TW201230358A - Optical electricity storage device - Google Patents

Abstract

Provided is an optical electricity storage device which uses a photoelectric conversion element to widen the wavelength band capable of photoelectric conversion, and which can be employed even when the power usage time is offset from the light reception time. An optical electricity storage device (1) is provided with a photovoltaic generator (2) and a power storage unit (3). The photovoltaic generator (2) includes first and second photoelectric conversion elements (10, 20). Each of the photoelectric conversion elements (10, 20) includes semiconductor layers (11, 21), conductive layers (12, 22), and metal nanostructures (13, 23) having a plurality of periodic structures (13c) of random periods. The semiconductor layer (11) of the first photoelectric conversion element (10) is an n-type semiconductor layer. The semiconductor layer (21) of the second photoelectric conversion element (20) is a p-type semiconductor layer.

Description

201230358 6. TECHNOLOGICAL FIELD OF THE INVENTION The present invention relates to an optical power storage device that performs power generation by photoelectric conversion and stores power generated by power generation. [Prior Art] For example, in the patent document, a photoelectric conversion element utilizing surface plasmon resonance is described. A concave-convex structure of a uniform period is formed on the surface of the metal layer of the element. A semiconductor layer is laminated on the uneven structure, and a transparent electrode is laminated on the semiconductor layer. The other layers of the back layer of the metal layer. When light is incident on the element ', the electrons on the surface of the uneven layer side of the metal layer vibrate in resonance with the incident light to generate an electric current. The photoelectric conversion element described in Patent Document 2 is provided with two or more kinds of fine particles on the surface, and causes surface plasmonic resonance in at least two wavelength bands. Further, since 1960, it has been known that visible light can be detected by a Schottky type photosensor having a thickness of 4111 or more laminated with 11 or more layers. Non-Patent Document 1 discloses that near-infrared light of 1 μm to 2 μm can be detected by a photosensor on a *nsSi layer. Non-Patent Document 2 describes that infrared light of 1 μm to 5 μm can be detected by a photosensor of a type 5 and a CoSh laminated thereon.

In Non-Patent Document 3, it is described that infrared light of 1 μm to 6 μm can be detected by the pt light sensor of the Quaternary & Non-Patent Document 4 describes that light of 10 μm or less can be detected by a photosensor in which Ir is laminated on S1. [Patent Document 1] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2007-073794 (Patent Document 2) Japanese Patent Laid-Open Publication No. 2010-021189 [Non-Patent Document]

The International Society for Optical Engineering 2525 (2), 456 (1995) ^ij S. Kolondinski, et al., Proceedings of SPIE-

