WO2017065251A1 - Organic photoelectric conversion element and organic thin-film solar battery module - Google Patents
Organic photoelectric conversion element and organic thin-film solar battery module Download PDFInfo
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- WO2017065251A1 WO2017065251A1 PCT/JP2016/080477 JP2016080477W WO2017065251A1 WO 2017065251 A1 WO2017065251 A1 WO 2017065251A1 JP 2016080477 W JP2016080477 W JP 2016080477W WO 2017065251 A1 WO2017065251 A1 WO 2017065251A1
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- photoelectric conversion
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- organic photoelectric
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Images
Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Definitions
- the present invention relates to an organic photoelectric conversion element and an organic thin film solar cell module including the organic photoelectric conversion element.
- organic thin-film solar cells have been actively studied.
- the organic thin film solar cell can use a transparent resin substrate having flexibility. Therefore, organic thin-film solar cells can be installed on the walls of buildings, window glass, etc., taking advantage of being flexible and lightweight compared to conventional solar cells using crystalline silicon substrates and glass substrates. It is being considered. Assuming that organic thin-film solar cells are installed on the walls and windows of buildings, the wall and windows of buildings are easily noticeable. It seems necessary to attach importance.
- Patent Document 1 discloses a method of absorbing a specific wavelength by arranging a light absorption layer behind the photoelectric conversion layer when viewed from the light receiving surface side. It is disclosed.
- Patent Document 2 discloses that a wide color selection of the dial is possible by setting the refractive index and thickness of the transparent electrode and the photoelectric conversion layer to specific values.
- Organic thin-film solar cells are required to have high conversion efficiency for practical use.
- it has been studied to install it on the wall surface of a building, a window glass, etc., and the design is also emphasized at present.
- the lower transparent electrode constituting the organic thin film solar cell is formed not by using only a transparent oxide conductor having high resistance but by using a metal layer having low resistance.
- a metal layer is used, a new problem has arisen in that an undesirable red or yellow interference color may be conspicuous due to the reflected light of the metal layer, generally assuming installation on windows or building materials. .
- Patent Documents 1 and 2 that disclose a color tone adjustment method.
- a light absorption layer is arrange
- a light absorption layer works as an internal resistance of a solar cell, and the power generation efficiency and lifetime of a solar cell As a result, the characteristics of the solar cell may be impaired.
- the thickness of a transparent electrode and a photoelectric converting layer is determined in order to adjust an external color, in order to exhibit the performance as a solar cell, the optimal film thickness of a transparent electrode or a photoelectric converting layer is selected.
- the power generation efficiency of the solar cell is lowered due to an increase in the resistance of the transparent electrode or a decrease in the amount of light absorption in the photoelectric conversion layer, which may impair the characteristics of the solar cell.
- the present invention solves such a new problem, and without affecting the characteristics of the solar cell, in particular, while preventing the solar cell from exhibiting a yellow or red color, while relating to the color of the organic active layer.
- An object of the present invention is to provide an organic photoelectric conversion element and an organic thin-film solar cell module that can be adjusted to a blue color desired as the appearance color of the surface of the solar cell to improve the design.
- the present inventor has intensively studied to solve the above problems, and when the organic thin-film solar cell module is viewed from the front from the transparent substrate side, the design defect that exhibits yellow or red is a transparent substrate of the organic photoelectric conversion element. It has been found that this phenomenon is prominent particularly when the transparent electrode includes a metal layer due to the transparent electrode existing between the organic active layer and the organic active layer.
- part of the light incident on the transparent substrate of the organic photoelectric conversion element is reflected by the metal layer of the transparent electrode, causing optical interference between the incident light and the reflected light.
- the resulting interference color occurs.
- the appearance color of the organic thin film solar cell module is strongly influenced by light interference generated between the transparent substrate and the transparent electrode of the organic photoelectric conversion element, particularly between the transparent substrate and the metal layer.
- the appearance color of the photoelectric conversion element can be prevented from exhibiting yellow or red due to the interference color of yellow or red. Furthermore, by making the blue interference color conspicuous, it is found that the appearance color of the organic photoelectric conversion element can be easily adjusted to a desired blue color regardless of the color tone of the organic active layer, and the present invention is completed. It came. Furthermore, since this invention adjusts the film thickness of the layer which is not an organic active layer which contributes directly to power generation efficiency, it can prevent that the characteristic of a solar cell falls significantly.
- the present invention is as follows.
- An organic photoelectric conversion element in which a transparent substrate, a lower transparent electrode including a metal layer, an organic active layer, and an upper electrode are sequentially stacked,
- the optical path length (n ⁇ d) between the transparent substrate and the metal layer expressed by the distance d and the refractive index n between the transparent substrate and the metal layer, is one of integers where m is 0 or more, the following formula ( The organic photoelectric conversion element characterized by satisfying 1). 480 nm ⁇ 4 ⁇ (n ⁇ d) ⁇ (2 ⁇ m + 1) ⁇ 380 nm (1)
- the organic photoelectric conversion element according to [1] including an undercoat layer between the transparent substrate and the metal layer.
- the appearance color of the solar cell surface is adjusted to a blue color while preventing the solar cell from exhibiting yellow or red without impairing the characteristics of the solar cell, and the design is improved.
- An organic photoelectric conversion element to be obtained can be provided.
- an organic thin-film solar cell module including the organic photoelectric conversion element, which is improved in design by suppressing yellow and red colors can be provided.
- FIG. 1 is a cross-sectional view schematically showing a configuration of an organic photoelectric conversion element in one embodiment of the present invention.
- FIG. 2 is a diagram illustrating the relationship between the optical path length and the phase of light.
- FIG. 3 is a cross-sectional view schematically showing the configuration of the organic thin-film solar cell module in one embodiment of the present invention.
- FIG. 1 is a cross-sectional view schematically showing a configuration of an organic photoelectric conversion element 1 in one embodiment of the present invention.
- the organic photoelectric conversion element 1 includes a transparent substrate 2, an undercoat layer 3, a first transparent conductive layer 4, a metal layer 5 and a second transparent conductive layer 6 sequentially laminated, an organic active layer 8 and the upper electrode 9 are sequentially laminated.
- the organic photoelectric conversion element according to the present embodiment is organic regardless of the color tone of the organic active layer while suppressing the appearance color of the organic photoelectric conversion element from being yellow or red when observed from the transparent substrate 2 side.
- the appearance color of the photoelectric conversion element can be adjusted to a blue color, and the design can be improved.
- the color of the organic active layer 8 is dominant in the appearance color of the organic photoelectric conversion element. This is because the organic active layer 8 is colored to absorb light in the visible light region, while the layers other than the organic active layer 8 are colorless and transparent so that the organic active layer 8 can absorb light efficiently. This is because it is considered preferable.
- the organic photoelectric conversion element when the organic photoelectric conversion element is actually observed from the transparent substrate 2 side, the organic photoelectric conversion element exhibits an unfavorable appearance color such as red or yellow due to light interference. It turns out that there may be. The following reasons can be considered as this reason.
- the lower transparent electrode 7 when the lower transparent electrode 7 is generally formed to have a metal layer 5 having a high reflectivity, a lot of reflected light is generated in the metal layer 5. Furthermore, some layers may be formed between the metal layer 5 and the transparent substrate 2. For example, in the embodiment according to FIG. 1, an undercoat layer 3 and a transparent conductive layer 6 constituting a lower transparent electrode are formed between the transparent substrate 2 and the metal layer 5. Therefore, depending on the film thickness of these layers, an optical interference effect due to the reflected light of the metal layer 5 may occur in the layers. Specifically, in the organic photoelectric conversion element 1 of the present embodiment, an example of interference of incident light will be described with reference to FIG.
- the transparent substrate 2 represented by a distance (film thickness) d and a refractive index n between the transparent substrate 2 and the metal layer 5.
- the reflected light of the wavelength ⁇ calculated by substituting the optical path length (n ⁇ d) with the metal layer 5 into the following formula (a) is enhanced by the optical interference condition. That is, the reflected light having the wavelength ⁇ affects the appearance color of the organic photoelectric conversion element.
- incident light 1 When incident light that does not reflect at the interface between the transparent substrate 2 and the undercoat layer 3 is reflected by the metal layer 5 (incident light 1), incident light that is reflected at the interface between the transparent substrate 2 and the undercoat layer 3 (incident light 2).
- incident light 2 incident light that is reflected at the interface between the transparent substrate 2 and the undercoat layer 3 (incident light 2).
- the appearance of the organic photoelectric conversion element with a tint means that the light intensifies in the visible light range.
- n ⁇ d the number of interference waves appearing in the visible light region increases, and the maximum peak of reflectance increases. That is, as m increases, many reflected colors tend to be mixed, and the interference color of a specific primary color becomes inconspicuous. In particular, when m is 4 or more, the interference color of a specific primary color becomes inconspicuous. Therefore, when m is an integer of 0 or more and 3 or less, the value of n ⁇ d is set so that the appearance color becomes a blue color. It is considered that the appearance of the organic photoelectric conversion element and the organic thin film solar cell module can be adjusted to a desirable blue color by adjusting the color.
- the organic photoelectric conversion element 1 is a transparent substrate represented by a distance (total thickness) d and a refractive index n between the transparent substrate 2 and the metal layer 5.
- n total thickness
- n refractive index
- the solar cell has a yellow or red color without impairing the solar cell characteristics.
- the present inventors have found that the appearance color of the solar cell surface can be adjusted to a desired blue color regardless of the color tone of the organic active layer while suppressing the presenting.
- equation (1) is satisfied when m is an integer of 0 or more, but as described above, when the value of m is 4 or more, the interference color of a specific primary color becomes inconspicuous. Therefore, when m is an integer of 0 or more and 3 or less, the appearance color of the organic photoelectric conversion element is controlled while suppressing the organic photoelectric conversion element from exhibiting yellow or red by satisfying the above formula (1). It is possible to adjust to a blue color.
- the film thickness d in the formula (1) can be measured by, for example, a spectroscopic ellipsometer, an optical interference film thickness meter, a stylus type step meter, an atomic force microscope, a transmission electron microscope, a scanning electron microscope, or the like. it can.
- the refractive index n in the formula (1) can be measured using, for example, an Abbe refractometer, a Pullfrich refractometer, a digital refractometer or the like according to the method described in JIS K 0062. It can also be measured by a prism coupler method, a liquid immersion method, or a spectroscopic method.
- the refractive index n varies depending on the wavelength, the transparent material used for the undercoat layer and the transparent conductive layer has a small wavelength dependency of the refractive index. Therefore, in the present invention, the refractive index n is 485 nm. A refractive index n shall be used. Specific examples of spectroscopic methods are described in Applied Physics Vol. 65, No. 11, pages 1125 to 1130, according to a) a method for obtaining by optical simulation using spectral reflectance and spectral transmittance, and b) spectroscopic method. There are methods such as obtaining by ellipsometry.
- nxd in the above formula (1) Can be calculated according to the following formula (b).
- n ⁇ d ⁇ (n i ⁇ d i ) (b)
- N i and d i mean the refractive index and film thickness of the material of the i-th layer from the transparent substrate 2 side, respectively.
- the undercoat layer 3 in order to improve the adhesiveness of the transparent substrate 2 and the lower transparent electrode 7, it is preferable to have the undercoat layer 3 so that it may mention later.
- the first transparent conductive layer 4 in order to improve the durability of the metal layer 5 constituting the lower transparent electrode 7, it is preferable to have the first transparent conductive layer 4 below the metal layer 5. That is, it is particularly preferable to have the undercoat layer 3 and the first transparent conductive layer 4 from the transparent substrate 2 side between the transparent substrate 2 and the metal layer 5.
- d 1 and the thickness of the undercoat layer 3, n 1 the refractive index of the undercoat layer 3, when the thickness of the first transparent conductive layer 4 and d 2, the refractive index of the first transparent conductive layer 4 and n 2 The solar cell without obstructing the characteristics of the solar cell by satisfying the following formula (3) when the optical path length (d 1 ⁇ n 1 + d 2 ⁇ n 2 ) is any integer greater than or equal to 0: Is preferable because the appearance color of the solar cell surface can be adjusted to a blue color and the design can be improved while suppressing yellow and red. 480 ⁇ 4 ⁇ (n 1 ⁇ d 1 + n 2 ⁇ d 2 ) ⁇ (2 ⁇ m + 1) ⁇ 380 (3)
- the optical path length ( n 1 ⁇ d 1 + n 2 ⁇ d 2 ) preferably satisfies the above formula (3).
- the transparent substrate 2 is a member that supports the organic photoelectric conversion element 1.
- the material of the transparent substrate 2 is not limited as long as the layers constituting the organic photoelectric conversion element 1 are stacked and supported.
- the material of the transparent substrate 2 examples include glass, quartz, and a transparent resin material.
- the transparent resin material include, for example, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, fluororesin, polyvinyl chloride, polyethylene, polypropylene, cyclic
- organic materials such as polyolefin, cellulose, acetyl cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, poly (meth) acrylic resin, phenol resin, epoxy resin, polyarylate, and polynorbornene.
- the transparent substrate 2 preferably has flexibility.
- the material having flexibility is not particularly limited, but polyethylene terephthalate, polyethylene naphthalate, polyimide, and poly (meth) acrylic resin are preferable from the viewpoint of easy formation of the organic photoelectric conversion element 1.
- 1 type may be used for the material of the transparent substrate 2, and 2 or more types may be used together by arbitrary combinations and a ratio.
- the material of the transparent substrate 2 may contain reinforcing fibers such as carbon fibers and glass fibers to reinforce the mechanical strength.
- the visible light transmittance of the transparent substrate 2 defined by JIS R 3106 is usually 70% or more, preferably 80% or more.
- the thickness of the transparent substrate 2 is not particularly limited as long as the visible light transmittance is satisfied, but from the viewpoint of ease of handling, it is usually 20 ⁇ m or more, preferably 50 ⁇ m or more, and usually 1000 ⁇ m or less, preferably Is 500 ⁇ m or less, more preferably 200 ⁇ m or less.
- the undercoat layer 3 is mainly disposed between the transparent substrate 2 and the lower transparent electrode 7 and has a function of improving the adhesion between the transparent substrate 2 and the lower transparent electrode 7.
- the organic photoelectric conversion element 1 shown in FIG. 1 is an embodiment using the undercoat layer 3, but is not necessarily essential. Note that the undercoat layer 3 is preferably transparent in order to allow light to enter the organic active layer 8 efficiently.
- the undercoat layer 3 being transparent means that the visible light transmittance defined by JIS R 3106 is 70% or more, and preferably 80% or more.
- the refractive index n 1 at a wavelength of 485 nm of the undercoat layer 3 is not particularly limited, but is usually 1.4 or more and 2.0 or less.
- the refractive index n 1 of the undercoat layer 3 at a wavelength of 485 nm is equal to the refractive index n 3 of the transparent substrate 2 at a wavelength of 485 nm and the 485 nm of the first transparent conductive layer. it is preferably smaller than the refractive index n 2 at.
- the reason for this is that light interference efficiently occurs between the transparent substrate 2 and the metal layer 5 due to Fabry-Perot interference, and the interference color in the undercoat layer is enhanced, so that the appearance color of the organic photoelectric conversion element is further increased. This is because it is easy to adjust.
- the refractive index n 1 of the undercoat layer 3 is the refractive index of the transparent substrate 2 so that the organic active layer 8 efficiently absorbs light while appropriately adjusting the appearance color of the organic photoelectric conversion element by light interference.
- n less than 3 and the difference between the refractive index n 1 and the refractive index n 3 of the transparent substrate 2 of the undercoat layer 3 (n 3 -n 1) is preferably 0.1 or more, 0. It is preferably 2 or more, on the other hand, preferably 0.4 or less, and particularly preferably 0.3 or less.
- Examples of the material of the undercoat layer 3 include substances generated by hydrolysis of resins such as acrylic resin, polyester resin, and polyamide resin, and organic silicon compounds such as hard coat agent SHC900 manufactured by Momentive Performance Materials. (Hydrolyzate), inorganic fine particles such as silica, and the like.
- the undercoat layer 3 is preferably formed of a hydrolysis product of an organosilicon compound for the purpose of further improving the adhesion with the lower transparent electrode 7.
- an acrylic resin, a polyester resin, a polyamide resin, and an epoxy resin are used together for the purpose of improving the adhesion strength with the transparent substrate 2 and the mechanical strength of the undercoat layer 3. Also good.
- inorganic substance fine particles having a diameter of 100 nm or less are used, it is desirable to use them together with an acrylic resin, a polyester resin and a polyamide resin for the purpose of improving the adhesion strength with the transparent substrate 2 and the mechanical strength of the undercoat layer 3.
- Silica is particularly desirable for the inorganic substance fine particles having a diameter of 100 nm or less. This is because the refractive index of silica is close to that of an acrylic resin, so that there is little irregular reflection and it is easy to obtain a transparent undercoat layer 3.
- an acrylic resin, a polyester resin, a polyamide resin, etc. you may make it bridge
- the thickness of the undercoat layer 3 may be selected in consideration of the optical path length between the transparent substrate 1 and the metal layer 5 as described above.
- the thickness of the undercoat layer 3 is preferably 10 nm or more, more preferably 50 nm or more, while cracks are generated. Is preferably 5 ⁇ m or less, more preferably 1 ⁇ m or less, still more preferably 500 nm or less, particularly preferably 300 nm or less, and most preferably 200 nm or less.
- One of the lower transparent electrode 7 and the upper electrode 9 is an anode that collects holes generated in the organic active layer 8, and the other is a cathode that collects electrons generated in the organic active layer 8.
- the lower transparent electrode 7 may be an anode
- the upper electrode 9 may be a cathode
- the lower transparent electrode 7 may be a cathode
- the upper electrode 9 may be an anode.
- the lower transparent electrode 7 is formed by laminating a first transparent conductive layer 4, a metal layer 5, and a second transparent conductive layer 6 in this order. That is, the first transparent conductive layer 4 is laminated between the undercoat layer 3 and the metal layer 5, and the second transparent conductive layer 6 is laminated between the metal layer 5 and the organic active layer 8. Yes.
- the lower transparent electrode 7 can be formed of a single transparent conductive layer, but the transparent conductive layer formed of a metal oxide tends to have high resistance. Therefore, in the present invention, the lower transparent electrode 7 is formed with the metal layer 5 in order to improve conductivity.
- the lower transparent electrode 7 only needs to include at least a metal layer, and may be a single layer of the metal layer 5 or a laminate of the metal layer 5 and the transparent conductive layer.
- a laminated structure of a metal layer and a transparent conductive layer is preferable, and in particular, as shown in FIG. 1, a laminated structure in which a transparent conductive layer is disposed on both sides of the metal layer. It is preferable.
- first transparent conductive layer 4 and the second transparent conductive layer 6 may be the same or different.
- excellent transparency means that when a thin film having a thickness of about 100 nm is formed, the visible light transmittance of the thin film is 60% or more, and excellent conductivity means that the thickness is about 100 nm.
- the thin film it means that the surface resistance value of the thin film is 1 ⁇ 10 7 ⁇ / ⁇ or less. The surface resistance value may be adjusted by doping impurities.
- Examples of materials that can be suitably used for the first transparent conductive layer 4 and the second transparent conductive layer 6 include metal oxides.
- metal oxides for example, indium oxide doped with tin (ITO), indium oxide doped with zinc (IZO), indium oxide doped with tungsten (IWO), indium oxide doped with gallium (IGO), cadmium and tin Oxide (CTO), aluminum oxide (Al 2 O 3 ), zinc oxide (ZnO), zinc-aluminum oxide (AZO), tin-zinc oxide (ZTO), magnesium oxide (MgO), oxidation Thorium (ThO 2 ), tin oxide (SnO 2 ), lanthanum oxide (La 2 O 3 ), indium oxide (In 2 O 3 ), niobium oxide (Nb 2 O 3 ), antimony oxide (Sb 2 O 3 ), oxidation Zirconium (ZrO 2 ), cerium oxide (CeO 2 ), titanium oxide (TiO 2 ), bismuth oxide (
- zinc sulfide (ZnS), cadmium sulfide (CdS), antimony sulfide (Sb 2 S 3 ), and the like can be given.
- indium oxide doped with tin (ITO), indium oxide doped with zinc (IZO), indium oxide doped with tungsten (IWO), indium oxide doped with gallium (IGO), tin and zinc Amorphous oxides such as oxide (ZTO) are preferred.
- the crystal transition temperature (Tc) of the first transparent conductive layer 4 and the second transparent conductive layer 6 is usually 150 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher.
- the crystal transition temperature (Tc) of the transparent conductive thin film layer is 150 ° C. or higher, it is preferable in that the surface unevenness of the transparent conductive layer does not occur when the organic photoelectric conversion element is formed on the transparent plastic substrate.
- the crystal transition temperature can be measured by a measuring method such as differential calorimetry.
- the thickness of the 1st transparent conductive layer 4 and the 2nd transparent conductive layer 6 considers the electric conductivity of the lower transparent electrode 7, the transmittance
- the organic photoelectric conversion element 1 is a transmission type (see-through type) photoelectric conversion element, it is preferable to select in consideration of the transmittance and reflectance of the lower transparent electrode 7 and the organic photoelectric conversion element 1 as a whole. .
- the thickness of the first transparent conductive layer 4 is selected in consideration of light interference between the metal layer 5 and the transparent substrate 2 as described above. There is a need to.
- the thickness of the first transparent conductive layer 4 takes into account the relationship with the thickness of the undercoat layer 3. And design.
- the film thickness of the first transparent conductive layer 4 is preferably 5 nm or more, more preferably 10 nm or more, more preferably 20 nm or more, while preferably 200 nm or less. More preferably, it is 100 nm or less, and particularly preferably 60 nm or less.
- the first transparent conductive layer 4 is not uniformly formed, and the metal layer 5 tends to be oxidized and deteriorated to lose its gloss, and the light interference effect tends to be impaired. At the same time, the electrical resistance may increase.
- the first transparent conductive layer 4 is usually formed by a vacuum deposition method such as a sputtering method or a CVD method. Since the conductive layer is formed, the first transparent conductive layer 4 is easily cracked by stress. As a result, oxygen enters the first lower transparent electrode 7 and the metal layer 5 tends to be oxidized and deteriorated.
- the thickness of the second transparent conductive layer 6 is not particularly limited, but is usually 20 nm or more, preferably 30 nm or more, and usually 60 nm or less. . On the other hand, it is preferable that the amount is not more than the above upper limit because flexibility can be ensured and the production rate does not decrease.
