shape as a regular crystal growth shape, and emits light in a blue region (Ca, Sr, Ba) ₂ Europium-activated alkaline earth chloroborate phosphor represented by B ₅ O ₉ Cl: Eu, fractured grains having a fracture surface Europium-activated alkaline earth aluminate composed of a luminescent element and represented by (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba) ₄ Al ₁₄ O ₂₅ : Eu System phosphors and the like.
Examples of blue phosphors include Sn-activated phosphate phosphors such as Sr ₂ P ₂ O ₇ : Sn, (Sr, Ca, Ba) Al ₂ O ₄ : Eu or (Sr, Ca, Ba). ₄ Al ₁₄ O ₂₅ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, BaMgAl ₁₀ O ₁₇ : Eu, Tb, Sm, BaAl ₈ O ₁₃ : with Eu, etc. Active aluminate phosphor, Ce-activated thiogallate phosphor such as SrGa ₂ S ₄ : Ce, CaGa ₂ S ₄ : Ce, Eu, Mn such as (Ba, Sr, Ca) MgAl ₁₀ O ₁₇ : Eu, Mn Active aluminate phosphor, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu, (Ba, Sr, Ca) ₅ (PO ₄ ) ₃ (Cl, F, Br, OH): Eu, Mn, Eu-activated halophosphate phosphor such as Sb, BaAl ₂ Si ₂ O ₈ : Eu, (Sr, Ba) ₃ MgSi ₂ O ₈ : Eu-activated silicate phosphor such as Eu, Sr ₂ P ₂ O ₇ : Eu-activated phosphate phosphors such as Eu, sulfide phosphors such as ZnS: Ag, ZnS: Ag, Al, Ce-activated silicate phosphors such as Y ₂ SiO ₅ : Ce, tungstic acids such as CaWO ₄ Salt phosphor, (Ba, Sr, Ca) BPO ₅ : Eu, Mn, (Sr, Ca) ₁₀ (PO ₄ ) ₆ · nB ₂ O ₃ : Eu, 2SrO · 0.84P ₂ O ₅ · 0.16B ₂ Eu, Mn activated boric acid phosphor phosphor such as O ₃ : Eu, Sr ₂ Si ₃ O ₈ · 2SrCl ₂ : Eu activated halosilicate phosphor such as Eu, SrSi ₉ Al ₁₉ ON ₃₁ : Eu, EuSi ₉ Al ₁₉ ON ₃₁ etc. Eu Tsukekatsusan Compound _{phosphor, La 1-x Ce x Al} (Si 6-z Al z) (N 10-z O z) ( here, x, and y are each 0 ≦ x ≦ 1,0 ≦ z ≦ 6 numbers _{satisfying.), La 1-x-} y Ce x Ca y Al (Si 6-z Al z) (N 10-z O z) ( here, x, y, and z, respectively, 0 ≦ It is also possible to use Ce-activated oxynitride phosphors such as x ≦ 1, 0 ≦ y ≦ 1, and 0 ≦ z ≦ 6.
In addition, as the blue phosphor, for example, naphthalic acid imide-based, benzoxazole-based, styryl-based, coumarin-based, pyralizone-based, triazole-based compound fluorescent dyes, thulium complexes and other organic phosphors can be used. .

Among the above examples, as the blue phosphor, (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : Eu or It is preferable to contain (Ba, Ca, Mg, Sr) ₂ SiO ₄ : Eu, and (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ ( Cl, F) ₂ : Eu or (Ba, Ca, Sr) ₃ MgSi ₂ O ₈ : Eu is more preferable, and BaMgAl ₁₀ O ₁₇ : Eu, Sr ₁₀ (PO ₄ ) ₆ (Cl, F) ₂ : More preferably, Eu or Ba ₃ MgSi ₂ O ₈ : Eu is included. Of these, (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆ Cl ₂ : Eu or (Ca, Sr, Ba) MgAl ₁₀ O ₁₇ : Eu is particularly preferred for illumination and display applications.

[Yellow phosphor]
The emission peak wavelength in the emission spectrum of the yellow phosphor is usually in the wavelength range of 530 nm or more, preferably 540 nm or more, more preferably 550 nm or more, and usually 620 nm or less, preferably 600 nm or less, more preferably 580 nm or less. Is preferred.
Further, the half-value width of the emission peak of the yellow phosphor is usually in the range of 60 nm to 200 nm.