The International Society for Optical Engineering 2554, 175 (1995) [Non-Patent Document 3] JM Mooneyanci J. Silverman, IEEE Trans Electron Devices ED-32, 33-39 (1985) [Non-Patent Document 4] BY. Tsaur, MM Weeks, R Trubiano and PW Pellegrini, IEEE Electron Device Left. 9, 650-653 (1988) [Problems to be Solved by the Invention] As also known from Non-Patent Documents 1 to 4, Schottky Photodiodes, etc. The sensing band of the photoelectric conversion element differs depending on whether the semiconductor is n-type or p-type. The η-type system has sensitivity to the visible region to the near-infrared region, and is less sensitive to the infrared region having a longer wavelength than the near-infrared region. The p-type system has sensitivity to the infrared region and poor sensing to the visible region. Moreover, when the power is used, it is not necessarily limited to the same as when the light is received or even when the power is generated. The present invention has been developed in view of the above circumstances, and an object of the present invention is to increase the wavelength band that can be photoelectrically converted, to improve the light use efficiency, and to cope with the fact that even when the power is used, the 156673.doc 201230358 is misaligned with the light receiving time, thereby improving convenience. Sex. [Means for Solving the Problems] The present invention has been made to solve the above problems, and the present invention includes a photovoltaic power generation unit that generates power by light, and a power storage unit that is connected to the photovoltaic power generation unit The photo power generation unit includes: a second photoelectric conversion element connected in series, in parallel, or in series and parallel, wherein each of the second and second photoelectric conversion elements includes a semiconductor layer; and a conductive layer laminated on the semiconductor And a metal nanostructure, which is laminated on the conductive layer and includes a plurality of (preferably a plurality of) periodic structures; each of the periodic structures includes a plurality of first protrusions 4 protruding in a direction of the layer, the first The arrangement interval of the convex portions differs depending on the periodic structure; the semiconductor layer of the first photoelectric conversion element is an n-type semiconductor layer, and the semiconductor layer of the second photoelectric conversion element is a p-type semiconductor layer. When light is incident on each of the photoelectric conversion elements, photons are generated by photoelectric conversion in the Schottky junction between the semiconductor layer and the conductive layer. Further, the sensitivity of the photoelectric conversion can be improved by the metal nanostructure in the vicinity of the Schottky junction. The first photoelectric conversion element can enhance the sensitivity of the light in the visible light region to the near-infrared region. The second photoelectric conversion element can enhance the sensitivity of the light in the infrared region. Therefore, by combining the second and second photoelectric conversion elements, the wavelength band which can be photoelectrically converted can be enlarged, and the light use efficiency can be improved. Since the electric power generated by the photoelectric conversion elements is stored in the electric storage unit, electric power can be supplied even during the non-light receiving process. The first photoelectric conversion element and the second photoelectric conversion element may be combined in the thickness direction of each other. 156673.doc 201230358 By this, the light receiving area of each photoelectric conversion element can be sufficiently increased. Therefore, the amount of received light or the amount of power generated can be increased. In particular, the amount of light received or the amount of power generated by the photoelectric conversion element disposed on the front side (the incident side of light) can be sufficiently increased. The first photoelectric conversion element may be disposed on the front side (light incident side), or the second photoelectric conversion element may be disposed on the front side (light incident side). In the case where the incident light is deflected from the visible region to the near-infrared region, it is preferable that the first photoelectric conversion element is disposed on the front side (light incident side). When the incident light is deflected toward the infrared region, it is preferable that the second photoelectric conversion element is disposed on the front side (light incident side). The first photoelectric conversion element and the second photoelectric conversion element may be arranged in the same manner. The thickness direction is orthogonal to the plane direction. Thereby, light can be directly incident on the first and second photoelectric conversion elements, respectively. Therefore, each of the first and second photoelectric conversion elements can sufficiently receive the induced wavelength component in the incident light to cause photoelectric conversion. Thereby, the amount of power generation by the photovoltaic power generation unit can be increased. Preferably, the first photoelectric conversion element is provided with a nanostructure including an n-type semiconductor having sensitivity to an ultraviolet region. Thereby, the photoelectric conversion sensitivity of the first photoelectric conversion element can be improved. In particular, the sensitivity of the short-wavelength side in the sensing band of the south first photoelectric conversion element can be mentioned. The semiconductor having sensitivity to the ultraviolet region means a semiconductor having a property that the carrier is excited when ultraviolet light having an irradiation wavelength of, for example, 0.4 μm or less is excited. As such a semiconductor, for example, an oxidized word (ΖηΟ) of the bismuth-type semiconductor is mentioned, and n-type gallium nitride (n-GaN# is preferable. Preferably, the η-type semiconductor nanostructure is a nanowire, Nano-needle, nanotube, nano 156673.doc 201230358 Nanostructures such as rods, which can improve the quantum efficiency and further positively increase the sensitivity of the first photoelectric conversion element. As a result, it can be increased. The amount of power generation is preferably 'in the second photoelectric conversion element described above, a nanostructure including a p-type semiconductor having sensitivity to the infrared region is provided. Thereby, the photoelectric conversion sensitivity of the second photoelectric conversion element can be improved. In particular, the sensitivity of the long-wavelength side in the inductive frequency band of the second photoelectric conversion element can be increased. The semiconductor having sensitivity to the infrared region means a semiconductor having a property that the carrier is excited when the irradiation wavelength is, for example, 0.7 μm or more. Examples of such a semiconductor include p-type gallium nitride (p_GaN), carbon, etc. Preferably, the p-type semiconductor nanostructure is a nanotube, a nanowire, a nanoneedle, or a nanotube. Nano By using a nanostructure, the quantum efficiency can be improved, and the sensitivity of the second photoelectric conversion element can be surely improved, and as a result, the amount of power generation can be increased. As a metal component of the conductive layer constituting each photoelectric conversion element, For example, Co, Fe' W, Ni, A or Ti may be mentioned. The metal elements listed above have a relatively high melting point' and are excellent in mechanical properties at high temperatures. The above-mentioned conductive layer may be either metal or metal. a mixture of semiconductors or an alloy. As a mixture or alloy of a metal and a semiconductor, for example, a metal telluride may be mentioned. When the semiconductor layer contains germanium, the conductive layer may be a surface portion of the metal component and the semiconductor layer. The metal oxide formed by interdiffusion, the diffusion can be carried out, for example, by annealing. The above-mentioned metals (Co, Fe, W, Ni, A, Ti) are suitable for deuteration. A positive and negative pair of electric 156673.doc 201230358 poles are disposed in the conductive layer of the conversion element, and the electrodes are connected to another photoelectric conversion element or power storage unit. Preferably, the polarity determining layer is interposed between the cathode electrode of the second photoelectric conversion element and the conductive layer. Preferably, the polarity determining layer is interposed between the anode electrode and the conductive layer of the second photoelectric conversion element. The polarity determining layer may be a barrier layer including an insulator such as a resin, or a bump layer integrally protruding from the semiconductor layer of the element. In the electric conversion element, the incident light is made of a semiconductor layer and a conductive layer. The Schottky junction of the layer absorbs to form a photocarrier (electron hole pair), and the electron moves toward the side of the semiconductor layer due to the electric field of the working layer. Accordingly, electrons flow from the anode electrode to the conductive layer. The conductive layer flows along the side of the cathode electrode. In the second photoelectric conversion element, the incident light is connected to the Schottky base of the semiconductor layer and the conductive layer. The photocarriers (electron-hole pairs) are generated by absorption, and the holes move toward the side of the semiconductor layer due to the electric field of the empty layer. The hole then flows from the cathode electrode to the conductive layer. The electric holes flow along the conductive layer toward the anode electrode. In this way, it is possible to surely determine the (four) electrode and the electrode to be the cathode of each photoelectric conversion element. In the first photoelectric conversion element, when the polarity determining layer is a barrier layer including the insulating f-seeking layer, the barrier electrode layer and the conductive layer sandwich the barrier layer and are raised into a capacitor. In this way, the thunder increases the electrons. In the second photoelectric conversion of the Dusit' ^ f 1 conversion TG, when the barrier layer of the above-mentioned polar insulator is opened, the % electrode and the conductive layer sandwich the barrier layer 156673.doc 201230358, Form a capacitor. Thereby, a hole is accumulated in a portion of the conductive layer opposite to the anode electrode. Therefore, the electrode serving as the anode and the electrode serving as the cathode can be surely determined. The thickness of the barrier layer is preferably less than 丨nm. Thereby, the carrier can surely pass through the barrier layer due to the tunneling effect or the like, so that the photo-induced flow can be surely taken out. Preferably, in the second photoelectric conversion element, the convex layer and the end surface of the conductive layer on the cathode electrode side are Schottky contacts, and are in ohmic contact with the cathode electrode, thereby forming a convex layer and a conductive layer. The Schottky connection: in the portion, the electrons of the carrier can be caused to flow toward the convex layer side or even the cathode electrode, so that the polarity can be surely determined. In the second photoelectric conversion element, it is preferable that the convex layer and the end surface on the anode electrode side of the conductive layer are in Schottky contact, and are in ohmic contact with the anode electrode. Thereby, the hole of the carrier can flow toward the convex layer side or the anode electrode in the Schottky junction portion between the convex layer and the conductive layer, so that the polarity can be surely determined. The electrode serving as the anode of the anode can be determined by making the composition of the above-mentioned conductive layer or the like non-uniform in the direction from the one electrode toward the other electrode. ', Hummer + If light is incident on the above metal nanostructure', it will cause electric resonance. Thereby the metal nanostructure will contribute to the increase of the photonic field. Preferably, the metal nanostructure is an aggregate of metal fine particles of a nanometer size. As the metal constituting the metal fine particles, it is preferable to use a metal element such as ^, ^, ^^, or the like. The chemical stability is 156673.doc 201230358. The qualitative property is relatively high, it is difficult to alloy, and it is difficult to combine with a semiconductor such as Si. . Therefore, the surface plasmonics can be surely formed. Preferably, the metal nanostructure is provided on a portion of the conductive layer between the pair of electrodes, and more preferably distributed over a portion of the pair of electrodes. The above metal nanostructure is formed, for example, in the following manner. The metal material to be the metal nanostructure described above is placed on the above-mentioned conductive layer, and an annealing treatment is performed. The shape and even the shape of the metal material are not particularly limited, and may be any of a film shape, a small piece shape, a small block shape, a granular shape, a powder shape, a gel shape, a fiber shape, a wire shape, and a dot shape. For other shapes and even traits. The fine particles of the metal raw material are diffused along the surface of the conductive layer by the annealing treatment. By this diffusion, the fine particles of the above-mentioned metal raw material are branched in a plurality of stages or even multiples, and become, for example, an aggregate of a fractal structure. Therefore, the above metal nanostructure can be easily formed. On the surface of the above metal nanostructure, irregularities of a submicron or nanometer order are formed. The surface of the metal nanostructure includes a plurality of convex portions protruding in the lamination direction (thickness direction), and is, for example, a cluster. The above electrode may also be used as a metal material for the above metal nanostructure. The metal constituting the electrode may be diffused in a shape or a shape around the electrode by annealing treatment. In this manner, the above-described metal nanostructure can be formed in the vicinity of the above electrode. In this case, the upper electrode and the metal nanostructure described above contain the same metal component as each other. In the above metal nanostructure, it is preferable that the periodic structure has a period in which the period (4) is a period of the periodic structure. That is, it is preferable that the arrangement interval of the first convex portions differs depending on the periodic structure, as compared with 156673.doc 201230358. Thereby, it is possible to induce light of a wavelength corresponding to a different periodic structure. 2, as a whole, the wavelength at which the metal nanostructure can be induced can be expanded. Thereby, it is possible to provide a photoelectric conversion element which can correspond to a wide frequency band which is spread over the infrared light region by the visible light region. The arrangement interval (period) of the first projection is preferably about 〇^ times 1U right' of the wavelength λ of the incident light, more preferably about 01 times the wavelength of the person. Alternatively, the arrangement interval (period) of the first convex portions is preferably about 0 to about 1 times the wavelength of the induction of the Schottky device made of the semiconductor layer and the conductive layer. The periodic structure is sensitive to the incident light having a wavelength of about i times to about 10 times (particularly about 10 times of the above-mentioned period) of the period of the ith convex portion constituting the periodic structure, causing the plasm Resonance, which helps to amplify the photo-induced field. The period of the periodic structure of the first photoelectric conversion element (the arrangement interval of the i-th convex portion) is preferably smaller than the period of the periodic structure of the second photoelectric conversion element (the arrangement interval of the i-th convex portion). The arrangement interval (period) of the i-th convex portion of the i-th photoelectric conversion element is more preferably about 100 nm or less. Thereby, the light in the infrared light region to the visible light region below the wavelength Μ (4) can have a good sensitivity. The arrangement interval (period) of the first convex portion of the second photoelectric conversion element is more preferably about 15 Å nm or less. Thereby, the infrared light having a wavelength of about 1 μηι to 4 (4) can have a good sensitivity. The protrusion height of the first protrusion 4 is preferably about 10 nm to 20 nm. And preferably, at least one of the periodic structures has a wavelength of about 〇.丨 times to 丨 times in a certain wavelength range (preferably from the visible light region to the infrared light region) (especially about 1 time Size) configuration interval. Thereby, if the 156673.doc 201230358 light is included in the above wavelength range, at least one periodic structure of the metal nanostructure can be made sensitive to the incident light. Preferably, the metal nanostructure further includes a plurality of second convex portions that are larger than the first convex portion, and the second convex portions are dispersed with each other, and each of the second convex portions and the periodic structure are A stacked or nearly grounded configuration. When the right light is incident on the metal-need structure, a near-field interaction occurs between the second convex portions constituting the random structure or the first and second convex portions (#A?, K.Kobayashi, et. Al., Progressin Nano-Electro-Optecs I. ed. M. Ohtsu, p. 119 (Sptinger-Verlag, Berlin, 2003)). The photo-induced field can be further amplified by the multiplication effect of the near-field interaction and the plasmon resonance, thereby improving the sensitivity. Even if the incident light is weak, the photoelectromotive force can be generated with high sensitivity. The protrusion height of the second convex portion is preferably about 5 〇 nm to 200 nm. The dispersion interval of the second convex portions (the separation distance between adjacent second convex portions) is preferably larger than the wavelength of the incident light, and is preferably larger than the sensing wavelength of the Schottky device made of the semiconductor layer and the conductive layer. . The dispersion interval of the second convex portion of the first photoelectric conversion element is preferably smaller than the dispersion interval of the second convex portion of the second photoelectric conversion element. For example, the dispersion interval of the second convex portion of the first photoelectric conversion element is preferably 1 μm or more, and more preferably about 2 μm to 3 μm. The second projection of the second photoelectric conversion element preferably has a dispersion interval of about 3 μm to 5 μm. Thereby, the adjacent second convex portions can be prevented from interfering with each other to weaken the electric field. The upper limit of the dispersion interval of the second convex portion of the first photoelectric conversion element is preferably about 3 μm to about 5 μm, and the upper limit of the dispersion interval of the second convex portion of the second photoelectric conversion element is preferably 156673.doc -12 - 201230358 5 μιη~6 μιη or so. Thereby, the density of the second convex portion can be ensured, and the number of periodic structures that can interact with the second convex portion can be ensured, and the induced frequency band can be surely expanded. An insulator such as a carbon compound may be mixed in the above metal nanostructure to form an M-I-M (metal-in SUlat〇r-metal, metal-insulator _ metal) structure. Port [Effect of the Invention] According to the present invention, light of a wide wavelength band extending from the visible light region in the infrared region can be converted into electric power, and the electric power can be stored. Therefore, even when power generation is not performed by the photovoltaic power generation unit or when the amount of power generation is small, the power stored in advance can be supplied, thereby improving convenience. [Embodiment] Hereinafter, embodiments of the present invention will be described based on the drawings. Fig. 1 is a view showing a light storage device according to an i-th embodiment of the present invention. The optical power storage device 1 includes a photovoltaic power generation unit 2 and a power storage unit 3 connected to the optical power generation unit 2. The photovoltaic power generation unit 2 generates electric power from incident light. Power storage unit 3 stores electric power generated by the above-described power generation. Hereinafter, a detailed description will be made. The photovoltaic power generation unit 2 includes a second photoelectric conversion element 1A and a second photoelectric conversion element 20. The photoelectric conversion elements 1 〇 and 2 〇 are electrically connected in parallel. The first photoelectric conversion element 1 includes an n-type semiconductor layer u, a conductive layer I, and a metal nanostructure 13. A conductive screen 12 is laminated on the n-type semiconductor layer. A metal nanostructure 13 〇 is deposited on the conductive layer 12