- the refractive index at 485 nm of the first transparent conductive layer 4 and the second transparent conductive layer 6 is not particularly limited, but each is usually 1.3 or more, while the organic active layer 8 is suppressed by suppressing the interface reflectance. In order to be able to absorb light efficiently, 2.5 or less is preferable, and 2.2 or less is more preferable.
- the refractive index n 2 of the first transparent conductive layer 4 is preferably selected so as to satisfy the above formulas (1) to (3) and formula (4) described later.
- the specific resistance of the first transparent conductive layer 4 and the second transparent conductive layer 6 is usually 1 ⁇ 10 ⁇ 7 ⁇ ⁇ cm or more, preferably 1 ⁇ 10 ⁇ 6 ⁇ ⁇ cm or more, while usually 5 ⁇ 10 ⁇ 3 ⁇ ⁇ cm or less, preferably 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less.
- the lower transparent electrode 7 is transparent, but preferably has high permeability from the viewpoint of conversion efficiency, and is usually 60% or more and preferably 70% or more.
- the upper limit is not particularly limited, but is usually 90% or less.
- the transmittance of the lower transparent electrode 7 can be measured using an ultraviolet-visible near-infrared spectrophotometer and a film sample holder. As a measurement result, the transmittance from a wavelength of 380 nm to 900 nm is calculated according to JIS R 3106: 1998, and the transmittance of the lower transparent electrode 7 is calculated as an average of the transmittance in these wavelength regions.
- Metal layer 5 There is no special restriction
- metals such as platinum, gold
- the thickness of the metal layer 5 is preferably 1 nm, more preferably 5 nm or more for improving the conductivity, while the organic active layer 8 efficiently absorbs light and improves conversion efficiency. Further, it is preferably 20 nm or less, and more preferably 10 nm or less.
- the thickness of the entire lower transparent electrode 7 may be adjusted by determining the film thickness of each layer in consideration of optical characteristics and electrical characteristics, but is usually 10 nm or more, preferably 60 nm or more, It is 300 nm or less, preferably 200 nm or less, and particularly preferably 100 nm or less.
- the upper electrode 9 can be formed of any material having conductivity.
- the material of the upper electrode 9 include metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, barium, sodium, and alloys thereof; metals such as indium oxide and tin oxide. Oxides or alloys thereof (ITO, etc.); conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene; acids such as hydrochloric acid, sulfuric acid, sulfonic acid, Lewis acids such as FeCl 3 , iodine, etc.
- a dopant such as a metal atom such as a halogen atom such as sodium or potassium; a conductive composite material in which conductive particles such as metal particles, carbon black, fullerene or carbon nanotubes are dispersed in a matrix such as a polymer binder
- a dopant such as a metal atom such as a halogen atom such as sodium or potassium
- a conductive composite material in which conductive particles such as metal particles, carbon black, fullerene or carbon nanotubes are dispersed in a matrix such as a polymer binder
- the lower transparent electrode 8 is a cathode for collecting electrons and the upper electrode 9 is an anode for collecting holes
- a material having a deep work function is used as the material constituting the upper electrode 9. Is preferred.
- the lower transparent electrode 8 is an anode and the upper electrode 9 is a cathode for collecting electrons
- the lower transparent electrode 7 and the upper electrode 9 can be formed of the same material by providing a buffer layer as will be described later.
- the present invention is effective in a transmissive organic photoelectric conversion element that requires high designability.
- each layer which comprises the lower transparent electrode 7 and the upper electrode 9 It can form by a well-known method. For example, it can be formed by a dry process such as vacuum deposition or sputtering. It can also be formed by a wet process using conductive ink or the like. At this time, any conductive ink can be used, and for example, a metal particle dispersion or the like can be used. Further, the lower transparent electrode 7 and / or the upper electrode 9 may be improved in characteristics such as electrical characteristics and wetting characteristics by surface treatment.
- the organic active layer 8 usually includes a p-type organic semiconductor compound and an n-type semiconductor compound.
- the p-type semiconductor compound is a compound that works as a p-type semiconductor material
- the n-type semiconductor compound is a compound that works as an n-type semiconductor material.
- a bulk heterostructure having a thin film stack type in which a p-type semiconductor compound layer and an n-type semiconductor compound layer are stacked, and a layer (i layer) in which a p-type semiconductor compound and an n-type semiconductor compound are mixed examples include a structure in which a junction type, a layer (i layer) in which a p-type semiconductor compound and an n-type semiconductor compound are mixed, and a p-type semiconductor compound layer and / or an n-type semiconductor compound layer are stacked.
- a bulk heterojunction type having a layer (i layer) in which a p-type semiconductor compound and an n-type semiconductor compound are mixed is preferable.
- the film thickness of the organic active layer 8 is not particularly limited, but is usually 10 nm or more, preferably 50 nm or more, more preferably 100 nm or more, and usually 1000 nm or less, preferably 500 nm or less, more preferably 400 nm or less. And particularly preferably 200 nm or less. If the film thickness of the organic active layer 8 is 10 nm or more, it is preferable because the uniformity of the film is maintained and a short circuit is hardly caused. Moreover, if the thickness of the organic active layer 8 is 1000 nm or less, it is preferable at the point from which internal resistance becomes small, and the spreading
- the present invention is particularly effective when the appearance color of the organic photoelectric conversion element is undesirable from yellow to red.
- the present invention is particularly effective when an organic active layer having a hue angle defined by Z 8781-4: 2013 in the range of ⁇ 60 ° to 110 ° is used. This is because, as described above, in the present invention, even if the organic active layer exhibits such a color tone, the appearance color is adjusted to a blue color by adjusting the optical path length between the transparent substrate 2 and the metal layer 5. This is because it can.
- the p-type organic semiconductor compound is not particularly limited, and examples thereof include a p-type low-molecular organic semiconductor compound or a p-type organic semiconductor polymer. Especially, when making the organic active layer 8 into a bulk heterojunction type, it is preferable to use the p-type organic-semiconductor polymer which is excellent in film forming property.
- the p-type semiconductor polymer is preferably a semiconductor polymer obtained by copolymerizing two or more monomer units, and specifically, a ⁇ -electron conjugate including an acceptor constituent unit and a donor constituent unit. Heavy.
- p-type semiconductor polymers include polythiophene-thienothiophene copolymers described in Nature Materials, 2006, 5, 328, and polythiophene-diketopyrrolopyrrole described in WO 2008/000664. Copolymer, Adv. Mater. , 2007, 4160, polythiophene copolymer such as PCPDTBT described in Nature Materials, 2007, 6,497, and imidothiophene described in WO 2011/028827 pamphlet. And a copolymer of thienothiophene and benzodithiophene described in International Publication No. 2011/011545 pamphlet.
- conjugated polymer compound as described in international publication 2013/180243 pamphlet, international publication 2013/065855 pamphlet, etc. is also mentioned.
- combined with the combination of the monomer quoted here can be used similarly.
- the substituents of these polymers and monomers can be appropriately selected in order to control solubility, crystallinity, film formability, HOMO energy level, LUMO energy level, and the like.
- the n-type semiconductor compound is not particularly limited. Specifically, fullerene; fullerene compound; quinolinol derivative metal complex represented by 8-hydroxyquinoline aluminum; naphthalenetetracarboxylic acid diimide or perylenetetracarboxylic acid diimide Condensed ring tetracarboxylic acid diimides: perylene diimide derivatives, terpyridine metal complexes, tropolone metal complexes, flavonol metal complexes, perinone derivatives, benzimidazole derivatives, benzoxazole derivatives, thiazole derivatives, benzthiazole derivatives, benzothiadiazole derivatives, oxadiazoles Derivatives, thiadiazole derivatives, triazole derivatives, aldazine derivatives, bisstyryl derivatives, pyrazine derivatives, phenanthroline derivatives, quinoxaline derivatives, ben Quinoline derivatives, bipyridine derivatives, bo
- the n-type semiconductor compound is preferably a fullerene compound.
- the fullerene compound is not particularly limited, and for example, those described in publicly known documents such as International Publication No. 2011-016430 or Japanese Unexamined Patent Publication No. 2012-191194 can be used.
- the fullerene compounds PC61BM or PC71BM is preferable.
- a kind of compound may be used among the above, and a mixture of a plurality of kinds of compounds may be used.
- the method for producing the organic active layer 8 is not particularly limited, and can be formed by any method according to the material to be used.
- a vacuum film forming method such as a vapor deposition method or a sputtering method, or a coating method can be given.
- a coating method it is preferable to use a coating method in order to improve productivity.
- any method can be used, for example, spin coating method, reverse roll coating method, gravure coating method, kiss coating method, roll brush method, spray coating method, air knife coating method, wire barber coating method, Examples include the pipe doctor method, the impregnation / coating method, and the curtain coating method.
- the organic active layer 8 when the organic active layer 8 is a stacked type of a p-type semiconductor compound layer and an n-type semiconductor compound layer, by applying a coating liquid containing a p-type semiconductor compound and a coating liquid containing an n-type semiconductor compound, respectively. Can be produced. Further, when the organic active layer 8 is a Berg heterojunction type having a layer in which a p-type semiconductor compound and an n-type semiconductor compound are mixed, a coating liquid containing a p-type semiconductor compound and an n-type semiconductor compound is prepared in advance. It can be prepared by applying the coating solution.
- the organic active layer is preferably produced by roll-to-roll, and in that case, it is preferably formed by a coating method.
- the organic photoelectric conversion element may have a layer other than the lower transparent electrode 7, the organic active layer 8, and the upper electrode 9, for example, the lower transparent electrode 7 and the organic active layer 8 and / or the organic active layer 8 and the upper portion.
- a buffer layer may be provided between the electrode 9 and the electrode 9.
- the buffer layer is a layer having a function of improving charge extraction efficiency from the organic active layer 8 to the anode and / or the cathode.
- the buffer layer can be classified into a hole extraction layer that improves hole extraction efficiency and an electron extraction layer that improves electron extraction efficiency.
- the buffer layer provided between the lower transparent electrode 7 and the organic active layer 8 is an electron extraction layer, and the organic active layer 8 and the upper electrode 9 It is preferable that the buffer layer provided between the layers is a hole extraction layer.
- the buffer layer provided between the lower transparent electrode 7 and the organic active layer 8 is a hole extraction layer, and the organic active layer 8 and the upper electrode 9 are used.
- the buffer layer provided between the two is preferably an electron extraction layer.
- the organic photoelectric conversion element may have only one layer among an electron taking-out layer and a hole taking-out layer.
- the film thickness of the buffer layer is not particularly limited and may be arbitrarily designed according to the material to be used. It is preferably 1 nm or more, more preferably 1 nm or more, particularly preferably 10 nm or more, on the other hand, preferably 400 nm or less, more preferably 200 nm or less.
- the material for the hole extraction layer is not particularly limited, and specifically, a conductive polymer in which polythiophene, polyaniline, polypyrrole, polyacetylene or the like is doped with sulfonic acid / and / or iodine, molybdenum oxide, vanadium oxide, Examples thereof include copper oxide.
- a conductive polymer in which polythiophene, polyaniline, polypyrrole, polyacetylene or the like is doped with sulfonic acid / and / or iodine, molybdenum oxide, vanadium oxide, Examples thereof include copper oxide.
- poly (ethylenedioxythiophene): poly (styrenesulfonic acid) (PEDOT: PSS) is preferable.
- the material for the electron extraction layer is not particularly limited, but lithium fluoride, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, phosphine oxide compound, phosphine sulfide compound, zinc oxide, or titanium oxide Is mentioned. Of these, zinc oxide or titanium oxide is preferable as the material for the electron extraction layer.
- the formation method of the electron extraction layer and the hole extraction layer is not particularly limited, and can be formed by any method according to the material to be used. For example, a vacuum deposition method, a coating method, etc. are mentioned.
- the organic thin film semiconductor element 1 may have layers other than the layers described above.
- a barrier layer may be provided between the transparent substrate 2 and the lower transparent electrode 7. By having the barrier layer, degassing from the transparent substrate 2 is suppressed when the first transparent conductive layer 4 is formed, the film formability of the first transparent conductive layer 4 is improved, and the heat resistance of the transparent substrate 2 is improved. And plasma resistance are preferable.
- the material of the barrier layer is not particularly limited as long as it can form a dense film, and specifically, silicon oxide, silicon nitride, silicon carbide, aluminum oxide, aluminum nitride, indium oxide, oxide Examples thereof include transparent inorganic compounds such as tin and zinc oxide, or mixed compounds thereof. Among these, silicon oxide, silicon nitride and a mixture thereof, and aluminum oxide, aluminum nitride and a mixture thereof are preferable.
- the thickness of the barrier layer is not particularly limited as long as it is a thickness that does not impair the transparency, and can maintain a gas barrier property and ensure adhesion with the transparent substrate 2, but is uniform.
- it is preferably 10 nm or more, more preferably 20 nm or more.
- it is preferably 500 nm or less, more preferably 200 nm or less. Particularly preferably, it is 100 nm or less.
- the barrier layer when a barrier layer is provided between the transparent substrate 2 and the lower transparent electrode 7, the barrier layer also affects optical interference between the transparent substrate 2 and the metal layer 5.
- the optical path length between the transparent substrate 2 and the lower transparent electrode 7 is such that the barrier layer satisfies the following equation (4) when m is an integer of 0 or more. It is preferable to adjust the film thickness.
- n 1, d 1, n 2 and d 2 are n 1, respectively formula (3) in, d 1, and n 2 and d 2 synonymous, n 4 is the refractive index of the barrier layer the stands, d 4 represents a thickness of the barrier layer.
- the configuration of the organic photoelectric conversion element is not particularly limited, but transparent substrate 2 / undercoat layer 3 / barrier layer / lower transparent electrode 7 / organic semiconductor layer 8 / upper electrode 9, or It is preferable to use transparent substrate 2 / barrier layer / undercoat layer 3 / lower transparent electrode 7 / organic semiconductor layer 8 / upper electrode 9.
- the photoelectric conversion element according to the above-described embodiment is preferably used as a solar cell module.
- the solar cell module is preferably sealed with a gas barrier layer or the like in order to prevent the organic photoelectric conversion element from being deteriorated by water, oxygen, or the like.
- FIG. 3 is a cross-sectional view schematically showing the configuration of the organic thin-film solar cell module 10 in one embodiment of the present invention.
- the organic thin film solar cell module 10 includes, for example, an organic photoelectric conversion element 1, a sealing layer 11 provided on each surface of the organic photoelectric conversion element 1, and a gas barrier layer 12 provided on one surface side of the sealing layer 11, respectively. And have. And the organic thin film solar cell module 10 produces
- stacking these layers on the material of the gas barrier layer 12 and the sealing layer 11 which comprise the solar cell module 10, and an organic photoelectric conversion element does not have a restriction
- a well-known technique can be used.
- those described in known documents such as International Publication No. 2011/016430 or Japanese Patent Application Laid-Open No. 2012-191194 can be used.
- the configuration of the solar cell module is not limited to the structure shown in FIG. 3, and may be any structure as long as it can generate power with the photoelectric conversion element.
- FIG. 3 shows a structure in which a laminated body of a sealing layer 11 and a barrier layer 12 is provided on both surfaces of the organic photoelectric conversion element 1, but the sealing layer is formed only on one side of the organic photoelectric conversion element 1. 11 and a barrier layer 12 may be provided.
- a collector wire on the organic photoelectric conversion element.
- the use of the organic thin film solar cell module 10 is not limited and is arbitrary. Examples of fields to which the organic thin-film solar cell module 10 is applied include building material solar cells, automotive solar cells, interior solar cells, railway solar cells, marine solar cells, airplane solar cells, and spacecraft solar cells. It is suitable for use in batteries, solar cells for home appliances, solar cells for mobile phones, solar cells for toys, and the like.
- it can be applied to house roofing materials, rooftops, top lights, walls, windows, etc. as solar cells for building materials, it can be applied to interiors etc. as solar cells for interiors, and hoods and roofs of automobiles as solar cells for automobiles. Applicable to the surface of trunk lids, doors, front fenders, rear fenders, pillars, bumpers and rearview mirrors, etc. It can be applied to outer walls and the like. In particular, it is preferably used as a wind film applied to a window or a glass curtain wall applied to a glass wall.
- ⁇ Measurement of film thickness of undercoat layer> The thickness of the undercoat layer was scratched with a spatula before heat-curing, and then stepped and then heat-cured at 140 ° C. for 15 minutes. It was obtained by measuring the step of the step portion using a system surface shape measuring device VertScan (manufactured by Ryoka System).
- the refractive indexes of the undercoat layer and the metal layer (indium oxide layer) were obtained by measurement using a spectroscopic ellipsometer UVISEL (manufactured by Horiba).
- the refractive index of the undercoat layer at a wavelength of 485 nm was 1.61.
- the refractive index of the first conductive layer (ITO layer) at a wavelength of 485 nm was 1.95.
- an organic thin film solar cell module having a size of 10 cm square was placed under a daylight fluorescent lamp with an illuminance of 700 lux, and the appearance color was determined at a position facing the organic thin film solar cell module.
- Example 1 On one side of a polyethylene naphthalate film (Q65 manufactured by Teijin DuPont Films Co., Ltd., thickness 125 ⁇ m, refractive index 1.9 at a wavelength of 485 nm), an undercoat layer 140 nm thick (hard coat agent SHC900 manufactured by Momentive) is applied by a bar coating method. And then cured by heating in air at 140 ° C. for 15 minutes.
- a polyethylene naphthalate film Q65 manufactured by Teijin DuPont Films Co., Ltd., thickness 125 ⁇ m, refractive index 1.9 at a wavelength of 485 nm
- an undercoat layer 140 nm thick hard coat agent SHC900 manufactured by Momentive
- a laminated lower transparent electrode was formed by laminating a first indium oxide layer of 50 nm, a silver layer of 8 nm, and a second indium oxide layer of 30 nm in this order by sputtering.
- PCBM The organic active layer of 2: 2.5 was laminated in the order of 320 nm, and the PEDOT: PSS layer was laminated in the order of 400 nm as the hole extraction layer. The organic active layer was reddish gray.
- a second electrode was formed on the organic semiconductor layer by laminating a silver layer with a thickness of 8 nm and an indium oxide layer with a thickness of 40 nm by sputtering to produce an organic photoelectric conversion element.
- an epoxy adhesive layer and a barrier film (Mitsubishi Resin View Barrier (R)) were used to form a barrier film, an adhesive layer, an organic photoelectric conversion element, an adhesive layer, and a barrier film. Then, the organic photoelectric conversion element was sealed by heating this laminated body at 140 ° C. for 1 hour to produce an organic thin film solar cell module.
- a barrier film Mitsubishi Resin View Barrier (R)
- Example 2 An organic thin-film solar cell module was produced in the same manner as in Example 1 except that the thickness of the undercoat layer was 162 nm.
- the organic thin-film solar cell modules of Example 1 and Example 2 that satisfy the formula (1) have a bright appearance color as expected from the calculated value of ⁇ . A blue color was exhibited, and both the lightness index a * value and b * value were small. Moreover, the organic thin-film solar cell module in Comparative Example 3 exhibited a bright red color as expected from the calculated value of ⁇ , and the lightness index a * value was large and the a * value was small.
- the organic thin film solar cell modules of Comparative Example 1 and Comparative Example 2 exhibited an undesirable yellow color tone.
- Lightness of Comparative Example 1 shows that the b * value than that of Comparative Example 2 is substantially the same value with a * value is small, a strong green body than the Comparative Example 2 towards the Comparative Example 1.
- Comparative Example 2 has an a * value larger than that of Comparative Example 1, indicating that Comparative Example 2 is more yellowish than Comparative Example 1. This is the color transition expected from the interference wavelength ⁇ calculated in Comparative Example 1 and Comparative Example 2, and the appearance color of the organic thin film solar cell module observed in these Examples and Comparative Examples was used. This indicates that the organic semiconductor layer is determined by light interference between the metal layer constituting the lower transparent electrode and the transparent substrate, even though the organic semiconductor layer has a reddish gray color.
- Example 3 An organic thin-film solar cell module was prepared in the same manner as in Example 1 except that the thickness of the undercoat layer was 139 nm, and the appearance color was evaluated. Moreover, the conversion efficiency (PCE) of the organic thin-film solar cell module was measured based on JIS C8934. The obtained results are shown in Table 2.
- the organic thin-film solar cell module according to Example 3 that satisfies the above formula (1) is organic, even though the organic active layer is reddish gray.
- the thin film solar cell module showed a bright blue appearance color
- the organic thin film solar cell module according to Comparative Example 4 that did not satisfy the above (1) showed a bright red purple appearance color.
- the conversion efficiencies of the organic thin film solar cell modules according to Example 3 and Comparative Example 4 were both 4.0%, and the organic thin film solar cell module was adjusted so as to show a blue appearance color as in Example 3. However, the conversion efficiency did not decrease. Therefore, it can be seen that the present invention can provide an organic thin film solar cell module exhibiting a desirable blue appearance color without lowering the conversion efficiency.
- Example 4 As a p-type semiconductor polymer, a copolymer containing a naphthobisthiadiazole unit and a benzodithiophene unit is used, the thickness of the PEDOT: PSS layer that is the hole extraction layer is changed to 150 nm, and the thickness of the undercoat layer is further changed.
- An organic thin-film solar cell module was produced by the same method as in Example 1 except that the thickness was 142 nm, and the appearance color was evaluated. The organic active layer was green. Moreover, the conversion efficiency (PCE) of the organic thin-film solar cell module was measured based on JIS C8934. The obtained results are shown in Table 3.
- SYMBOLS 1 Organic photoelectric conversion element, 2 ... Transparent substrate, 3 ... Undercoat layer, 4 ... 1st transparent conductive layer, 5 ... Metal layer, 6 ... 2nd transparent conductive layer, 7 ... Bottom transparent Electrode, 8 ... Organic active layer, 9 ... Upper electrode, 10 ... Organic thin film solar cell module, 11 ... Sealing layer, 12 ... Gas barrier layer
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Abstract
The present invention provides an organic photoelectric conversion element and organic thin-film solar battery module capable of adjusting the exterior color of a solar battery surface to a bluish color regardless of the color tone of an organic active layer, thereby enhancing design without impeding the solar battery characteristics and while preventing the solar battery from exhibiting the color of yellow or red.
