WO2014061719A1 - Dispositif de conversion photoélectrique, structure construite et instrument électronique - Google Patents

Dispositif de conversion photoélectrique, structure construite et instrument électronique Download PDF

Info

Publication number
WO2014061719A1
WO2014061719A1 PCT/JP2013/078139 JP2013078139W WO2014061719A1 WO 2014061719 A1 WO2014061719 A1 WO 2014061719A1 JP 2013078139 W JP2013078139 W JP 2013078139W WO 2014061719 A1 WO2014061719 A1 WO 2014061719A1
Authority
WO
WIPO (PCT)
Prior art keywords
light
photoelectric conversion
semiconductor layer
optical waveguide
planar optical
Prior art date
Application number
PCT/JP2013/078139
Other languages
English (en)
Japanese (ja)
Inventor
石橋　晃
松岡　隆志
Original Assignee
国立大学法人北海道大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 国立大学法人北海道大学 filed Critical 国立大学法人北海道大学
Priority to JP2014542164A priority Critical patent/JP6261088B2/ja
Publication of WO2014061719A1 publication Critical patent/WO2014061719A1/fr

Links

Images

Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/24—Coupling light guides
    • G02B6/26—Optical coupling means
    • G02B6/34—Optical coupling means utilising prism or grating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
    • H01L31/0543—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the refractive type, e.g. lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/12—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type of the integrated circuit kind
    • G02B2006/12035—Materials
    • G02B2006/12078—Gallium arsenide or alloys (GaAs, GaAlAs, GaAsP, GaInAs)
    • 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
    • Y02E10/52—PV systems with concentrators