Examples of such yellow phosphors include various oxide-based, nitride-based, oxynitride-based, sulfide-based, and oxysulfide-based phosphors. In particular, for example, RE ₃ M ₅ O ₁₂ : Ce (where RE represents at least one element selected from the group consisting of Y, Tb, Gd, Lu, and Sm, and M represents Al, Ga, And at least one element selected from the group consisting of Sc and M ^a ₃ M ^b ₂ M ^c ₃ O ₁₂ : Ce (where M ^a is a divalent metal element, M ^b is a trivalent element) metal element, ^{M c} represents a tetravalent metal element) garnet phosphor having a garnet structure represented by ^{_{like, AE 2 M d O 4:}} . Eu ( where, AE is, Ba, Sr, Ca, Mg And at least one element selected from the group consisting of Zn, M ^d represents Si and / or Ge, etc.), etc., and constituent elements of the phosphors of these systems Place some of the oxygen in nitrogen Oxynitride-based _{phosphors, AEAlSi (N, O) 3} : Ce (. , Where, AE is, Ba, Sr, Ca, represents at least one element selected from the group consisting of Mg and Zn) such as Examples include phosphors activated with Ce, such as a nitride-based phosphor having a CaAlSiN ₃ structure.
As the yellow phosphor, for _{example, CaGa 2 S 4: Eu,} (Ca, Sr) Ga 2 S 4: Eu, (Ca, Sr) (Ga, Al) 2 S 4: sulfide fluorescent such Eu It is also possible to use a phosphor activated with Eu such as an oxynitride phosphor having a sialon structure such as a body, Ca _x (Si, Al) ₁₂ (O, N) ₁₆ : Eu.
Moreover, as yellow fluorescent substance, for example, brilliant sulfoflavine
FF (Color Index Number 56205), basic yellow HG (Color Index Number 46040), eosine (Color Index Number 45380), rhodamine
It is also possible to use fluorescent dyes such as 6G (Color Index Number 45160).

[Other matters concerning phosphor]
Only 1 type may be used for fluorescent substance and it may use 2 or more types together by arbitrary combinations and a ratio.
Further, the weight median diameter of the phosphor is usually 10 μm or more, preferably 12 μm or more, and usually 30 μm or less, particularly preferably 25 μm or less. When the weight median diameter is too small, the luminance is lowered and the phosphor particles tend to aggregate. On the other hand, if the weight median diameter is too large, there is a tendency for coating unevenness and blockage of the dispenser to occur.

[Sealing material]
In the phosphor light emitting element, the phosphor is usually used in a state of being dispersed and sealed in a sealing material. As the sealing material, either an inorganic material or an organic material may be used.
Examples of the inorganic material include a solution obtained by hydrolyzing a solution containing a metal alkoxide, a ceramic precursor polymer, or a metal alkoxide by a sol-gel method (for example, an inorganic material having a siloxane bond). it can.
On the other hand, examples of the organic material include thermoplastic resins, thermosetting resins, and photocurable resins. Specific examples include methacrylic resins such as polymethylmethacrylate; styrene resins such as polystyrene and styrene-acrylonitrile copolymers; polycarbonate resins; polyester resins; phenoxy resins; butyral resins; polyvinyl alcohols; Cellulose-based resins such as cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins.

Among these, it is preferable to use a silicon-containing compound for the purpose of improving heat resistance, light resistance and the like.
The silicon-containing compound refers to a compound having a silicon atom in the molecule, for example, an organic material (silicone material) such as polyorganosiloxane, an inorganic material such as silicon oxide, silicon nitride, silicon oxynitride, and borosilicate. And glass materials such as phosphosilicate and alkali silicate. Among these, silicone materials are preferable from the viewpoint of ease of handling.

The silicone material generally refers to an organic polymer having a siloxane bond as a main chain, and examples thereof include a compound represented by the general composition formula (i) and / or a mixture thereof.
(R ¹ R ² R ³ SiO _1/2 ) _M (R ⁴ R ⁵ SiO _2/2 ) _D (R ⁶ SiO _3/2 ) _T (SiO _4/2 ) _Q Formula (i)
In the general composition formula (i), R ¹ to R ⁶ represent those selected from the group consisting of an organic functional group, a hydroxyl group, and a hydrogen atom. R ¹ to R ⁶ may be the same or different. In the above formula (i), M, D, T, and Q are numbers that are 0 or more and less than 1, respectively, and that satisfy M + D + T + Q = 1.

When used for sealing a semiconductor light emitting device, the silicone material can be used after being sealed with a liquid silicone material and then cured by heat or light.
When silicone materials are classified according to the curing mechanism, silicone materials such as an addition polymerization curing type, a condensation polymerization curing type, an ultraviolet curing type, and a peroxide vulcanization type can be generally cited. Among these, addition polymerization curing type (addition type silicone material), condensation curing type (condensation type silicone material), and ultraviolet curing type are preferable.

  The addition-type silicone material refers to a material in which a polyorganosiloxane chain is crosslinked by an organic addition bond. Typical examples include compounds having a Si—C—C—Si bond at the crosslinking point obtained by reacting vinylsilane and hydrosilane in the presence of an addition catalyst such as a Pt catalyst. As these, commercially available products can be used. Specific examples of addition polymerization curing type trade names include “LPS-1400”, “LPS-2410”, and “LPS-3400” manufactured by Shin-Etsu Chemical Co., Ltd.