The semiconductor layer 11 contains germanium (Si). However, it is not limited thereto, and the semiconductor layer 11 may include other semiconductors such as Ge or GaAs. In the semiconductor layer U 156673.doc -13- 201230358, a type 11 impurity such as P (phosphorus) is doped. The semiconductor layer u constitutes an n-type half. The n-type semiconductor layer 11 also serves as a substrate for the second photoelectric conversion element 1〇. The semiconductor layer 11 includes a germanium substrate. The ruthenium substrate is doped with an n-type impurity. As the germanium substrate, a germanium wafer or the like can be used. The first! The shape retention of the photoelectric conversion element 1 is ensured by the germanium substrate, and the substrate may be separately provided separately from the n-type semiconductor layer. For example, the n-type semiconductor layer 11β may be coated on the substrate including the glass or the resin film, or the n-type semiconductor may be formed by CVD (Chemical Vapor Deposition) or the like on the surface of the separately provided substrate. Layer 11 is formed into a film. The conductive layer 12 covers the entire surface of the substrate 11 (the upper surface conductive layer 12 is composed of a metal telluride in FIG. 1 and has electrical conductivity. The lanthanum of the surface layer of the ruthenium substrate is self-assembled to form a conductive layer 12. The metal component constituting the conductive layer 12 is c〇, Fe, W, Ni, A, Ti, etc. However, the above metal component is not limited thereto. Here, Co is used as the conductive layer 12 The metal component>>the conductive layer 12 is composed of CoSix, preferably CoSh. Thereby, a good Schottky interface is formed between the conductive layer 12 and the semiconductor layer 11. The conductive layer 12 may also be composed only of a metal component. The thickness of the layer 12 is about several nm to several tens of nm, preferably about several nm. The thickness of the conductive layer 12 of the drawing is expressed with respect to the thickness of the substrate 11, the electrode 14, 15, or the metal nanostructure 13 and the like. The surface of the layer 12 (the upper surface in Fig. 1) is provided with a metal nanostructure 13. The metal nanostructure 13 is widely distributed on the surface of the conductive layer 12. Here, the metal nanostructure 13 is disposed on the conductive layer 12 On the surface of the following 156673.doc • 14· 201230358 The portion between the electrodes 14, 15 (hereinafter referred to as "interelectrode portion") is more preferably distributed over the entire interelectrode portion. The metal nanostructure 13 may be laminated only on one portion of the conductive layer 12. For example, the metal nanostructure 3 may be provided only in the vicinity of the electrode 丨 4 or 15 of the conductive layer 12. The metal nanostructure 13 is mainly composed of a metal such as Au, Ag, Pt, Cu, or Pd. Here, Au is used as the metal constituting the metal nanostructure 13. The metal nanostructure 13 is a structure rich in Au, and an insulator such as a carbon compound can be mixed in the metal constituting the metal nanostructure 13, and the metal nanostructure 13 can also be formed into a metal-insulator-metal metaMnsulat〇r_metal structure. On the surface of the metal nanostructure 13 'forms a sub-micron or nano-scale convex sheep, 'Tian s, metal nanostructure 13 series to make the Au nano-particles into a mis- or a fragment Structure (refer to Figs. 8 and 9). The aggregate of the gold layer nano-junction and the Au nano-particles is included in the convex portion of the photoelectric conversion element 10 in the thickness direction or even in the lamination direction (above in Fig. 4). The convex portions are gathered into a stealth shape. Alternatively, it becomes a fractal structure in which an aggregate of AU nanoparticles is diffused in a multi-branch manner. The metal nanostructures include a plurality of first convex portions (5) and second convex portions (10). One of the plurality of convex portions constitutes a first convex portion and the other portion constitutes a second convex portion 13b. The metal nanostructure 13 comprises at least one periodic structure. Preferably, the gold layer has a plurality of or even a plurality of even periodic structures. The adjacent ones of the plurality of convex portions of the metal nanostructure 13 are adjacent. The plurality of convex portions 13a, 13a m ^ ··· constitute a periodic structure 〖3c. Each of the I56673.doc 201230358 (the direction with the parent of the lamination direction) is arranged at a certain interval (period). The arrangement interval (period) of the second convex portion 13a differs depending on the periodic structure pupil. The arrangement interval (period) of the second convex portion 13a in the periodic structure Uc is preferably about several tens of nm to several μm, more preferably about 4 〇 nm to about 1 〇〇 nm. The arrangement interval period is preferably about 倍 to about 丨 times the wavelength of the incident light L, and more preferably about 1. Preferably, the arrangement interval (period) is preferably about 0' times to about 丨 times the inductive wavelength (from the visible light region to the infrared light region) of the Schottky element including the n-type semiconductor layer 11 and the conductive layer 12. More preferably about 〇 times. The metal nanostructure 13 is preferably a periodic structure having at least one arrangement interval having a size of about 1 to 1 times the arbitrary wavelength of the sensing region in the Schottky element. Further, a plurality of second convex portions 13b are dispersedly arranged on the metal nanostructure 13. Each of the second convex portions 13b is disposed so as to overlap with any of the periodic structures 13c. Alternatively, each of the second convex portions 13b is disposed in close proximity to any of the periodic structures 13c. The second convex portion 13b has a protruding height greater than the first! The convex portion Ua has a kurtosis (ratio of the protruding width to the bottom width) larger than the first convex portion 3a. The degree of occurrence of the second convex portion i3b is preferably about 50 nm to 200 nm. The dispersion interval of the second convex portions 13b is preferably larger than the wavelength of the incident light. For example, the dispersion interval is preferably 1 μm or more, and preferably about 2 μm to 3 μm. The upper limit of the interval between the second convex portions 13b is preferably about 3 μm to about 5. A pair of electrodes μ, 15 are disposed on the conductive layer 12 at positions separated from each other. Here, an electrode 14 (cathode electrode) is disposed at one end of the upper surface of the conductive layer 12 (the right side in Fig. 1). Further, the electrode 15 (anode electrode) is disposed at the other end of the upper surface of the conductive layer 12 (left side in 圊j). Electrode, -16 - 156673.doc