Definitions

  • the present invention relates to a photoelectric conversion device, a building, and an electronic device.
  • the photoelectric conversion device suitable for use as a solar cell installed on a building window or a display of various electronic devices, and the photoelectric conversion device are used. It relates to buildings and electronic equipment.
  • a solar cell using amorphous or crystalline silicon, a solar cell using GaAs crystal, a solar cell using an organic semiconductor, and the like are known. These solar cells have a structure in which a pn junction composed of a p-type semiconductor layer and an n-type semiconductor layer is sandwiched between an anode electrode and a cathode electrode, and sunlight is vertically incident on the junction surface of the pn junction.
  • a pn junction composed of a p-type semiconductor layer and an n-type semiconductor layer is sandwiched between an anode electrode and a cathode electrode, and sunlight is vertically incident on the junction surface of the pn junction.
  • FIG. 1 This conventional solar cell is shown in FIG.
  • a p-type semiconductor layer 151 and an n-type semiconductor layer 152 form a pn junction
  • an anode electrode 153 is formed on the p-type semiconductor layer 151
  • an n-type semiconductor is formed.
  • a cathode electrode 154 is formed on the layer 152 and has a plate-like shape as a whole.
  • the traveling direction of the light 156 incident perpendicularly to one main surface 155, and the cathode electrode 154 and the electrons and holes generated in the pn junction by the incidence of the light 156 are caused by drift or diffusion, respectively.
  • the direction toward the anode electrode 153 in other words, the net moving direction of the carriers is parallel.
  • the distance between the anode electrode 153 and the cathode electrode 154 becomes large. It has been extremely difficult to achieve both an increase in absorption and an improvement in carrier collection efficiency, and this has hindered improvement in photoelectric conversion efficiency. That is, in the conventional solar cell, the number of absorbed photons and the photocarrier collection efficiency both depend on the electrode spacing, in other words, the total thickness d of the p-type semiconductor layer 151 and the n-type semiconductor layer 152, and have a trade-off relationship.
  • a solar cell of a type in which sunlight is incident in parallel to the joint surface of a pn junction has recently been proposed (for example, see Patent Document 1).
  • an anode electrode and a cathode electrode are formed in a spiral shape with a pn junction composed of a p-type semiconductor layer and an n-type semiconductor layer interposed therebetween, and have a thin disk shape as a whole.
  • the band gap E g of the p-type semiconductor layer and the n-type semiconductor layer decreases stepwise from the light incident surface in the thickness direction of the disk in n steps (n ⁇ 2).
  • FIG. 4 shows an example of a solar cell described in Patent Document 1 manufactured by a roll-to-roll process, and shows a cross section in the diameter direction of a disk.
  • an anode electrode, a semiconductor layer, and a cathode electrode of a solar cell are formed on a transparent resin base film, and a spiral structure is formed while the base film is wound.
  • anode electrodes 202, 203, 204, and 205 are sequentially formed in the width direction of the base film 201 (the thickness direction of the disk). These anode electrodes 202, 203, 204, and 205 are formed to be elongated in the longitudinal direction of the base film 201.
  • a cathode electrode 210 which is a full-surface electrode is formed on the surface of these regions 206, 207, 208 and 209 opposite to the anode electrodes 202, 203, 204 and 205.
  • the width in the thickness direction of the disk in the regions 206, 207, 208, and 209 is typically about several tens of ⁇ m, and the width in the diameter direction of the disk is typically about 150 nm.
  • the thickness of the base film 201 is drawn extremely small for convenience of illustration, but the thickness of the base film 201 is about 100 ⁇ m, for example, and the regions 206, 207, 208, and 209 are drawn. It is about three orders of magnitude larger than the width of the disk in the diameter direction.
  • Non-Patent Document 2 3
  • the area of the element can be reduced relative to the area that receives sunlight, and the photoelectric conversion efficiency can be improved by increasing the number of photons by condensing.
  • the temperature of the solar cell also rises due to light collection, leading to a decrease in photoelectric conversion efficiency.
  • SW Stebbler-Lonsky
  • the problem to be solved by the present invention is that the insensitive area for incident light can be eliminated, deterioration of the organic semiconductor due to the Stebbler-Lonsky effect and ultraviolet components can be suppressed, and extremely high photoelectric conversion efficiency can be obtained. It is possible to provide a photoelectric conversion device suitable for use as a solar cell and the like, and a building and an electronic device using this excellent photoelectric conversion device, which can be increased in area and extremely easily.
  • Another problem to be solved by the present invention is that, in the concentrating solar power generation, the temperature increase as a by-product due to the introduction of the condensed light cancels out the photoelectric conversion efficiency that is higher than that in the case without the original condensing. It is providing the photoelectric conversion apparatus which can prevent that.
  • Another problem to be solved by the present invention is that, in concentrating solar power generation using a lens or the like, the photoelectric conversion efficiency decreases when the direct sunlight of the sun is lost, that is, when the diffused light becomes main.
  • the present invention provides: A structure that converts three-dimensional spatially propagated light into two-dimensional spatially propagated light; A planar optical waveguide for guiding the two-dimensional spatial propagation light; Having a semiconductor layer for photoelectric conversion provided at an end of the planar optical waveguide, The light incident on the main surface of the planar optical waveguide is configured to be guided in the planar optical waveguide and incident on the semiconductor layer, A net traveling direction of light guided in the planar optical waveguide, and a net moving direction of carriers generated in the semiconductor layer by light incident on the semiconductor layer from an end surface of the planar optical waveguide;
  • the photoelectric conversion device is characterized in that the angle ⁇ formed by is substantially a right angle.
  • planar optical waveguide and the semiconductor layer are provided integrally with each other, and, for example, their ends are joined together.
  • a first electrode and a second electrode are provided on a pair of surfaces of the semiconductor layer facing each other.
  • One of the first electrode and the second electrode is used as an anode electrode, and the other is used as a cathode electrode.
  • ⁇ / 2 ⁇ ⁇ ⁇ ⁇ ⁇ / 2 + ⁇ is selected as ⁇ .
  • ⁇ is used as the anode electrode of the first electrode and the second electrode, the ratio of the thickness of the semiconductor layer to the width (electrode width) in the direction parallel to the light traveling direction in the semiconductor layer ⁇ to semiconductor layer thickness / electrode width.
  • the structure for converting the three-dimensional spatially propagated light into the two-dimensional spatially propagated light includes, for example, a first band-shaped portion and a second band-shaped portion having different refractive indexes alternately periodically or at regular intervals. It has an ordered structure.
  • the structure that converts the three-dimensional spatially propagated light into two-dimensional spatially propagated light is typically provided in the main surface of the planar optical waveguide or in the planar optical waveguide.
  • the structure that converts three-dimensional spatially propagated light into two-dimensional spatially propagated light is, for example, a main surface of a planar optical waveguide or a diffraction grating provided in the planar optical waveguide.
  • This diffraction grating can be formed by a conventionally known method.
  • the diffraction grating can be formed by embedding or changing the refractive index by ion exchange.
  • a transparent plastic film on which a diffraction grating having a periodic structure is formed can be attached to the main surface of the planar optical waveguide.
  • a light wave traveling direction converting sheet see, for example, Non-Patent Document 4; Is provided).
  • the planar optical waveguide may be a planar optical waveguide or a curved optical waveguide.
  • the planar shape of the planar optical waveguide is selected as necessary, but typically has a quadrangular shape, for example, a rectangular shape or a square shape.
  • a semiconductor layer is provided at an end of the planar optical waveguide corresponding to at least one of a pair of opposite sides of the rectangular optical waveguide.
  • a light reflection mechanism is provided at the end of the planar optical waveguide corresponding to at least one of a pair of sides different from the pair of sides facing each other. In this case, the light incident on the main surface of the planar optical waveguide is reflected when entering the light reflecting mechanism when guided in the planar optical waveguide, and the optical path is bent in the direction toward the semiconductor layer. The amount of light incident on the end face of the semiconductor layer increases.
  • the light is not directly incident on the semiconductor layer when the light is incident on the main surface of the planar optical waveguide.
  • the light when light is incident on the main surface of the photoelectric conversion device, the light is incident on the main surface of the planar optical waveguide, but the light is not directly incident on the surface of the semiconductor layer.
  • the thickness of the planar optical waveguide is generally larger than the thickness of the semiconductor layer, it is preferably guided in the planar optical waveguide in order to effectively use the light guided in the planar optical waveguide.
  • the collected light is collected and incident on the semiconductor layer.
  • the planar optical waveguide has a portion (having the same thickness as the semiconductor layer) in which the light guided in the planar optical waveguide is in contact with the semiconductor layer of the planar optical waveguide.
  • a refractive index profile that is collected asymptotically is provided. That is, the light guided in the planar optical waveguide is guided according to the refractive index distribution of the planar optical waveguide, and thus is collected asymptotically to the portion that contacts the semiconductor layer while being guided.
  • the semiconductor layer is composed of an inorganic semiconductor or an organic semiconductor, and is typically a pn junction composed of a p-type semiconductor layer and an n-type semiconductor layer.
  • the thickness of the semiconductor layer is appropriately selected as a function of the diffusion length of carriers in the semiconductor layer, and is typically 10 nm or more and 100 ⁇ m or less.
  • the semiconductor constituting the semiconductor layer may be amorphous (amorphous), polycrystalline, or single crystal.
  • inorganic semiconductors include II-VI group compound semiconductors such as CdSe, PbS, PbSe, and PbTe, III-V group compound semiconductors such as GaSb, InAs, InN, AlInN, GaInN, GaN, AlGaN, GaAsN, and GaPN, and Si and SiGe.
  • Group IV semiconductors such as Si x Ge y Sn 1-xy O, SiN x , SiO x , CIS (CuInSe), CIGS (CuInGaSe), CuInGaSeTe, and the like can be used (see, for example, Non-Patent Documents 5 to 10). ).