  On the other hand, examples of the condensation type silicone material include a compound having a Si—O—Si bond obtained by hydrolysis and polycondensation of an alkylalkoxysilane at a crosslinking point. Specific examples thereof include polycondensates obtained by hydrolysis and polycondensation of compounds represented by the following general formula (ii) and / or (iii) and / or oligomers thereof.

M ^{m +} X _n Y ¹ _mn (ii)
(In formula (ii), M represents at least one element selected from silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y ¹ represents a monovalent organic group. M represents one or more integers representing the valence of M, and n represents one or more integers representing the number of X groups, provided that m ≧ n.

^{_{(M s + X t Y 1}} s-t-1) u Y 2 (iii)
(In the formula (iii), M represents at least one element selected from silicon, aluminum, zirconium, and titanium, X represents a hydrolyzable group, and Y ¹ represents a monovalent organic group. Y ² represents a u-valent organic group, s represents an integer of 1 or more representing the valence of M, t represents an integer of 1 or more and s−1 or less, u represents 2 or more Represents an integer.)

  Further, the condensation type silicone material may contain a curing catalyst. As this curing catalyst, for example, a metal chelate compound or the like can be suitably used. The metal chelate compound preferably contains one or more of Ti, Ta, and Zr, and more preferably contains Zr. In addition, only 1 type may be used for a curing catalyst and it may use 2 or more types together by arbitrary combinations and a ratio.

  Examples of such condensation type silicone materials include members for semiconductor light emitting devices described in JP-A Nos. 2007-112973 to 112975, JP-A No. 2007-19459, and Japanese Patent Application No. 2006-176468. Is preferred.

In addition, 1 type may be used for a sealing material and it may use 2 or more types together by arbitrary combinations and a ratio.
In addition, the sealing material can contain a metal element that can be a metal oxide having a high refractive index in order to adjust the refractive index. Examples of metal elements that give a metal oxide having a high refractive index include Si, Al, Zr, Ti, Y, Nb, and B. These metal elements may be used alone or in combination of two or more in any combination and ratio.
The presence form of such a metal element is not particularly limited as long as the transparency of the sealing material is not impaired. For example, even if a uniform glass layer is formed as a metalloxane bond, it exists in the sealing material in a particulate form. It may be. When present in the form of particles, the structure inside the particles may be either amorphous or crystalline, but is preferably a crystalline structure in order to provide a high refractive index. In addition, the particle diameter is usually not more than the emission wavelength of the semiconductor light emitting device, preferably not more than 100 nm, more preferably not more than 50 nm, particularly preferably not more than 30 nm so as not to impair the transparency of the sealing material. For example, by mixing particles of silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, yttrium oxide, niobium oxide, etc. with a silicone material, the above metal elements can be present in the sealing material in the form of particles. .
Moreover, as said sealing material, you may contain well-known additives, such as a spreading | diffusion agent, a filler, a viscosity modifier, and an ultraviolet absorber. In addition, only 1 type may be used for these additives, and 2 or more types may be used together by arbitrary combinations and a ratio.

Further, the phosphor light emitting element is usually formed by arranging the above-described excitation light source and phosphor on an appropriate frame. At this time, the phosphor is excited by the light emission of the excitation light source to generate light emission, and the light emission of this excitation light source and / or the light emission of the phosphor is arranged to be taken out to the outside.
In the phosphor light emitting element, members other than the above-described excitation light source, phosphor, and frame may be used. Examples thereof include the aforementioned sealing materials. The sealing material can be used for the purpose of bonding the excitation light source, the phosphor and the frame in addition to the purpose of dispersing the phosphor in the phosphor light emitting element.

[Light emission control device 50]
The light emission control device 50 is a device that performs control (light emission control) so that at least the intensity and / or wavelength of light emitted from the light emitting device 40 to the organism 70 is changed over time. In the present embodiment, FIG. , 2 are connected to the charge / discharge control device 30 and the light emitting device 40.

Here, the control performed by the light emission control device 50 will be described.
The light emission control device 50 performs control to change the wavelength of light emitted from the light emitting device 40 with time, and can select which light of the first and second wavelengths is emitted at each time point. Yes. In the present embodiment, as described above, the light emitting device 40 can emit red light (first wavelength light) and blue light (second wavelength light). By controlling which of the light emitting elements 41 and 42 is supplied with electric power, the light emitting device 40 controls which of red light and blue light is emitted. Thus, the light emission control device 50 functions as a wavelength selection unit.