The configuration of S 201230358 15 is not limited to the above. For example, one of the electrodes i4 and φ may be disposed in the central portion of the first photoelectric conversion element 10, and the other of the electrodes 14 and 15 may be disposed at the four corners (peripheral portion) of the ith photoelectric conversion element 1A. The electrodes 14, 15 include metals such as Ag, Pt, Cu, and Pd. Here, Au is used as the second metal constituting the electrodes 14, 15. Therefore, the electrodes 14 and 15 contain the same metal component as the metal component constituting the metal nanostructure 13. The metal component constituting the metal nanostructure 13 and the metal components constituting the electrodes 14 and 15 may be different from each other. The two electrodes 14, 15 may also contain mutually different metal components. A barrier layer 16 (polarity determining layer) is interposed between the cathode electrode 14 and the conductive layer 12. The barrier layer 16 contains an insulator such as aluminum, Si 〇 2, SiN, or a carbon compound (e.g., a resin). The thickness of the barrier layer 16 is small enough to produce a tunneling effect. For example, the barrier layer 16 has a thickness of angstroms, i.e., less than 丨. In the drawings, the thickness of the barrier layer 16 is exaggerated relative to the thickness of the conductive layer 12 or the metal nanostructure 13 or the like. The capacitor 14 is formed by the electrode 14 and the conductive layer 12 facing each other across the barrier layer 16. As described below, a carrier (electron) generated by photoelectric conversion is accumulated in a portion of the conductive layer 12 opposed to the electrode 14. Thereby, the electrode 14 becomes a cathode. The electrode 15 becomes an anode. The anode electrode 15 is in direct contact with the conductive layer 12. Preferably, the anode electrode 15 is ohmically bonded to the conductive layer 12. Next, the second photoelectric conversion element 20 will be described. The second photoelectric conversion device 20 has substantially the same configuration as that of the first photoelectric conversion element 1A. That is, the second photoelectric conversion element 20 includes the semiconductor layer 21, the conductive layer 22, and the gold structure 156673.doc 201230358. The conductive layer 22 is laminated on the conductor layer 21 of the bob. A metal nanostructure 23 is laminated on the conductive layer 22. The second photoelectric conversion 70 2G differs from the first photoelectric conversion element 10 in that the 'semiconductor layer 21 is p-type. In the semiconductor layer pair, the impurity (b) and the conductor layer 21 in the P layer are included in the semiconductor layer. However, the semiconductor layer 21 may not include other semiconductors such as Ge or GaAs. The P-type semiconductor layer 21 also serves as a substrate of the second photoelectric conversion element 20. The p-type semiconductor layer 21 includes a germanium substrate doped with a P-type impurity. As the ruthenium substrate, a ruthenium wafer or the like can be used. The shape retention of the second photoelectric conversion element 2 is ensured by the ruthenium substrate. The substrate may be separately provided separately from the p-type semiconductor layer 21. For example, the p-type semiconductor layer 21 may be coated on a substrate including a glass or a resin film. The p-type semiconductor layer 21 may be formed on the surface of the substrate separately provided as described above by CVD or the like. The conductive layer 22 covers the entire surface of the substrate 21 (the upper surface in Fig. 1). The conductive layer 22 contains a metal halide and is electrically conductive. The ruthenium of the surface layer of the ruthenium substrate 21 is self-assembled into a ruthenium component constituting the conductive layer 22. Examples of the metal component constituting the conductive layer 22 include c〇, Fe, W, Ni, and bab Ti. However, the above metal components are not limited to these. Here, c 〇 is used as the metal component constituting the conductive layer 22. The conductive layer 22 comprises c〇Six, preferably containing CoSi2^, thereby forming a good Schottky interface between the conductive layer 22 and the semiconductor layer 21. The conductive layer 22 may also be composed only of a metal component. The thickness of the conductive layer 22 is about several nm to several tens of nm. The thickness of the conductive layer 22 of the drawing is exaggerated with respect to the thickness of the substrate 21, the metal nanostructure 23, and the like. 156673.doc 201230358 A metal nanostructure 23 is provided on the surface of the conductive layer 22 (the upper surface in FIG. 1). The metal nanostructures 23 are widely distributed on the surface of the conductive layer 22. Here, the metal nanostructure 23 is disposed on a portion of the surface of the conductive layer 22 between the electrodes 24 and 25 (hereinafter referred to as "interelectrode portion"), and more preferably distributed between the electrodes. In the whole. The metal nanostructure 23 is not limited to being substantially entirely laminated on the surface of the conductive layer 22, but may be laminated only on one portion of the conductive layer 22. The metal nanostructure 23 is mainly composed of a metal such as Au, Ag, Pt, Cu or Pd. Here, Au is used as the metal constituting the metal nanostructure 23. The metal nanostructure 23 is a structure rich in Au. An insulator such as a carbon compound may be mixed with the metal constituting the metal nanostructure 23, and the metal nanostructure 23 may also have an M-I-M structure. On the surface of the metal nanostructure 23, irregularities of a submicron or nanometer order are formed. Specifically, the metal nanostructure 23 is a structure in which the nanoparticles of the eight 11 are aggregated into a cluster or a fractal (refer to FIGS. 8 and 9 ). The collection system of the Au nanoparticles of the metal nanostructure 23 A plurality of convex portions that protrude along the thickness direction of the second photoelectric conversion element 20 or even in the lamination direction (upward in FIG. 2) are included. The protrusions are grouped into a town. Alternatively, it is a fractal structure in which aggregates of Au nanoparticles are diffused in multiple branches. The metal nanostructure 23 includes a plurality of i-th convex portions 23a and a second convex portion 23, and one of the plurality of convex portions in the metal rice structure 23 constitutes an i-th convex portion, and a portion constitutes a second convex portion. Part 23b. The metal nanostructures 2 3 comprise at least one periodic structure 2 3 c. Preferably, the metal nanostructure 23 contains a plurality of or even more than a few _ 156673.doc -19· 201230358 structures 23c. A periodic structure 23<^ is formed by a plurality of adjacent convex portions 23a, 23a, ... among the plurality of convex portions of the metal nanostructure 23. The i-th convex portions 23a and 23a constituting each periodic structure 23c are arranged at intervals of (a period) along the plane direction of the element ι (the direction orthogonal to the lamination direction). The arrangement interval (period) of the first convex portions 23a differs depending on the periodic structure 23β. The first of these periodic structures 23c! The arrangement interval (period) of the convex portions 23a is preferably tens of nm to several (four) left ^, more preferably slightly larger than the arrangement interval in the second photoelectric conversion element and more preferably about 6 〇 nm to 15 〇 . The arrangement interval (period) is preferably about 1 to about 1 times the wavelength of the incident light L, more preferably about 0.1 times. Further, the arrangement interval (period) is preferably about 0 to about 1 times, more preferably about 1 time, of the money wavelength (infrared light region) of the Schottky element including the germanium-type semiconductor layer 21 and the conductive layer 22. about. The metal nanostructure 23 preferably includes a period of at least one arrangement interval having a size of about 1 to 1 times the arbitrary wavelength of the Schottky element including the p-type semiconductor layer 21 and the conductive layer 22. structure. Further, in the metal nanostructure 23, a plurality of second convex portions 23b are dispersedly arranged. Each of the second convex portions 23b is disposed so as to overlap with any of the periodic structures 23c. Alternatively, each of the second convex portions 23b is disposed in close proximity to any of the periodic structures 23c. The second convex portion 23b has a protruding height greater than the first! The convex portion 23a, and the kurtosis (ratio of the protruding height to the bottom width) is larger than the first! Concave portion 23a. The dog's exiting degree of the second convex portion is preferably about 5 〇 nm to 2 〇〇 nm. The dispersion distance between the second convex portions 23b is preferably larger than the incident wavelength or even the inductive wavelength of the special element including the p-type semiconductor layer 21 and the conductive layer 22, and is preferably larger than the second convex portion of the first photoelectric conversion element 10. The dispersion interval of 13b. For example, the second convex portion 156673.doc 201230358 23b is preferably spaced apart from each other by about 3 gm to 5 μm. The upper limit of the dispersion interval of the second convex portions 23b is preferably about 5 μηη to 6 μηι. A pair of electrodes 24, 25 are disposed at positions spaced apart from each other on the conductive layer 22. Here, an electrode 24 (anode electrode) is disposed at one end of the upper surface of the conductive layer 22 (right side in Fig. 1). The other electrode 25 (cathode electrode) is disposed on the other end of the upper surface of the conductive layer 22 (left side in Fig.). The configuration of the electrodes 24, 25 is not limited to the above. For example, one of the electrodes 24 and 25 may be disposed in the central portion of the second photoelectric conversion element 2, and the other of the electrodes 24 and 25 may be disposed in the four corners (peripheral portion) of the second photoelectric conversion element 2 . The electrodes 24 and 25 are made of a metal such as Au, Ag, Pt, Cu, or Pd. Here, AU is used as the second metal constituting the electrodes 24 and 25. Therefore, the electrodes 24, 25 contain the same metal component as the metal component constituting the metal nanostructure 23. The metal component constituting the metal nanostructure 23 and the metal components constituting the electrodes 24 and 25 may be different from each other. The two electrodes 24 may contain metal components different from each other. The electrodes 24 and 25 may also contain a metal component different from the electrodes I4 and 15 of the first photoelectric conversion element 10. A barrier layer 26 (polarity determining layer) is interposed between the anode electrode 24 and the conductive layer 22. The barrier layer 26 contains an insulator such as aluminum, Si 〇 2, SiN, or a carbon compound (e.g., a resin). The thickness of the barrier layer 26 is small enough to produce a tunneling effect. For example, the barrier layer 26 has a thickness of angstroms, i.e., less than 丄. In the drawings, the thickness of the barrier layer 26 is exaggerated relative to the thickness of the conductive layer 22 or the metallic nanostructure. The capacitor is formed by the electrode 24 and the conductive layer 22 facing the opposite side of the barrier layer 26. As described below, in the portion of the conductive layer 22 opposite to the electrode 24, 156673.doc • 21 · 201230358 has a carrier (hole) generated by photoelectric conversion. Thereby, the electrode 24 becomes an anode. The electrode 25 serves as a cathode. The cathode electrode 25 is in direct contact with the conductive layer 22. Preferably, the cathode electrode 25 is ohmically bonded to the conductive layer 22. The first photoelectric conversion element 10 and the second photoelectric conversion element 20 are superposed on each other in the thickness direction (upper and lower in Fig. 1). Here, the first photoelectric conversion element 1 is disposed on the front side (the incident side and the upper side of the light L), and the second photoelectric conversion element 20 is disposed on the back side (lower side). A plurality of gaps are formed between the photoelectric conversion elements 10, 20 with each other. Each of the photoelectric conversion elements 10 and 20 is disposed so as to intersect with the incident direction of the light L. It is preferably arranged to be substantially orthogonal to the incident direction. The metal nanostructures 13 and 23 of the respective photoelectric conversion elements 10 and 20 are oriented toward the front side (the incident side of the light L), and the substrates 11 and 21 are oriented toward the back side. The first photoelectric conversion element 10 and the second photoelectric conversion element 2 are connected in parallel. The power storage unit 3 includes a counter electrode 31, 32 and a dielectric layer 33' interposed between the electrodes ^, 32 to constitute a capacitor. The material of the dielectric layer 33 is a dielectric (insulator), and examples thereof include a neon, a resin, an oxidized oxide, and a nitrogen oxide. However, the above materials are not limited to these. A terminal 31e is provided in the negative electrode 31. A terminal 32e is provided on the positive electrode 32. A negative electrode terminal 31e of the lightning storage + & π other page electrode 3 is connected to the negative electrode of the photovoltaic power generation unit 2. The positive electrode terminal of the power storage unit 2 is connected to the positive electrode of the photovoltaic power generation unit 2. A method of manufacturing the light storage device 以下 will be described below. The first photoelectric conversion element 1 was produced in the following manner. 156673.doc