The organic photoelectric conversion element comprises a transparent substrate, a lower transparent electrode including a metal layer, an organic active layer, and an upper electrode which are successively layered, and is characterized in that an optical path length (n × d) between the transparent substrate and the metal layer which is expressed by a distance d between the transparent substrate and the metal layer and a refractive index n satisfies the following expression (1):
480 nm ≥ 4 × (n × d) / (2 × m + 1) ≥ 380 nm (1)
where m is an integer of zero or more.
Description
本発明は、有機光電変換素子及び該有機光電変換素子を含む有機薄膜太陽電池モジュールに関する。
The present invention relates to an organic photoelectric conversion element and an organic thin film solar cell module including the organic photoelectric conversion element.
近年、有機薄膜太陽電池が盛んに検討されている。特に、有機薄膜太陽電池は、可撓性を有する透明樹脂基板を用いることが可能となる。そのため、有機薄膜太陽電池は、従来の結晶シリコン基板やガラス基板を用いた太陽電池と比較して、柔軟・軽量であるという利点を生かして、建築物の壁面、窓ガラス等へ設置することが検討されている。有機薄膜太陽電池を建築物の壁面や窓ガラス等に設置することを想定すると、建築物の壁面や窓ガラス等は、人目に付き易いことから、有機薄膜太陽電池モジュールも色調等の外観色を重要視する必要があると考えられる。
In recent years, organic thin-film solar cells have been actively studied. In particular, the organic thin film solar cell can use a transparent resin substrate having flexibility. Therefore, organic thin-film solar cells can be installed on the walls of buildings, window glass, etc., taking advantage of being flexible and lightweight compared to conventional solar cells using crystalline silicon substrates and glass substrates. It is being considered. Assuming that organic thin-film solar cells are installed on the walls and windows of buildings, the wall and windows of buildings are easily noticeable. It seems necessary to attach importance.
有機薄膜太陽電池の色調を調整する方法として、例えば、特許文献1には、受光面側から目視した場合における光電変換層の背後に光吸収層を配置して、特定の波長を吸収させる方法が開示されている。また、特許文献2には、透明電極と光電変換層の屈折率と厚みを特定の値にして、文字盤の幅広い色選択が可能になることが開示されている。
As a method of adjusting the color tone of the organic thin film solar cell, for example, Patent Document 1 discloses a method of absorbing a specific wavelength by arranging a light absorption layer behind the photoelectric conversion layer when viewed from the light receiving surface side. It is disclosed. Patent Document 2 discloses that a wide color selection of the dial is possible by setting the refractive index and thickness of the transparent electrode and the photoelectric conversion layer to specific values.
有機薄膜太陽電池はそもそも実用化のためには、高い変換効率が要求される。また、上記のとおり柔軟・軽量であるという利点を生かして、建築物の壁面、窓ガラス等へ設置することが検討されており、意匠性も重視されるのが現状である。
高効率の観点からは、有機薄膜太陽電池を構成する下部透明電極を、抵抗が高い透明酸化物導電体のみで形成するのではなく、抵抗の低い金属層を用いて形成することが好ましい。しかしながら金属層を用いると、金属層の反射光により、一般的に窓や建材等への設置を想定した場合に望ましくない赤色や黄色の干渉色が目立つ場合があるという、新たな問題が生じた。 Organic thin-film solar cells are required to have high conversion efficiency for practical use. In addition, taking advantage of being flexible and lightweight as described above, it has been studied to install it on the wall surface of a building, a window glass, etc., and the design is also emphasized at present.
From the viewpoint of high efficiency, it is preferable that the lower transparent electrode constituting the organic thin film solar cell is formed not by using only a transparent oxide conductor having high resistance but by using a metal layer having low resistance. However, when a metal layer is used, a new problem has arisen in that an undesirable red or yellow interference color may be conspicuous due to the reflected light of the metal layer, generally assuming installation on windows or building materials. .
高効率の観点からは、有機薄膜太陽電池を構成する下部透明電極を、抵抗が高い透明酸化物導電体のみで形成するのではなく、抵抗の低い金属層を用いて形成することが好ましい。しかしながら金属層を用いると、金属層の反射光により、一般的に窓や建材等への設置を想定した場合に望ましくない赤色や黄色の干渉色が目立つ場合があるという、新たな問題が生じた。 Organic thin-film solar cells are required to have high conversion efficiency for practical use. In addition, taking advantage of being flexible and lightweight as described above, it has been studied to install it on the wall surface of a building, a window glass, etc., and the design is also emphasized at present.
From the viewpoint of high efficiency, it is preferable that the lower transparent electrode constituting the organic thin film solar cell is formed not by using only a transparent oxide conductor having high resistance but by using a metal layer having low resistance. However, when a metal layer is used, a new problem has arisen in that an undesirable red or yellow interference color may be conspicuous due to the reflected light of the metal layer, generally assuming installation on windows or building materials. .
当該新たな問題は、色調の調整方法を開示する特許文献1や2に開示の技術では解決できるものではなかった。更に、特許文献1では、太陽電池の内部(透明電極層及び対向電極層間)に光吸収層を配置するため、例えば、光吸収層が太陽電池の内部抵抗として働き、太陽電池の発電効率や寿命が低下するなど、太陽電池の特性を阻害するおそれがあった。また、特許文献2では、外観色を調整するために透明電極と光電変換層の厚みを決定するため、太陽電池としての性能を発揮するために透明電極や光電変換層の最適な膜厚を選択できず、例えば、透明電極の抵抗が高くなる、光電変換層での光吸収量が少なくなる、などにより太陽電池の発電効率が低下し、太陽電池の特性を阻害するおそれがあった。
The new problem cannot be solved by the techniques disclosed in Patent Documents 1 and 2 that disclose a color tone adjustment method. Furthermore, in patent document 1, since a light absorption layer is arrange | positioned inside a solar cell (a transparent electrode layer and a counter electrode layer), for example, a light absorption layer works as an internal resistance of a solar cell, and the power generation efficiency and lifetime of a solar cell As a result, the characteristics of the solar cell may be impaired. Moreover, in patent document 2, since the thickness of a transparent electrode and a photoelectric converting layer is determined in order to adjust an external color, in order to exhibit the performance as a solar cell, the optimal film thickness of a transparent electrode or a photoelectric converting layer is selected. However, for example, the power generation efficiency of the solar cell is lowered due to an increase in the resistance of the transparent electrode or a decrease in the amount of light absorption in the photoelectric conversion layer, which may impair the characteristics of the solar cell.
本発明はこのような新たな課題を解決するものであり、太陽電池の特性を阻害することなく、特に太陽電池が黄色や赤色を呈すのを防ぎつつ、一方で、有機活性層の色に関わらず、太陽電池表面の外観色として望ましい青系色に調整し、意匠性を向上させ得る有機光電変換素子及び有機薄膜太陽電池モジュールを提供することを目的とする。
The present invention solves such a new problem, and without affecting the characteristics of the solar cell, in particular, while preventing the solar cell from exhibiting a yellow or red color, while relating to the color of the organic active layer. An object of the present invention is to provide an organic photoelectric conversion element and an organic thin-film solar cell module that can be adjusted to a blue color desired as the appearance color of the surface of the solar cell to improve the design.
本発明者は上記課題を解決すべく鋭意検討したところ、透明基板側から有機薄膜太陽電池モジュールを正面から目視した場合に、黄色や赤色を呈する意匠性の不良は、有機光電変換素子の透明基板と有機活性層との間に存在する透明電極に起因し、特に、透明電極が金属層を含む場合に顕著になることを見出した。
The present inventor has intensively studied to solve the above problems, and when the organic thin-film solar cell module is viewed from the front from the transparent substrate side, the design defect that exhibits yellow or red is a transparent substrate of the organic photoelectric conversion element. It has been found that this phenomenon is prominent particularly when the transparent electrode includes a metal layer due to the transparent electrode existing between the organic active layer and the organic active layer.
すなわち、有機光電変換素子の透明基板に入射した光の一部が透明電極の金属層で反射され、入射光と反射光との間で光干渉が起こり、特定の条件の場合に黄色や赤色を呈する干渉色が生じる。
In other words, part of the light incident on the transparent substrate of the organic photoelectric conversion element is reflected by the metal layer of the transparent electrode, causing optical interference between the incident light and the reflected light. The resulting interference color occurs.
この干渉色は、有機活性層の外部で発生し、かつ、光強度の大きい光入射面側で発生するため、有機活性層で発生する反射色よりも光強度が大きい。そのため、有機薄膜太陽電池モジュールの外観色は、有機光電変換素子の透明基板と透明電極、特に、透明基板と金属層との間で生じる光干渉によって強く影響されると考えられる。
Since this interference color is generated outside the organic active layer and is generated on the light incident surface side where the light intensity is high, the light intensity is larger than the reflected color generated in the organic active layer. Therefore, it is considered that the appearance color of the organic thin film solar cell module is strongly influenced by light interference generated between the transparent substrate and the transparent electrode of the organic photoelectric conversion element, particularly between the transparent substrate and the metal layer.
従って、有機光電変換素子の透明基板と金属層との間の距離を調整することにより、黄色や赤色の干渉色により有光電変換素子の外観色が黄色や赤色を呈するのを防ぐことができる。さらには、青系の干渉色を目立たせることによって、有機活性層の色調に関わらず、有機光電変換素子の外観色を望ましい青系の色に容易に調整できることを見出し、本発明を完成させるに至った。さらに、本発明は、発電効率に直接的に寄与する有機活性層ではない層の膜厚を調整しているため、太陽電池の特性を大幅に低下することを防ぐことができる。
Therefore, by adjusting the distance between the transparent substrate of the organic photoelectric conversion element and the metal layer, the appearance color of the photoelectric conversion element can be prevented from exhibiting yellow or red due to the interference color of yellow or red. Furthermore, by making the blue interference color conspicuous, it is found that the appearance color of the organic photoelectric conversion element can be easily adjusted to a desired blue color regardless of the color tone of the organic active layer, and the present invention is completed. It came. Furthermore, since this invention adjusts the film thickness of the layer which is not an organic active layer which contributes directly to power generation efficiency, it can prevent that the characteristic of a solar cell falls significantly.
すなわち、本発明は、以下のとおりである。
[1]透明基板と、金属層を含む下部透明電極と、有機活性層と、上部電極と、が順次積層された有機光電変換素子であって、
前記透明基板と前記金属層間の距離d及び屈折率nで表される、前記透明基板と前記金属層間の光路長(n×d)が、mが0以上の整数のいずれかにおいて、下記式(1)を満たすことを特徴とする有機光電変換素子。
480nm≧4×(n×d)÷(2×m+1)≧380nm……(1)
[2]前記透明基板と前記金属層との間にアンダーコート層を含む、[1]に記載の有機光電変換素子。
[3]前記下部透明電極は、透明導電層を含み、前記透明導電層が、前記透明基板と、前記金属層との間に配置されている[1]又は[2]に記載の有機光電変換素子。
[4]前記アンダーコート層の厚さは、10nm以上5000nm以下である、[2]又は[3]に記載の有機光電変換素子。
[5]前記透明導電層の厚さは、5nm以上200nm以下であることを特徴とする[3]又は[4]に記載の有機光電変換素子。
[6]前記金属層の厚さは、1nm以上20nm以下である、[1]~[5]のいずれかに記載の有機光電変換素子。
[7][1]~[6]のいずれかに記載の有機光電変換素子を含む、有機薄膜太陽電池モジュール。 That is, the present invention is as follows.
[1] An organic photoelectric conversion element in which a transparent substrate, a lower transparent electrode including a metal layer, an organic active layer, and an upper electrode are sequentially stacked,
When the optical path length (n × d) between the transparent substrate and the metal layer, expressed by the distance d and the refractive index n between the transparent substrate and the metal layer, is one of integers where m is 0 or more, the following formula ( The organic photoelectric conversion element characterized by satisfying 1).
480 nm ≧ 4 × (n × d) ÷ (2 × m + 1) ≧ 380 nm (1)
[2] The organic photoelectric conversion element according to [1], including an undercoat layer between the transparent substrate and the metal layer.
[3] The organic photoelectric conversion according to [1] or [2], wherein the lower transparent electrode includes a transparent conductive layer, and the transparent conductive layer is disposed between the transparent substrate and the metal layer. element.
[4] The organic photoelectric conversion element according to [2] or [3], wherein the thickness of the undercoat layer is 10 nm or more and 5000 nm or less.
[5] The organic photoelectric conversion element according to [3] or [4], wherein the transparent conductive layer has a thickness of 5 nm to 200 nm.
[6] The organic photoelectric conversion element according to any one of [1] to [5], wherein the metal layer has a thickness of 1 nm to 20 nm.
[7] An organic thin film solar cell module comprising the organic photoelectric conversion device according to any one of [1] to [6].
[1]透明基板と、金属層を含む下部透明電極と、有機活性層と、上部電極と、が順次積層された有機光電変換素子であって、
前記透明基板と前記金属層間の距離d及び屈折率nで表される、前記透明基板と前記金属層間の光路長(n×d)が、mが0以上の整数のいずれかにおいて、下記式(1)を満たすことを特徴とする有機光電変換素子。
480nm≧4×(n×d)÷(2×m+1)≧380nm……(1)
[2]前記透明基板と前記金属層との間にアンダーコート層を含む、[1]に記載の有機光電変換素子。
[3]前記下部透明電極は、透明導電層を含み、前記透明導電層が、前記透明基板と、前記金属層との間に配置されている[1]又は[2]に記載の有機光電変換素子。
[4]前記アンダーコート層の厚さは、10nm以上5000nm以下である、[2]又は[3]に記載の有機光電変換素子。
[5]前記透明導電層の厚さは、5nm以上200nm以下であることを特徴とする[3]又は[4]に記載の有機光電変換素子。
[6]前記金属層の厚さは、1nm以上20nm以下である、[1]~[5]のいずれかに記載の有機光電変換素子。
[7][1]~[6]のいずれかに記載の有機光電変換素子を含む、有機薄膜太陽電池モジュール。 That is, the present invention is as follows.
[1] An organic photoelectric conversion element in which a transparent substrate, a lower transparent electrode including a metal layer, an organic active layer, and an upper electrode are sequentially stacked,
When the optical path length (n × d) between the transparent substrate and the metal layer, expressed by the distance d and the refractive index n between the transparent substrate and the metal layer, is one of integers where m is 0 or more, the following formula ( The organic photoelectric conversion element characterized by satisfying 1).
480 nm ≧ 4 × (n × d) ÷ (2 × m + 1) ≧ 380 nm (1)
[2] The organic photoelectric conversion element according to [1], including an undercoat layer between the transparent substrate and the metal layer.
[3] The organic photoelectric conversion according to [1] or [2], wherein the lower transparent electrode includes a transparent conductive layer, and the transparent conductive layer is disposed between the transparent substrate and the metal layer. element.
[4] The organic photoelectric conversion element according to [2] or [3], wherein the thickness of the undercoat layer is 10 nm or more and 5000 nm or less.
[5] The organic photoelectric conversion element according to [3] or [4], wherein the transparent conductive layer has a thickness of 5 nm to 200 nm.
[6] The organic photoelectric conversion element according to any one of [1] to [5], wherein the metal layer has a thickness of 1 nm to 20 nm.
[7] An organic thin film solar cell module comprising the organic photoelectric conversion device according to any one of [1] to [6].
本発明によれば、太陽電池の特性を阻害することなく、太陽電池が黄色や赤色を呈するのを抑制しつつ、太陽電池表面の外観色を青系の色に調整し、意匠性を向上させ得る有機光電変換素子を提供することができる。また、該有機光電変換素子を含む、黄色や赤色を呈するのを抑制して意匠性を向上させた有機薄膜太陽電池モジュールを提供できる。
According to the present invention, the appearance color of the solar cell surface is adjusted to a blue color while preventing the solar cell from exhibiting yellow or red without impairing the characteristics of the solar cell, and the design is improved. An organic photoelectric conversion element to be obtained can be provided. In addition, an organic thin-film solar cell module including the organic photoelectric conversion element, which is improved in design by suppressing yellow and red colors can be provided.
以下、本発明について実施形態及び例示物等を示して詳細に説明するが、本発明は以下の実施形態及び例示物等に限定されるものではなく、本発明の要旨を逸脱しない範囲において任意に変更して実施できる。
Hereinafter, the present invention will be described in detail with reference to embodiments, examples, etc., but the present invention is not limited to the following embodiments, examples, etc., and can be arbitrarily set within the scope of the present invention. Can be changed and implemented.
<有機光電変換素子1>
図1は、本発明の一実施形態における有機光電変換素子1の構成を模式的に示す断面図である。有機光電変換素子1は、透明基板2と、アンダーコート層3と、第1透明導電層4、金属層5及び第2透明導電層6とが順次積層された下部透明電極7と、有機活性層8と、上部電極9とが順次積層されている。
本実施形態に係る有機光電変換素子は、透明基板2側から観察した際に、有機光電変換素子の外観色が黄色や赤色を呈するのを抑制しつつ、有機活性層の色調に関わらず、有機光電変換素子の外観色を青系の色に調整でき、意匠性を向上させ得るものである。 <Organicphotoelectric conversion element 1>
FIG. 1 is a cross-sectional view schematically showing a configuration of an organicphotoelectric conversion element 1 in one embodiment of the present invention. The organic photoelectric conversion element 1 includes a transparent substrate 2, an undercoat layer 3, a first transparent conductive layer 4, a metal layer 5 and a second transparent conductive layer 6 sequentially laminated, an organic active layer 8 and the upper electrode 9 are sequentially laminated.
The organic photoelectric conversion element according to the present embodiment is organic regardless of the color tone of the organic active layer while suppressing the appearance color of the organic photoelectric conversion element from being yellow or red when observed from thetransparent substrate 2 side. The appearance color of the photoelectric conversion element can be adjusted to a blue color, and the design can be improved.
図1は、本発明の一実施形態における有機光電変換素子1の構成を模式的に示す断面図である。有機光電変換素子1は、透明基板2と、アンダーコート層3と、第1透明導電層4、金属層5及び第2透明導電層6とが順次積層された下部透明電極7と、有機活性層8と、上部電極9とが順次積層されている。
本実施形態に係る有機光電変換素子は、透明基板2側から観察した際に、有機光電変換素子の外観色が黄色や赤色を呈するのを抑制しつつ、有機活性層の色調に関わらず、有機光電変換素子の外観色を青系の色に調整でき、意匠性を向上させ得るものである。 <Organic
FIG. 1 is a cross-sectional view schematically showing a configuration of an organic
The organic photoelectric conversion element according to the present embodiment is organic regardless of the color tone of the organic active layer while suppressing the appearance color of the organic photoelectric conversion element from being yellow or red when observed from the
通常、有機光電変換素子の外観色は、有機活性層8の色が支配的になると考えられる。この理由は、有機活性層8は可視光領域の光を吸収するために着色されている一方で、有機活性層8が光を効率良く吸収できるように有機活性層8以外の層は無色透明の方が好ましいと考えられるからである。しかしながら、本発明者らの検討によると、実際には、透明基板2側から有機光電変換素子を観察した場合、光の干渉により有機光電変換素子が赤色や黄色等、好ましくない外観色を呈している場合があることが判明した。この理由としては、以下の理由が考えられる。
Usually, it is considered that the color of the organic active layer 8 is dominant in the appearance color of the organic photoelectric conversion element. This is because the organic active layer 8 is colored to absorb light in the visible light region, while the layers other than the organic active layer 8 are colorless and transparent so that the organic active layer 8 can absorb light efficiently. This is because it is considered preferable. However, according to the study by the present inventors, when the organic photoelectric conversion element is actually observed from the transparent substrate 2 side, the organic photoelectric conversion element exhibits an unfavorable appearance color such as red or yellow due to light interference. It turns out that there may be. The following reasons can be considered as this reason.
後述するように下部透明電極7が一般的に反射率の高い金属層5を有して形成されている場合、金属層5において、多くの反射光が発生する。さらには、金属層5と透明基板2との間にはいくつかの層が形成されている場合がある。例えば、図1に係る実施態様においては、透明基板2と金属層5との間には、アンダーコート層3、下部透明電極を構成する透明導電層6が形成されている。そのため、これらの層の膜厚によっては、該層内において、金属層5の反射光による光干渉効果が発生する場合がある。具体的に、本実施形態の有機光電変換素子1において、入射する光の干渉の例について、図2を用いて説明する。
As will be described later, when the lower transparent electrode 7 is generally formed to have a metal layer 5 having a high reflectivity, a lot of reflected light is generated in the metal layer 5. Furthermore, some layers may be formed between the metal layer 5 and the transparent substrate 2. For example, in the embodiment according to FIG. 1, an undercoat layer 3 and a transparent conductive layer 6 constituting a lower transparent electrode are formed between the transparent substrate 2 and the metal layer 5. Therefore, depending on the film thickness of these layers, an optical interference effect due to the reflected light of the metal layer 5 may occur in the layers. Specifically, in the organic photoelectric conversion element 1 of the present embodiment, an example of interference of incident light will be described with reference to FIG.
有機光電変換素子1の透明基板2に対して垂直方向に光が入射すると、透明基板2と、金属層5との間の距離(膜厚)d及び屈折率nで表される、透明基板2と、金属層5との間の光路長(n×d)を、以下の式(a)に代入して算出される波長λの反射光が光干渉条件により増強されることになる。すなわち、波長λの反射光が、有機光電変換素子の外観色に影響を及ぼすことになる。
2×n×d=(2×m+1)×λ÷2 (mは0以上の整数)……(a)
なお、金属層5は一般的に、金属層5の表面に存在するアンダーコート層3や第1の透明導電層4よりも屈折率が高いために、式(a)は、金属層5における反射光の位相が180°ずれることを想定した式である。 When light is incident in a direction perpendicular to thetransparent substrate 2 of the organic photoelectric conversion element 1, the transparent substrate 2 represented by a distance (film thickness) d and a refractive index n between the transparent substrate 2 and the metal layer 5. Then, the reflected light of the wavelength λ calculated by substituting the optical path length (n × d) with the metal layer 5 into the following formula (a) is enhanced by the optical interference condition. That is, the reflected light having the wavelength λ affects the appearance color of the organic photoelectric conversion element.
2 × n × d = (2 × m + 1) × λ ÷ 2 (m is an integer greater than or equal to 0) (a)
Since themetal layer 5 generally has a higher refractive index than the undercoat layer 3 and the first transparent conductive layer 4 existing on the surface of the metal layer 5, the formula (a) is reflected on the metal layer 5. This is an equation assuming that the phase of light is shifted by 180 °.