Further, the light emission control device 50 can control to change the light emission intensity of the light emitting device 40 with time. Thus, the light emission control device 50 functions as a light emission intensity control means.
Thereby, first, the light emission control device 50 controls whether or not the light emission intensity of the light emitting device 40 is zero (that is, controls the presence or absence of light emission), and controls the timing at which the light emitting device 40 emits light. The intermittent light emission of the light emitting device 40 can be realized. In the present embodiment, since power is supplied to the light emitting device 40 via the light emission control device 50 as shown in FIG. 2, the light emission control device 50 supplies the power to the light emitting device 40 at a time. By controlling the power supply period, the power supply interval, and the like, the light emission time, the light emission period, the light emission interval, and the like of the light emitting device 40 are controlled. Thus, the light emission control device 50 functions as a light emission time control means.
Secondly, the light emission control device 50 can control the change of the light emission intensity of the light emitting device 40 to control the spectrum waveform of each light emission. In the present embodiment, since power is supplied to the light emitting device 40 via the light emission control device 50 as shown in FIG. 2, the light emission control device 50 continuously supplies power supplied to the light emitting device 40. It is possible to control whether the light emitted from the light emitting device 40 is continuous light or pulse light by controlling whether the light is supplied to the light source or as a pulse. As described above, the light emission control device 50 also functions as a light emission waveform control means.
Thirdly, the light emission control device 50 can adjust the light emission intensity ratio of red light and blue light by controlling the maximum value of the light emission intensity of each time of the light emitting device 40. In the present embodiment, as shown in FIG. 2, power is supplied to the light emitting device 40 via the light emission control device 50, so the light emission control device 50 determines the amount of power supplied to the light emitting device 40. By controlling, the maximum intensity of each emission emitted by the light emitting device 40 can be adjusted to adjust the emission intensity ratio of red light and blue light. As described above, the light emission control device 50 also functions as a light emission intensity ratio control means.

4A to 4F show examples of light emission patterns of the light emitting device 40 under the control of the light emission control means 50. FIG. 4A to 4F, the vertical axis indicates the emission intensity, the horizontal axis indicates time, “red on” indicates the period during which red light is emitted, and “blue on” indicates blue light. “Off” indicates a period during which the light emitting device 40 does not emit light. Red light is indicated by a solid line, and blue light is indicated by a broken line.
For example, as shown in FIG. 4A, the light emission control means 50 may emit red light and blue light alternately and intermittently with continuous light. Further, for example, as shown in FIG. 4B, red light and blue light may be alternately and intermittently emitted with pulsed light. For example, as shown in FIG.4 (c), you may change the period which emits red light and / or blue light for every light emission. For example, as shown in FIG. 4D, red light and blue light may be emitted continuously. Further, for example, as shown in FIG. 4 (e), not only one of red light and blue light but also a period for emitting both may be provided. For example, as shown in FIG. 4 (f), one or both of red light and blue light may be continuously emitted twice or more.

5A to 5D show another example of the light emission pattern of the light emitting device 40 under the control of the light emission control means 50. FIG. 5A to 5D, the vertical axis indicates the emission intensity, the horizontal axis indicates time, “red on” indicates the period during which red light is emitted, and “blue on” indicates blue light. “Off” indicates a period during which the light emitting device 40 does not emit light. Red light is indicated by a solid line, and blue light is indicated by a broken line.
For example, as shown in FIG. 5A, the light emission control means 50 may emit red light and blue light alternately and continuously emit red light and blue light as a whole. Further, as shown in FIG. 5B, for example, red light and blue light may be partially overlapped to emit light, and the entire red light and blue light may be emitted intermittently. Further, for example, as shown in FIG. 5C, the emission periods of the red light and the blue light may be matched by emitting the red light and the blue light at the same timing. For example, as shown in FIG. 5 (d), while red light is continuously emitted for a relatively long period of time, blue light is intermittently emitted for a relatively short period of time while red light is emitted. You may make it make it.

4A to 4F and FIGS. 5A to 5D show examples in which the maximum light emission intensity is uniform, it is also possible to change the light emission intensity for each light emission.
In addition to emitting light with a uniform emission intensity during the emission period, for example, the emission intensity may be gradually increased or decreased.
Furthermore, the emission intensity of red light and blue light may be the same, but may be different.
The light emission time may be set to any time from a short time of about several microseconds to a long time of about several hours.

  In this embodiment, as shown in FIG. 2, a plurality of light emitting devices 40 are installed on the ceiling of each shelf 82. Usually, in such a case, the same species of organism 70 is often planted or raised on the same shelf 82. Moreover, when using it for the test which investigates the optimal environment for growing the living thing 70, a growing condition may be changed for every shelf 82. FIG. For this reason, normally, the light emission control device 50 is provided for each shelf 82 so that the light emission of the light emitting device 40 can be controlled for each shelf 82.

  The hardware configuration of the light emission control device 50 is not limited, but is usually configured by sensors such as an ammeter and a voltmeter; a processor such as a CPU, a memory such as a RAM and a ROM, and an interface such as an input / output terminal. A computer that includes an energization circuit having a variable resistor, a switch, and the like according to the control of the computer. The light emission of the light emitting device 40 is controlled according to the control content recorded in advance in a memory or the like. In the present embodiment, when the light emission control device 50 receives a living thing 70 to be raised from a controller 60 described later, the light emission control device 50 responds to the breeding status (growth degree, etc.) of the living thing 70 according to the appropriate control content recorded in a memory or the like. By controlling the light emission over time, it is possible to improve the growth rate and nutrients.