  • These semiconductors are characterized in that the band gap can be controlled, for example, by controlling the composition ratio of group III elements such as In and Ga or mixing sulfur (S).
  • the semiconductor layer can also be constituted by fine particles made of these inorganic semiconductors.
  • organic solar cell materials all materials generally reported as organic solar cell materials can be used.
  • polyacenes such as pentacene, polyacetylene (preferably disubstituted polyacetylene), poly (p -Phenylene vinylene), poly (2,5-thienylene vinylene), polypyrrole, poly (3-methylthiophene), polyaniline, poly (9,9-dialkylfluorene) (PDAF), poly (9,9-dioctylfluorene- co-bithiophene) (F8T2), poly (1-hexyl-2-phenylacetylene) (PH X PA) (shows blue emission as the light-emitting material), poly (diphenylacetylene) derivative (PDPA- n Bu) (light emission)
  • the materials are green light emission), poly (pyridine) (PPy), poly (pyridylbi) Ren) (PPyV), cyano-substituted poly (p-phenylene vinylen
  • alkali metals Li, Na, K, Cs
  • halogens Br 2 , I 2 , CI 2
  • Lewis acids BF 3 , PF 5 , AsF 5 , SbF 5 , SO 3
  • transition metal halides FeCl 3 , MoCl 5 , WCl 5 , SnCl 4
  • TCNE TCNQ
  • dopant ions used in the tetraethylammonium ions as cations TEA +
  • tetrabutylammonium Ion TAA +
  • specific examples of the polymer electrolyte include polyanions such as sulfonate polyaniline, poly (thiophene-3-acetic acid), sulfonate polystyrene, poly (3-thiophene).
  • polycations such as alkane sulfonates include polyallylamine, poly (p-phenylene-vinylene) precursor polymer, poly (p-methylpyridinium vinylene), protonated poly (p-pyridylvinylene), and polotone (2- N-methylpyridinium acetylene) and the like can be used.
  • the organic semiconductor layer doped with a low impurity concentration is used as the semiconductor layer, the organic semiconductor layer can have a heterojunction type or bulk heterojunction type structure. In the organic semiconductor layer having the heterojunction structure, the p-type organic semiconductor film and the n-type organic semiconductor film are joined so as to be in contact with the first electrode and the second electrode.
  • the organic semiconductor layer having a bulk heterojunction structure is composed of a mixture of p-type organic semiconductor molecules and n-type organic semiconductor molecules, and has a fine structure in which the p-type organic semiconductor and the n-type organic semiconductor are intertwined with each other.
  • an organic-inorganic hybrid semiconductor can be used in addition to an inorganic semiconductor and an organic semiconductor.
  • an organic-inorganic hybrid semiconductor for example, a perovskite-based semiconductor (see, for example, Non-Patent Document 11) can be used.
  • the first electrode and the second electrode are in ohmic contact with the semiconductor layer.
  • the first electrode and the second electrode may not be in ohmic contact with the semiconductor layer.
  • various transparent conductive oxides such as indium tin oxide (ITO) as well as metals such as gold (Au), nickel (Ni), and aluminum (Al) are used. Although it can be used, it is not limited to this.
  • the band gap of the semiconductor layer or, if the semiconductor layer is made of an organic semiconductor, the HOMO (highest occupied molecular orbital) -LUMO (lowest unoccupied molecular orbital) gap is stepwise and / or sequentially in the light traveling direction. Or make it decrease continuously.
  • the band gap or HOMO ⁇ When sunlight is incident on the main surface of the semiconductor layer of the photoelectric conversion device, when the sunlight is guided through the planar optical waveguide and incident on the semiconductor layer, the band gap or HOMO ⁇ The light enters the semiconductor with the largest LUMO gap first, and finally enters the semiconductor with the smallest band gap. In this process, the short wavelength light to the long wavelength light in the solar spectrum are spread.
  • the semiconductor layer includes a plurality of regions in which a band gap or a HOMO-LUMO gap gradually decreases in the light traveling direction, and the first electrode and the second electrode are formed on a pair of surfaces facing each other. Two electrodes are provided, and at least one of the first electrode and the second electrode is provided separately between the regions.
  • the semiconductor layer includes a plurality of regions in which a band gap or a HOMO-LUMO gap is gradually reduced in the light traveling direction, and the width in the light traveling direction of each region is equal to the band gap or HOMO of each region. It is greater than or equal to the reciprocal of the absorption coefficient in each region of light having energy equal to the LUMO gap.
  • the semiconductor layer is composed of a plurality of regions in which the band gap or the HOMO-LUMO gap gradually decreases in the light traveling direction
  • these regions include Si x C 1 in order in the light traveling direction.
  • -x (0 ⁇ x ⁇ 1) region consisting of a region consisting of a region made of Si and Si y Ge 1-y (0 ⁇ y ⁇ 1) or a region consisting of Si x C 1-x, made of Si
  • a region composed of a region and a microcrystal Si y Ge 1 -y or a region containing at least one semiconductor selected from the group consisting of AlGaN, GaN and IGZO (In, Ga, Zn oxide), Si x C 1 -x region, Si region and Si y Ge 1 -y region, or Si x C 1 -x region, Si region, Si y Ge 1 -y region and Ge Territory It is an area.
  • Photoelectric conversion device includes not only solar cells but also optical sensors. If necessary, a plurality of photoelectric conversion devices or solar cells may be combined to form a module or system.
  • the photoelectric conversion device is A structure that converts three-dimensional spatially propagated light into two-dimensional spatially propagated light;
  • the light incident on the main surface of the planar optical waveguide is configured to be guided in the planar optical waveguide and incident on the semiconductor layer, A net traveling direction of light guided in the planar optical waveguide, and a net moving direction of carriers generated in the semiconductor layer by light incident on the semiconductor layer from an end surface of the planar optical waveguide;
  • the building is characterized in that the angle ⁇ formed by is substantially a right angle.
  • the building may basically be any building as long as it can install a photoelectric conversion device.
  • a building a condominium, a detached house
  • the installation location of the photoelectric conversion device in these buildings is not particularly limited, and is selected as necessary. Examples of installation locations are the glass windows and daylighting sections of these buildings.
  • the photoelectric conversion device is, for example, a solar cell used as a power source for these buildings and electrical products installed therein.
  • the semiconductor layer is disposed in a shaded part of the building so that the light does not directly enter the semiconductor layer when the light enters the main surface of the planar optical waveguide.
  • the planar optical waveguide includes a portion having a gentle curvature, and this portion is disposed, for example, under a tile, under a protruding central portion of a roof, on a window frame or a crosspiece.
  • the photoelectric conversion device is A structure that converts three-dimensional spatially propagated light into two-dimensional spatially propagated light;
  • the light incident on the main surface of the planar optical waveguide is configured to be guided in the planar optical waveguide and incident on the semiconductor layer, A net traveling direction of light guided in the planar optical waveguide, and a net moving direction of carriers generated in the semiconductor layer by light incident on the semiconductor layer from an end surface of the planar optical waveguide;
  • the electronic device is characterized in that the angle ⁇ formed by is substantially a right angle.
  • Electronic devices may be basically any type, including both portable and stationary types, but specific examples include mobile phones, mobile devices, robots, personal computers. , In-vehicle equipment, various home appliances.
  • the photoelectric conversion device is, for example, a solar battery used as a power source for these electronic devices.
  • the net traveling direction of light guided in the planar optical waveguide and the net movement of carriers generated in the semiconductor layer by light incident on the semiconductor layer from the end surface of the planar optical waveguide Since the angle ⁇ formed with the direction is substantially a right angle, it is possible to achieve both the maximization of the amount of light absorption and the minimization of the distance between the electrodes by selecting the thickness of the photoelectric conversion layer in the light incident direction. For this reason, extremely high photoelectric conversion efficiency can be obtained. Further, since the incident light can be received by the entire main surface of the planar optical waveguide, there is no insensitive region for the incident light.
  • the planar optical waveguide since light incident on the main surface of the planar optical waveguide is guided through the planar optical waveguide and incident on the semiconductor layer, it is possible to prevent light from directly entering the semiconductor layer. For this reason, even when the semiconductor layer is made of, for example, amorphous silicon or an organic semiconductor, the deterioration of the organic semiconductor due to the Stebbler-Lonsky (SW) effect or an ultraviolet component can be suppressed. Further, it is very easy to increase the area of the photoelectric conversion device by increasing the area of the planar optical waveguide. Further, when the band gap of the semiconductor layer or the semiconductor layer is made of an organic semiconductor, the HOMO-LUMO gap is decreased stepwise and / or continuously in the light incident direction, so that the main part of the solar spectrum can be obtained. Alternatively, photoelectric conversion can be performed by absorbing light of all wavelengths, and ultimately, photoelectric conversion efficiency approaching the theoretical maximum efficiency can be obtained.
  • SW Stebbler-Lonsky
  • FIG. 18 is a schematic diagram showing the results of measuring the current density-voltage characteristics of the SiGe element portion of the sample shown in FIGS. 17A and 17B.
  • FIG. 18 is a schematic diagram showing the results of measuring the current density-voltage characteristics of the Si element portion of the sample shown in FIGS. 17A and 17B.
  • FIG. 18 is a schematic diagram showing a result of measuring current-voltage characteristics of the SiC element portion of the sample shown in FIGS. 17A and 17B.
  • It is a top view for demonstrating an example of the growth method of the semiconductor layer of the photoelectric conversion apparatus by 1st Embodiment of this invention.
  • It is sectional drawing for demonstrating an example of the growth method of the semiconductor layer of the photoelectric conversion apparatus by 1st Embodiment of this invention.
  • Photoelectric conversion device 5A and 5B show the photoelectric conversion device according to the first embodiment.
  • this photoelectric conversion device includes a rectangular or square planar optical waveguide 20 and a photoelectric conversion provided on end faces corresponding to a pair of parallel sides of the planar optical waveguide 20.
  • the semiconductor layer 30 generally has an elongated rectangular shape.
  • the planar optical waveguide 20 and the semiconductor layer 30 are provided integrally with each other and have a planar shape as a whole.
  • the planar optical waveguide 20 and the semiconductor layer 30 are provided on the support substrate 40.
  • a first electrode 50 and a second electrode 60 are provided on a pair of mutually opposing surfaces (upper surface and lower surface) of the semiconductor layer 30, respectively.