2×n×d=(2×m+1)×λ÷2 (mは0以上の整数)……(a)
なお、金属層5は一般的に、金属層5の表面に存在するアンダーコート層3や第1の透明導電層4よりも屈折率が高いために、式(a)は、金属層5における反射光の位相が180°ずれることを想定した式である。 When light is incident in a direction perpendicular to the
2 × n × d = (2 × m + 1) × λ ÷ 2 (m is an integer greater than or equal to 0) (a)
Since the
透明基板2とアンダーコート層3との界面で反射しない入射光が金属層5で反射した場合(入射光1)、透明基板2とアンダーコート層3との界面で反射した入射光(入射光2)との光路差は式(a)の左に表されるように2×n×dとなり、これが(2m+1)×λ/2の場合に光の位相が一致して、光が強め合うこととなる。本実施形態において、有機光電変換素子の外観の色味を帯びて見えることは可視光の範囲において光が強め合うことを意味する。つまりは、上記式(a)において、理論上、λ=380nm~780nmとなるように、透明基板2と金属層5との間の光路長(n×d)が選択された場合に可視光領域内の光が干渉することになるために、当該干渉色により有機光電変換素子の外観色は影響を受けることになる。
When incident light that does not reflect at the interface between the transparent substrate 2 and the undercoat layer 3 is reflected by the metal layer 5 (incident light 1), incident light that is reflected at the interface between the transparent substrate 2 and the undercoat layer 3 (incident light 2). ) Is 2 × n × d as shown on the left of the equation (a), and when this is (2m + 1) × λ / 2, the phases of the light coincide and the light strengthens. Become. In the present embodiment, the appearance of the organic photoelectric conversion element with a tint means that the light intensifies in the visible light range. That is, in the above formula (a), when the optical path length (n × d) between the transparent substrate 2 and the metal layer 5 is theoretically selected so that λ = 380 nm to 780 nm, the visible light region. Therefore, the appearance color of the organic photoelectric conversion element is affected by the interference color.
例えば、上記式(a)において、λが380nm以上480nm以下となるように該光路長(n×d)が選択された場合、有機光電変換素子は青系色の干渉色が目立つことになる。一方、該光路長(n×d)が大きくなるにつれて、望ましくない黄色や赤色等の干渉色が目立つことになる。すなわち、透明基板2と金属層5との間の光路長(n×d)が特定の値となる場合に、特定の可視光内の干渉色が目立つことになり、当該干渉色が有機光電変換素子の外観色に影響を及ぼすことになる。
For example, in the above formula (a), when the optical path length (n × d) is selected so that λ is not less than 380 nm and not more than 480 nm, blue interference colors are conspicuous in the organic photoelectric conversion element. On the other hand, as the optical path length (n × d) increases, undesirable interference colors such as yellow and red become conspicuous. That is, when the optical path length (n × d) between the transparent substrate 2 and the metal layer 5 has a specific value, the interference color in the specific visible light becomes conspicuous, and the interference color is converted into organic photoelectric conversion. The appearance color of the element will be affected.
なお、上記式(a)においてmが大きくなる、すなわちn×dの値が大きくなるにつれて可視光領域に現れる干渉波の数は多くなり、反射率の極大ピークは多くなることになる。つまり、mが大きくなるにつれて、多くの反射色が混色される傾向にあり、特定の原色の干渉色が目立たなくなる。特に、mが4以上の場合、特定の原色の干渉色が目立たなくなるために、mが0以上3以下のいずれかの整数の場合について外観色が青系色になるようにn×dの値を調整すれば、有機光電変換素子及び有機薄膜太陽電池モジュールの外観が望ましい青系色に調整できると考えられる。
In the above formula (a), as m increases, that is, as the value of n × d increases, the number of interference waves appearing in the visible light region increases, and the maximum peak of reflectance increases. That is, as m increases, many reflected colors tend to be mixed, and the interference color of a specific primary color becomes inconspicuous. In particular, when m is 4 or more, the interference color of a specific primary color becomes inconspicuous. Therefore, when m is an integer of 0 or more and 3 or less, the value of n × d is set so that the appearance color becomes a blue color. It is considered that the appearance of the organic photoelectric conversion element and the organic thin film solar cell module can be adjusted to a desirable blue color by adjusting the color.
上記式(a)及び実施例を含む各種検討の結果、有機光電変換素子1は、透明基板2と金属層5間の距離(膜厚の総和)d及び屈折率nで表される、透明基板と金属層間の光路長(n×d)が、mが0以上の整数のいずれかにおいて下記式(1)を満たすことで、太陽電池の特性を阻害することなく、太陽電池が黄色や赤色を呈するのを抑制しつつ、さらには、有機活性層の色調に関わらず、太陽電池表面の外観色を望ましい青系色に調整できることを見出した。
480nm≧4×(n×d)÷(2×m+1)≧380nm……(1) As a result of various studies including the above formula (a) and examples, the organicphotoelectric conversion element 1 is a transparent substrate represented by a distance (total thickness) d and a refractive index n between the transparent substrate 2 and the metal layer 5. When the optical path length (n × d) between the metal layer and the metal layer satisfies the following formula (1) when m is an integer greater than or equal to 0, the solar cell has a yellow or red color without impairing the solar cell characteristics. Furthermore, the present inventors have found that the appearance color of the solar cell surface can be adjusted to a desired blue color regardless of the color tone of the organic active layer while suppressing the presenting.
480 nm ≧ 4 × (n × d) ÷ (2 × m + 1) ≧ 380 nm (1)
480nm≧4×(n×d)÷(2×m+1)≧380nm……(1) As a result of various studies including the above formula (a) and examples, the organic
480 nm ≧ 4 × (n × d) ÷ (2 × m + 1) ≧ 380 nm (1)
なお、mが0以上の整数のいずれかにおいて式(1)を満たすが、上述の通り、mの値が4以上の場合には特定の原色の干渉色が目立たなくなる。そのため、mが0以上3以下の整数のいずれかの場合に上記式(1)を満たすことにより、有機光電変換素子が黄色や赤色を呈するのを抑制しつつ、有機光電変換素子の外観色を青系色に調整することが可能となる。
It should be noted that equation (1) is satisfied when m is an integer of 0 or more, but as described above, when the value of m is 4 or more, the interference color of a specific primary color becomes inconspicuous. Therefore, when m is an integer of 0 or more and 3 or less, the appearance color of the organic photoelectric conversion element is controlled while suppressing the organic photoelectric conversion element from exhibiting yellow or red by satisfying the above formula (1). It is possible to adjust to a blue color.
式(1)中の膜厚dは、例えば、分光エリプソメーター、光干渉式膜厚計、触針式段差計、原子間力顕微鏡、透過型電子顕微鏡、走査型電子顕微鏡等により測定することができる。
式(1)中の屈折率nは、例えば、JIS K 0062記載の方法に従って、アッベ屈折率計やプルフリッヒ屈折率計、ディジタル屈折率計などを用いて測定することができる。また、プリズムカップラ法や液浸法、分光学的方法によっても測定することができる。波長によって屈折率nに変動が生じるが、アンダーコート層や透明導電層に使用されるような透明材料は屈折率の波長依存性は小さいために、本発明において、屈折率nは485nmの波長における屈折率nを使用するものとする。分光学的方法の具体的な例は、応用物理第65巻第11号1125頁~1130頁に記載に従って、a)分光反射率や分光透過率を用いて光学シミュレーションによって求める方法や、b)分光エリプソメトリによって求める方法等がある。 The film thickness d in the formula (1) can be measured by, for example, a spectroscopic ellipsometer, an optical interference film thickness meter, a stylus type step meter, an atomic force microscope, a transmission electron microscope, a scanning electron microscope, or the like. it can.
The refractive index n in the formula (1) can be measured using, for example, an Abbe refractometer, a Pullfrich refractometer, a digital refractometer or the like according to the method described in JIS K 0062. It can also be measured by a prism coupler method, a liquid immersion method, or a spectroscopic method. Although the refractive index n varies depending on the wavelength, the transparent material used for the undercoat layer and the transparent conductive layer has a small wavelength dependency of the refractive index. Therefore, in the present invention, the refractive index n is 485 nm. A refractive index n shall be used. Specific examples of spectroscopic methods are described in Applied Physics Vol. 65, No. 11, pages 1125 to 1130, according to a) a method for obtaining by optical simulation using spectral reflectance and spectral transmittance, and b) spectroscopic method. There are methods such as obtaining by ellipsometry.
式(1)中の屈折率nは、例えば、JIS K 0062記載の方法に従って、アッベ屈折率計やプルフリッヒ屈折率計、ディジタル屈折率計などを用いて測定することができる。また、プリズムカップラ法や液浸法、分光学的方法によっても測定することができる。波長によって屈折率nに変動が生じるが、アンダーコート層や透明導電層に使用されるような透明材料は屈折率の波長依存性は小さいために、本発明において、屈折率nは485nmの波長における屈折率nを使用するものとする。分光学的方法の具体的な例は、応用物理第65巻第11号1125頁~1130頁に記載に従って、a)分光反射率や分光透過率を用いて光学シミュレーションによって求める方法や、b)分光エリプソメトリによって求める方法等がある。 The film thickness d in the formula (1) can be measured by, for example, a spectroscopic ellipsometer, an optical interference film thickness meter, a stylus type step meter, an atomic force microscope, a transmission electron microscope, a scanning electron microscope, or the like. it can.
The refractive index n in the formula (1) can be measured using, for example, an Abbe refractometer, a Pullfrich refractometer, a digital refractometer or the like according to the method described in JIS K 0062. It can also be measured by a prism coupler method, a liquid immersion method, or a spectroscopic method. Although the refractive index n varies depending on the wavelength, the transparent material used for the undercoat layer and the transparent conductive layer has a small wavelength dependency of the refractive index. Therefore, in the present invention, the refractive index n is 485 nm. A refractive index n shall be used. Specific examples of spectroscopic methods are described in Applied Physics Vol. 65, No. 11, pages 1125 to 1130, according to a) a method for obtaining by optical simulation using spectral reflectance and spectral transmittance, and b) spectroscopic method. There are methods such as obtaining by ellipsometry.
なお、透明基板2と、金属層5との間に、アンダーコート層3と第1の透明導電層4等、2種類以上の層が積層されている場合、上記式(1)におけるn×dは下記式(b)に従って算出することができる。
n×d=Σ(ni×di)……(b)
(niおよびdiは、それぞれ、透明基板2側からi番目の層の材料の屈折率及び膜厚を意味する。) In addition, when two or more types of layers such as the undercoat layer 3 and the first transparent conductive layer 4 are laminated between thetransparent substrate 2 and the metal layer 5, nxd in the above formula (1) Can be calculated according to the following formula (b).
n × d = Σ (n i × d i ) (b)
(N i and d i mean the refractive index and film thickness of the material of the i-th layer from thetransparent substrate 2 side, respectively.)
n×d=Σ(ni×di)……(b)
(niおよびdiは、それぞれ、透明基板2側からi番目の層の材料の屈折率及び膜厚を意味する。) In addition, when two or more types of layers such as the undercoat layer 3 and the first transparent conductive layer 4 are laminated between the
n × d = Σ (n i × d i ) (b)
(N i and d i mean the refractive index and film thickness of the material of the i-th layer from the
すなわち、透明基板2と金属層5との間に複数の層が存在する場合、mが0以上の整数のいずれかにおいて下記式(2)を満たすことが好ましい。
480≧4×Σ(ni×di)÷(2×m+1)≧380……(2) That is, when there are a plurality of layers between thetransparent substrate 2 and the metal layer 5, it is preferable to satisfy the following formula (2) when m is an integer of 0 or more.
480 ≧ 4 × Σ (n i × d i ) ÷ (2 × m + 1) ≧ 380 (2)
480≧4×Σ(ni×di)÷(2×m+1)≧380……(2) That is, when there are a plurality of layers between the
480 ≧ 4 × Σ (n i × d i ) ÷ (2 × m + 1) ≧ 380 (2)
なお、上述の通り、mの値が4以上の場合には、特定の干渉色が目立ちにくくなる傾向があるために、黄色や赤色の干渉色を抑えつつ、有機活性層の色調に関わらず、有機光電変換素子の外観色を青系色に調整したい場合は、mは0以上3以下の整数の場合に、光路長Σ(ni×di)が上記式(2)を充足することが好ましい。
As described above, when the value of m is 4 or more, a specific interference color tends to be inconspicuous, and thus, while suppressing yellow and red interference colors, regardless of the color tone of the organic active layer, When it is desired to adjust the appearance color of the organic photoelectric conversion element to a blue color, when m is an integer of 0 or more and 3 or less, the optical path length Σ (n i × d i ) satisfies the above formula (2). preferable.
なかでも、本発明においては、後述するように、透明基板2と下部透明電極7との密着性を高めるためにアンダーコート層3を有することが好ましい。また、下部透明電極7を構成する金属層5の耐久性を向上させるために、金属層5の下方には第1の透明導電層4を有することが好ましい。すなわち、透明基板2と、金属層5との間には、透明基板2側から、アンダーコート層3と、第1の透明導電層4とを有することが特に好ましい。従って、アンダーコート層3の厚みをd1、アンダーコート層3の屈折率をn1、第1透明導電層4の厚みをd2、第1透明導電層4の屈折率をn2としたとき、光路長(d1×n1+d2×n2)が、mが0以上の整数のいずれかにおいて以下の式(3)を満たすことによって、太陽電池の特性を阻害することなく、太陽電池が黄色や赤色を呈するのを抑制しつつ、太陽電池表面の外観色を青系色に調整し、意匠性を向上させることができるために好ましい。
480≧4×(n1×d1+n2×d2)÷(2×m+1)≧380……(3) Especially, in this invention, in order to improve the adhesiveness of thetransparent substrate 2 and the lower transparent electrode 7, it is preferable to have the undercoat layer 3 so that it may mention later. In order to improve the durability of the metal layer 5 constituting the lower transparent electrode 7, it is preferable to have the first transparent conductive layer 4 below the metal layer 5. That is, it is particularly preferable to have the undercoat layer 3 and the first transparent conductive layer 4 from the transparent substrate 2 side between the transparent substrate 2 and the metal layer 5. Therefore, d 1 and the thickness of the undercoat layer 3, n 1 the refractive index of the undercoat layer 3, when the thickness of the first transparent conductive layer 4 and d 2, the refractive index of the first transparent conductive layer 4 and n 2 The solar cell without obstructing the characteristics of the solar cell by satisfying the following formula (3) when the optical path length (d 1 × n 1 + d 2 × n 2 ) is any integer greater than or equal to 0: Is preferable because the appearance color of the solar cell surface can be adjusted to a blue color and the design can be improved while suppressing yellow and red.
480 ≧ 4 × (n 1 × d 1 + n 2 × d 2 ) ÷ (2 × m + 1) ≧ 380 (3)
480≧4×(n1×d1+n2×d2)÷(2×m+1)≧380……(3) Especially, in this invention, in order to improve the adhesiveness of the
480 ≧ 4 × (n 1 × d 1 + n 2 × d 2 ) ÷ (2 × m + 1) ≧ 380 (3)
なお、上記式(2)と同様に、mの値が4以上の場合には、特定の干渉色が目立たなくなるために、mが0以上3以下のいずれかの整数の場合に、光路長(n1×d1+n2×d2)が上記式(3)を充足することが好ましい。
Similarly to the above formula (2), when the value of m is 4 or more, the specific interference color is not noticeable. Therefore, when m is an integer of 0 or more and 3 or less, the optical path length ( n 1 × d 1 + n 2 × d 2 ) preferably satisfies the above formula (3).
以下、図1に示す本発明の一実施形態における有機光電変換素子1の各構成部材又は層について説明する。
Hereinafter, each component or layer of the organic photoelectric conversion element 1 according to the embodiment of the present invention shown in FIG. 1 will be described.
<透明基板2>
透明基板2は、有機光電変換素子1を支持する部材である。透明基板2の材料は、有機光電変換素子1を構成する層を積層し、支持できる限り制限されない。 <Transparent substrate 2>
Thetransparent substrate 2 is a member that supports the organic photoelectric conversion element 1. The material of the transparent substrate 2 is not limited as long as the layers constituting the organic photoelectric conversion element 1 are stacked and supported.
透明基板2は、有機光電変換素子1を支持する部材である。透明基板2の材料は、有機光電変換素子1を構成する層を積層し、支持できる限り制限されない。 <
The
透明基板2の材料は、例えば、ガラス、石英、透明樹脂材料等があげられる。透明樹脂材料の具体例としては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリエーテルスルホン、ポリイミド、ナイロン、ポリスチレン、ポリビニルアルコール、エチレンビニルアルコール共重合体、フッ素樹脂、ポリ塩化ビニル、ポリエチレン、ポリプロピレン、環状ポリオレフィン、セルロース、アセチルセルロース、ポリ塩化ビニリデン、アラミド、ポリフェニレンスルフィド、ポリウレタン、ポリカーボネート、ポリ(メタ)アクリル樹脂、フェノール樹脂、エポキシ樹脂、ポリアリレート、ポリノルボルネン等の有機材料などが挙げられる。これらの中でも、有機光電変換素子1を含む有機薄膜太陽電池モジュールの設置の自由度の観点から、透明基板2は可撓性を有するものが好ましい。可撓性を有する材料は特に限定されないが、好ましくは、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリイミド、ポリ(メタ)アクリル樹脂が、有機光電変換素子1の形成しやすさの点で好ましい。
Examples of the material of the transparent substrate 2 include glass, quartz, and a transparent resin material. Specific examples of the transparent resin material include, for example, polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, fluororesin, polyvinyl chloride, polyethylene, polypropylene, cyclic Examples thereof include organic materials such as polyolefin, cellulose, acetyl cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate, poly (meth) acrylic resin, phenol resin, epoxy resin, polyarylate, and polynorbornene. Among these, from the viewpoint of the degree of freedom of installation of the organic thin film solar cell module including the organic photoelectric conversion element 1, the transparent substrate 2 preferably has flexibility. The material having flexibility is not particularly limited, but polyethylene terephthalate, polyethylene naphthalate, polyimide, and poly (meth) acrylic resin are preferable from the viewpoint of easy formation of the organic photoelectric conversion element 1.
なお、透明基板2の材料は、1種を用いてもよく、2種以上を任意の組み合わせ及び比率で併用してもよい。また、これら透明基板2の材料に炭素繊維、ガラス繊維などの強化繊維を含ませ、機械的強度を補強させてもよい。
In addition, 1 type may be used for the material of the transparent substrate 2, and 2 or more types may be used together by arbitrary combinations and a ratio. Further, the material of the transparent substrate 2 may contain reinforcing fibers such as carbon fibers and glass fibers to reinforce the mechanical strength.
透明基板2のJIS R 3106で定義される可視光線透過率が通常70%以上、好ましくは80%以上である。透明基板2の厚さは、上記可視光線透過率を満たせば特段の制限はないが、取り扱いの容易さの観点からは、通常20μm以上、好ましくは50μm以上であり、一方、通常1000μm以下、好ましくは500μm以下、より好ましくは200μm以下である。
The visible light transmittance of the transparent substrate 2 defined by JIS R 3106 is usually 70% or more, preferably 80% or more. The thickness of the transparent substrate 2 is not particularly limited as long as the visible light transmittance is satisfied, but from the viewpoint of ease of handling, it is usually 20 μm or more, preferably 50 μm or more, and usually 1000 μm or less, preferably Is 500 μm or less, more preferably 200 μm or less.
<アンダーコート層3>
アンダーコート層3は、主として、透明基板2と下部透明電極7との間に配置され、透明基板2と下部透明電極7の密着性を向上させる機能を有する。図1に示す有機光電変換素子1は、アンダーコート層3を用いる実施形態ではあるが、必ずしも必須とされるものではない。なお、有機活性層8へ効率良く光を入射せるために、アンダーコート層3は透明であることが好ましい。なお、アンダーコート層3が透明であるとは、JIS R 3106で定義される可視光線透過率が70%以上であることを意味し、好ましくは80%以上である。 <Undercoat layer 3>
The undercoat layer 3 is mainly disposed between thetransparent substrate 2 and the lower transparent electrode 7 and has a function of improving the adhesion between the transparent substrate 2 and the lower transparent electrode 7. The organic photoelectric conversion element 1 shown in FIG. 1 is an embodiment using the undercoat layer 3, but is not necessarily essential. Note that the undercoat layer 3 is preferably transparent in order to allow light to enter the organic active layer 8 efficiently. The undercoat layer 3 being transparent means that the visible light transmittance defined by JIS R 3106 is 70% or more, and preferably 80% or more.
アンダーコート層3は、主として、透明基板2と下部透明電極7との間に配置され、透明基板2と下部透明電極7の密着性を向上させる機能を有する。図1に示す有機光電変換素子1は、アンダーコート層3を用いる実施形態ではあるが、必ずしも必須とされるものではない。なお、有機活性層8へ効率良く光を入射せるために、アンダーコート層3は透明であることが好ましい。なお、アンダーコート層3が透明であるとは、JIS R 3106で定義される可視光線透過率が70%以上であることを意味し、好ましくは80%以上である。 <Undercoat layer 3>
The undercoat layer 3 is mainly disposed between the
アンダーコート層3の波長485nmにおける屈折率n1は、特段の制限はないが、通常、1.4以上であり、2.0以下であり、上記式(1)~(3)及び後述する式(4)を満たすように適宜設計すればよい。
The refractive index n 1 at a wavelength of 485 nm of the undercoat layer 3 is not particularly limited, but is usually 1.4 or more and 2.0 or less. The above formulas (1) to (3) and formulas described later What is necessary is just to design suitably so that (4) may be satisfy | filled.