S -22- 201230358 [Step 1 of the first conductive layer material preparation] An n-type ruthenium substrate 掺杂 doped with P is prepared. Co is formed as a material of the conductive layer 12 on the substrate 成为. As the Co film formation method, PVD (Physical Vapour Deposition) such as sputtering or steaming can be used. It is not limited to PVD, and c〇 is coated by another film forming method such as spin coating. [First barrier arranging step] A barrier layer 16 including an insulator (e.g., angstrom) having an angstrom thickness is disposed at a position on the Co film where the first electrode 14 is to be placed. The arrangement of the barrier layer 16 can be carried out by various film forming methods for CVD. [First Electrode Arrangement Step] A metal material (Au) serving as the second electrode 14 is provided on the barrier layer 16 described above. Further, a metal material (Au) serving as the second electrode 15 is provided on the Co film at a position where the second electrode 15 is to be placed. The arrangement of the metal material (Au) for the electrodes 14 and 15 can be carried out by various film forming methods such as sputtering and vapor deposition. [First metal nanostructure material arrangement step] Further, a metal material (Au) which is a metal nanostructure U is disposed in a portion between the electrodes 14 and 15 on the Co film. The metal nanostructure Μ metal material (Au) is not particularly limited in shape and properties, and may be in the form of a film, a small piece, a small piece, a granule, a powder, a colloid, a wire, a dot, or the like. Anyone can also be in other shapes or even traits. In the case where the above-mentioned raw material (Au) is in the form of a film, for example, film formation can be carried out by sputtering or the like. Alternatively, the metal-forming material (Au) may be diffused to the inter-electrode portion in the diffusion step described below to form the metal nanostructure 13. In this case, the metal nanostructure may be omitted. 156673.doc -23· 201230358 Material configuration steps. [First Diffusion Step] Next, the substrate 11 is placed in an annealing treatment bath to be annealed. The temperature condition for the annealing treatment is preferably 400. (: ~800 ° C or so, more preferably about 600 ° C. Annealing treatment as much as possible in 100% inert gas environment. As an inert gas for annealing, you can use rare gases such as He, Ar, Ne' In addition, Ns can also be used. The pressure condition of the annealing treatment is near atmospheric pressure, for example, a low pressure of a large pressure of about several pa. The Co is diffused to the surface constituting the surface portion of the substrate by the above annealing treatment. 'Forming the surface portion of the Si substrate 11 to be self-assembled into the obtained CoSix layer 12' so that the semiconductor layer 丨丨 and the conductive layer 12 can be subjected to Schottky bonding and further 'disposed by the above annealing treatment The particles of Au on the layer 2 are diffused along the surface of the conductive layer 12 to form clusters or fractals. That is, the 'Au particles are diffused in multiple branches to form a collection of fractal structures. It has a submicron or nano-scale unevenness and becomes a cluster shape. Thus, the metal nanostructure 13 can be naturally formed. In this manner, the first photoelectric conversion element 10 can be produced. 2. The order of fabrication of the photoelectric conversion element 20. When the second photoelectric conversion element 20 is produced, a p-type Si-Xy substrate 21 doped with B is prepared as a substrate. Then, in the same manner as the first photoelectric conversion element 1 is produced. 'The p-type germanium substrate 21 is sequentially subjected to a conductive layer material material coating step, a barrier arrangement step, a metal nanostructure material arrangement step, and a diffusion step. 156673.doc -24-

S 201230358 [Second conductive layer material covering step] Co is formed as a raw material component of the conductive layer 22 on the P-type slab substrate 21 by pVD or the like. [2nd barrier configuration step]