  • One of the first electrode 50 and the second electrode 60 is used as an anode electrode, and the other as a cathode electrode.
  • the first electrode 50 is used as an anode electrode
  • the second electrode 60 is used as a cathode electrode.
  • the semiconductor layer 30 is divided into a plurality of regions made of different semiconductors, the first electrode 50 and the second electrode 60 may be provided for each region, or one of them may be on all the regions. It may be a full-surface electrode extending to the surface.
  • the refractive index of the material constituting the planar optical waveguide 20 is n 1 .
  • stripe-shaped (band-shaped) buried layers 70 made of a material having a refractive index of n 2 (n 2 > n 1 ) are provided in a predetermined arrangement on the light incident surface 20 a that is the main surface of the planar optical waveguide 20.
  • the strict periodicity has rather a delta function-like wavelength discrimination, it has a periodicity globally, but is locally random or systematic. It is effective to provide a quasi-periodic refractive index modulation structure that has fluctuations or deviates from strict periodicity. That is, as shown in FIGS.
  • the stripe-shaped buried layer 70 and the stripe-like planar light between the buried layers 70 are within a certain range in the plane of the planar optical waveguide 20.
  • the waveguides 20 are arranged alternately at regular intervals P at regular intervals or at regular intervals, whereby the three-dimensional spatially propagated light incident on the light incident surface 20a of the planar optical waveguide 20 is converted into the two-dimensional spatially propagated light.
  • a structure 80 to be converted into is formed.
  • the buried layer 70 is shown on the entire surface of the planar optical waveguide 20 for convenience.
  • the buried layer 70 extends parallel to the side of the planar optical waveguide 20 where the semiconductor layer 30 is provided.
  • the light having the wavelength ⁇ that is perpendicularly incident on the light incident surface 20 a of the planar optical waveguide 20 has a planar shape on both sides of the light that has passed through the buried layer 70 and the buried layer 70.
  • a phase difference expressed by 2 ⁇ (n 2 ⁇ n 1 ) D / ⁇ is obtained when the light passes through the structure 80 with respect to the light passing through the optical waveguide 20.
  • D so that this phase difference is ⁇ or an odd multiple thereof, the amplitude of the light traveling in the vertical direction when passing through the structure 80 can be made zero.
  • an antireflection film nonreflective coating
  • the three-dimensional spatially propagated light becomes two-dimensional spatially propagated light and is efficiently guided in the planar optical waveguide 20.
  • SiN is preferable as a material having a refractive index of ⁇ 2 and transparent in the ultraviolet (UV) to infrared (IR) region, but is not limited thereto.
  • Multiplicity here means that there is a periodic structure of a plurality of layers in the thickness direction of the planar optical waveguide 20 (this periodicity is along the extending direction of the planar optical waveguide 20). By doing so, it is possible to convert the three-dimensional spatially propagated light into the two-dimensional spatially propagated light with respect to the entire sunlight spectrum.
  • the multiplicity N is made equal to the number of later-described E gi regions constituting the semiconductor layer 30, in other words, the number of band gaps set stepwise in the light traveling direction in the semiconductor layer 30.
  • the multiplicity of the periodic structure or the plurality of the structure interval may be set in the plane of the structure 80, or may be set in the depth direction. This corresponds to the configuration of the bandpass multilayer structure in the lateral direction.
  • the three-dimensional spatially propagated light (incident light) incident on the light incident surface 20 a of the planar optical waveguide 20 is converted into two-dimensional spatially propagated light and guided through the planar optical waveguide 20.
  • the light is collected and then incident on the semiconductor layer 30.
  • the net traveling direction of the light guided in the planar optical waveguide 20 and the light incident on the semiconductor layer 30 from the end surface of the planar optical waveguide 20 The angle ⁇ formed by the net movement direction of the carriers (photocarriers) generated in (the direction connecting the first electrode 50 and the second electrode 60 in the shortest) is substantially a right angle.
  • the angle ⁇ is divided into a plurality of regions in which the width of the light travel direction of the first electrode 50 or the semiconductor layer 30 is made of different semiconductors, and the first electrode 50 is provided for each region. If the width of the first electrode 50 provided in each region in the light traveling direction is W ′ and the thickness of the semiconductor layer 30 is d, then ⁇ / 2 ⁇ ⁇ ⁇ ⁇ ⁇ / 2 + ⁇ (provided that ⁇ ⁇ d / W ′), typically 80 ° ⁇ ⁇ ⁇ 100 °, and most preferably 90 °.
  • the light incident surface 20a of the planar optical waveguide 20 in FIG. A membrane is provided. A conventionally known antireflection film can be used.
  • a periodic multilayer structure composed of a plurality of materials having different refractive indexes can be given.
  • it is also effective to arrange a fine structure (nanostructure / microstructure) generated by pyramid or etching on the surface.
  • the fine structure provided on the surface of the planar optical waveguide 20, that is, the buried layer 70 has a functional structure having a distance x along the optical waveguide direction and has a diffractive action, so that FIGS.
  • the redirection wave guide (that is, the direction-reducing optical waveguide) (that is, the incident light, which is a three-dimensional spatial propagation light, is converted into a two-dimensional spatial propagation light by, for example, diffraction, A functional thin film structure that can be guided in the lateral direction immediately).
  • These low reflectance structures are selected as needed.
  • an antireflection film is preferably provided on the joint surface between the planar optical waveguide 20 and the semiconductor layer 30 in order to prevent reflection of light incident on the semiconductor layer 30 from the planar optical waveguide 20.
  • a light reflecting mechanism is provided on the end face of the planar optical waveguide 20 corresponding to a pair of sides different from the pair of sides on which the semiconductor layer 30 is provided.
  • the light reflecting film provided on the end surface of the planar optical waveguide 20 or the end surface of the planar optical waveguide 20 is configured as a mirror surface.
  • light incident on the main surface of the planar optical waveguide 20 is reflected when entering the light reflecting mechanism when guided in the planar optical waveguide 20, and the optical path is bent in the direction toward the semiconductor layer 30. As a result, the amount of light incident on the semiconductor layer 30 increases.
  • This photoelectric conversion device is configured such that light does not directly enter the semiconductor layer 30 when light enters the light incident surface 20a of the planar optical waveguide 20.
  • the photoelectric conversion device when light is incident on the photoelectric conversion device, the light is incident on the light incident surface 20 a of the planar optical waveguide 20, but the light is not directly incident on the surface of the semiconductor layer 30.
  • a light shielding layer is provided above the semiconductor layer 30 so as to cover the first electrode 50.
  • a conventionally well-known thing can be used for a light shielding layer, and it selects as needed, For example, it is the aluminum laminated film etc. in which the plastic film was formed on both surfaces of the aluminum foil.
  • This light shielding layer can prevent light from directly entering the semiconductor layer 30.
  • the support substrate 40 constitutes a part of the outer surface of a building or an electronic device
  • sunlight is incident on the planar optical waveguide 20, but sunlight is not incident on the semiconductor layer 30.
  • the semiconductor layer 30 is covered with a member or the like so as to be shaded.
  • the window glass serves as the support substrate 40
  • the planar optical waveguide 20 is provided on the window glass exposed to the outside
  • the semiconductor layer 30 is made of, for example, aluminum. Hide inside the window frame.
  • the end portions of adjacent photoelectric conversion devices overlap each other, and the lower photoelectric conversion device is formed by the semiconductor layer 30 at the end portion of the upper photoelectric conversion device.
  • the semiconductor layer 30 is covered at the end.
  • the planar optical waveguide 20 is made of transparent glass or transparent plastic.
  • the transparent plastic include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetyl cellulose, brominated phenoxy, aramids, polyimides, polystyrenes, polyarylates, Examples include polysulfones and polyolefins.
  • a fluorine-based material used for a plastic optical fiber (POF) or the like is particularly suitable because of its low light loss.
  • the thickness of the planar optical waveguide 20 is selected as necessary, and is, for example, 1 to 1000 ⁇ m.
  • the size (vertical and horizontal lengths) of the planar optical waveguide 20 is appropriately selected according to the location where the photoelectric conversion device is installed. Generally, for example, (1 cm to 1 m) ⁇ (1 cm to 1 m). is there.
  • the semiconductor layer 30 is selected, for example, from those already listed as necessary.
  • the semiconductor layer 30 is typically a pn junction composed of a p-type semiconductor layer and an n-type semiconductor layer.
  • a portion of the semiconductor layer 30 in contact with the first electrode 50 and the second electrode 60 is doped with a high impurity concentration, and the first electrode 50 and the second electrode 60 are doped with the semiconductor layer 30.
  • the length of one side of the semiconductor layer 30 is typically selected to be the same as the length of the side of the planar optical waveguide 20 on which the semiconductor layer 30 is provided, but the length of the side perpendicular to this side is generally For example, the thickness is 10 ⁇ m to 1 cm, typically 20 ⁇ m to 1 mm.
  • the area of the semiconductor layer 30 is generally much larger than the area of the planar optical waveguide 20. It's small. That is, in this photoelectric conversion device, the planar optical waveguide 20 occupies most and the semiconductor layer 30 occupies only a small part at the end. For example, when the size of the planar optical waveguide 20 is 10 cm ⁇ 10 cm and the size of the semiconductor layer 30 is 1 mm ⁇ 10 cm, the two semiconductor layers occupy the entire area of the planar optical waveguide 20 and the two semiconductor layers 30.
  • the thickness of the semiconductor layer 30 is generally as small as several tens of ⁇ m or less, the volume of the semiconductor layer 30 is extremely small. That is, the amount of semiconductor layer 30 used can be extremely small. For this reason, the manufacturing cost of the photoelectric conversion device can be reduced.
  • the end portion of the planar optical waveguide 20 is bent (bended), for example, by 90 degrees downward with a finite radius of curvature, so that the light propagates in the semiconductor layer 30 in the vertical direction in FIG. 5B. be able to. Thereby, as described above, it is possible to minimize the light shielding loss that occurs when the light shielding layer is provided above the semiconductor layer 30 so as to cover the first electrode 50.