また、前述の式(1)~(3)を満たす場合において、アンダーコート層3の波長485nmにおける屈折率n1は透明基板2の波長485nmにおける屈折率n3及び第1の透明導電層の485nmにおける屈折率n2より小さいことが好ましい。この理由は、ファブリペロー干渉により透明基板2と金属層5との間で光干渉が効率的に起こり、アンダーコート層での干渉色が増強されるために、有機光電変換素子の外観色をさらに調整しやすくなるためである。なかでも、光干渉により有機光電変換素子の外観色を適切に調整しつつ、有機活性層8が効率良く光を吸収させるために、アンダーコート層3の屈折率n1は透明基板2の屈折率n3よりも小さく、かつ、アンダーコート層3の屈折率n1と透明基板2の屈折率n3との差(n3-n1)が、0.1以上であることが好ましく、0.2以上であることが好ましく、一方、0.4以下であることが好ましく、0.3以下であることが特に好ましい。
Further, when satisfying the above-mentioned formulas (1) to (3), the refractive index n 1 of the undercoat layer 3 at a wavelength of 485 nm is equal to the refractive index n 3 of the transparent substrate 2 at a wavelength of 485 nm and the 485 nm of the first transparent conductive layer. it is preferably smaller than the refractive index n 2 at. The reason for this is that light interference efficiently occurs between the transparent substrate 2 and the metal layer 5 due to Fabry-Perot interference, and the interference color in the undercoat layer is enhanced, so that the appearance color of the organic photoelectric conversion element is further increased. This is because it is easy to adjust. In particular, the refractive index n 1 of the undercoat layer 3 is the refractive index of the transparent substrate 2 so that the organic active layer 8 efficiently absorbs light while appropriately adjusting the appearance color of the organic photoelectric conversion element by light interference. n less than 3, and the difference between the refractive index n 1 and the refractive index n 3 of the transparent substrate 2 of the undercoat layer 3 (n 3 -n 1) is preferably 0.1 or more, 0. It is preferably 2 or more, on the other hand, preferably 0.4 or less, and particularly preferably 0.3 or less.
アンダーコート層3の材料としては、例えば、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂などの樹脂や、モメンティブ・パフォーマンス・マテリアルズ社製のハードコート剤SHC900のような有機ケイ素化合物の加水分解により生成する物質(加水分解物)、シリカなどの無機物質微粒子、などがある。
Examples of the material of the undercoat layer 3 include substances generated by hydrolysis of resins such as acrylic resin, polyester resin, and polyamide resin, and organic silicon compounds such as hard coat agent SHC900 manufactured by Momentive Performance Materials. (Hydrolyzate), inorganic fine particles such as silica, and the like.
アンダーコート層3は、これらの中でも、下部透明電極7との密着性をより向上する目的で、有機ケイ素化合物の加水分解生成物により形成することが好ましい。有機ケイ素化合物の加水分解生成物を用いる場合は、透明基板2との密着強度改善やアンダーコート層3の機械強度を向上する目的で、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂、エポキシ樹脂を共に用いてもよい。
Among these, the undercoat layer 3 is preferably formed of a hydrolysis product of an organosilicon compound for the purpose of further improving the adhesion with the lower transparent electrode 7. When using a hydrolyzed product of an organosilicon compound, an acrylic resin, a polyester resin, a polyamide resin, and an epoxy resin are used together for the purpose of improving the adhesion strength with the transparent substrate 2 and the mechanical strength of the undercoat layer 3. Also good.
また、アンダーコート層3と下部透明電極7との密着性を向上する目的で、100nm以下の直径を有する無機物質微粒子を含むことも好ましい。100nm以下の直径を有する無機物質微粒子を用いる場合は、透明基板2との密着強度改善やアンダーコート層3の機械強度を向上する目的で、アクリル樹脂、ポリエステル樹脂、ポリアミド樹脂と共に用いることが望ましい。
100nm以下の直径を有する無機物質微粒子は、特に、シリカが望ましい。この理由は、シリカの屈折率はアクリル樹脂のそれと近いので乱反射が少なく、透明なアンダーコート層3を得やすいためである。
なお、アクリル樹脂やポリエステル樹脂、ポリアミド樹脂などを用いる場合は、架橋させて用いてもよい。 In addition, for the purpose of improving the adhesion between the undercoat layer 3 and the lower transparent electrode 7, it is preferable to include inorganic substance fine particles having a diameter of 100 nm or less. When inorganic fine particles having a diameter of 100 nm or less are used, it is desirable to use them together with an acrylic resin, a polyester resin and a polyamide resin for the purpose of improving the adhesion strength with thetransparent substrate 2 and the mechanical strength of the undercoat layer 3.
Silica is particularly desirable for the inorganic substance fine particles having a diameter of 100 nm or less. This is because the refractive index of silica is close to that of an acrylic resin, so that there is little irregular reflection and it is easy to obtain a transparent undercoat layer 3.
In addition, when using an acrylic resin, a polyester resin, a polyamide resin, etc., you may make it bridge | crosslink.
100nm以下の直径を有する無機物質微粒子は、特に、シリカが望ましい。この理由は、シリカの屈折率はアクリル樹脂のそれと近いので乱反射が少なく、透明なアンダーコート層3を得やすいためである。
なお、アクリル樹脂やポリエステル樹脂、ポリアミド樹脂などを用いる場合は、架橋させて用いてもよい。 In addition, for the purpose of improving the adhesion between the undercoat layer 3 and the lower transparent electrode 7, it is preferable to include inorganic substance fine particles having a diameter of 100 nm or less. When inorganic fine particles having a diameter of 100 nm or less are used, it is desirable to use them together with an acrylic resin, a polyester resin and a polyamide resin for the purpose of improving the adhesion strength with the
Silica is particularly desirable for the inorganic substance fine particles having a diameter of 100 nm or less. This is because the refractive index of silica is close to that of an acrylic resin, so that there is little irregular reflection and it is easy to obtain a transparent undercoat layer 3.
In addition, when using an acrylic resin, a polyester resin, a polyamide resin, etc., you may make it bridge | crosslink.
アンダーコート層3の厚さは、上述の通り、透明基板1と金属層5間の光路長を考慮した上で、選択すればよい。本実施形態においては、下部透明電極7との密着性を向上させるために、アンダーコート層3の膜厚は、好ましくは10nm以上であり、さらに好ましくは50nm以上であり、一方、亀裂が生じるのを防ぐために、好ましくは5μm以下であり、より好ましくは1μm以下であり、さらに好ましくは、500nm以下であり、特に好ましくは300nm以下であり、最も好ましくは200nm以下である。
The thickness of the undercoat layer 3 may be selected in consideration of the optical path length between the transparent substrate 1 and the metal layer 5 as described above. In the present embodiment, in order to improve the adhesion with the lower transparent electrode 7, the thickness of the undercoat layer 3 is preferably 10 nm or more, more preferably 50 nm or more, while cracks are generated. Is preferably 5 μm or less, more preferably 1 μm or less, still more preferably 500 nm or less, particularly preferably 300 nm or less, and most preferably 200 nm or less.
<下部透明電極7及び上部電極9>
下部透明電極7及び上部電極9は、一方が有機活性層8において発生した正孔を捕集するアノードであり、他方が有機活性層8において発生した電子を捕集するカソードである。下部透明電極7をアノードとし、上部電極9をカソードとしてもよいし、下部透明電極7をカソードとし、上部電極9をアノードとしてもよい。 <Lower transparent electrode 7 andupper electrode 9>
One of the lower transparent electrode 7 and theupper electrode 9 is an anode that collects holes generated in the organic active layer 8, and the other is a cathode that collects electrons generated in the organic active layer 8. The lower transparent electrode 7 may be an anode, the upper electrode 9 may be a cathode, the lower transparent electrode 7 may be a cathode, and the upper electrode 9 may be an anode.
下部透明電極7及び上部電極9は、一方が有機活性層8において発生した正孔を捕集するアノードであり、他方が有機活性層8において発生した電子を捕集するカソードである。下部透明電極7をアノードとし、上部電極9をカソードとしてもよいし、下部透明電極7をカソードとし、上部電極9をアノードとしてもよい。 <Lower transparent electrode 7 and
One of the lower transparent electrode 7 and the
図1に係る実施態様において、下部透明電極7は、第1透明導電層4、金属層5及び第2透明導電層6が順次積層されてなる。すなわち、第1透明導電層4は、アンダーコート層3と金属層5との間に積層されており、第2透明導電層6は、金属層5と有機活性層8との間に積層されている。なお、通常、下部透明電極7は、単層の透明導電層により形成することができるが、金属酸化物により形成される透明導電層は、抵抗が高い傾向がある。そのために、本発明においては、導電性向上のために、下部透明電極7は金属層5を有して形成される。すなわち、本発明において、下部透明電極7は、少なくとも金属層を含んでいればよく、金属層5の単層又は金属層5と透明導電層との積層であってもよいが、下部透明電極7の耐久性を向上させるために、金属層及び透明導電層の積層構造であることが好ましく、なかでも、図1に示すように、金属層の両側に透明導電層が配置された積層構造であることが好ましい。
In the embodiment according to FIG. 1, the lower transparent electrode 7 is formed by laminating a first transparent conductive layer 4, a metal layer 5, and a second transparent conductive layer 6 in this order. That is, the first transparent conductive layer 4 is laminated between the undercoat layer 3 and the metal layer 5, and the second transparent conductive layer 6 is laminated between the metal layer 5 and the organic active layer 8. Yes. Normally, the lower transparent electrode 7 can be formed of a single transparent conductive layer, but the transparent conductive layer formed of a metal oxide tends to have high resistance. Therefore, in the present invention, the lower transparent electrode 7 is formed with the metal layer 5 in order to improve conductivity. That is, in the present invention, the lower transparent electrode 7 only needs to include at least a metal layer, and may be a single layer of the metal layer 5 or a laminate of the metal layer 5 and the transparent conductive layer. In order to improve the durability, a laminated structure of a metal layer and a transparent conductive layer is preferable, and in particular, as shown in FIG. 1, a laminated structure in which a transparent conductive layer is disposed on both sides of the metal layer. It is preferable.
<第1透明導電層4及び第2透明導電層6>
第1透明導電層4及び第2透明導電層6の材料は、同一でも異なっていてもよい。第1透明導電層4及び第2透明導電層6に用いられる材料としては、透明性及び導電性に優れたものであることが好ましい。ここで、透明性に優れるとは、膜厚100nm程度の薄膜を形成したときに、その薄膜の可視光線透過率が60%以上であることを指し、導電性に優れるとは、膜厚100nm程度の薄膜を形成したときに、その薄膜の表面抵抗値が1×107Ω/□以下であることを意味する。なお、不純物をドープすることで表面抵抗値を調整してもよい。 <First transparent conductive layer 4 and second transparentconductive layer 6>
The materials of the first transparent conductive layer 4 and the second transparentconductive layer 6 may be the same or different. As a material used for the 1st transparent conductive layer 4 and the 2nd transparent conductive layer 6, it is preferable that it is excellent in transparency and electroconductivity. Here, excellent transparency means that when a thin film having a thickness of about 100 nm is formed, the visible light transmittance of the thin film is 60% or more, and excellent conductivity means that the thickness is about 100 nm. When the thin film is formed, it means that the surface resistance value of the thin film is 1 × 10 7 Ω / □ or less. The surface resistance value may be adjusted by doping impurities.
第1透明導電層4及び第2透明導電層6の材料は、同一でも異なっていてもよい。第1透明導電層4及び第2透明導電層6に用いられる材料としては、透明性及び導電性に優れたものであることが好ましい。ここで、透明性に優れるとは、膜厚100nm程度の薄膜を形成したときに、その薄膜の可視光線透過率が60%以上であることを指し、導電性に優れるとは、膜厚100nm程度の薄膜を形成したときに、その薄膜の表面抵抗値が1×107Ω/□以下であることを意味する。なお、不純物をドープすることで表面抵抗値を調整してもよい。 <First transparent conductive layer 4 and second transparent
The materials of the first transparent conductive layer 4 and the second transparent
第1透明導電層4及び第2透明導電層6に好適に用いることができる材料としては、金属酸化物が挙げられる。例えば、スズをドープしたインジウム酸化物(ITO)、亜鉛をドープしたインジウム酸化物(IZO)、タングステンをドープしたインジウム酸化物(IWO)、ガリウムをドープしたインジウム酸化物(IGO)、カドミウムとスズとの酸化物(CTO)、酸化アルミニウム(Al2O3)、酸化亜鉛(ZnO)、亜鉛とアルミニウムとの酸化物(AZO)、スズと亜鉛の酸化物(ZTO)、酸化マグネシウム(MgO)、酸化トリウム(ThO2)、酸化スズ(SnO2)、酸化ランタン(La2O3)、酸化インジウム(In2O3)、酸化ニオブ(Nb2O3)、酸化アンチモン(Sb2O3)、酸化ジルコニウム(ZrO2)、酸化セリウム(CeO2)、酸化チタン(TiO2)、酸化ビスマス(BiO2)等である。
また、透明性の高い高屈折率硫化物を用いてもよい。具体的には、硫化亜鉛(ZnS)、硫化カドミウム(CdS)、硫化アンチモン(Sb2S3)等があげられる。特に、スズをドープしたインジウム酸化物(ITO)、亜鉛をドープしたインジウム酸化物(IZO)、タングステンをドープしたインジウム酸化物(IWO)、ガリウムをドープしたインジウム酸化物(IGO)、スズと亜鉛の酸化物(ZTO)等の酸化物の非晶質が好ましい。 Examples of materials that can be suitably used for the first transparent conductive layer 4 and the second transparentconductive layer 6 include metal oxides. For example, indium oxide doped with tin (ITO), indium oxide doped with zinc (IZO), indium oxide doped with tungsten (IWO), indium oxide doped with gallium (IGO), cadmium and tin Oxide (CTO), aluminum oxide (Al 2 O 3 ), zinc oxide (ZnO), zinc-aluminum oxide (AZO), tin-zinc oxide (ZTO), magnesium oxide (MgO), oxidation Thorium (ThO 2 ), tin oxide (SnO 2 ), lanthanum oxide (La 2 O 3 ), indium oxide (In 2 O 3 ), niobium oxide (Nb 2 O 3 ), antimony oxide (Sb 2 O 3 ), oxidation Zirconium (ZrO 2 ), cerium oxide (CeO 2 ), titanium oxide (TiO 2 ), bismuth oxide (BiO) 2 ) etc.
Moreover, you may use the high refractive index sulfide with high transparency. Specifically, zinc sulfide (ZnS), cadmium sulfide (CdS), antimony sulfide (Sb 2 S 3 ), and the like can be given. In particular, indium oxide doped with tin (ITO), indium oxide doped with zinc (IZO), indium oxide doped with tungsten (IWO), indium oxide doped with gallium (IGO), tin and zinc Amorphous oxides such as oxide (ZTO) are preferred.
また、透明性の高い高屈折率硫化物を用いてもよい。具体的には、硫化亜鉛(ZnS)、硫化カドミウム(CdS)、硫化アンチモン(Sb2S3)等があげられる。特に、スズをドープしたインジウム酸化物(ITO)、亜鉛をドープしたインジウム酸化物(IZO)、タングステンをドープしたインジウム酸化物(IWO)、ガリウムをドープしたインジウム酸化物(IGO)、スズと亜鉛の酸化物(ZTO)等の酸化物の非晶質が好ましい。 Examples of materials that can be suitably used for the first transparent conductive layer 4 and the second transparent
Moreover, you may use the high refractive index sulfide with high transparency. Specifically, zinc sulfide (ZnS), cadmium sulfide (CdS), antimony sulfide (Sb 2 S 3 ), and the like can be given. In particular, indium oxide doped with tin (ITO), indium oxide doped with zinc (IZO), indium oxide doped with tungsten (IWO), indium oxide doped with gallium (IGO), tin and zinc Amorphous oxides such as oxide (ZTO) are preferred.
第1透明導電層4及び第2透明導電層6の結晶転移温度(Tc)は、通常150℃以上、好ましくは180℃以上、さらに好ましくは200℃以上である。透明導電薄膜層の結晶転移温度(Tc)が150℃以上であることにより、透明プラスチック基板上に有機光電変換素子を形成する際に透明導電層の表面凹凸が生じない点で好ましい。結晶転移温度は、示差熱量分析等の測定方法で測定できる。
The crystal transition temperature (Tc) of the first transparent conductive layer 4 and the second transparent conductive layer 6 is usually 150 ° C. or higher, preferably 180 ° C. or higher, more preferably 200 ° C. or higher. When the crystal transition temperature (Tc) of the transparent conductive thin film layer is 150 ° C. or higher, it is preferable in that the surface unevenness of the transparent conductive layer does not occur when the organic photoelectric conversion element is formed on the transparent plastic substrate. The crystal transition temperature can be measured by a measuring method such as differential calorimetry.
第1透明導電層4及び第2透明導電層6の厚さは、下部透明電極7及び有機光電変換素子1全体の透過率及び/又は反射率、並びに下部透明電極7の電気伝導性を考慮して任意で調整することができる。特に、有機光電変換素子1を透過型(シースルー型)の光電変換素子とする場合には、下部透明電極7及び有機光電変換素子1全体の透過率及び反射率を考慮して選択することが好ましい。
The thickness of the 1st transparent conductive layer 4 and the 2nd transparent conductive layer 6 considers the electric conductivity of the lower transparent electrode 7, the transmittance | permeability and / or reflectance of the whole organic photoelectric conversion element 1, and the lower transparent electrode 7. Can be adjusted arbitrarily. In particular, when the organic photoelectric conversion element 1 is a transmission type (see-through type) photoelectric conversion element, it is preferable to select in consideration of the transmittance and reflectance of the lower transparent electrode 7 and the organic photoelectric conversion element 1 as a whole. .
特に、下部透明電極が第1の透明導電層4を有する場合、第1透明導電層4の厚さは、上述の通り、金属層5と、透明基板2間の光の干渉を考慮して選択する必要がある。特に、有機光電変換素子が、アンダーコート層3と、第1の透明導電層を有する場合は、第1の透明導電層4の膜厚は、アンダーコート層3の膜厚との関係性を考慮して、設計すればよい。但し、以下の理由により、第1の透明導電層4の膜厚は、好ましくは5nm以上であり、さらに好ましくは10nm以上であり、より好ましくは20nm以上であり、一方、好ましくは200nm以下であり、さらに好ましくは100nm以下であり、特に好ましくは60nm以下である。第1透明導電層4の膜厚が小さすぎると、第1透明導電層4が均一に成膜されずに金属層5が酸化劣化して光沢を失い、光干渉効果を損ないやすくなる傾向があると同時に、電気抵抗が増大する場合がある。一方、第1の透明導電層4の膜厚が大きすぎると、通常、第1の透明導電層4はスパッタ法又はCVD法等の真空蒸着法により形成されるが、この場合、密度の大きい透明導電層が形成されることになるため応力により第1透明導電層4に亀裂が入りやすくなる。その結果、第1の下部透明電極7内に酸素が浸入し、金属層5が酸化劣化してしまう傾向がある。
In particular, when the lower transparent electrode has the first transparent conductive layer 4, the thickness of the first transparent conductive layer 4 is selected in consideration of light interference between the metal layer 5 and the transparent substrate 2 as described above. There is a need to. In particular, when the organic photoelectric conversion element has the undercoat layer 3 and the first transparent conductive layer, the thickness of the first transparent conductive layer 4 takes into account the relationship with the thickness of the undercoat layer 3. And design. However, for the following reasons, the film thickness of the first transparent conductive layer 4 is preferably 5 nm or more, more preferably 10 nm or more, more preferably 20 nm or more, while preferably 200 nm or less. More preferably, it is 100 nm or less, and particularly preferably 60 nm or less. If the film thickness of the first transparent conductive layer 4 is too small, the first transparent conductive layer 4 is not uniformly formed, and the metal layer 5 tends to be oxidized and deteriorated to lose its gloss, and the light interference effect tends to be impaired. At the same time, the electrical resistance may increase. On the other hand, if the film thickness of the first transparent conductive layer 4 is too large, the first transparent conductive layer 4 is usually formed by a vacuum deposition method such as a sputtering method or a CVD method. Since the conductive layer is formed, the first transparent conductive layer 4 is easily cracked by stress. As a result, oxygen enters the first lower transparent electrode 7 and the metal layer 5 tends to be oxidized and deteriorated.
下部透明電極7が第2の透明導電層6を有する場合、第2透明導電層6の厚さは、特段の制限はないが、通常20nm以上、好ましくは30nm以上、一方、通常60nm以下である。一方、上記上限以下であると、可撓性が担保でき、かつ、生産速度が低下することがないので好ましい。
When the lower transparent electrode 7 has the second transparent conductive layer 6, the thickness of the second transparent conductive layer 6 is not particularly limited, but is usually 20 nm or more, preferably 30 nm or more, and usually 60 nm or less. . On the other hand, it is preferable that the amount is not more than the above upper limit because flexibility can be ensured and the production rate does not decrease.
第1透明導電層4及び第2透明導電層6の485nmにおける屈折率は、特段の制限はないが、それぞれ、通常1.3以上であり、一方、界面反射率を抑えて有機活性層8が効率良く光を吸収できるようにするために、2.5以下が好ましく、2.2以下がさらに好ましい。特に、第1の透明導電層4の屈折率n2は、上記式(1)~(3)及び後述の式(4)を満たすように選択することが好ましい。
The refractive index at 485 nm of the first transparent conductive layer 4 and the second transparent conductive layer 6 is not particularly limited, but each is usually 1.3 or more, while the organic active layer 8 is suppressed by suppressing the interface reflectance. In order to be able to absorb light efficiently, 2.5 or less is preferable, and 2.2 or less is more preferable. In particular, the refractive index n 2 of the first transparent conductive layer 4 is preferably selected so as to satisfy the above formulas (1) to (3) and formula (4) described later.
第1透明導電層4及び第2透明導電層6は、その比抵抗が通常1×10-7Ω・cm以上、好ましくは1×10-6Ω・cm以上であり、一方、通常5×10-3Ω・cm以下、好ましくは1×10-4Ω・cm以下である。
The specific resistance of the first transparent conductive layer 4 and the second transparent conductive layer 6 is usually 1 × 10 −7 Ω · cm or more, preferably 1 × 10 −6 Ω · cm or more, while usually 5 × 10 −3 Ω · cm or less, preferably 1 × 10 −4 Ω · cm or less.
下部透明電極7は透明であるが、変換効率の観点から透過性が高いことが好ましく、通常60%以上であり、70%以上であることが好ましい。上限は特段限定されないが、通常90%以下である。
The lower transparent electrode 7 is transparent, but preferably has high permeability from the viewpoint of conversion efficiency, and is usually 60% or more and preferably 70% or more. The upper limit is not particularly limited, but is usually 90% or less.
下部透明電極7の透過率は、紫外可視近赤外分光光度計とフィルムサンプルホルダーを用いて測定できる。測定結果は、JIS R 3106:1998に従って波長380nm~900nmまでの透過率が算出され、これらの波長領域の透過率の平均として、下部透明電極7の透過率が算出される。
The transmittance of the lower transparent electrode 7 can be measured using an ultraviolet-visible near-infrared spectrophotometer and a film sample holder. As a measurement result, the transmittance from a wavelength of 380 nm to 900 nm is calculated according to JIS R 3106: 1998, and the transmittance of the lower transparent electrode 7 is calculated as an average of the transmittance in these wavelength regions.