• A barrier layer 26 of an insulator (for example, aluminum) having a thickness of an ergic layer is formed by CVD ' or the like at a position on the C 〇 film where the first electrode 24 is to be placed. [Second Electrode Arrangement Step] A metal material (AU) serving as the first electrode 24 is disposed on the barrier layer 26 described above. Further, a metal material (Au) serving as the second electrode 25 is disposed on the Co film at a position where the second electrode 25 is to be placed. The arrangement of the metal material (Au) for the electrodes 24 and 25 can be carried out by various film forming methods such as sputtering and vapor deposition. [Second metal nanostructure material arrangement step] Further, a metal material (Au) serving as the metal nanostructure 23 is disposed in a portion between the electrodes 24 and 25 on the Co film. The shape and even the shape of the metal material (Au) of the metal nanostructure 23 are not particularly limited, and may be in the form of a film, a small piece, a small piece, a granule, a powder, a gel, a fiber, or a wire. Any of the dots or the like may be other shapes or even traits. In the case where the metal material (Au) of the metal nanostructure 23 is in the form of a film, for example, film formation can be performed by PVD such as sputtering or vapor deposition. A part of the metal material (Au) serving as the electrodes 24 and 25 may be diffused into the inter-electrode portion in the second diffusion step described below to form the metal nanostructure 23, and in this case, the second metal may be omitted. Nano structure raw material configuration steps. [Second Diffusion Step] 156673.doc -25- 201230358 Next, the substrate 21 is placed in an annealing treatment bath to be annealed. The temperature condition for the annealing treatment is preferably about 40 CTC to 800 ° C, more preferably about 6 〇〇〇 c. The annealing treatment is carried out as much as possible in an inert gas atmosphere of 1%. As the inert gas for annealing treatment, a rare gas such as He, Ar or Ne can be used, and N2 can also be used. The pressure condition for the annealing treatment is close to atmospheric pressure, for example, a relatively large pressure of about several Pa. By the above annealing treatment, (:0 is diffused to S?* which constitutes the surface portion of the substrate 21. Thereby, the surface portion of the magic substrate 2 is formed by self-combination into the obtained CoSix layer 22, thereby reliably making The semiconductor layer 21 and the conductive layer 22 are Schottky-bonded. Further, by the annealing treatment, the particles of Au disposed on the conductive layer 22 are formed along the surface of the conductive layer 22 to form clusters or fractals. Diffusion. #,Au microparticles are diffused in multiple branches, and the surface of the collection of β-body aggregates consists of submicron or nano-scale bumps and becomes clusters. The nanostructure 23 ° can be produced in this manner. The second photoelectric conversion element 2 can be fabricated in this manner. The fabrication of the second photoelectric conversion element 1 and the second photoelectric conversion of the 7G photoelectric element 20 can also be performed in parallel with the substrate! ^, The first and second diffusion steps are simultaneously performed in the annealing treatment tank in which the η is placed in the same manner. The first photoelectric conversion element W and the second photoelectric conversion 70# 20« itn produced in the above manner are further referred to as the photovoltaic power generation unit 2 Connected to the power storage unit 3. This can be Type, making an optical storage device Shang. Next, the operation of the optical storage device 1. 156673.doc

S -26· 201230358 Light L is incident on the first photoelectric conversion element 1〇. Thereby, photoelectric conversion is caused in the first photoelectric conversion element 10, and electric power is generated. The light L that has passed through the first photoelectric conversion element 10 is further incident on the second photoelectric conversion element 20. As a result, photoelectric conversion is caused in the second photoelectric conversion element 2A, thereby generating electric power. The electric power generated by the photoelectric conversion elements 1A and 20 is stored in the electric storage unit 3. As a result, power can be supplied even in a light-receiving process or a power generation process. The optical power storage device 1 can make the area of each of the photoelectric conversion elements 1A and 2B substantially the same as the area where the optical power storage device 1 is disposed. Therefore, the light receiving efficiency can be sufficiently improved. The role of the photoelectric conversion elements 10, 20 will be described in more detail below. The first photoelectric conversion element 1 generates photocarriers in the Schottky junction between the n-type semiconductor layer U and the conductive layer 12 by the incident light L. In particular, the n-type first photoelectric conversion element 10 has sensitivity to light in the incident light L from the visible light region to the near-infrared region (specifically, the wavelength is about 〇·4 μηη to 2 μηι). The electrons of the above photocarriers move toward the center by the electric field of the depletion layer. Accordingly, electrons flow from the electrode 15 to the conductive layer 12. On the electrode. The current can flow smoothly with the % layer 12. The electrons flow along the conductive layer 12 toward the electrode 14 side. Electrons are accumulated in a portion of the conductive layer 12 opposite to the electrode 14. The electrons can travel through the barrier layer to the electrode 14 by tunneling. Thereby, the photocurrent can be taken out. Due to &, the electrode 14 becomes a cathode. The electrode 15 becomes an anode. In this manner, the electrode 15 which becomes the anode and the electrode 14 which becomes the cathode can be determined, so that the flow of the photocurrent can be controlled. As a result, the current characteristics of the current can be made positive on the positive side and the negative side, and the sharp diode characteristics can be obtained by the term "156673.doc -27· 201230358". Since the photo-electric field is formed along the surface direction of the conductive layer 12, the carrier can be accelerated in the above-described plane direction and moved at a high speed of the compound semiconductor level. Further, the sensitivity of photoelectric conversion of the first photoelectric conversion element 10 can be improved by the metal nanostructure 13 in the vicinity of the Schottky junction. A plasmonic is locally present on the surface of the Au nanoparticle constituting the metal nanostructure 13. § The surface plasmon resonates with the incident light to produce a large electric field. The periodic structure 13c of the metal nanostructure 13 enhances the sensitivity of the photoelectric conversion to the incident light of the wavelength corresponding to the period (the arrangement interval of the first convex portions 13a). The periodic structure 13c is sensitively induced to incident light of a wavelength of about 1 to 1 〇, especially about 1 其 of its period to cause plasmon resonance. The period of the first convex portion 13a is different depending on the periodic structure 13c, so that the wavelength band which the metal nanostructure 13 can sense can be enlarged. Further, near-field light is generated around the second convex portion 13b. A large photo-emission field can be generated by the multiplication effect of the near-field light and the plasmon resonance of the periodic structure 13c. By this, it is possible to positively cause photoelectric conversion for light sensitive to light from the wavelength of the visible light region throughout the infrared light region. Even if the incident light is weak, the photoelectromotive force can be generated with high sensitivity. The dispersion interval of the second convex portion 13b can be made larger than the wavelength of the incident light (visible light region to infrared light region), preferably 1 or more, more preferably 2 μm to 3 μm, and the adjacent second convex portion 13b can be avoided. And 13b interfere with each other to weaken the electric field. By keeping the upper limit of the dispersion interval of the second convex portion 1 3 b to 3 μπι to 5 μηη′, the density of the second convex portion 13b can be maintained high, so that the interaction with the second convex portion 13b can be ensured. The number 156673.doc -28 - 201230358 of the periodic structure 13c can thus positively expand the sensing band. Thereby, it is possible to provide a photoelectric conversion element capable of coping with a wide frequency band from the visible light region to the infrared light region. 1 ° Part of the light L incident on the first photoelectric conversion element 10 will penetrate the J. photoelectric conversion element 10. The transmitted light mainly has a wavelength outside the sensing band of the first photoelectric conversion element 10. The above-mentioned transmitted light can be surely obtained by thinning the films 12 and 13 constituting the first photoelectric conversion element 10. The above-mentioned transmitted light is incident on the second photoelectric conversion element 20, whereby a photocarrier is generated at the Schottky junction of the p-type semiconductor layer 21 and the conductive layer 22. In particular, the P-type second photoelectric conversion element 2 has sensitivity to light in the infrared region (specifically, a wavelength of about i μπι to 4 μηη). The hole of the photocarrier described above moves toward the layer of the layer 21 due to the electric field of the depletion layer. Accordingly, the holes flow from the electrode 25 to the conductive layer 22. Between the electrode 25 and the conductive layer 22, current can flow smoothly. The hole flows along the conductive layer 22 toward the electrode 24 side. A hole is formed in a portion of the conductive layer 22 opposite to the electrode 24. The hole can pass through the barrier layer 26 by tunneling effect and move to the electrode 24, whereby the photocurrent can be taken out. Therefore, the electrode 24 becomes an anode. Electricity. The pole 25 becomes the cathode. In this way, the electrode 24 which becomes the anode and the electrode 25 which becomes the cathode can be determined, so that the flow of the photocurrent can be controlled. Thereby, the current-voltage characteristics can be surely asymmetrical on the positive side and the negative side, so that clear diode characteristics can be obtained. Since the photo-electric field is formed along the surface of the conductive layer 22, the carrier can be twisted in the above-mentioned plane direction, and the high-speed movement of the conductor can be performed at a high speed of 0 156673.doc -29-201230358. The photoelectric conversion sensitivity β of the second photoelectric conversion element 20 is increased by the metal nanostructure 23 in the vicinity of the Schottky junction, and the electropolymer is locally present on the surface of the Au nanoparticle constituting the metal nanostructure 23. The mysterious surface electropolymer resonates with the incident light to generate a large electric field. The periodic structure 23c of the metal nanostructure 23 enhances the sensitivity of photoelectric conversion of incident light of a wavelength corresponding to the period (the arrangement interval of the first convex portions 23 & The periodic structure 2 3 c is sensitively induced to incident light having a wavelength of about 1 to 1 〇, especially about 1 〇 of its period, thereby causing plasmon resonance. The period of the first convex «Ρ 2 3 a is different depending on the periodic structure 2 3 c , and therefore, the wavelength band which the metal nanostructure 23 can induce can be enlarged. Further, near-field light is generated around the second convex portion 23B. A large photo-emission field can be generated by the multiplication effect of the near-field light and the plasmon resonance of the periodic structure 23c. Therefore, it is possible to sensitively sense the light of the infrared light region of about i μΓη to 4 μm which penetrates the first photoelectric conversion element i, thereby surely causing photoelectric conversion. Even if the incident light is weak, the photoelectromotive force can be generated with high sensitivity. By making the dispersion interval of the second convex portions 23b larger than the wavelength ' of the incident light, the adjacent second convex portions 23 23b and 23b can be prevented from interfering with each other to weaken the electric field. By setting the upper limit of the dispersion interval of the second convex portion 23b (for example, about 5 μηι to 6 μηι), the density of the second convex portion 23b can be maintained high, so that mutual interference with the second convex portion 23b can be ensured. The number of periodic structures 23c is such that the induced frequency band can be surely expanded. Thereby, a photoelectric conversion element 1A which can sufficiently correspond to the infrared light region can be provided. According to the optical power storage device 1, it is needless to say that even after sunset, the infrared light scattered in the atmosphere can be photoelectrically converted to obtain electric power, and the 156673.doc can be obtained.