[Controller 60]
The controller 60 is connected to the light emission control device 50, inputs / outputs information to / from the light emission control device 50, and changes the control content of the light emission control device 50. For example, when a camera (not shown) for observing the organism 70 is provided on each shelf 82 to monitor the growth status of the organism 70, the light emission control device according to the type and the growth status of the organism 70, etc. 50 control patterns are changed. In particular, if the controller 60 is configured so that the light emission control device 50 can be remotely operated, it is possible to carry out the breeding management of a very large number of organisms 70 in one place, and the cost can be reduced.

  The hardware configuration of the controller 60 can be realized by, for example, a computer including a processor such as a CPU, a memory such as a RAM and a ROM, and an interface such as an input / output terminal.

[Living organism 70]
There is no restriction on the organism 70. For example, grains such as rice, millet, millet, millet, sugarcane, sorghum, corn, buckwheat, wheat, barley, rye, rye wheat, oats, pearl barley, tartary buckwheat, cricket; soybean, azuki bean, pea, broad bean, Beans such as kidney bean, alfalfa, groundnut, walnut, almond, poppy, coffee, pistachio, macadamia; sweet potato, potato, yam, taro, cassava, yam, taro, etc .; sesame, rapeseed, safflower, sunflower, coconut, palm , Olives, cottonseed, cacao, safflower, avocado and other oily plants; carrot, radish, turnip, radish, lotus root, burdock, onion, leek, celery, leek, honey bee, shungiku, chingensai, Chinese cabbage, spinach Vegetables such as cucumber, mizuna, parsley, lettuce, cabbage, broccoli, asparagus, cauliflower, peppers, shrimp, cucumber, cucumber, bitter gourd, zucchini, watermelon, tomato, pumpkin, eggplant, ginger, ginger, garlic, rakkyo, komatsuna Orange, grapefruit, lemon, grape, muscat, peach, plum, apricot, apple, pear, oyster, plum, fig, pomegranate, strawberry, melon, pineapple, mango, mangosteen, papaya, acerola, kiwi, blueberry, raspberry, cranberry Fruits such as cherries; cedar, cypress, pine, willow, giraffe, maple, poplar, oak, elm, pecan, teak, cherry, ume, maple, etc .; Arabidopsis, rose, carnation, tulip, tor Gypsophila, Gentian, Petunia, Gypsophila, Nadesico, Lily, Violet, Pansy, Lavender, Gerbera, Cosmos, Chrysanthemum, Geranium, Periwinkle, Begonia, Cyclamen, Nilebergia, Periwinkle, Periwinkle, Orchid, Sunflower, Ivy, Asian Plants such as Indian rubber, orchid orchid, sansevieria, chevrela, spatiphyllum, dracaena, neoregelia, pachira, benjamin, potos, monstera, poinsettia, anemone, and kyoto are listed. In addition, animals, fungi, bacteria and the like can also be mentioned. Note that only one species of the organism 70 may be grown, or two or more species may be grown in any combination and ratio. Among them, leafy vegetables such as lettuce, sanchu, green leaf, lorain lettuce, arugula, mizuna, spring chrysanthemum, komatsuna and green wave are preferred.

[Other configurations]
The main components are as described above, but the growing device 1 may be provided with other components.
For example, in this embodiment, a rack 81 is provided, and a plant is planted as a living thing 70 on a shelf 82 of the rack 81. Although the shelf 82 may be one stage, it is preferable to provide it with two or more stages from the viewpoint of effectively utilizing the space. Usually, it is often provided in about 10 stages.
In this embodiment, a rack 81 is installed in the room 80, and plants are grown in the room 80. Thereby, it is possible to control the growing environment precisely and stably. Moreover, since it grows in the room 80, it is possible to prevent pests and the like from entering from the outside, and usually there is no need to use agricultural chemicals. The room 80 may be installed either on the ground or underground, and its dimensions are arbitrary.
Further, although not shown, temperature adjusting means such as a heater, water supply means such as a sprinkler, air conditioning control means such as an air conditioning control device, liquid fertilizer control device, and the like may be provided.