  • the band gap or HOMO-LUMO gap E g of the semiconductor layer 30 decreases stepwise in N stages (N ⁇ 2) in the light traveling direction in the semiconductor layer 30, and in order, E g1 , E g2,. E gN (E g1 > E g2 >...> E gN ).
  • the semiconductor layer 30 is composed of regions 31, 32, 33, and 34 having band gaps or HOMO-LUMO gaps E g of E g1 , E g2 , E g3 , and E g4 , respectively.
  • Each of the regions 31, 32, 33, and 34 has an elongated stripe shape extending in a direction parallel to the side where the semiconductor layer 30 of the planar optical waveguide 20 is provided.
  • first electrodes 51, 52, 53, and 54 are provided on the respective regions 31, 32, 33, and 34 so as to be separated from each other.
  • the second electrode 60 is a full-surface electrode and is a common electrode for each of the regions 31, 32, 33, and 34. (The width in the traveling direction of light, the length of the lateral direction in FIG.
  • each E gi region constituting the semiconductor layer 30 the photoelectric conversion target photons (bandgap E of the E gi region of the E gi region If the absorption coefficient of this E gi region with respect to the one having the lowest energy among the photons having the energy of gi or higher) is ⁇ i , it is 1 / ⁇ i or higher.
  • E gi can be set as follows.
  • the wavelength is divided into N sections in the entire wavelength range of the AM1.5 sunlight spectrum or its main wavelength range (including a portion with a high incident energy). These sections are numbered in order from the short wavelength side (high energy side) 1, 2,..., N, and E gi is selected to be equal to the minimum photon energy in the i-th section. In this way, when a photon having photon energy in the kth section is incident on the E gi region, an electron-hole pair is generated and photoelectric conversion is performed.
  • the photon having the photon energy in the k-th section reaches each Egi region and is sufficiently absorbed, so that the Egi is introduced from the junction surface between the planar optical waveguide 20 and the semiconductor layer 30. Choose the distance to the area.
  • sunlight that is guided through the planar optical waveguide 20 and incident on the semiconductor layer 30 first enters the E g1 region, and in the spectrum, the photon energy of E g1 or higher is absorbed and photoelectric conversion is performed. Then, it enters the E g2 region and the spectrum whose photon energy is greater than or equal to E g2 and smaller than E g1 is absorbed and photoelectrically converted, and finally enters the E gN region and enters the photon of the spectrum. Those whose energy is greater than or equal to E gN and less than E gN-1 are absorbed and photoelectrically converted. As a result, light in almost the entire solar spectrum or in the main wavelength range can be used for photoelectric conversion.
  • FIG. 3 shows the relationship between the photon energy h ⁇ of the AM1.5 sunlight spectrum and the number of photons n (h ⁇ ).
  • the photon energy of the AM1.5 sunlight spectrum is equally divided into 10 sections of energy width ⁇ .
  • Each E gi can be set by changing the composition of the semiconductor constituting each E gi region, the form of the semiconductor (amorphous, polycrystalline, single crystal), or the like. Specifically, each E gi region is formed of a different type of semiconductor. In this case, the semiconductor has a wide range of choices because it can be selected to have a high carrier mobility ⁇ regardless of the absorption coefficient ⁇ .
  • N 2
  • N 4
  • ⁇ 1.8eV
  • the CdSe fine particles (absorption peak wavelength 445 nm) having a diameter of about 1.9 nm in the E g1 region, the CdSe fine particles (absorption peak wavelength 585 nm) having a diameter of about 4.0 nm in the E g2 region,
  • the Eg3 region has a PbSe fine particle (absorption peak wavelength 800 nm) with a diameter of about 2 nm
  • the Eg4 region has a PbSe fine particle with a diameter of about 4.5 nm (absorption peak wavelength 1100 nm)
  • the Eg5 region has a PbSe fine particle with a diameter of about 90 nm (absorption peak wavelength).
  • E gi region in the case of N to 10 by controlling x only using GaInN x As 1-x or GaInN x P 1-x .
  • it may be configured E gi region using the group II-VI compound semiconductor to exhibit significant bowing the inclusion of Te (bowing) is known.
  • Specific examples of the case where an organic semiconductor and an inorganic semiconductor are used are as follows.
  • photons that cause the Stebler-Lonsky reaction which has been shown to be generated by light having a wavelength of 450 nm or less, are photoelectrically converted in advance before entering the a-Si layer. Therefore, the reaction can be suppressed, and therefore the lifetime of the photoelectric conversion region composed of the a-Si layer can be extended.
  • This high-energy photon removal function that suppresses coherent energy while performing effective photoelectric conversion is not just passivation, but also improves the reliability and extends the life of organic semiconductor photoelectric conversion units, which are also considered to be weak for outdoor use. Is also effective.
  • each E gi region is selected as necessary, and is several ⁇ m to several tens ⁇ m, for example.
  • the width of each E gi region (the width of the light traveling direction in the semiconductor layer 30) is also selected as necessary, and is, for example, several tens ⁇ m to several hundreds ⁇ m.
  • FIG. 8 is an enlarged view of the regions 31 to 34 in FIG. 7.
  • the thickness d of each region 31 to 34 is several ⁇ m to several tens of ⁇ m, and the widths w 1 to w 4 of each region 31 to 34 are several. Select from 10 ⁇ m to several hundred ⁇ m, for example, to 100 ⁇ m.
  • each of the regions 31 to 34 is composed of a pn junction composed of a p-type semiconductor layer and an n-type semiconductor layer.
  • the junction surfaces of the pn junctions constituting the regions 31 to 34 are indicated by broken lines.
  • a light wave traveling direction conversion sheet 85 (for example, non-patent document) is formed on the structure 80 of the planar optical waveguide 20 that converts the three-dimensional space propagation light into the two-dimensional space propagation light. It is desirable to provide 4).
  • the antireflection film non-reflective coating
  • the planar optical waveguide 20 it is formed on the light wave traveling direction changing sheet 85, and the effective refraction due to the nanostructure that the light wave traveling direction changing sheet 85 itself has on its surface.
  • FIG. 11A, FIG. 11B, and FIG. 11C are photographs of the light orientation characteristics with respect to the incident light of the light wave traveling direction conversion sheet 85. Was taken in a photo. From FIG. 11A, FIG. 11B, and FIG.
  • the light wave traveling direction changing sheet 85 can be a parabolic aggregate or a prismatic aggregate.
  • the support substrate 40 may be basically any type, but is typically a transparent substrate that is at least transparent to visible light.
  • the transparent substrate is, for example, a glass plate or a transparent plastic plate.
  • the transparent plastic constituting the transparent plastic plate include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polystyrene, polyethylene, polypropylene, polyphenylene sulfide, polyvinylidene fluoride, acetyl cellulose, brominated phenoxy, aramids, polyimides, and polystyrene.
  • Polyarylates, polysulfones, polyolefins and the like can be used.
  • the support substrate 40 is, for example, a window glass of various buildings (public facilities, building diggs, condominiums, detached houses, etc.), various electronic devices (cell phones, smartphones, notebook personal computers, desktop personal computers, TV, liquid crystal display, organic EL display) and the like, but not limited thereto.
  • the semiconductor layer 30 is a pn junction.
  • three-dimensional spatial propagation light for example, the sun, is formed on the light incident surface 20a of the planar optical waveguide 20 of the photoelectric conversion device on which the structure 80 that converts to two-dimensional spatial propagation light is formed. Light enters. Light does not directly enter the surface of the semiconductor layer 30.
  • the three-dimensional spatial propagation light incident on the light incident surface 20a of the planar optical waveguide 20 is converted into two-dimensional spatial propagation light by the structure 80 that converts the three-dimensional spatial propagation light into the two-dimensional spatial propagation light.
  • the two-dimensional spatially propagated light is efficiently guided through the planar optical waveguide 20 while being repeatedly reflected on its upper and lower surfaces (see FIG. 24 described later), and exits from the end surface of the planar optical waveguide 20.
  • the electrons and holes thus generated move in the semiconductor layer 30 by drift or diffusion, and are collected by one and the other of the first electrode 50 and the second electrode 60. In this way, photoelectric conversion is performed in the semiconductor layer 30, and current (photocurrent) is extracted from the first electrode 50 and the second electrode 60 to the outside.
  • the number of absorbed photons of the semiconductor layer 30 is governed by the width in the incident direction of light (in the case where the semiconductor layer 30 is composed of regions 31 to 34, for example, the widths w 1 to w 4 of the regions 31 to 34).
  • the conversion efficiency ⁇ is not controlled by the thickness d of the semiconductor layer 30 in the light absorption rate limiting region (thick dashed line in FIG. 2). That is, the photoelectric conversion device is extremely advantageous in that it optimizes light absorption and carrier collection efficiency by making the incident direction of light with respect to the planar optical waveguide 20 and the moving direction of carriers orthogonal to each other, for example. Is completely compatible with each other.
  • the small absorption coefficient ⁇ of the semiconductor layer 30 is determined by the width of the semiconductor layer 30 in the light incident direction (in the case where the semiconductor layer 30 is composed of the regions 31 to 34, for example, the widths w 1 to w 4 ) Can be compensated for, so that the material of the semiconductor layer 30 can be a material having a large ⁇ that is the only dominant parameter, regardless of the size of ⁇ . By doing so, it is possible to obtain a high photoelectric conversion efficiency ⁇ as shown by a thick dashed line in FIG. Thereby, it is possible to obtain the photoelectric conversion efficiency approaching the thermodynamic limit.
  • 12 and 13 show the results of experiments conducted to verify that the photoelectric conversion efficiency ⁇ is released from the constraint due to ⁇ in this photoelectric conversion device.
  • an IZO (indium zinc oxide) film, a PEDOT: PSS film, and a P3HT: PCBM film are sequentially formed on a PEN (polyethylene naphthalate) film, and the P3HT: PCBM film is formed.
  • An Al film was formed.
  • the thickness of the P3HT: PCBM film is d.
  • the result of measuring the voltage-current characteristics by applying a voltage between the IZO film and the Al film is shown in the lower inset of FIG. The black rhombus plot in FIG.
  • FIG. 12 is ⁇ when light is incident on the P3HT: PCBM film from the vertical direction, and the white ellipse plot is ⁇ measurement results when light is incident from the end face of the P3HT: PCBM film. Indicates. The dotted straight line in FIG. 12 indicates ⁇ d.
  • FIG. 13 shows the results of another lot (sample). The dependence of I SC V OC (I SC is the saturation current, V OC is the open circuit voltage) on the thickness d of the P3HT: PCBM film is shown as P3HT: PCBM. The measurement result about the case where light is incident on the film from the vertical direction and the case where light is incident from the end face of the P3HT: PCBM film is shown.
  • FIG. 14 shows the relationship between the photon energy h ⁇ of the AM1.5 sunlight spectrum and the number of photons n ph .