<金属層5>
金属層5の材料としては、特段の制限はなく、例えば、白金、金、銀、アルミニウム、クロム、ニッケル、銅、チタン、マグネシウム、カルシウム、バリウム、ナトリウム等の金属又はそれらの金属の合金が挙げられる。なかでも、電気伝導性の高い材料が好ましく、銀であることが特に好ましい。銀は、比抵抗が約1.59×10-6Ω・cmであり、電気伝導性に優れる上に、薄膜における可視光線透過率が優れるため、最も好適に用いられる。 <Metal layer 5>
There is no special restriction | limiting as a material of themetal layer 5, For example, metals, such as platinum, gold | metal | money, silver, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, barium, sodium, or those metal alloys are mentioned. It is done. Among these, a material having high electrical conductivity is preferable, and silver is particularly preferable. Silver has a specific resistance of about 1.59 × 10 −6 Ω · cm, is excellent in electrical conductivity, and has excellent visible light transmittance in a thin film, and thus is most preferably used.
金属層5の材料としては、特段の制限はなく、例えば、白金、金、銀、アルミニウム、クロム、ニッケル、銅、チタン、マグネシウム、カルシウム、バリウム、ナトリウム等の金属又はそれらの金属の合金が挙げられる。なかでも、電気伝導性の高い材料が好ましく、銀であることが特に好ましい。銀は、比抵抗が約1.59×10-6Ω・cmであり、電気伝導性に優れる上に、薄膜における可視光線透過率が優れるため、最も好適に用いられる。 <
There is no special restriction | limiting as a material of the
金属層5の厚さは、電導度の向上のために、好ましくは1nmであり、さらに好ましくは5nm以上であり、一方、有機活性層8が効率良く光を吸収し、変換効率を向上させるために、好ましくは20nm以下であり、さらに好ましくは10nm以下である。
The thickness of the metal layer 5 is preferably 1 nm, more preferably 5 nm or more for improving the conductivity, while the organic active layer 8 efficiently absorbs light and improves conversion efficiency. Further, it is preferably 20 nm or less, and more preferably 10 nm or less.
下部透明電極7全体の厚さは、光学特性及び電気特性を考慮した上で、各層の膜厚を決定して調整すればよいが、通常10nm以上、好ましくは60nm以上であり、一方、通常、300nm以下であり、好ましくは200nm以下であり、特に好ましくは100nm以下である。
The thickness of the entire lower transparent electrode 7 may be adjusted by determining the film thickness of each layer in consideration of optical characteristics and electrical characteristics, but is usually 10 nm or more, preferably 60 nm or more, It is 300 nm or less, preferably 200 nm or less, and particularly preferably 100 nm or less.
<上部電極9>
上部電極9は、導電性を有する任意の材料により形成することが可能である。上部電極9の材料の例を挙げると、白金、金、銀、アルミニウム、クロム、ニッケル、銅、チタン、マグネシウム、カルシウム、バリウム、ナトリウム等の金属あるいはそれらの合金;酸化インジウムや酸化錫等の金属酸化物、あるいはその合金(ITO等);ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン等の導電性高分子;前記導電性高分子に、塩酸、硫酸、スルホン酸等の酸、FeCl3等のルイス酸、ヨウ素等のハロゲン原子、ナトリウム、カリウム等の金属原子などのドーパントを含有させたもの;金属粒子、カーボンブラック、フラーレン、カーボンナノチューブ等の導電性粒子をポリマーバインダー等のマトリクスに分散した導電性の複合材料、前記下部透明電極7に例示した材料などが挙げられる。 <Upper electrode 9>
Theupper electrode 9 can be formed of any material having conductivity. Examples of the material of the upper electrode 9 include metals such as platinum, gold, silver, aluminum, chromium, nickel, copper, titanium, magnesium, calcium, barium, sodium, and alloys thereof; metals such as indium oxide and tin oxide. Oxides or alloys thereof (ITO, etc.); conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene; acids such as hydrochloric acid, sulfuric acid, sulfonic acid, Lewis acids such as FeCl 3 , iodine, etc. Containing a dopant such as a metal atom such as a halogen atom such as sodium or potassium; a conductive composite material in which conductive particles such as metal particles, carbon black, fullerene or carbon nanotubes are dispersed in a matrix such as a polymer binder The materials exemplified for the lower transparent electrode 7 can be used.
上部電極9は、導電性を有する任意の材料により形成することが可能である。上部電極9の材料の例を挙げると、白金、金、銀、アルミニウム、クロム、ニッケル、銅、チタン、マグネシウム、カルシウム、バリウム、ナトリウム等の金属あるいはそれらの合金;酸化インジウムや酸化錫等の金属酸化物、あるいはその合金(ITO等);ポリアニリン、ポリピロール、ポリチオフェン、ポリアセチレン等の導電性高分子;前記導電性高分子に、塩酸、硫酸、スルホン酸等の酸、FeCl3等のルイス酸、ヨウ素等のハロゲン原子、ナトリウム、カリウム等の金属原子などのドーパントを含有させたもの;金属粒子、カーボンブラック、フラーレン、カーボンナノチューブ等の導電性粒子をポリマーバインダー等のマトリクスに分散した導電性の複合材料、前記下部透明電極7に例示した材料などが挙げられる。 <
The
特に、下部透明電極8を電子を捕集するカソードとし、上部電極9を正孔を捕集するアノードとする場合には、上部電極9を構成する材料は、深い仕事関数を有する材料を用いることが好ましい。一方、下部透明電極8をアノードとし、上部電極9を電子を捕集するカソードとする場合には、上部電極9を構成する材料は、浅い仕事関数を有する材料を用いることが好ましい。仕事関数を最適化することにより、光吸収により生じた正孔及び電子を良好に捕集することができる。なお、後述するようなバッファ層を設けることにより、下部透明電極7と、上部電極9と、を同じ材料により形成することもできる。
また、上部電極9を下部透明電極7と同様に透明性を有する電極とすることにより、透過型(シースルー型)の有機光電変換素子とすることができる。特に、本発明においては高い意匠性が求められる透過型の有機光電変換素子において有効となる。 In particular, when the lower transparent electrode 8 is a cathode for collecting electrons and theupper electrode 9 is an anode for collecting holes, a material having a deep work function is used as the material constituting the upper electrode 9. Is preferred. On the other hand, when the lower transparent electrode 8 is an anode and the upper electrode 9 is a cathode for collecting electrons, it is preferable to use a material having a shallow work function as the material constituting the upper electrode 9. By optimizing the work function, holes and electrons generated by light absorption can be collected well. Note that the lower transparent electrode 7 and the upper electrode 9 can be formed of the same material by providing a buffer layer as will be described later.
Further, by using theupper electrode 9 as a transparent electrode in the same manner as the lower transparent electrode 7, a transmission type (see-through type) organic photoelectric conversion element can be obtained. In particular, the present invention is effective in a transmissive organic photoelectric conversion element that requires high designability.
また、上部電極9を下部透明電極7と同様に透明性を有する電極とすることにより、透過型(シースルー型)の有機光電変換素子とすることができる。特に、本発明においては高い意匠性が求められる透過型の有機光電変換素子において有効となる。 In particular, when the lower transparent electrode 8 is a cathode for collecting electrons and the
Further, by using the
なお、下部透明電極7及び上部電極9を構成する各層の形成方法に特段の制限はなく、公知の方法により形成することができる。例えば、真空蒸着、スパッタ等のドライプロセスにより形成することができる。また、導電性インク等を用いたウェットプロセス等により形成することもできる。この際、導電性インクとしては任意のものを使用することができ、例えば、金属粒子分散液等を用いることができる。また、下部透明電極7及び/又は上部電極9は、表面処理により、電気特性や、ぬれ特性等の特性を改良してもよい。
In addition, there is no special restriction | limiting in the formation method of each layer which comprises the lower transparent electrode 7 and the upper electrode 9, It can form by a well-known method. For example, it can be formed by a dry process such as vacuum deposition or sputtering. It can also be formed by a wet process using conductive ink or the like. At this time, any conductive ink can be used, and for example, a metal particle dispersion or the like can be used. Further, the lower transparent electrode 7 and / or the upper electrode 9 may be improved in characteristics such as electrical characteristics and wetting characteristics by surface treatment.
<有機活性層8>
有機活性層8は、通常、p型有機半導体化合物と、n型半導体化合物と、を含む。p型半導体化合物とは、p型半導体材料として働く化合物であり、n型半導体化合物とは、n型半導体材料として働く化合物である。有機光電変換素子が光を受けると、光が有機活性層に吸収され、p型半導体化合物とn型半導体化合物との界面で電気が発生し、発生した電気が電極から取り出される。 <Organic active layer 8>
The organic active layer 8 usually includes a p-type organic semiconductor compound and an n-type semiconductor compound. The p-type semiconductor compound is a compound that works as a p-type semiconductor material, and the n-type semiconductor compound is a compound that works as an n-type semiconductor material. When the organic photoelectric conversion element receives light, the light is absorbed by the organic active layer, electricity is generated at the interface between the p-type semiconductor compound and the n-type semiconductor compound, and the generated electricity is extracted from the electrode.
有機活性層8は、通常、p型有機半導体化合物と、n型半導体化合物と、を含む。p型半導体化合物とは、p型半導体材料として働く化合物であり、n型半導体化合物とは、n型半導体材料として働く化合物である。有機光電変換素子が光を受けると、光が有機活性層に吸収され、p型半導体化合物とn型半導体化合物との界面で電気が発生し、発生した電気が電極から取り出される。 <Organic active layer 8>
The organic active layer 8 usually includes a p-type organic semiconductor compound and an n-type semiconductor compound. The p-type semiconductor compound is a compound that works as a p-type semiconductor material, and the n-type semiconductor compound is a compound that works as an n-type semiconductor material. When the organic photoelectric conversion element receives light, the light is absorbed by the organic active layer, electricity is generated at the interface between the p-type semiconductor compound and the n-type semiconductor compound, and the generated electricity is extracted from the electrode.
有機活性層の層構成としては、p型半導体化合物層とn型半導体化合物層とが積層された薄膜積層型、p型半導体化合物とn型半導体化合物とが混合した層(i層)を有するバルクヘテロ接合型、p型半導体化合物とn型半導体化合物とが混合した層(i層)と、p型半導体化合物層及び/又はn型半導体化合物層とが積層された構成等が挙げられる。なかでも、p型半導体化合物とn型半導体化合物が混合した層(i層)を有するバルクヘテロ接合型が好ましい。
As the layer configuration of the organic active layer, a bulk heterostructure having a thin film stack type in which a p-type semiconductor compound layer and an n-type semiconductor compound layer are stacked, and a layer (i layer) in which a p-type semiconductor compound and an n-type semiconductor compound are mixed. Examples include a structure in which a junction type, a layer (i layer) in which a p-type semiconductor compound and an n-type semiconductor compound are mixed, and a p-type semiconductor compound layer and / or an n-type semiconductor compound layer are stacked. Among these, a bulk heterojunction type having a layer (i layer) in which a p-type semiconductor compound and an n-type semiconductor compound are mixed is preferable.
有機活性層8の膜厚は特に限定されないが、通常10nm以上であり、好ましくは50nm以上であり、さらに好ましくは100nm以上であり、一方、通常1000nm以下、好ましくは500nm以下、より好ましくは400nm以下であり、特に好ましくは200nm以下である。有機活性層8の膜厚が10nm以上であれば、膜の均一性が保たれ、短絡を起こしにくくなるため、好ましい。また、有機活性層8の厚さが1000nm以下であれば、内部抵抗が小さくなる点、及び電極間が離れすぎず電荷の拡散が良好となる点で、好ましい。
The film thickness of the organic active layer 8 is not particularly limited, but is usually 10 nm or more, preferably 50 nm or more, more preferably 100 nm or more, and usually 1000 nm or less, preferably 500 nm or less, more preferably 400 nm or less. And particularly preferably 200 nm or less. If the film thickness of the organic active layer 8 is 10 nm or more, it is preferable because the uniformity of the film is maintained and a short circuit is hardly caused. Moreover, if the thickness of the organic active layer 8 is 1000 nm or less, it is preferable at the point from which internal resistance becomes small, and the spreading | diffusion of an electric charge becomes good without being separated too much between electrodes.
有機活性層8の色調に特段の制限はないが、本発明は、有機光電変換素子の外観色として望ましくない黄色~赤色の際に特に有効となる。具体的には、Z 8781-4:2013で定義される色相角が-60°から110°の範囲である有機活性層を用いる際に本発明は特に有効である。この理由は、上述の通り、本発明においては、有機活性層がこのような色調を示していても透明基板2と金属層5間の光路長を調整することにより外観色を青系色に調整できるためである。
Although there is no particular limitation on the color tone of the organic active layer 8, the present invention is particularly effective when the appearance color of the organic photoelectric conversion element is undesirable from yellow to red. Specifically, the present invention is particularly effective when an organic active layer having a hue angle defined by Z 8781-4: 2013 in the range of −60 ° to 110 ° is used. This is because, as described above, in the present invention, even if the organic active layer exhibits such a color tone, the appearance color is adjusted to a blue color by adjusting the optical path length between the transparent substrate 2 and the metal layer 5. This is because it can.
p型有機半導体化合物は、特段の制限はないが、p型の低分子有機半導体化合物又はp型の有機半導体ポリマーが挙げられる。なかでも、有機活性層8をバルクヘテロ接合型とする場合は、成膜性に優れるp型の有機半導体ポリマーを用いることが好ましい。
The p-type organic semiconductor compound is not particularly limited, and examples thereof include a p-type low-molecular organic semiconductor compound or a p-type organic semiconductor polymer. Especially, when making the organic active layer 8 into a bulk heterojunction type, it is preferable to use the p-type organic-semiconductor polymer which is excellent in film forming property.
具体的に、p型半導体ポリマーとしては、二種以上のモノマー単位を共重合させた半導体ポリマーであることが好ましく、具体的には、アクセプター性構成単位と、ドナー性構成単位を含むπ電子共役重であることが好ましい。
Specifically, the p-type semiconductor polymer is preferably a semiconductor polymer obtained by copolymerizing two or more monomer units, and specifically, a π-electron conjugate including an acceptor constituent unit and a donor constituent unit. Heavy.
より具体的な、p型半導体ポリマーの例としては、Nature Materials,2006,5,328に記載のポリチオフェン-チエノチオフェン共重合体、国際公開第2008/000664号パンフレットに記載のポリチオフェン-ジケトピロロピロール共重合体、Adv.Mater.,2007,4160に記載のポリチオフェン-チアゾロチアゾール共重合体、Nature Materials,2007,6,497に記載のPCPDTBT等のようなポリチオフェン共重合体、国際公開第2011/028827号パンフレットに記載のイミドチオフェンを含む共重合体、国際公開第2011/011545号パンフレットに記載のチエノチオフェンとベンゾジチオフェンとの共重合体等が挙げられる。また、国際公開第2013/180243号パンフレット、国際公開第2013/065855号パンフレット等に記載の共役高分子化合物も挙げられる。また、これらのポリマーの誘導体や、ここに挙げたモノマーの組み合わせで合成し得るポリマーも同様に用いることができる。これらポリマーやモノマーの置換基は、溶解性、結晶性、成膜性、HOMOエネルギー準位、LUMOエネルギー準位等を制御するために適宜選択しうる。
More specific examples of p-type semiconductor polymers include polythiophene-thienothiophene copolymers described in Nature Materials, 2006, 5, 328, and polythiophene-diketopyrrolopyrrole described in WO 2008/000664. Copolymer, Adv. Mater. , 2007, 4160, polythiophene copolymer such as PCPDTBT described in Nature Materials, 2007, 6,497, and imidothiophene described in WO 2011/028827 pamphlet. And a copolymer of thienothiophene and benzodithiophene described in International Publication No. 2011/011545 pamphlet. Moreover, the conjugated polymer compound as described in international publication 2013/180243 pamphlet, international publication 2013/065855 pamphlet, etc. is also mentioned. Moreover, the derivative | guide_body of these polymers, and the polymer which can be synthesize | combined with the combination of the monomer quoted here can be used similarly. The substituents of these polymers and monomers can be appropriately selected in order to control solubility, crystallinity, film formability, HOMO energy level, LUMO energy level, and the like.
n型半導体化合物としては、特段の制限はないが、具体的には、フラーレン;フラーレン化合物;8-ヒドロキシキノリンアルミニウムに代表されるキノリノール誘導体金属錯体;ナフタレンテトラカルボン酸ジイミド又はペリレンテトラカルボン酸ジイミド等の縮合環テトラカルボン酸ジイミド類;ペリレンジイミド誘導体、ターピリジン金属錯体、トロポロン金属錯体、フラボノール金属錯体、ペリノン誘導体、ベンズイミダゾール誘導体、ベンズオキサゾール誘導体、チアゾール誘導体、ベンズチアゾール誘導体、ベンゾチアジアゾール誘導体、オキサジアゾール誘導体、チアジアゾール誘導体、トリアゾール誘導体、アルダジン誘導体、ビススチリル誘導体、ピラジン誘導体、フェナントロリン誘導体、キノキサリン誘導体、ベンゾキノリン誘導体、ビピリジン誘導体、ボラン誘導体;アントラセン、ピレン、ナフタセン又はペンタセン等の縮合多環芳香族炭化水素の全フッ化物;単層カーボンナノチューブ、n型ポリマー(n型高分子半導体材料)等が挙げられる。
The n-type semiconductor compound is not particularly limited. Specifically, fullerene; fullerene compound; quinolinol derivative metal complex represented by 8-hydroxyquinoline aluminum; naphthalenetetracarboxylic acid diimide or perylenetetracarboxylic acid diimide Condensed ring tetracarboxylic acid diimides: perylene diimide derivatives, terpyridine metal complexes, tropolone metal complexes, flavonol metal complexes, perinone derivatives, benzimidazole derivatives, benzoxazole derivatives, thiazole derivatives, benzthiazole derivatives, benzothiadiazole derivatives, oxadiazoles Derivatives, thiadiazole derivatives, triazole derivatives, aldazine derivatives, bisstyryl derivatives, pyrazine derivatives, phenanthroline derivatives, quinoxaline derivatives, ben Quinoline derivatives, bipyridine derivatives, borane derivatives; total fluorides of condensed polycyclic aromatic hydrocarbons such as anthracene, pyrene, naphthacene or pentacene; single-walled carbon nanotubes, n-type polymers (n-type polymer semiconductor materials), etc. .
これらの中でも、n型半導体化合物は、フラーレン化合物であることが好ましい。フラーレン化合物としては、特段の制限はないが、例えば、国際公開第2011/016430号又は日本国特開2012-191194号公報等の公知文献に記載のものを使用することができる。フラーレン化合物のなかでも、PC61BM又はPC71BMが好ましい。なお、上記のうち一種の化合物を用いてもよいし、複数種の化合物の混合物を用いてもよい。
Among these, the n-type semiconductor compound is preferably a fullerene compound. The fullerene compound is not particularly limited, and for example, those described in publicly known documents such as International Publication No. 2011-016430 or Japanese Unexamined Patent Publication No. 2012-191194 can be used. Among the fullerene compounds, PC61BM or PC71BM is preferable. In addition, a kind of compound may be used among the above, and a mixture of a plurality of kinds of compounds may be used.
有機活性層8の作成方法としては、特段に制限はなく、使用する材料に合わせて任意の方法により形成することができる。例えば、蒸着法、スパッタ法等の真空成膜法、又は塗布法が挙げられる。なかでも、生産性の向上のために、塗布法を用いることが好ましい。塗布法としては、任意の方法を用いることができるが、例えば、スピンコート法、リバースロールコート法、グラビアコート法、キスコート法、ロールブラッシュ法、スプレーコート法、エアナイフコート法、ワイヤーバーバーコート法、パイプドクター法、含浸・コート法、カーテンコート法等が挙げられる。
The method for producing the organic active layer 8 is not particularly limited, and can be formed by any method according to the material to be used. For example, a vacuum film forming method such as a vapor deposition method or a sputtering method, or a coating method can be given. Among these, it is preferable to use a coating method in order to improve productivity. As the coating method, any method can be used, for example, spin coating method, reverse roll coating method, gravure coating method, kiss coating method, roll brush method, spray coating method, air knife coating method, wire barber coating method, Examples include the pipe doctor method, the impregnation / coating method, and the curtain coating method.
例えば、有機活性層8をp型半導体化合物層及びn型半導体化合物層の積層型とする場合は、p型半導体化合物を含む塗布液、及びn型半導体化合物を含む塗布液をそれぞれ塗布することにより作製することができる。また、有機活性層8をp型半導体化合物とn型半導体化合物とが混合した層を有するベルクヘテロ接合型とする場合は、予め、p型半導体化合物及びn型半導体化合物を含む塗布液を作製しておき、当該塗布液を塗布することにより作製することができる。
なお、有機活性層は、ロール・ツー・ロールにより製造されることが好ましく、その場合には、塗布法により形成されることが好ましい。 For example, when the organic active layer 8 is a stacked type of a p-type semiconductor compound layer and an n-type semiconductor compound layer, by applying a coating liquid containing a p-type semiconductor compound and a coating liquid containing an n-type semiconductor compound, respectively. Can be produced. Further, when the organic active layer 8 is a Berg heterojunction type having a layer in which a p-type semiconductor compound and an n-type semiconductor compound are mixed, a coating liquid containing a p-type semiconductor compound and an n-type semiconductor compound is prepared in advance. It can be prepared by applying the coating solution.
The organic active layer is preferably produced by roll-to-roll, and in that case, it is preferably formed by a coating method.
なお、有機活性層は、ロール・ツー・ロールにより製造されることが好ましく、その場合には、塗布法により形成されることが好ましい。 For example, when the organic active layer 8 is a stacked type of a p-type semiconductor compound layer and an n-type semiconductor compound layer, by applying a coating liquid containing a p-type semiconductor compound and a coating liquid containing an n-type semiconductor compound, respectively. Can be produced. Further, when the organic active layer 8 is a Berg heterojunction type having a layer in which a p-type semiconductor compound and an n-type semiconductor compound are mixed, a coating liquid containing a p-type semiconductor compound and an n-type semiconductor compound is prepared in advance. It can be prepared by applying the coating solution.
The organic active layer is preferably produced by roll-to-roll, and in that case, it is preferably formed by a coating method.