[how to use]
Since the breeding apparatus 1 of the present embodiment is configured as described above, the creature 70 is grown in the following manner when used.
First, the solar cell 10 receives natural light and generates power. The generated electric power is sent to the charge / discharge control device 30 and is sent to the light emission control device 50 by the amount necessary for the light emission of the light emitting device 40. Further, surplus power is sent to the secondary battery 20, and the secondary battery 20 is charged.
The electric power sent to the light emission control device 50 is supplied to the light emitting device 40, and the light emitting device 40 emits light. At this time, the intensity and / or wavelength of the light emission of the light emitting device 40 can be changed over time according to the control content predetermined by the light emission control device 50. As a result, the organism 70 is repeatedly irradiated with one or a combination of red light and blue light continuously or intermittently as continuous light or pulsed light for a predetermined period. And the plant which is the living thing 70 performs photosynthesis by the irradiated light, and is nurtured. The control content of the light emission control device 50 may be set according to the type and breeding status of the organism 70. For example, the light emission is completely switched on or off in a period of 8 hours so that the organism 70 is not stressed. Can be. In addition, for example, even in the case of a period of 8 hours, instead of continuously emitting light at the time of light emission, high-speed blinking with pulsed light (including those that appear to be continuous light emission to the human eye) may be performed. it can.

In addition, since power generation of the solar cell 10 cannot be expected at night or the like, the charge / discharge control device 30 discharges the secondary battery 20 and causes the light emitting device 40 to emit light with the electric power stored in the secondary battery 20.
Furthermore, when it is desired to change the light emission pattern of the light emitting device 40, the control content of the light emission control device 50 may be changed by the controller 60.

[advantage]
As described above, according to the breeding apparatus 1 of the present embodiment, it is possible to grow a living organism more efficiently at a lower cost than in the past. That is, since the solar battery 10 is used, no power is required for light emission of the light emitting device 40, and the surplus power can be effectively used by the secondary battery 20. Is possible. In particular, the solar cell 10 including an organic photoelectric conversion element can reduce the installation cost.

  Further, the light intensity emitted from the light source 40 to the organism 70 and / or the combination of light emitting elements that emit light are changed over time, whereby red light and blue light are combined and controlled by the light emission control device 50. Since it is possible to irradiate the organism 70 with an optimal pattern, it is possible to grow the organism 70 efficiently. Furthermore, the controller 60 can appropriately change the light emission pattern of the light emitting device 40 in accordance with the type of the growth target and the growth situation, so that the efficiency can be further increased. At this time, since light emission can be controlled for each shelf 82, precise control is possible. In addition, since the degree of growth of the organism 70 can be predicted by controlling the light irradiation, it is possible to easily carry out the growth management using a computer or the like.

  Moreover, according to the breeding apparatus 1 of this embodiment, the test which investigates the optimal environment for growing the living thing 70 can also be performed. That is, if each light emission control device 50 is controlled to perform different light emission controls, the pattern of light irradiation on the organism 70 can be irradiated by examining the growth status of the organism 70 corresponding to each light emission control device 50. Knowing what to do, you can know the optimal training environment.

[Others]
As mentioned above, although 1st embodiment of this invention was described in detail, this invention is not limited to the said embodiment, In the range which does not deviate from the summary of this invention, it can change arbitrarily and can implement.
For example, in addition to providing the light emission control device 50 for each shelf 82, only one common light emission control device 50 may be provided for each shelf 82 or one light emission device 40 may be provided. .
Further, for example, the light emission control device 50 may perform control such that only one of the light wavelength and intensity is changed.

  Further, for example, the ceiling or wall of the room 80 may be made transparent, and the living thing 70 may be grown using not only the light emission of the light emitting device 40 but also natural light. In addition, the solar cell 10 is usually installed on the roof portion of the room 80. In order not to prevent the natural light from being taken into the room 80 through the ceiling, the solar cell is provided with an organic photoelectric conversion element. Alternatively, it is preferable to use a solar cell that transmits sunlight, such as an amorphous silicon solar cell in which a notch is formed.

  Further, for example, when the organism 70 is periodically photographed with a camera, the photographed image is compared with an image recorded on the average growth degree stored in the controller 60, and there is a great difference between the two. The controller 60 may determine that something is wrong and issue a warning to the user. In addition to the warning or instead of the warning, the controller 60 may instruct the light emission control device 50 to change the control content of the light.

Further, for example, the creature 70 may be periodically photographed with a camera, and the photographed image and the light irradiation pattern may be combined and output to an output device such as a display. Thereby, since the optimal breeding environment can be converted into data, a test for examining the optimum environment for growing the organism 70 can be appropriately performed. Further, if the growing environment is converted into data in this way, irradiation can be controlled only by an instruction from the controller 60 without physical change even when the organism 70 to be grown changes.
Further, for example, the power of the charge / discharge control device 30, the light emission control device 50, and the controller 60 may be supplied from the solar cell 10 or the secondary battery 20.

[Second Embodiment]
[Overview]
6 and 7 (a) and 7 (b) schematically show a growth apparatus as a second embodiment of the present invention, FIG. 6 is a schematic view, and FIGS. 7 (a) and 7 (b) are perspective views. It is.
As shown in FIG. 6, the growing apparatus 100 according to the present embodiment includes a container 90 as a living room, and includes a temperature adjusting apparatus 91 as a means for adjusting the temperature in the container 90 (temperature adjusting means). The rest is the same as in the first embodiment. That is, the growing device 100 of the present embodiment includes the solar cell 10, the secondary battery 20, the charge / discharge control device 30, the light emitting device 40, the light emission control device 50, and the controller 60. The generated electric power is supplied to the light emitting device 40, and the light emitting device 40 emits light by the supplied electric power, and this light emission is irradiated to the living organism 70 to grow the living organism 70.