S •30· 201230358 Electricity is stored. By absorbing infrared light and preventing thermal conversion of infrared light, it is expected to be a means of countermeasures for global warming. Next, other embodiments of the present invention will be described. In the following embodiments, the same reference numerals are given to the same as those in the above-described embodiments, and the description thereof will be omitted. Fig. 2 is a view showing a second embodiment of the present invention. In the second embodiment, the photoelectric conversion elements 10 and 20 are connected in series instead of the parallel connection of the first embodiment. The other embodiments of the second embodiment are the same as those of the second embodiment. In the first and second embodiments described above, the light receiving area of each of the photoelectric conversion elements 10 and 20 and the area where power can be generated can be sufficiently increased. On the other hand, as for the photoelectric conversion element 20 on the lower side, a part of the incident light will be shielded by the photoelectric conversion element 10 on the upper side. In particular, in the sensing band of the lower side photoelectric conversion element 2, the wavelength of the wavelength overlapping with the sensing band of the upper photoelectric conversion element 易 is easily blocked by the upper photoelectric conversion element. In the following third and fourth embodiments, the above disadvantages of the first and second embodiments are eliminated. Fig. 3 is a view showing a third embodiment of the present invention. In the third embodiment, the first photoelectric conversion element 10 and the second photoelectric conversion element 20 are arranged in a direction orthogonal to the thickness direction of each other. The photoelectric conversion elements 10 and 20 are connected in parallel. In the third embodiment, the light 1 is directly incident on the first photoelectric conversion element and the second photoelectric conversion element 20, respectively. Regardless of whether the photoelectric conversion element 1 is degraded or the photoelectric conversion element 2 〇 'incident light is not blocked by the other photoelectric conversion element, the two photoelectric conversion elements 10 and 20 can sufficiently receive the light of the mutually inductive frequency band for photoelectric conversion. . Thereby, the photoelectric conversion capability of the photoelectric conversion elements 10, 20 such as 156673.doc 31 201230358 can be sufficiently exhibited. As shown in Fig. 4, in the fourth embodiment of the present invention, the photoelectric conversion elements 1A and 2B are connected in series instead of the parallel connection in the third embodiment. The other configuration of the fourth embodiment is the same as that of the third embodiment. In the third and fourth embodiments, the light-receiving area of each of the photoelectric conversion elements 1 and 2 is about half of that of the first and second embodiments. * In the case of the preferential light receiving area, it is preferable to adopt ρ and the second embodiment. Alternatively, in the case where the wavelength band of the light for photoelectric conversion is biased to the sensing band of any of the photoelectric conversion elements 1 and 20, the first and second embodiments are preferably employed. In the case where it is necessary to make full use of the photoelectric conversion capabilities of the photoelectric conversion elements 1 and 2, it is preferable to adopt the third and fourth embodiments. Fig. 5 is a view showing a fifth embodiment of the present invention. The fifth embodiment is a modification of the fourth embodiment. A zinc oxide nanostructure 41 is provided on the surface (upper surface in Fig. 5) of the i-th photoelectric conversion element ι. The oxidized word structure constitutes an n-type semiconductor. The nanostructure 41 includes a nanowire and protrudes from the surface of the [photoelectric conversion element 10]. Here, the nanostructures 41 protrude from the metal nanostructures 13. Further, in the case where the metal nanostructure 丨3 is partially covered only by one of the conductive layers 12, the nanostructures 41 may be self-conductive in terms of the uncoated portion of the metal nanostructures 13. Layer 12 is prominent. The nanowires can be formed by CVD, PVD, sol-gel methods, and the like. The nanostructure 41 is not limited to a nanowire, and may be a nanoneedle, a nanotube, or a nanorod. A carbon nanostructure 42 is provided on the surface (upper surface in Fig. 5) of the second photoelectric conversion element 2A. The carbon nanostructure 42 contains carbon (carbon) 156673.doc ^.