  • E g1 , E g2 , E g3 , and E g4 are described as E g (1), E g (2), E g (3), and E g (4).
  • N can be increased by using a gradient composition structure in which the composition of the semiconductor layer 30 can be easily realized by using the gradient parameter arrangement described later, and the composition of the semiconductor layer 30 is inclined in the direction of light traveling in the semiconductor layer 30.
  • at least one of the electrodes 50 and 60 is allowed to be formed in batch with respect to N regions (segments) (that is, a tandem structure connected in parallel). Taking advantage of this photoelectric conversion device, it is possible to realize an ideal condensing system that can be as thin as 85% of the thermodynamic limit.
  • FIG. 15 shows the temperature dependence of the diffusion coefficients of various elements in Si. From FIG. 15, for example, Si x C 1-x can be produced by diffusing C in the Si layer, and Si y Ge 1-y can be produced by diffusing Ge.
  • FIG. 16 shows the result of Raman scattering measurement of a sample obtained by using an a-Si layer doped with phosphorus (P) as the semiconductor layer 30 and crystallizing the a-Si layer by laser annealing.
  • Laser annealing was performed using laser light having a wavelength of 514 nm obtained using an argon (Ar) laser.
  • the irradiation energy density was 6.1 mW and the irradiation time was 10 minutes.
  • the number of times of laser light irradiation was changed to 1, 2, 3, and 4. From this result, it can be seen that the a-Si layer can be selectively converted into crystalline Si only at the portion irradiated with light. Since a-Si and crystalline Si have different band gaps, it can be seen that two regions having different band gaps can be formed.
  • the stripe width can be controlled by the irradiation width of the laser beam.
  • FIG. 17A shows a sample in which Ge is partially diffused on the surface of the Si substrate to form a striped SiGe region, and C is diffused to another portion of the surface of the Si substrate to form a striped SiC region. It is the photograph which image
  • FIG. 17B shows the cross-sectional shape of this sample.
  • 18 to 20 show measurement results of current density (J) -voltage (V) characteristics of the SiGe element portion, JV characteristics of the Si element portion, and IV characteristics of the SiC element portion, respectively.
  • J current density
  • V voltage
  • the SiGe element, the Si element, and the SiC element have different built-in voltages, and the open-circuit voltages V oc are 0.22 to 0.24 V, .about.0.42 V,. Since it is 45 to 0.6 V, it can be seen that the band gap of the pn junction surface can be changed by controlling the composition by diffusing elements other than Si into the Si substrate. This is evidence that photons in different energy ranges of the sunlight spectrum can be photoelectrically converted.
  • the semiconductor layer 30 is composed of three types of semiconductors having a gradient composition in the light traveling direction in the semiconductor layer 30 and the band gap decreasing in the light traveling direction.
  • This growth method is not limited to this, and can generally be applied to the case of N kinds of semiconductors.
  • these three types of semiconductors are A p B 1-p C, A q B 1-q C, and A r B 1-r C (p>q> r or p
  • ⁇ q ⁇ r will be described.
  • the present invention is not limited to this, and in general, a binary or quaternary or higher semiconductor may be used.
  • C ⁇ (empty set)
  • these three types of semiconductors become binary materials (for example, Si x Ge 1-x ).
  • an A p B 1-p C layer 102, an A q B 1-q C layer 103, and an A r B 1-r C layer 104 are grown in this order on the substrate 101 in the x-axis direction.
  • the A p B 1-p C layer 102, the A q B 1-q C layer 103, and the A r B 1-r C layer 104 have an elongated stripe shape extending in the y-axis direction.
  • the growth of these A p B 1-p C layer 102, A q B 1-q C layer 103, and A r B 1-r C layer 104 occurs on the substrate 101 in the x-axis direction.
  • an inclination parameter arrangement is performed at this time. That is, the parameter value monotonously changes (increases or decreases) along the x-axis direction of FIGS. 21A and 21B.
  • the parameters include the growth temperature, the lattice constant of the substrate 101, the number of off-angles of the substrate 101, and the light intensity at the time of light irradiation when using light during growth. It is also effective to combine a plurality of these.
  • Examples of a method for changing the lattice constant of the substrate 101 include ion implantation and diffusion. As an atomic species used for ion implantation or diffusion, use of a constituent element of the substrate 101 or a constituent element of a target growth layer has high affinity, but is not limited thereto.
  • the light irradiation is selected according to the purpose, such as a case where the crystal growth reaction itself is promoted or a case where the substrate temperature rises.
  • Examples of the raw material flux include a raw material-containing gas, a molecular beam, and a raw material-containing solution.
  • a multi-stripe semiconductor layer can be grown on a virtually infinitely long tape-like substrate. Since doping can be performed simultaneously with growth, a pn junction can also be formed, the semiconductor layer 30 can be easily formed, and a photoelectric conversion device can be easily manufactured. Note that when the substrate 101 is left as it is after the growth of the semiconductor layer 30, a conductive substrate is used as the substrate 101. Either a conductive substrate or a non-conductive substrate may be used.
  • the raw material flux supply device 105 supplies the raw material flux 106 for supplying A and C
  • the raw material flux supply device 107 supplies the raw material flux 108 for supplying B and C, for example, from the other side in the left-right direction.
  • the raw material fluxes 106 and 108 are, for example, a raw material gas, a molecular beam, a mist spray (for example, see Non-Patent Documents 12 to 13), and the like.
  • the semiconductor layer 30 made of three kinds of semiconductors having a gradient composition in the light traveling direction in the semiconductor layer 30 and having a band gap decreasing in the light traveling direction.
  • a necessary number of raw material flux supply devices are prepared. Further, the combined use of the growth method shown in FIGS. 21A and 21B and the growth method shown in FIG. 22 is also effective.
  • the planar optical waveguide 20 occupies most of the area, and the entire planar optical waveguide 20 can receive incident light. Absent. Further, in this photoelectric conversion device, the light incident on the light incident surface 20a of the planar optical waveguide 20 and guided by being condensed in the planar optical waveguide 20 is incident on the semiconductor layer 30. As shown in the inset of FIG. 3, extremely high photoelectric conversion efficiency can be obtained.
  • the light collection rate is (planar optical waveguide).
  • the photoelectric conversion efficiency at this time exceeds 60% from the inset of FIG.
  • the semiconductor layer 30 is composed of a plurality of regions in which the band gap or the HOMO-LUMO gap decreases stepwise in the light traveling direction in the semiconductor layer 30, a high-energy ultraviolet component of sunlight Can be absorbed in the region of the first stage, for example, so that the ultraviolet component can be prevented from entering the region of the subsequent stage.
  • this photoelectric conversion device can be easily increased in area simply by increasing the area of the planar optical waveguide 20.
  • the semiconductor layer 30 is provided at the end of the planar optical waveguide 20, and the light guided in the planar optical waveguide 20 exits from the end surface of the planar optical waveguide 20 and enters the semiconductor layer 30.
  • a lens for condensing light is not necessary, the configuration is extremely simple, and optical axis alignment is not necessary, so that not only manufacturing is easy, but also manufacturing cost is reduced. It is also possible to prevent changes over time and changes over time.
  • the point that the photoelectric conversion efficiency decreases with respect to the diffused light which was a drawback of the lens-type condensing system, is extremely compatible with the light wave traveling direction changing sheet 85 in the sense that they are mutually planar and can be bonded together.
  • the structure of the planar optical waveguide 20 even diffused light can be recovered to about 95% (which is the efficiency of the light wave traveling direction changing sheet 85) compared to the photoelectric conversion efficiency for direct light. .
  • the space charge effect that is a problem in the amorphous silicon solar cell can be suppressed. That is, the amorphous silicon solar cell has a problem that even if the thickness of the amorphous silicon is increased to increase the light absorption, the internal electric field is canceled by the space charge and the characteristics are not improved.
  • the amorphous silicon solar cell has a problem that even if the thickness of the amorphous silicon is increased to increase the light absorption, the internal electric field is canceled by the space charge and the characteristics are not improved.
  • this photoelectric conversion device when a partial region of the semiconductor layer 30 is composed of amorphous silicon, the region between the first electrode 50 and the second electrode 60 provided above and below the semiconductor layer 30 is used. The distance can be reduced, and at the same time, the length of the amorphous silicon region in the light traveling direction in the semiconductor layer 30 can be increased, so that the space charge effect can be suppressed.
  • the surface that can convert the three-dimensional spatially propagated light into the two-dimensional spatially propagated light and efficiently propagate the two-dimensional spatially propagated light that is, the light receiving surface (planar optical waveguide 20).
  • the semiconductor layer 30 which is a photoelectric conversion region can be spatially separated, so that an increase in the temperature of the semiconductor layer 30 due to direct sunlight can be suppressed.
  • the planar optical waveguide 30 includes a portion having a gentle curvature, and the other portion is disposed under the tile, under the protruding central portion of the roof, under the window rail, etc. When light is incident on the light incident surface 20a, the semiconductor layer 30 can be disposed in a shaded portion.
  • this photoelectric conversion device on the basis of the suppression of the temperature rise (through the reduction of energy lost as heat) due to the high efficiency, further, the bad place of the condensing system (due to the incidence of high intensity light) Temperature rise) can be eliminated, and only a good point (a point where the conversion efficiency increases by about 20% as shown in the inset in FIG. 3 as compared with the non-condensing system) can be utilized.
  • the advantages of this photoelectric conversion device can be summarized as follows. (1) The optical absorption and carrier collection efficiency can be independently and simultaneously optimized by the orthogonality between the photon traveling direction and the photocarrier moving direction. (2) Multi-stage multi-striping with a gradient composition is possible, and full-width photoelectric conversion of the sunlight spectrum is possible. (3) Due to the light condensing system, an efficiency increase of about 20% is expected compared to the non-light condensing system. (4) Since it is possible to perform photoelectric conversion using multi-stage multi-gap semiconductors, energy dissipated as heat can be minimized, so that temperature rise, which was a weak point of a concentrated solar power generation system, can be suppressed. .