[Solar cell 10]
The solar cell 10 can use the same thing as 1st embodiment similarly.
If the solar cell 10 is installed in the roof part of the container 90 as shown to Fig.7 (a), (b), it can receive sunlight effectively and is preferable.

[Secondary battery 20]
The secondary battery 20 can be the same as that of the first embodiment.
The secondary battery 20 is usually installed in the container 90, but may be installed outside the container 90.

[Charge / Discharge Control Device 30]
The charging / discharging control device 30 is a device that controls charging / discharging of the secondary battery 20, and in this embodiment, as shown in FIG. 6, the solar cell 10, the secondary battery 20, the power generation amount control device 50, and the temperature adjustment device 91. It is connected to the. In principle, the electric power generated by the solar cell 10 is supplied to the light emitting device 40 via the charge / discharge control device 30 and the light emission control device 50, and further supplied to the temperature adjustment device 91 via the charge / discharge control device 30. . At this time, since the power generation amount of the solar cell 10 varies depending on the weather or the like, the charge / discharge control device 30 sends excess power to the secondary battery 20 if the power generation amount in the solar cell 10 becomes excessive. Control is performed to charge the battery. On the other hand, if the power generation amount in the solar cell 10 is insufficient, the power stored in the secondary battery 20 (this is also the power generated by the solar cell 10) is discharged to extract the power, and the light emitting device 40 and the temperature. It is sent to the adjusting device 91.
The hardware configuration of the charge / discharge control device 30 can be the same as that described in the first embodiment.

The charging / discharging control device 30 is usually installed in the container 90, but may be installed outside the container 90.
From the viewpoint of storage in the container 90, it is preferable that the power for operating the charge / discharge control device 30 is supplied from the solar cell 10 or the secondary battery 20. Thereby, it is possible to grow the organism 70 without relying on external electric power.

[Light Emitting Device 40]
The light emitting device 40 can be the same as that of the first embodiment.

[Light emission control device 50]
The light emission control device 50 can be the same as that of the first embodiment.
The light emission control device 50 is normally installed in the container 90, but may be installed outside the container 90.
Further, from the viewpoint of storage in the container 90, it is preferable that the power for operating the light emission control device 50 is supplied from the solar cell 10 or the secondary battery 20. Thereby, it is possible to grow the organism 70 without relying on external electric power.

[Controller 60]
The controller 60 can be the same as that of the first embodiment.
The controller 60 is usually installed in the container 90, but may be installed outside the container 90.
From the viewpoint of storage in the container 90, it is preferable that the power for operating the controller 60 is supplied from the solar battery 10 or the secondary battery 20. Thereby, it is possible to grow the organism 70 without relying on external electric power.

[Living organism 70]
The living thing 70 can grow up the thing similar to 1st embodiment similarly.

[Container 90]
In the present embodiment, the secondary battery 20, the charge / discharge control device 30, the light emitting device 40, the light emission control device 50 and the controller 60, and the organism 70 to be grown are housed in a container 90. Cultivate In this embodiment, the rack 81 is provided in the container 90 similarly to 1st embodiment, and the plant is planted as the living organism 70 on the shelf 82 of the rack 81.
Although the shape, dimension, etc. of the container 90 are arbitrary, it is preferable to use the commercially available container manufactured by the existing specification from a cost surface.

As shown in FIGS. 6 and 7B, the container 90 is usually provided with a temperature adjusting device 91 as temperature adjusting means. In general, a container having such temperature adjusting means is called a reefer container. By providing the temperature adjusting device 91, the temperature in the container 90 can be adjusted to a preferable range, and the organism 70 can be grown efficiently and under various conditions.
The temperature adjustment device 91 is connected to the charge / discharge control device 30, and is connected to the solar cell 10 and the secondary battery 20 via the charge / discharge control device 30. Then, the electric power generated by the solar cell 10 is directly supplied or supplied after being stored in the secondary battery 20 to operate. With such a configuration, the temperature in the container 90 can be adjusted without relying on external power.
In this embodiment, as shown in FIGS. 7A and 7B, the container 90 having the temperature adjustment device 91 provided on the side wall opposite to the door 92 will be described. There is no particular restriction on the installation position.

  Moreover, it is preferable to use as the container 90 what equips a wall with a heat insulating material (not shown). This is because the container 90 of the present embodiment can be used in harsh environments such as polar regions, deserts, and tropical regions, so that the temperature in the container 90 can be adjusted at low cost. Although there is no restriction | limiting in the kind of heat insulating material, For example, foaming urethane, a polystyrene foam, etc. can be used. In addition, 1 type may be used for a heat insulating material and it may use 2 or more types together by arbitrary combinations and a ratio.