有機光電変換素子は、下部透明電極7、有機活性層8、上部電極9以外の層を有していてもよく、例えば、下部透明電極7と有機活性層8及び/又は有機活性層8と上部電極9との間にバッファ層を有していてもよい。なお、バッファ層とは、有機活性層8からアノード及び/又はカソードへの電荷の取り出し効率を向上させる機能を有する層である。バッファ層は、正孔の取り出し効率を向上させる正孔取り出し層及び電子の取り出し効率を向上させる電子取り出し層に分類することができる。すなわち、下部透明電極7をカソードとし、上部電極9をアノードとする場合、下部透明電極7と有機活性層8との間に設けるバッファ層を電子取り出し層とし、有機活性層8と上部電極9との間に設けるバッファ層を正孔取り出し層とすることが好ましい。一方、下部透明電極7をアノードとし、上部電極9をカソードとする場合、下部透明電極7と有機活性層8との間に設けるバッファ層を正孔取り出し層とし、有機活性層8と上部電極9との間に設けるバッファ層を電子取り出し層とすることが好ましい。なお、有機光電変換素子は、電子取り出し層及び正孔取り出し層のうち、1層のみ有していてもよい。
The organic photoelectric conversion element may have a layer other than the lower transparent electrode 7, the organic active layer 8, and the upper electrode 9, for example, the lower transparent electrode 7 and the organic active layer 8 and / or the organic active layer 8 and the upper portion. A buffer layer may be provided between the electrode 9 and the electrode 9. The buffer layer is a layer having a function of improving charge extraction efficiency from the organic active layer 8 to the anode and / or the cathode. The buffer layer can be classified into a hole extraction layer that improves hole extraction efficiency and an electron extraction layer that improves electron extraction efficiency. That is, when the lower transparent electrode 7 is a cathode and the upper electrode 9 is an anode, the buffer layer provided between the lower transparent electrode 7 and the organic active layer 8 is an electron extraction layer, and the organic active layer 8 and the upper electrode 9 It is preferable that the buffer layer provided between the layers is a hole extraction layer. On the other hand, when the lower transparent electrode 7 is an anode and the upper electrode 9 is a cathode, the buffer layer provided between the lower transparent electrode 7 and the organic active layer 8 is a hole extraction layer, and the organic active layer 8 and the upper electrode 9 are used. The buffer layer provided between the two is preferably an electron extraction layer. In addition, the organic photoelectric conversion element may have only one layer among an electron taking-out layer and a hole taking-out layer.
バッファ層(正孔取り出し層及び電子取り出し層)の膜厚は、特段の制限はなく、使用する材料等に合わせて任意で設計すればよいが、電荷の取り出し効率を向上させるために、0.1nm以上であることが好ましく、1nm以上であることがさらに好ましく、10nm以上であることが特に好ましく、一方、400nm以下であることが好ましく、200nm以下であることがさらに好ましい。
The film thickness of the buffer layer (hole extraction layer and electron extraction layer) is not particularly limited and may be arbitrarily designed according to the material to be used. It is preferably 1 nm or more, more preferably 1 nm or more, particularly preferably 10 nm or more, on the other hand, preferably 400 nm or less, more preferably 200 nm or less.
正孔取り出し層の材料として、特段の制限はないが、具体的には、ポリチオフェン、ポリアニリン、ポリピロール、ポリアセチレン等にスルホン酸/及び又はヨウ素等がドーピングされた導電性ポリマー、酸化モリブデン、酸化バナジウム、酸化銅等が挙げられる。なかでも、ポリ(エチレンジオキシチオフェン):ポリ(スチレンスルホン酸)(PEDOT:PSS)が好ましい。
The material for the hole extraction layer is not particularly limited, and specifically, a conductive polymer in which polythiophene, polyaniline, polypyrrole, polyacetylene or the like is doped with sulfonic acid / and / or iodine, molybdenum oxide, vanadium oxide, Examples thereof include copper oxide. Of these, poly (ethylenedioxythiophene): poly (styrenesulfonic acid) (PEDOT: PSS) is preferable.
電子取り出し層の材料として、特段の制限はないが、フッ化リチウム、2,9-ジメチル-4,7-ジフェニル-1,10-フェナントロリン、ホスフィンオキサイド化合物、ホスフィンスルフィド化合物、酸化亜鉛、又は酸化チタンが挙げられる。なかでも、電子取り出し層の材料として酸化亜鉛又は酸化チタンが好ましい。
The material for the electron extraction layer is not particularly limited, but lithium fluoride, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, phosphine oxide compound, phosphine sulfide compound, zinc oxide, or titanium oxide Is mentioned. Of these, zinc oxide or titanium oxide is preferable as the material for the electron extraction layer.
電子取り出し層及び正孔取り出し層の形成方法は特段の制限はなく、使用する材料に合わせて任意の方法により形成することができる。例えば、真空蒸着法、塗布法等が挙げられる。
The formation method of the electron extraction layer and the hole extraction layer is not particularly limited, and can be formed by any method according to the material to be used. For example, a vacuum deposition method, a coating method, etc. are mentioned.
<その他の層>
有機薄膜半導体素子1は、上記説明した層以外の層を有してもよい。例えば、透明基板2と下部透明電極7との間にバリア層を有してもよい。該バリア層を有することにより、第1透明導電層4の成膜時に、透明基板2からの脱ガスが抑えられ、第1透明導電層4の成膜性が改善し、かつ透明基板2の耐熱性、耐プラズマ性が生じるため好ましい。 <Other layers>
The organic thinfilm semiconductor element 1 may have layers other than the layers described above. For example, a barrier layer may be provided between the transparent substrate 2 and the lower transparent electrode 7. By having the barrier layer, degassing from the transparent substrate 2 is suppressed when the first transparent conductive layer 4 is formed, the film formability of the first transparent conductive layer 4 is improved, and the heat resistance of the transparent substrate 2 is improved. And plasma resistance are preferable.
有機薄膜半導体素子1は、上記説明した層以外の層を有してもよい。例えば、透明基板2と下部透明電極7との間にバリア層を有してもよい。該バリア層を有することにより、第1透明導電層4の成膜時に、透明基板2からの脱ガスが抑えられ、第1透明導電層4の成膜性が改善し、かつ透明基板2の耐熱性、耐プラズマ性が生じるため好ましい。 <Other layers>
The organic thin
バリア層の材料としては、緻密な膜を形成できるものであればよく、特段の制限はないが、具体的には、酸化珪素、窒化珪素、炭化珪素、酸化アルミニウム、窒化アルミニウム、酸化インジウム、酸化錫、酸化亜鉛等の透明無機化合物、あるいは、その混合化合物からなるものが挙げられる。そのなかでも好ましくは、酸化珪素や窒化珪素およびその混合物、酸化アルミニウムや窒化アルミニウムおよびその混合物である。
The material of the barrier layer is not particularly limited as long as it can form a dense film, and specifically, silicon oxide, silicon nitride, silicon carbide, aluminum oxide, aluminum nitride, indium oxide, oxide Examples thereof include transparent inorganic compounds such as tin and zinc oxide, or mixed compounds thereof. Among these, silicon oxide, silicon nitride and a mixture thereof, and aluminum oxide, aluminum nitride and a mixture thereof are preferable.
バリア層の厚みに関しては、特に限定するものではないが、透明性を損ねない範囲で、かつ、ガスバリア性を保ち、透明基板2との密着性を確保できる厚さであればよいが、均一な膜とするために、好ましくは10nm以上であり、さらに好ましくは20nm以上であり、一方、バリア層に亀裂が入りやすくするのを防ぐために、好ましくは500nm以下であり、さらに好ましくは200nm以下であり、特に好ましくは100nm以下である。一方で、透明基板2と下部透明電極7との間にバリア層を設ける場合、バリア層も透明基板2と金属層5間の光干渉に影響を与えることになる。そのため、上記式(2)を考慮して、透明基板2と下部透明電極7との間の光路長が、mが0以上の整数のいずれかにおいて下記式(4)を満たすようにバリア層の膜厚を調整することが好ましい。
480≧4×(n1×d1+n2×d2+n4×d4)÷(2×m+1)≧380……(4)
上記式(4)中、n1、d1、n2及びd2はそれぞれ式(3)中のn1、d1、n2及びd2と同義であり、n4はバリア層の屈折率を表し、d4はバリア層の膜厚を表す。 The thickness of the barrier layer is not particularly limited as long as it is a thickness that does not impair the transparency, and can maintain a gas barrier property and ensure adhesion with thetransparent substrate 2, but is uniform. In order to form a film, it is preferably 10 nm or more, more preferably 20 nm or more. On the other hand, in order to prevent the barrier layer from being easily cracked, it is preferably 500 nm or less, more preferably 200 nm or less. Particularly preferably, it is 100 nm or less. On the other hand, when a barrier layer is provided between the transparent substrate 2 and the lower transparent electrode 7, the barrier layer also affects optical interference between the transparent substrate 2 and the metal layer 5. Therefore, in consideration of the above equation (2), the optical path length between the transparent substrate 2 and the lower transparent electrode 7 is such that the barrier layer satisfies the following equation (4) when m is an integer of 0 or more. It is preferable to adjust the film thickness.
480 ≧ 4 × (n 1 × d 1 + n 2 × d 2 + n 4 × d 4 ) ÷ (2 × m + 1) ≧ 380 (4)
In theformula (4), n 1, d 1, n 2 and d 2 are n 1, respectively formula (3) in, d 1, and n 2 and d 2 synonymous, n 4 is the refractive index of the barrier layer the stands, d 4 represents a thickness of the barrier layer.
480≧4×(n1×d1+n2×d2+n4×d4)÷(2×m+1)≧380……(4)
上記式(4)中、n1、d1、n2及びd2はそれぞれ式(3)中のn1、d1、n2及びd2と同義であり、n4はバリア層の屈折率を表し、d4はバリア層の膜厚を表す。 The thickness of the barrier layer is not particularly limited as long as it is a thickness that does not impair the transparency, and can maintain a gas barrier property and ensure adhesion with the
480 ≧ 4 × (n 1 × d 1 + n 2 × d 2 + n 4 × d 4 ) ÷ (2 × m + 1) ≧ 380 (4)
In the
なお、バリア層を設ける場合、有機光電変換素子の構成は特段の制限はないが、透明基板2/アンダーコート層3/バリア層/下部透明電極7/有機半導体層8/上部電極9、又は、透明基板2/バリア層/アンダーコート層3/下部透明電極7/有機半導体層8/上部電極9とすることが好ましい。
In the case of providing a barrier layer, the configuration of the organic photoelectric conversion element is not particularly limited, but transparent substrate 2 / undercoat layer 3 / barrier layer / lower transparent electrode 7 / organic semiconductor layer 8 / upper electrode 9, or It is preferable to use transparent substrate 2 / barrier layer / undercoat layer 3 / lower transparent electrode 7 / organic semiconductor layer 8 / upper electrode 9.
<有機薄膜太陽電池モジュール>
上述の実施形態に係る光電変換素子は、太陽電池モジュールとして使用することが好ましい。なお、太陽電池モジュールは、有機光電変換素子が水や酸素等により劣化するのを防止するために、ガスバリア層等により封止されていることが好ましい。 <Organic thin film solar cell module>
The photoelectric conversion element according to the above-described embodiment is preferably used as a solar cell module. The solar cell module is preferably sealed with a gas barrier layer or the like in order to prevent the organic photoelectric conversion element from being deteriorated by water, oxygen, or the like.
上述の実施形態に係る光電変換素子は、太陽電池モジュールとして使用することが好ましい。なお、太陽電池モジュールは、有機光電変換素子が水や酸素等により劣化するのを防止するために、ガスバリア層等により封止されていることが好ましい。 <Organic thin film solar cell module>
The photoelectric conversion element according to the above-described embodiment is preferably used as a solar cell module. The solar cell module is preferably sealed with a gas barrier layer or the like in order to prevent the organic photoelectric conversion element from being deteriorated by water, oxygen, or the like.
図3は、本発明の一実施形態における有機薄膜太陽電池モジュール10の構成を模式的に示す断面図である。有機薄膜太陽電池モジュール10は、例えば、有機光電変換素子1と、有機光電変換素子1の両面にそれぞれ設けられた封止層11と、封止層11の一面側にそれぞれ設けられたガスバリア層12とを有している。そして、有機薄膜太陽電池モジュール10は、例えば、図中下方のガスバリア層12が形成された側から光が照射されることにより、有機光電変換素子1が発電する。
FIG. 3 is a cross-sectional view schematically showing the configuration of the organic thin-film solar cell module 10 in one embodiment of the present invention. The organic thin film solar cell module 10 includes, for example, an organic photoelectric conversion element 1, a sealing layer 11 provided on each surface of the organic photoelectric conversion element 1, and a gas barrier layer 12 provided on one surface side of the sealing layer 11, respectively. And have. And the organic thin film solar cell module 10 produces | generates the organic photoelectric conversion element 1 by light being irradiated from the side in which the gas barrier layer 12 of the downward direction in the figure was formed, for example.
なお、太陽電池モジュール10を構成するガスバリア層12及び封止層11の材料及び有機光電変換素子にこれらの層を積層する方法は特段の制限はなく、周知の技術を用いることができる。例えば、国際公開第2011/016430号又は日本国特開2012-191194号公報等の公知文献に記載のものを使用することができる。
In addition, the method of laminating | stacking these layers on the material of the gas barrier layer 12 and the sealing layer 11 which comprise the solar cell module 10, and an organic photoelectric conversion element does not have a restriction | limiting in particular, A well-known technique can be used. For example, those described in known documents such as International Publication No. 2011/016430 or Japanese Patent Application Laid-Open No. 2012-191194 can be used.
また、太陽電池モジュールの構成は、図3の構造に限定されるものではなく、光電変換素子により発電可能である限りにおいてどのような構造であってもよい。特に、図3においては、有機光電変換素子1の両面に、封止層11及びバリア層12の積層体を設けた構造を示しているが、有機光電変換素子1の片面側のみに封止層11及びバリア層12の積層体を設けた構造であってもよい。また、有機光電変換素子1で発電した電気を外部に取り出すために、有機光電変換素子上に集電線を設けることが好ましい。
Further, the configuration of the solar cell module is not limited to the structure shown in FIG. 3, and may be any structure as long as it can generate power with the photoelectric conversion element. In particular, FIG. 3 shows a structure in which a laminated body of a sealing layer 11 and a barrier layer 12 is provided on both surfaces of the organic photoelectric conversion element 1, but the sealing layer is formed only on one side of the organic photoelectric conversion element 1. 11 and a barrier layer 12 may be provided. Moreover, in order to take out the electric power generated with the organic photoelectric conversion element 1, it is preferable to provide a collector wire on the organic photoelectric conversion element.
<用途>
有機薄膜太陽電池モジュール10の用途は、制限はなく任意である。有機薄膜太陽電池モジュール10を適用する分野の例を挙げると、建材用太陽電池、自動車用太陽電池、インテリア用太陽電池、鉄道用太陽電池、船舶用太陽電池、飛行機用太陽電池、宇宙機用太陽電池、家電用太陽電池、携帯電話用太陽電池及び玩具用太陽電池などに用いて好適である。 <Application>
The use of the organic thin filmsolar cell module 10 is not limited and is arbitrary. Examples of fields to which the organic thin-film solar cell module 10 is applied include building material solar cells, automotive solar cells, interior solar cells, railway solar cells, marine solar cells, airplane solar cells, and spacecraft solar cells. It is suitable for use in batteries, solar cells for home appliances, solar cells for mobile phones, solar cells for toys, and the like.
有機薄膜太陽電池モジュール10の用途は、制限はなく任意である。有機薄膜太陽電池モジュール10を適用する分野の例を挙げると、建材用太陽電池、自動車用太陽電池、インテリア用太陽電池、鉄道用太陽電池、船舶用太陽電池、飛行機用太陽電池、宇宙機用太陽電池、家電用太陽電池、携帯電話用太陽電池及び玩具用太陽電池などに用いて好適である。 <Application>
The use of the organic thin film
具体例としては、建材用太陽電池としてハウス屋根材、屋上、トップライト、壁、窓等に適用したり、インテリア用太陽電池として内装等に適用したり、自動車用太陽電池として自動車のボンネット、ルーフ、トランクリッド、ドア、フロントフェンダー、リアフェンダー、ピラー、バンパーおよびバックミラーの表面等に適用したり、その他としてひさし、ルーバー、手摺、野菜工場や駐車場の外壁、高速道路の遮音壁及び浄水場の外壁等に適用することができる。特に、窓に適用したウインドフイルムや、ガラス壁に適用したガラスカーテンウォールとして使用されるのが好ましい。
As specific examples, it can be applied to house roofing materials, rooftops, top lights, walls, windows, etc. as solar cells for building materials, it can be applied to interiors etc. as solar cells for interiors, and hoods and roofs of automobiles as solar cells for automobiles. Applicable to the surface of trunk lids, doors, front fenders, rear fenders, pillars, bumpers and rearview mirrors, etc. It can be applied to outer walls and the like. In particular, it is preferably used as a wind film applied to a window or a glass curtain wall applied to a glass wall.
本発明を実施例によって更に具体的に説明するが、本発明はその要旨を超えない限り、以下の実施例の記載に限定されるものではない。まず、本実施例で行った測定試験について説明する。
The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist. First, the measurement test performed in this example will be described.
<アンダーコート層の膜厚の測定>
アンダーコート層の膜厚は、加熱硬化前にスパチュラで傷をつけて段差を設けてから、140℃で15分間加熱硬化した後、段差部に銀を約5nmスパッタリング成膜し、ついで、白色干渉方式表面形状測定装置VertScan(菱化システム製)を用いて段差部の段差を測定して得た。 <Measurement of film thickness of undercoat layer>
The thickness of the undercoat layer was scratched with a spatula before heat-curing, and then stepped and then heat-cured at 140 ° C. for 15 minutes. It was obtained by measuring the step of the step portion using a system surface shape measuring device VertScan (manufactured by Ryoka System).
アンダーコート層の膜厚は、加熱硬化前にスパチュラで傷をつけて段差を設けてから、140℃で15分間加熱硬化した後、段差部に銀を約5nmスパッタリング成膜し、ついで、白色干渉方式表面形状測定装置VertScan(菱化システム製)を用いて段差部の段差を測定して得た。 <Measurement of film thickness of undercoat layer>
The thickness of the undercoat layer was scratched with a spatula before heat-curing, and then stepped and then heat-cured at 140 ° C. for 15 minutes. It was obtained by measuring the step of the step portion using a system surface shape measuring device VertScan (manufactured by Ryoka System).
<屈折率の測定>
アンダーコート層及び金属層(酸化インジウム層)の屈折率は、分光エリプソメーターUVISEL(ホリバ製作所製)を用いて測定して得た。アンダーコート層の波長485nmでの屈折率は、1.61であった。また、第1導電層(ITO層)の波長485nmでの屈折率は、1.95であった。 <Measurement of refractive index>
The refractive indexes of the undercoat layer and the metal layer (indium oxide layer) were obtained by measurement using a spectroscopic ellipsometer UVISEL (manufactured by Horiba). The refractive index of the undercoat layer at a wavelength of 485 nm was 1.61. The refractive index of the first conductive layer (ITO layer) at a wavelength of 485 nm was 1.95.
アンダーコート層及び金属層(酸化インジウム層)の屈折率は、分光エリプソメーターUVISEL(ホリバ製作所製)を用いて測定して得た。アンダーコート層の波長485nmでの屈折率は、1.61であった。また、第1導電層(ITO層)の波長485nmでの屈折率は、1.95であった。 <Measurement of refractive index>
The refractive indexes of the undercoat layer and the metal layer (indium oxide layer) were obtained by measurement using a spectroscopic ellipsometer UVISEL (manufactured by Horiba). The refractive index of the undercoat layer at a wavelength of 485 nm was 1.61. The refractive index of the first conductive layer (ITO layer) at a wavelength of 485 nm was 1.95.
<外観色の観測>
有機薄膜太陽電池モジュールの外観色は、照度700ルクスの昼光色蛍光灯下に10cm角の大きさの有機薄膜太陽電池モジュールを置き、有機薄膜太陽電池モジュールに正対する位置で外観色を判定した。 <Observation of appearance color>
As for the appearance color of the organic thin film solar cell module, an organic thin film solar cell module having a size of 10 cm square was placed under a daylight fluorescent lamp with an illuminance of 700 lux, and the appearance color was determined at a position facing the organic thin film solar cell module.
有機薄膜太陽電池モジュールの外観色は、照度700ルクスの昼光色蛍光灯下に10cm角の大きさの有機薄膜太陽電池モジュールを置き、有機薄膜太陽電池モジュールに正対する位置で外観色を判定した。 <Observation of appearance color>
As for the appearance color of the organic thin film solar cell module, an organic thin film solar cell module having a size of 10 cm square was placed under a daylight fluorescent lamp with an illuminance of 700 lux, and the appearance color was determined at a position facing the organic thin film solar cell module.
<明度指数L*、a*、b*の測定>
外観色および明度指数L*、a*、b*は、JIS Z 8722条件Cに従って、コニカミノルタ社製分光測色計CM-700dを用いて行った。 <Measurement of lightness index L * , a * , b * >
Appearance color and lightness index L * , a * , b * were measured using a spectrophotometer CM-700d manufactured by Konica Minolta in accordance with JIS Z 8722 Condition C.
外観色および明度指数L*、a*、b*は、JIS Z 8722条件Cに従って、コニカミノルタ社製分光測色計CM-700dを用いて行った。 <Measurement of lightness index L * , a * , b * >
Appearance color and lightness index L * , a * , b * were measured using a spectrophotometer CM-700d manufactured by Konica Minolta in accordance with JIS Z 8722 Condition C.
<干渉波長λの算出>
金属層である銀層と、透明基板であるポリエチレンナフタレートフィルム間の干渉波長λを、上記式(a)を変形した以下の式(c)を用いて算出した。
λ=4×(n×d)÷(2×m+1)……(c) <Calculation of interference wavelength λ>
The interference wavelength λ between the silver layer as the metal layer and the polyethylene naphthalate film as the transparent substrate was calculated using the following formula (c) obtained by modifying the above formula (a).
λ = 4 × (n × d) ÷ (2 × m + 1) (c)
金属層である銀層と、透明基板であるポリエチレンナフタレートフィルム間の干渉波長λを、上記式(a)を変形した以下の式(c)を用いて算出した。
λ=4×(n×d)÷(2×m+1)……(c) <Calculation of interference wavelength λ>
The interference wavelength λ between the silver layer as the metal layer and the polyethylene naphthalate film as the transparent substrate was calculated using the following formula (c) obtained by modifying the above formula (a).