  • this photoelectric conversion device is the ultimate photoelectric conversion system having many characteristics.
  • ⁇ Second Embodiment> [Photoelectric conversion device]
  • three-dimensional spatial propagation light incident on the light incident surface 20 a of the planar optical waveguide 20 is provided by providing the buried layer 70 on the light incident surface 20 a that is the main surface of the planar optical waveguide 20.
  • a periodic concavo-convex structure is provided on the light incident surface 20a by stamping or nano-microimprinting.
  • the structure 80 that converts the three-dimensional space propagation light into the two-dimensional space propagation light is formed.
  • the periodic concavo-convex structure has, for example, a comb tooth shape, a sawtooth shape, a sinusoidal shape, or the like. Others are the same as in the first embodiment.
  • a simulation was performed to verify the optical waveguide performance of the planar optical waveguide 20 in which the structure 80 that converts the three-dimensional spatially propagated light into the two-dimensional spatially propagated light is formed on the light incident surface 20a.
  • the model used for the simulation is shown in FIG.
  • convex portions 112 a having a rectangular cross section are periodically formed in a part of one main surface (light incident surface) of the planar optical waveguide 111 to form a periodic concavo-convex structure 112.
  • the planar optical waveguide 111 corresponds to the planar optical waveguide 20
  • the periodic uneven structure 92 corresponds to the structure 80 that converts the three-dimensional spatial propagation light into the two-dimensional spatial propagation light.
  • a back metal 113 made of Al that functions as a reflection film is formed over a larger area than the periodic uneven structure 112.
  • the interface between the back metal 113 and the planar optical waveguide 111 is formed in a sawtooth shape, and light hitting a minute inclined surface of the back metal 113 on the sawtooth interface is reflected in various directions. ing.
  • the simulation conditions are as follows.
  • the (x, y, z) coordinate system was taken as shown in FIG.
  • the width of the planar optical waveguide 111 in the x-axis direction was 80 ⁇ m, and the thickness in the z-axis direction was 4 ⁇ m.
  • the direction in which the convex portions 112 a are arranged is the x-axis direction, the direction orthogonal to the x-axis direction in the plane of the planar optical waveguide 111 is the y-axis direction, and the direction perpendicular to the plane of the planar optical waveguide 111 is the z-axis direction. It is.
  • the number of protrusions 112a is 5, the pitch of protrusions 112a in the x-axis direction is 2.0 ⁇ m, the width of protrusions 112a in the x-axis direction is 1.0 ⁇ m, and the groove between the protrusions 112a and 112a The width is 1.0 ⁇ m, the height in the z-axis direction of the projection 112a is 1.5384 ⁇ m, and the width in the y-axis direction of the projection 112a is 3.9 ⁇ m.
  • Light having a wavelength of 2.1 ⁇ m plane wave
  • the y component E y of the electric field in the planar optical waveguide 111 was calculated using the Maxwell equation.
  • the distribution of the amplitude of Ey thus calculated is shown in the upper diagram of FIG.
  • most of the light incident perpendicularly to the periodic concavo-convex structure 112 is diffracted by the periodic concavo-convex structure 112 and the traveling direction thereof is changed by 90 °, and the light travels in the planar optical waveguide 111.
  • Waveguide. the redirection wave guide was shown to be feasible, and the structural parameters were also clarified. It is possible to cope with light of other wavelengths by appropriately changing the size and period of the convex portion 112a (or the embedded layer 70).
  • the lower part of FIG. 24 shows the result of the same calculation performed by setting the height of the projection 112a in the z-axis direction to 1.0 ⁇ m.
  • the diffraction condition is not satisfied, the diffraction hardly occurs, and the light incident perpendicularly to the periodic concavo-convex structure 112 hardly guides the planar optical waveguide 111. From the above results, it was verified that the optical waveguide performance of the planar optical waveguide 20 in which the periodic concavo-convex structure of the photoelectric conversion device is provided on the light incident surface 20a is high.
  • the above result is similarly established when the structure 80 for converting the three-dimensional spatial propagation light into the two-dimensional spatial propagation light is formed by providing the embedded layer 70 as in the first embodiment. . According to the second embodiment, advantages similar to those of the first embodiment can be obtained.
  • a minute uneven structure (a jagged structure) is provided on the side surface of the semiconductor layer 30 in contact with the end face of the planar optical waveguide 20. Others are the same as in the first embodiment.
  • Non-Patent Document 14 a p-type polycrystalline silicon wafer doped with boron is immersed in an aqueous solution containing 15 wt% H 2 O 2 and 25 wt% HF at room temperature, and is applied to the surface of the p-type polycrystalline silicon wafer.
  • a fine concavo-convex structure is formed by contacting the platinum mesh attached to the roller and etching the surface of the p-type polycrystalline silicon wafer from the opening of the platinum mesh while rotating the roller.
  • Non-Patent Document 14 the reflectance of the p-type polycrystalline silicon wafer can be suppressed to 1 to 3% in the wavelength range of 300 nm to 800 nm. Further, as can be seen from FIGS. 1 (b) and 2 (a) of Non-Patent Document 14, since the structure has no periodicity in the range of 0 to 10 ⁇ m, it is almost the same in the wavelength range of 800 nm to 2.4 ⁇ m. Low reflectance can be obtained.
  • the solar cell When such a micro uneven structure is used in a conventional planar solar cell, the solar cell may be used outdoors, and if dust or the like accumulates on the surface, the effect tends to be reduced.
  • this minute uneven structure is formed on the side surface of the semiconductor layer 30, it is not only horizontally oriented, but also directly coupled to the end surface of the planar optical waveguide 20, so that dust can be contained in the unevenness. Since there is no room for such deposition, high characteristics can be constantly maintained and long-term stability is achieved.
  • the third embodiment in addition to the same advantages as those of the first embodiment, it is possible to obtain the advantage that the long-term stability of the photoelectric conversion device can be realized. .
  • the semiconductor layer 30 includes two semiconductor layers 30 having four band gaps, that is, photoelectric conversion devices 121 and 122.
  • photoelectric conversion devices 121 and 122 have, for example, the configuration shown in FIG. E g (1), E g (2), E g (3), and E g (4) correspond to the E g1 region, the E g2 region, the E g3 region, and the E g4 region.
  • these photoelectric conversion devices 121 and 122 are connected to each other.
  • the first electrode 51, the first electrode 52, the first electrode 53, and the first electrode 54 of the photoelectric conversion device 121 are respectively connected to the first electrode 54, the first electrode 53, and the photoelectric conversion device 122. Connected to the first electrode 52 and the first electrode 51.
  • the same advantages as those of the first embodiment can be obtained, and a composite photoelectric conversion device having a high photoelectric conversion efficiency ⁇ can be realized while maintaining a single output voltage. be able to.
  • a layer having a small refractive index has been formed from the back side by changing the refractive index of the glass waveguide, for example, by ion exchange, and has been guided two-dimensionally.
  • the light is condensed also in the direction perpendicular to the surface, and gathers to the same thickness as the semiconductor layer 30 at the contact portion between the planar optical waveguide 20 and the semiconductor layer 30 ( Asymptotically concentrate the light).
  • the UV light component in the sunlight spectrum does not have a high ratio, as can be seen from FIG. 3, so that it is not converted into two-dimensional spatially propagated light from the beginning, and therefore is guided in the planar optical waveguide 20. Instead, only the light having a lower energy component than this is converted into two-dimensional spatially propagated light, guided in the planar optical waveguide 20 and incident on the semiconductor layer 30 to be photoelectrically converted.
  • a-Si or an organic semiconductor is included, the lifetime of the photoelectric conversion device can be improved and the reliability can be improved.
  • the connection as shown in FIG. 25 is achieved.
  • the probability / risk of the malfunction of the photoelectric conversion device due to the defect generated in the element unit of the tandem structure that occurs when the operation is performed can be reduced. This is because in the conventional series-connected tandem structure, the larger the area, the higher the probability of the above-mentioned problem, whereas in the photoelectric conversion device according to the present invention, the element unit of the tandem structure is in a line shape and the area is small. In addition to being extremely small, this element unit is segmented in the stripe direction as described above, and as described above, the probability that a local defect will cause the entire photoelectric conversion device to be defective is markedly increased. Can be lowered.
  • a photoelectric conversion device system (or a solar cell system) may be configured by laying a plurality of photoelectric conversion devices according to the first to fourth embodiments.
  • the entire side surface of the building is wrapped around in a headband shape, and the photoelectric conversion element portion (semiconductor layer 30) coupled thereto is, for example, one place on the north side surface of the building (that is, For example, they may be arranged collectively in a region of several meters in the vertical direction and several millimeters to 1 cm in the lateral direction.
  • this headband-shaped redirection wave guide itself has a so-called reverse redirection (that is, two-dimensional spatial propagation light is returned to three-dimensional spatial propagation light) in a part of the shade that exists in the building. Therefore, it can also be used for applications that substantially eliminate the shade formed by the building.
  • a structure that converts three-dimensional spatially propagated light into two-dimensional spatially propagated light can be omitted. That is, it has a planar optical waveguide that guides two-dimensional spatially propagated light, and a photoelectric conversion semiconductor layer provided at an end of the planar optical waveguide, and is incident on the main surface of the planar optical waveguide. Light is guided in the planar optical waveguide and incident on the semiconductor layer, and the net traveling direction of the light guided in the planar optical waveguide and the planar optical waveguide A photoelectric conversion device is also effective in that the angle ⁇ formed with the net movement direction of carriers generated in the semiconductor layer by light incident on the semiconductor layer from the end face is substantially a right angle. In this case, the three-dimensional spatial propagation light is incident on the main surface of the planar optical waveguide, the light enters the planar optical waveguide, and the two-dimensional spatial propagation light is guided through the planar optical waveguide.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Optics & Photonics (AREA)
  • Photovoltaic Devices (AREA)
  • Diffracting Gratings Or Hologram Optical Elements (AREA)