  Further, although not shown, this embodiment may also include components other than those described above as in the first embodiment. For example, water supply means such as a sprinkler, air conditioning control means such as an air conditioning control device, liquid fertilizer A control device or the like may be provided.

[how to use]
Since the growing apparatus 100 of the present embodiment is configured as described above, it is possible to grow the organism 70 in the same manner as in the first embodiment.

[advantage]
According to the growing apparatus 100 of the present embodiment, it is possible to grow an organism more efficiently at a lower cost than in the past.
In addition, since the apparatus is configured using the container 90, it is portable and can be easily installed, so that it can be manufactured and transported at a low cost.
With regard to the container in particular, by using a container that has already been used, it is possible to reuse the container for purposes other than transportation or storage. Furthermore, even under harsh environmental conditions, the use of a container makes it possible to grow organisms stably without being influenced by the environment.
Furthermore, the same advantages as those of the first embodiment can be obtained.

[Others]
As mentioned above, although 2nd embodiment of this invention was described in detail, this invention is not limited to the said embodiment, In the range which does not deviate from the summary of this invention, it can change arbitrarily and can implement.
In addition, regarding the installation location of the container, the effect of the present invention can be further expected if it is installed in the following location. For example, under harsh climate conditions, by filling the ground with a portion of the container or the entire area excluding the solar cell installation surface rather than being installed on the ground, the energy used by the entire container can be reduced regardless of the outside temperature. It can be suppressed and can grow organisms with lower power.
For example, it can be implemented in the same manner as in the first embodiment.

  The present invention can be used in the field related to the growth of living organisms, and is suitable for use in, for example, the growth and testing of agricultural products.

It is a functional block diagram showing typically a breeding device as a first embodiment of the present invention. It is a schematic diagram showing typically the breeding device as a first embodiment of the present invention. It is sectional drawing which shows typically the structure of the solar cell as one Embodiment of this invention. (A)-(f) is a figure explaining 1st embodiment of this invention, Comprising: It is a figure which shows the example of the light emission pattern of the light-emitting device by control of the light emission control means. (A)-(d) is a figure explaining 1st embodiment of this invention, Comprising: It is a figure which shows the example of the light emission pattern of the light-emitting device by control of the light emission control means. It is a schematic diagram which shows typically the breeding apparatus as 2nd embodiment of this invention. (A), (b) is a perspective view which shows typically the growth apparatus as 2nd embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1,100 Growing device 10 Solar cell 11 Photoelectric conversion element 20 Secondary battery 30 Charge / discharge control device 40 Light emitting device 41, 42 Light emitting device 43 Substrate 44 Cover 50 Light emission control device 60 Controller 70 Biology 80 Room 81 Rack 82 Shelf 90 Container 91 Temperature control device 92 Door

Claims (11)

A growth apparatus for irradiating a living organism with light and growing the organism,
A solar cell that receives light and generates electricity;
A light source that emits light by being supplied with electric power generated by the solar cell, and irradiates the organism with light; and
A growth apparatus comprising: a light emission control unit that changes the intensity and / or wavelength of light emitted from the light source to the organism over time. A growing device for irradiating a plant with light to grow the plant,
A solar cell that receives light and generates electricity;
A light source that emits light by being supplied with electric power generated by the solar cell, and irradiates the plant with light; and
A growth apparatus comprising: a light emission control unit that changes the intensity and / or wavelength of light irradiated to the plant from the light source over time. The growth apparatus according to claim 1, further comprising: a secondary battery that is charged by the electric power generated by the solar battery and that discharges to supply electric power to the light source. The growth apparatus according to claim 3, further comprising a charge / discharge control device that controls charge / discharge of the secondary battery. The growing apparatus according to any one of claims 1 to 4, further comprising a controller that changes the control content of the light emission control means.   The growing apparatus according to claim 1, wherein the light source is selected from the group consisting of a light emitting diode, a laser diode, an inorganic electroluminescent element, and an organic electroluminescent element.   The growing apparatus according to claim 1, wherein the light source emits light at two or more wavelengths. The intensity of light emitted by the light source is 150 μmolm ⁻² s ⁻¹ or more and 800 μmolm ⁻² s ⁻¹ or less,
The wavelength of light emitted by the light source is 150 nm or more and 800 nm or less,
The growth apparatus according to any one of claims 1 to 6, wherein the light emission control means controls light emission of the light emitted from the light source with a pulse width of 10 microseconds or more and 400 microseconds or less.   The breeding apparatus according to claim 1, further comprising a container that stores the organism and the light source.   The growing apparatus according to claim 7, wherein the container includes a heat insulating material selected from any one of urethane foam and polystyrene. From a light source that is supplied with power generated by a solar cell and emits light, it is a growth method for irradiating light on a living thing and growing the living thing,
A growing method, wherein the intensity and / or wavelength of light irradiated to the organism is changed over time.

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