λ = 4 × (n × d) ÷ (2 × m + 1) (c)
<実施例1>
ポリエチレンナフタレートフィルム(帝人デュポンフィルム社製Q65、厚さ125μm、波長485nmにおける屈折率1.9)の片面に、厚さ140nmのアンダーコート層(モメンティブ社製ハードコート剤SHC900)をバー塗布法により形成し、その後、空気中において140℃で15分間加熱し、硬化させた。 <Example 1>
On one side of a polyethylene naphthalate film (Q65 manufactured by Teijin DuPont Films Co., Ltd., thickness 125 μm, refractive index 1.9 at a wavelength of 485 nm), an undercoat layer 140 nm thick (hard coat agent SHC900 manufactured by Momentive) is applied by a bar coating method. And then cured by heating in air at 140 ° C. for 15 minutes.
ポリエチレンナフタレートフィルム(帝人デュポンフィルム社製Q65、厚さ125μm、波長485nmにおける屈折率1.9)の片面に、厚さ140nmのアンダーコート層(モメンティブ社製ハードコート剤SHC900)をバー塗布法により形成し、その後、空気中において140℃で15分間加熱し、硬化させた。 <Example 1>
On one side of a polyethylene naphthalate film (Q65 manufactured by Teijin DuPont Films Co., Ltd., thickness 125 μm, refractive index 1.9 at a wavelength of 485 nm), an undercoat layer 140 nm thick (hard coat agent SHC900 manufactured by Momentive) is applied by a bar coating method. And then cured by heating in air at 140 ° C. for 15 minutes.
次に、アンダーコート層の上に、スパッタリング法により、第1酸化インジウム層を50nm、銀層を8nm、第2酸化インジウム層30nmをこの順に積層することにより積層型の下部透明電極を形成した。
Next, on the undercoat layer, a laminated lower transparent electrode was formed by laminating a first indium oxide layer of 50 nm, a silver layer of 8 nm, and a second indium oxide layer of 30 nm in this order by sputtering.
次に、下部透明電極の上に、塗布法により、電子取り出し層として酸化亜鉛層を50nm、p型半導体ポリマーとして、イミドチオフェン単位と、ジチエノシロール単位と、を有して構成されるコポリマー:PCBM=2:2.5からなる有機活性層を320nm、正孔取り出し層としてPEDOT:PSS層を400nmをこの順にそれぞれ積層した。なお、有機活性層は、赤みのある灰色を呈した。
Next, on the lower transparent electrode, a copolymer composed of a zinc oxide layer as an electron extraction layer of 50 nm and an imidothiophene unit and a dithienosilole unit as a p-type semiconductor polymer by a coating method: PCBM = The organic active layer of 2: 2.5 was laminated in the order of 320 nm, and the PEDOT: PSS layer was laminated in the order of 400 nm as the hole extraction layer. The organic active layer was reddish gray.
次に、有機半導体層の上に、スパッタリング法により銀層を8nm、酸化インジウム層を40nmの順に積層することにより第2電極を形成して、有機光電変換素子を作製した。
Next, a second electrode was formed on the organic semiconductor layer by laminating a silver layer with a thickness of 8 nm and an indium oxide layer with a thickness of 40 nm by sputtering to produce an organic photoelectric conversion element.
次に、エポキシ接着剤層とバリアフィルム(三菱樹脂製ビューバリア(R))を用いて、バリアフィルム、接着剤層、有機光電変換素子、接着剤層、バリアフィルムとなるように積層させた。その後、この積層体を140℃1時間加熱することにより有機光電変換素子を封止して、有機薄膜太陽電池モジュールを作製した。
Next, an epoxy adhesive layer and a barrier film (Mitsubishi Resin View Barrier (R)) were used to form a barrier film, an adhesive layer, an organic photoelectric conversion element, an adhesive layer, and a barrier film. Then, the organic photoelectric conversion element was sealed by heating this laminated body at 140 ° C. for 1 hour to produce an organic thin film solar cell module.
<実施例2>
アンダーコート層の厚さを162nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製した。 <Example 2>
An organic thin-film solar cell module was produced in the same manner as in Example 1 except that the thickness of the undercoat layer was 162 nm.
アンダーコート層の厚さを162nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製した。 <Example 2>
An organic thin-film solar cell module was produced in the same manner as in Example 1 except that the thickness of the undercoat layer was 162 nm.
<比較例1>
アンダーコート層の厚さを178nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製した。 <Comparative Example 1>
An organic thin film solar cell module was produced in the same manner as in Example 1 except that the thickness of the undercoat layer was 178 nm.
アンダーコート層の厚さを178nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製した。 <Comparative Example 1>
An organic thin film solar cell module was produced in the same manner as in Example 1 except that the thickness of the undercoat layer was 178 nm.
<比較例2>
アンダーコート層の厚さを205nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製した。 <Comparative Example 2>
An organic thin-film solar cell module was produced in the same manner as in Example 1 except that the thickness of the undercoat layer was 205 nm.
アンダーコート層の厚さを205nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製した。 <Comparative Example 2>
An organic thin-film solar cell module was produced in the same manner as in Example 1 except that the thickness of the undercoat layer was 205 nm.
<比較例3>
アンダーコート層の厚さを221nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製した。 <Comparative Example 3>
An organic thin film solar cell module was produced in the same manner as in Example 1 except that the thickness of the undercoat layer was 221 nm.
アンダーコート層の厚さを221nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製した。 <Comparative Example 3>
An organic thin film solar cell module was produced in the same manner as in Example 1 except that the thickness of the undercoat layer was 221 nm.
実施例1~実施例2の有機薄膜太陽電池モジュール、並びに比較例1~比較例3の有機薄膜太陽電池モジュールにおけるm0、1、2、3のときの波長λ、明度指数L*、a*、b*及び外観色を測定した。表1は測定結果である。
Wavelength λ, lightness index L * , a * at m0, 1, 2, 3 in the organic thin film solar cell modules of Examples 1 to 2 and the organic thin film solar cell modules of Comparative Examples 1 to 3. b * and appearance color were measured. Table 1 shows the measurement results.
表1において、a*値が大きいほど赤みが強くなり、小さいほど緑みが強くなることを示している。また、b*値が大きいほど黄みが強くなり、小さいほど青みが強くなることを示している。したがって、有機薄膜太陽電池モジュールの外観色が黄色や赤色になるのを避けるには、なるべくa*値とb*値も小さくすればよい。
In Table 1, it shows that redness becomes strong, so that a * value is large, and greenness becomes strong, so that it is small. Moreover, it shows that yellow becomes stronger as the b * value is larger, and blue becomes stronger as the b * value is smaller. Therefore, in order to avoid the appearance color of the organic thin-film solar cell module from becoming yellow or red, the a * value and the b * value should be made as small as possible.
表1からわかるとおり、m=1の際に、式(1)を満たす実施例1および実施例2の有機薄膜太陽電池モジュールは、算出したλの値から予想される通り、外観色は鮮やかな青系色を呈し、明度指数a*値、b*値ともに小さかった。また、比較例3での有機薄膜太陽電池モジュールは、算出したλの値から予想される通り鮮やかな赤みの色を呈し、明度指数a*値は大きくa*値は小さくなった。
As can be seen from Table 1, when m = 1, the organic thin-film solar cell modules of Example 1 and Example 2 that satisfy the formula (1) have a bright appearance color as expected from the calculated value of λ. A blue color was exhibited, and both the lightness index a * value and b * value were small. Moreover, the organic thin-film solar cell module in Comparative Example 3 exhibited a bright red color as expected from the calculated value of λ, and the lightness index a * value was large and the a * value was small.
比較例1および比較例2の有機薄膜太陽電池モジュールでは、望ましくない黄色の色調を呈した。比較例1の明度指数は比較例2と比べb*値はほぼ同じ値ながらa*値は小さく、比較例1の方が比較例2よりも緑みが強いことを示している。また、比較例2は比較例1よりもa*値は大きく、比較例2の方が比較例1よりも黄みが強いことを示している。このことは、比較例1および比較例2で算出した干渉波長λから予想される色調推移の通りであり、これら実施例および比較例で観察される有機薄膜太陽電池モジュールの外観色は、用いた有機半導体層が赤みの灰色を呈していたにもかかわらず、下部透明電極を構成する金属層と透明基板間の光干渉によって決められていることを示している。
The organic thin film solar cell modules of Comparative Example 1 and Comparative Example 2 exhibited an undesirable yellow color tone. Lightness of Comparative Example 1 shows that the b * value than that of Comparative Example 2 is substantially the same value with a * value is small, a strong green body than the Comparative Example 2 towards the Comparative Example 1. Further, Comparative Example 2 has an a * value larger than that of Comparative Example 1, indicating that Comparative Example 2 is more yellowish than Comparative Example 1. This is the color transition expected from the interference wavelength λ calculated in Comparative Example 1 and Comparative Example 2, and the appearance color of the organic thin film solar cell module observed in these Examples and Comparative Examples was used. This indicates that the organic semiconductor layer is determined by light interference between the metal layer constituting the lower transparent electrode and the transparent substrate, even though the organic semiconductor layer has a reddish gray color.
<実施例3>
アンダーコート層の厚さを139nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製し、外観色の評価を行った。また、JIS C8934に準拠して、有機薄膜太陽電池モジュールの変換効率(PCE)を測定した。得られた結果を表2に示す。 <Example 3>
An organic thin-film solar cell module was prepared in the same manner as in Example 1 except that the thickness of the undercoat layer was 139 nm, and the appearance color was evaluated. Moreover, the conversion efficiency (PCE) of the organic thin-film solar cell module was measured based on JIS C8934. The obtained results are shown in Table 2.
アンダーコート層の厚さを139nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製し、外観色の評価を行った。また、JIS C8934に準拠して、有機薄膜太陽電池モジュールの変換効率(PCE)を測定した。得られた結果を表2に示す。 <Example 3>
An organic thin-film solar cell module was prepared in the same manner as in Example 1 except that the thickness of the undercoat layer was 139 nm, and the appearance color was evaluated. Moreover, the conversion efficiency (PCE) of the organic thin-film solar cell module was measured based on JIS C8934. The obtained results are shown in Table 2.
<比較例4>
アンダーコート層の厚さを240nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製し、外観色の評価を行った。また、実施例3と同様に、有機薄膜太陽電池モジュールの変換効率(PCE)を測定した。得られた結果を表2に示す。 <Comparative Example 4>
An organic thin-film solar cell module was produced in the same manner as in Example 1 except that the thickness of the undercoat layer was 240 nm, and the appearance color was evaluated. Moreover, the conversion efficiency (PCE) of the organic thin film solar cell module was measured similarly to Example 3. The obtained results are shown in Table 2.
アンダーコート層の厚さを240nmとした以外は、実施例1と同様に有機薄膜太陽電池モジュールを作製し、外観色の評価を行った。また、実施例3と同様に、有機薄膜太陽電池モジュールの変換効率(PCE)を測定した。得られた結果を表2に示す。 <Comparative Example 4>
An organic thin-film solar cell module was produced in the same manner as in Example 1 except that the thickness of the undercoat layer was 240 nm, and the appearance color was evaluated. Moreover, the conversion efficiency (PCE) of the organic thin film solar cell module was measured similarly to Example 3. The obtained results are shown in Table 2.
表1の結果と同様に、m=1の際に、上記式(1)を満たす実施例3に係る有機薄膜太陽電池モジュールは、有機活性層が赤みのある灰色であるにも関わらず、有機薄膜太陽電池モジュールは鮮やかな青色の外観色を示しており、上記(1)を満たさない比較例4に係る有機薄膜太陽電池モジュールは、鮮やかな赤紫の外観色を示した。一方、実施例3及び比較例4に係る有機薄膜太陽電池モジュールの変換効率は共に、4.0%となり、実施例3のように、青色の外観色を示すように有機薄膜太陽電池モジュールを調整しても変換効率が低下しなかった。従って、本発明により、変換効率を低下させることなく、望ましい青色の外観色を示す有機薄膜太陽電池モジュールを提供できることが分かる。
Similar to the results of Table 1, when m = 1, the organic thin-film solar cell module according to Example 3 that satisfies the above formula (1) is organic, even though the organic active layer is reddish gray. The thin film solar cell module showed a bright blue appearance color, and the organic thin film solar cell module according to Comparative Example 4 that did not satisfy the above (1) showed a bright red purple appearance color. On the other hand, the conversion efficiencies of the organic thin film solar cell modules according to Example 3 and Comparative Example 4 were both 4.0%, and the organic thin film solar cell module was adjusted so as to show a blue appearance color as in Example 3. However, the conversion efficiency did not decrease. Therefore, it can be seen that the present invention can provide an organic thin film solar cell module exhibiting a desirable blue appearance color without lowering the conversion efficiency.
<実施例4>
p型半導体ポリマーとして、ナフトビスチアジアゾール単位及びベンゾジチオフェン単位を含むコポリマーを用い、正孔取り出し層であるPEDOT:PSS層の膜厚を150nmに変更し、さらには、アンダーコート層の膜厚を142nmとした以外は、実施例1と同様の方法により有機薄膜太陽電池モジュールを作製し、外観色の評価を行った。なお、有機活性層は緑色を呈していた。また、JIS C8934に準拠して、有機薄膜太陽電池モジュールの変換効率(PCE)を測定した。得られた結果を表3に示す。 <Example 4>
As a p-type semiconductor polymer, a copolymer containing a naphthobisthiadiazole unit and a benzodithiophene unit is used, the thickness of the PEDOT: PSS layer that is the hole extraction layer is changed to 150 nm, and the thickness of the undercoat layer is further changed. An organic thin-film solar cell module was produced by the same method as in Example 1 except that the thickness was 142 nm, and the appearance color was evaluated. The organic active layer was green. Moreover, the conversion efficiency (PCE) of the organic thin-film solar cell module was measured based on JIS C8934. The obtained results are shown in Table 3.
p型半導体ポリマーとして、ナフトビスチアジアゾール単位及びベンゾジチオフェン単位を含むコポリマーを用い、正孔取り出し層であるPEDOT:PSS層の膜厚を150nmに変更し、さらには、アンダーコート層の膜厚を142nmとした以外は、実施例1と同様の方法により有機薄膜太陽電池モジュールを作製し、外観色の評価を行った。なお、有機活性層は緑色を呈していた。また、JIS C8934に準拠して、有機薄膜太陽電池モジュールの変換効率(PCE)を測定した。得られた結果を表3に示す。 <Example 4>
As a p-type semiconductor polymer, a copolymer containing a naphthobisthiadiazole unit and a benzodithiophene unit is used, the thickness of the PEDOT: PSS layer that is the hole extraction layer is changed to 150 nm, and the thickness of the undercoat layer is further changed. An organic thin-film solar cell module was produced by the same method as in Example 1 except that the thickness was 142 nm, and the appearance color was evaluated. The organic active layer was green. Moreover, the conversion efficiency (PCE) of the organic thin-film solar cell module was measured based on JIS C8934. The obtained results are shown in Table 3.
<比較例5>
アンダーコート層の膜厚を176nmとした以外は、実施例4と同様に有機薄膜太陽電池モジュールを作製し、外観色の評価、及び変換効率を測定した。得られた結果を表3に示す。 <Comparative Example 5>
An organic thin film solar cell module was produced in the same manner as in Example 4 except that the film thickness of the undercoat layer was 176 nm, and the appearance color was evaluated and the conversion efficiency was measured. The obtained results are shown in Table 3.
アンダーコート層の膜厚を176nmとした以外は、実施例4と同様に有機薄膜太陽電池モジュールを作製し、外観色の評価、及び変換効率を測定した。得られた結果を表3に示す。 <Comparative Example 5>
An organic thin film solar cell module was produced in the same manner as in Example 4 except that the film thickness of the undercoat layer was 176 nm, and the appearance color was evaluated and the conversion efficiency was measured. The obtained results are shown in Table 3.
<比較例6>
アンダーコート層を設けなかった以外は、実施例4と同様に有機薄膜太陽電池モジュールを作製し、外観色の評価、及び変換効率を測定した。得られた結果を表3に示す。 <Comparative Example 6>
An organic thin-film solar cell module was produced in the same manner as in Example 4 except that no undercoat layer was provided, and the appearance color was evaluated and the conversion efficiency was measured. The obtained results are shown in Table 3.
アンダーコート層を設けなかった以外は、実施例4と同様に有機薄膜太陽電池モジュールを作製し、外観色の評価、及び変換効率を測定した。得られた結果を表3に示す。 <Comparative Example 6>
An organic thin-film solar cell module was produced in the same manner as in Example 4 except that no undercoat layer was provided, and the appearance color was evaluated and the conversion efficiency was measured. The obtained results are shown in Table 3.
表3の結果から、m=1の際に、式(1)を満たす実施例4に係る有機薄膜太陽電池モジュールは、有機活性層が緑色を呈しているにも関わらず、有機薄膜太陽電池モジュールは緑青色の外観色を呈していることが確認できる。一方、式(1)を満たさない比較例5は、m=1の際に、緑色の干渉色が目立つことから、有機薄膜太陽電池モジュールの外観色は青系の色にならなかった。同様に、式(1)を満たさない比較例6に係る有機薄膜太陽電池モジュールも、m=0の際に、黄色の干渉色が目立ち、青系の色に調整することができなかった。従って、表1の結果と同様に、式(1)を満たすことにより、有機薄膜太陽電池モジュールの外観色を青系の色に調整できることが分かる。また、表2の結果と同様に、各有機薄膜太陽電池モジュールの変換効率はほとんど差がないことが分かる。従って、本発明によれば、変換効率の低下を防ぎつつ、有機薄膜太陽電池モジュールの色を青系の色に調整出来る。
From the results of Table 3, when m = 1, the organic thin film solar cell module according to Example 4 that satisfies the formula (1) is an organic thin film solar cell module even though the organic active layer is green. Can be confirmed to have a green-blue appearance color. On the other hand, in Comparative Example 5 that does not satisfy Formula (1), when m = 1, the green interference color is conspicuous, and thus the appearance color of the organic thin-film solar cell module did not become a blue color. Similarly, in the organic thin-film solar cell module according to Comparative Example 6 that does not satisfy the formula (1), when m = 0, the yellow interference color is conspicuous and cannot be adjusted to the blue color. Therefore, similarly to the results in Table 1, it can be seen that the appearance color of the organic thin-film solar cell module can be adjusted to a blue color by satisfying the formula (1). Moreover, it turns out that there is almost no difference in the conversion efficiency of each organic thin-film solar cell module similarly to the result of Table 2. Therefore, according to the present invention, it is possible to adjust the color of the organic thin film solar cell module to a blue color while preventing a decrease in conversion efficiency.
1……有機光電変換素子、2……透明基板、3……アンダーコート層、4……第1透明導電層、5……金属層、6……第2透明導電層、7……下部透明電極、8……有機活性層、9……上部電極、10……有機薄膜太陽電池モジュール、11……封止層、12……ガスバリア層
DESCRIPTION OF SYMBOLS 1 ... Organic photoelectric conversion element, 2 ... Transparent substrate, 3 ... Undercoat layer, 4 ... 1st transparent conductive layer, 5 ... Metal layer, 6 ... 2nd transparent conductive layer, 7 ... Bottom transparent Electrode, 8 ... Organic active layer, 9 ... Upper electrode, 10 ... Organic thin film solar cell module, 11 ... Sealing layer, 12 ... Gas barrier layer
Claims (7)
- 透明基板上と金属層を含む下部透明電極と、有機活性層と、上部電極と、が順次積層された有機光電変換素子であって、
前記透明基板と前記金属層間の距離d及び屈折率nで表される、前記透明基板と前記金属層間の光路長(n×d)が、mが0以上の整数のいずれかにおいて下記式(1)を満たすことを特徴とする有機光電変換素子。
480nm≧4×(n×d)÷(2×m+1)≧380nm・・・(1) An organic photoelectric conversion element in which a lower transparent electrode including a transparent substrate and a metal layer, an organic active layer, and an upper electrode are sequentially laminated,
The optical path length (n × d) between the transparent substrate and the metal layer represented by the distance d and the refractive index n between the transparent substrate and the metal layer is expressed by the following formula (1) when m is an integer of 0 or more: The organic photoelectric conversion element characterized by satisfy | filling.
480 nm ≧ 4 × (n × d) ÷ (2 × m + 1) ≧ 380 nm (1) - 前記透明基板と前記金属層との間にアンダーコート層を含む、請求項1に記載の有機光電変換素子。 The organic photoelectric conversion element according to claim 1, further comprising an undercoat layer between the transparent substrate and the metal layer.
- 前記下部透明電極は透明導電層を含み、前記透明導電層が、前記透明基板と前記金属層との間に配置されている、請求項1又は2に記載の有機光電変換素子。 The organic photoelectric conversion element according to claim 1 or 2, wherein the lower transparent electrode includes a transparent conductive layer, and the transparent conductive layer is disposed between the transparent substrate and the metal layer.
- 前記アンダーコート層の厚さは、10nm以上5000nm以下である、請求項2又は3に記載の有機光電変換素子。 The organic photoelectric conversion element according to claim 2 or 3, wherein the thickness of the undercoat layer is 10 nm or more and 5000 nm or less.
- 前記透明導電層の厚さは、5nm以上200nm以下である、請求項3又は4に記載の有機光電変換素子。 The organic photoelectric conversion element according to claim 3 or 4, wherein the transparent conductive layer has a thickness of 5 nm to 200 nm.
- 前記金属層の厚さは、1nm以上20nm以下である、請求項1~5のいずれか1項に記載の有機光電変換素子。 6. The organic photoelectric conversion element according to claim 1, wherein the metal layer has a thickness of 1 nm to 20 nm.
- 請求項1~6のいずれか1項に記載の有機光電変換素子を含む、有機薄膜太陽電池モジュール。 An organic thin film solar cell module comprising the organic photoelectric conversion device according to any one of claims 1 to 6.
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JP2019175917A (en) * | 2018-03-27 | 2019-10-10 | 三菱ケミカル株式会社 | Photoelectric conversion element and solar cell module |
WO2021006567A1 (en) * | 2019-07-05 | 2021-01-14 | 동우화인켐 주식회사 | Transparent electrode structure and electrical device comprising same |
JP2022016427A (en) * | 2020-07-08 | 2022-01-21 | 信越化学工業株式会社 | Gallium oxide thin film and laminated structure |
CN114041212A (en) * | 2019-07-05 | 2022-02-11 | 东友精细化工有限公司 | Transparent electrode structure and electric device comprising same |
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