Abstract

La présente invention concerne un dispositif de conversion photoélectrique qui permet à des régions qui sont insensibles à la lumière incidente d'être éliminées, permet à la dégradation du semi-conducteur organique due à l'effet Staebler-Wronski ou à des composants UV d'être supprimée, permet d'obtenir une efficacité de conversion photoélectrique extrêmement élevée, permet à la zone d'être augmentée avec une facilité exceptionnelle, et peut être utilisé de manière appropriée comme cellule photovoltaïque ou similaire. Le dispositif de conversion photoélectrique a : un corps structurel (80) pour convertir la lumière se propageant dans l'espace 3D en lumière se propageant dans l'espace 2D ; un guide d'ondes optiques planar (20) pour guider la lumière se propageant dans l'espace 2D ; et des couches semi-conductrices (30) pour la conversion photoélectrique, prévues sur les parties de bord du guide d'ondes optiques planar (20). La lumière incidente sur une surface principale du guide d'ondes optiques planar (20) est guidée à travers son intérieur et amenée à être incidente sur une couche semi-conductrice (30). L'angle (θ) entre la direction nette de progression de la lumière guidée à travers le guide d'ondes optiques planar (20) et la direction nette de mouvement des vecteurs générés dans la couche semi-conductrice (30) par la lumière incidente sur la couche semi-conductrice (30) à partir de la surface de bord du guide d'ondes optiques planar (20) est sensiblement un angle droit.
PCT/JP2013/078139 2012-10-19 2013-10-17 Dispositif de conversion photoélectrique, structure construite et instrument électronique WO2014061719A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014542164A JP6261088B2 (ja) 2012-10-19 2013-10-17 光電変換装置、建築物および電子機器

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-231508 2012-10-19
JP2012231508 2012-10-19

Publications (1)

Publication Number Publication Date
WO2014061719A1 true WO2014061719A1 (fr) 2014-04-24

Family

ID=50488279

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/078139 WO2014061719A1 (fr) 2012-10-19 2013-10-17 Dispositif de conversion photoélectrique, structure construite et instrument électronique

Country Status (2)

Country Link
JP (1) JP6261088B2 (fr)
WO (1) WO2014061719A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017061448A1 (fr) * 2015-10-09 2017-04-13 国立大学法人北海道大学 Dispositif de guide d'onde optique, dispositif de conversion photoélectrique, structure architecturale, appareil électronique et dispositif électroluminescent
KR20190052981A (ko) * 2017-11-09 2019-05-17 엘지전자 주식회사 태양전지

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013166467A1 (fr) 2012-05-03 2013-11-07 Vioptix, Inc. Sélection de longueur d'onde de lumière permettant de ne pas utiliser de colorants chirurgicaux

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11281833A (ja) * 1998-03-31 1999-10-15 Minolta Co Ltd グレーティングカプラ
JP4022631B2 (ja) * 2004-09-09 2007-12-19 国立大学法人 北海道大学 太陽電池および光電変換素子
JP2009139418A (ja) * 2007-12-03 2009-06-25 Hikari Energy Kenkyusho:Kk 集光装置および集光方法
JP2009229581A (ja) * 2008-03-19 2009-10-08 Hikari Energy Kenkyusho:Kk 集光装置
WO2010126162A1 (fr) * 2009-04-28 2010-11-04 国立大学法人北海道大学 Cellule solaire et élément de conversion photoélectrique
JP2012079749A (ja) * 2010-09-30 2012-04-19 Dainippon Screen Mfg Co Ltd 光起電力装置用集光シートおよび光起電力装置
JP2012099681A (ja) * 2010-11-04 2012-05-24 Toyota Industries Corp 集光構造体及び光発電装置
WO2012111768A1 (fr) * 2011-02-18 2012-08-23 国立大学法人北海道大学 Photopile

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2248189A1 (fr) * 2008-02-12 2010-11-10 QUALCOMM MEMS Technologies, Inc. Concentrateur/collecteur solaire holographique à film mince bicouche

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11281833A (ja) * 1998-03-31 1999-10-15 Minolta Co Ltd グレーティングカプラ
JP4022631B2 (ja) * 2004-09-09 2007-12-19 国立大学法人 北海道大学 太陽電池および光電変換素子
JP2009139418A (ja) * 2007-12-03 2009-06-25 Hikari Energy Kenkyusho:Kk 集光装置および集光方法
JP2009229581A (ja) * 2008-03-19 2009-10-08 Hikari Energy Kenkyusho:Kk 集光装置
WO2010126162A1 (fr) * 2009-04-28 2010-11-04 国立大学法人北海道大学 Cellule solaire et élément de conversion photoélectrique
JP2012079749A (ja) * 2010-09-30 2012-04-19 Dainippon Screen Mfg Co Ltd 光起電力装置用集光シートおよび光起電力装置
JP2012099681A (ja) * 2010-11-04 2012-05-24 Toyota Industries Corp 集光構造体及び光発電装置
WO2012111768A1 (fr) * 2011-02-18 2012-08-23 国立大学法人北海道大学 Photopile

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
IKUO SUEMUNE: "Conversion of Light Propagation Direction for Highly Efficient Solar Cells", APPLIED PHYSICS EXPRESS, vol. 4, 2011, pages 102301-1 - 102301-3 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017061448A1 (fr) * 2015-10-09 2017-04-13 国立大学法人北海道大学 Dispositif de guide d'onde optique, dispositif de conversion photoélectrique, structure architecturale, appareil électronique et dispositif électroluminescent
KR20190052981A (ko) * 2017-11-09 2019-05-17 엘지전자 주식회사 태양전지
KR102591913B1 (ko) * 2017-11-09 2023-10-20 상라오 징코 솔라 테크놀러지 디벨롭먼트 컴퍼니, 리미티드 태양전지

Also Published As

Publication number Publication date
JPWO2014061719A1 (ja) 2016-09-05
JP6261088B2 (ja) 2018-01-17

Similar Documents

Publication Publication Date Title
Hossain et al. Perovskite/silicon tandem solar cells: from detailed balance limit calculations to photon management
Chen et al. A 19.9%-efficient ultrathin solar cell based on a 205-nm-thick GaAs absorber and a silver nanostructured back mirror
Khattak et al. Effect of CZTSe BSF and minority carrier life time on the efficiency enhancement of CZTS kesterite solar cell
Abdelraouf et al. Towards nanostructured perovskite solar cells with enhanced efficiency: Coupled optical and electrical modeling
Karimi et al. Simulation of perovskite solar cell with P3HT hole-transporting materials
CN104106145A (zh) 垂直结太阳能电池的结构和方法
Dorodnyy et al. Efficient multiterminal spectrum splitting via a nanowire array solar cell
Yan et al. A spiro-MeOTAD/Ga2O3/Si pin junction featuring enhanced self-powered solar-blind sensing via balancing absorption of photons and separation of photogenerated carriers
Um et al. Flexible crystalline-silicon photovoltaics: light management with surface structures
Zhu et al. Three-dimensional nanopillar arrays-based efficient and flexible perovskite solar cells with enhanced stability
JP6261088B2 (ja) 光電変換装置、建築物および電子機器
Chen et al. Three-dimensional radial junction solar cell based on ordered silicon nanowires
JP6763614B2 (ja) 光導波装置、光電変換装置、建築物、電子機器および発光装置
Yang et al. Broadband quantum efficiency enhancement in high index nanowire resonators
Bhattarai et al. Performance enhancement by an embedded microlens array in perovskite solar cells
JP2015201563A (ja) 光電変換装置、建築物および電子機器
Kathalingam et al. Effect of indium on photovoltaic property of n-ZnO/p-Si heterojunction device prepared using solution-synthesized ZnO nanowire film
Banerjee et al. Tailored interfaces of the bulk silicon nanowire/TiO2 heterojunction promoting enhanced photovoltaic performances
GB2451108A (en) Photovoltaic Device
JP7270252B2 (ja) 光導波装置、光電変換装置、建築物、電子機器、移動体および電磁波導波装置
Akhtar et al. Photovoltaic-based nanomaterials: synthesis and characterization
Guo et al. High-efficiency core–shell solar cell array from Si wafer
US20110155215A1 (en) Solar cell having a two dimensional photonic crystal
WO2022124283A1 (fr) Dispositif de conversion photoélectrique, bâtiment, et objet mobile
US9379261B2 (en) Ultra thin film nanostructured solar cell

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13847018

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2014542164

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13847018

Country of ref document: EP

Kind code of ref document: A1