S 201230358 tube, and stands on the surface of the second photoelectric conversion element 2〇. Here, the carbon nanotube structure 42 protrudes from the metal nanostructures 23. Further, in the case where the metal nanostructure 23 is partially covered only by one of the conductive layers 22, the carbon nanostructures a may be self-conductive in terms of the uncoated portion of the metal nanostructures 23. Layer 22 is prominent. The carbon nanotubes can be formed by CVD, pVD, sol-gel method, etc. "The nanostructures 42 are not limited to the nanotubes, but also nanowires, nanoneedles, and nanorods. According to the fifth embodiment, the photoelectric conversion sensitivity of the first photoelectric conversion element 10 can be improved by oxidizing the Nylon structure. In particular, the sensitivity of the short wavelength side in the sensing band of the second photoelectric conversion element 10 can be improved. Specifically, the sensitivity can be improved for light from a visible light region of about 0.4 μηκ ultraviolet light to about μ μηη. Since the zinc oxide nanostructure 41 is a nanowire, the quantum efficiency can be improved, and the sensitivity of the third photoelectric conversion element can be surely improved. Further, the photoelectric conversion sensitivity of the second photoelectric conversion element 20 can be improved by the carbon nanostructure 42. In particular, the sensitivity of the long wavelength side in the sensing band of the second photoelectric conversion element 20 can be improved. Specifically, the sensitivity can be increased for light from a visible light region of about 2 μπι to an infrared light region of about 4 μιηη. Since the carbon nanostructures 41 include carbon nanotubes, the vector sub-efficiency can be improved, and the sensitivity of the second photoelectric conversion element 20 can be surely improved. Thereby, the wavelength band capable of photoelectric conversion can be further expanded regardless of the short wavelength side or the long wavelength side. Fig. 6 is a view showing a sixth embodiment of the present invention. The sixth embodiment relates to a modification of the polarity determining layer. In the n-type first photoelectric conversion element 1A, the convex layer 17 is provided as the polarity determining layer instead of the barrier layer 16 as described above. The bump layer 156673.doc -33- 201230358 17 is formed integrally with the n-type semiconductor layer 11. A portion of the surface (upper surface) of the semiconductor layer which is close to the cathode electrode 14 is protruded, and the protrusion constitutes the convex layer 17. The protruding height of the convex layer 17 is the same as the thickness of the conductive layer 12, for example, about 1 nm to 10 nm or so, preferably about several nrn. The width dimension of the convex layer 17 (the size of the left and right in Fig. 6) is, for example, about 1 〜 to about i mm. In Fig. 6, the protruding height (upper and lower dimensions) of the convex layer 17 is exaggerated with respect to the width (left and right dimensions). The convex layer 17 is interposed between the end of the conductive layer 12 on the cathode electrode 14 side and the cathode electrode 14. One side surface (left side in FIG. 6) of the convex layer 17 is in Schottky contact with the end surface of the conductive layer 12. The other side of the convex layer 17 (the right side in Fig. 6) is in ohmic contact with the cathode electrode 14. The metal nanostructure 13 is formed so as to straddle the upper surface of the convex layer 17 from the conductive layer 12. The metal nanostructure 13 may also be provided only on the upper surface of the convex layer 17. Alternatively, the metal nanostructure 13 may be provided only on the upper surface of the conductive layer 12. In the P-type second photoelectric conversion element 20, the convex layer 27 is provided as a polarity determining layer instead of the barrier layer % as described above. The convex layer 27 is integrally formed with the p-type semiconductor layer 21. A portion of the surface (upper surface) of the semiconductor layer 21 which is close to the anode electrode 24 is protruded, and the protrusion constitutes the convex layer 27. The protruding degree of the convex layer 27 is the same as the thickness of the conductive layer 22, for example, about 1 nm to 10 nm, preferably about several nm, and the width dimension of the convex layer 27 (the left and right dimensions in Fig. 6), for example. It is about 100 μηι~ about 1 mm. In Fig. 6, the protruding height (upper and lower dimensions) of the convex layer 27 is exaggerated with respect to the width (left and right dimensions). The bump 27 is interposed between the end of the conductive layer 22 on the anode electrode 24 side and the anode electrode 156673.doc -34 - 201230358. One side surface (the right side surface in FIG. 6) of the convex layer 27 is in Schottky contact with the end surface of the conductive layer 22. The other side of the convex layer 27 (the left side in Fig. 6) is in ohmic contact with the anode electrode 24. The metal nanostructure B is formed so as to straddle the upper surface of the convex layer 27 from the conductive layer 22. The metal nanostructure 23 may be placed on the upper surface of the convex layer 27 only 3 or the metal nanostructure 23 may be provided only on the upper surface of the conductive layer 22. When the light is incident on the photovoltaic power generation unit 2 of the sixth embodiment, the n-type first photoelectric conversion element 10 generates photocarriers not only in the Schottky junction between the bottom of the conductive layer 12 and the semiconductor layer η. And a photocarrier is also generated in the Schottky junction of the end of the conductive layer 12 and the convex layer 17. The electrons of this carrier flow toward the side of the convex layer 17 or the electrode 14 due to the electric field of the depletion layer between the conductive layer 12 and the convex layer 17. Therefore, the electrode 14 can be made the cathode. The electrode 15 can be made to be an anode. Further, in the p-type second photoelectric conversion element 2, not only a photo-carrier is generated in the Schottky junction between the bottom of the conductive layer 22 and the semiconductor layer 21, but also at the end of the conductive layer 22. A photocarrier is generated in the Schottky junction of the convex layer 27. The hole of the carrier flows toward the convex layer 27 side or the electrode 24 due to the depletion layer electricity between the conductive layer 22 and the convex layer 27. Therefore, the electrode 24 can be made to be an anode. The electrode 25 can be made a cathode. The present invention is not limited to the above embodiment, and various modifications can be made without changing the spirit of the invention. For example, the photovoltaic power generation unit 2 may include at least one of two or more second photoelectric conversion elements 10 and second photoelectric conversion elements 2A. The photovoltaic power generation unit 2 may also include three or more photoelectric conversion elements 1A and 2B. It is also possible to connect two photoelectric conversion elements ίο, 20 on 156673.doc •35· 201230358 in series and in parallel. The barrier layers 16, 26 need only be interposed between at least a portion of the conductive layers 12, 22 and the electrodes 14, 24, and need not be interposed between the conductive layers 12, 22 and the electrodes 14, 24. The metal component constituting the conductive layers I2 and 22 is not limited to Co, and may be Fe, W, Ni, Al, Ti, or the like. The metal components constituting the metal nanostructures 13 and 23 are not limited to Au, and may be Ag, Pt, Cu, Pd or the like. A plurality of embodiments may also be combined with each other. For example, the i-th photoelectric conversion element and the second photoelectric conversion element may be partially overlapped in the thickness direction of each other and may be displaced in a direction orthogonal to the thickness direction. In the photoelectric conversion elements 1A and 2B of the first to third embodiments, the nanostructures 41 and 42 similar to those of the fifth embodiment can be provided. In the first to fourth embodiments, as the polarity determining layer, the convex layers 7 and 27 which are the same as those in the sixth embodiment (Fig. 6) may be used instead of the barrier layer 16 and %. The zinc oxide nanostructures 41 of the two types of nanostructures 41 and 42 may be provided in the first photoelectric conversion element 1〇, and the carbon nanostructures may not be provided in the second photoelectric conversion element 2〇. 42. In the second type of nanostructures 41 and 42 , only the nunion structure 42 of τ may be provided in the second photoelectric conversion element 2 , and τ may be provided in the first photoelectric conversion element 10 without oxidizing the symmetry. Structure 41. The manufacturing steps & of the optical power storage device 1 can be appropriately replaced or changed in sequence. In the first and second embodiments, the second photoelectric conversion element 20 can also be provided with 156673.doc.

-36 - 201230358 is placed on the front side (incident side, upper side), and the first photoelectric conversion element 1 〇 is placed on the back side (lower side). The substrate 11 of the photoelectric conversion element 10 may be directed toward the front side (the incident side of the light L), and the metal nanostructure 13 may be oriented toward the back side. Alternatively, the substrate 21 of the photoelectric conversion element 2 may be oriented toward the front side (the incident side of the light L), and the metal nano-structure 23 may be oriented toward the back side. [Example 1] Hereinafter, examples will be described. Of course, the present invention is not limited to the following embodiment. Example 1 is the production and observation of a metal nanostructure. The metal nanostructure is produced in the following manner. On the entire surface of the substantially square n-type Si substrate, the Co film was formed by recording. The thickness of the c〇 film is set to 8 nm. Next, after performing organic cleaning for 5 minutes, mask printing was performed, and the Au film was formed by sputtering at the four corners and the center of the c〇 film surface. The thickness of the au film is about 10 nm. Then, an annealing treatment is performed. The ambient gas to be annealed was set to 1% by weight of He. The annealing temperature was 600 eC ^ The annealing treatment time was set to 3 minutes. Co is diffused to the surface portion of the n-type Si substrate by annealing treatment to form CoSix. Two sites in the vicinity of the Au film were observed by SEM (scanning electron microscope). Figures 7(a) and (b) are images thereof. It was confirmed that the fine particles of the Au film were diffused along the surface of the CoSix film, and a metal nanostructure was naturally formed around the Au film. Shape of the metal nanostructure 156673.doc •37- 201230358 The state system differs depending on the location. As shown in Fig. 2(b), a fractal structure is formed in the metal nanostructure. The laser light (wavelength 635 nm) is irradiated to several places of the above metal nanostructures and the zero bias (zero bias) is observed by AFM (at mic 显微镜 f 〇 ce mic , 原子 原子 原子 原子 原子 原子 原子 原子 原子 原子The surface structure where the photoinduced current reaches its maximum. Figure 8 is an image thereof. Figure 9 is a diagram of the image of Figure 8 being copied. On the surface of the metal nanostructure, irregularities of the sub-nano or nano-scale are formed, and a cluster structure or a fractal structure is confirmed. Further, among the concave and convex shapes, a plurality of periodic structures Uc and a plurality of second convex portions 12b are confirmed. Each of the periodic structures 13c includes a plurality of first convex portions 13& and the first convex portions 13a are arranged in a random cycle (arrangement interval) corresponding to the periodic structure 13c. The period of the periodic structure l3c is about 1 〇〇 nm or less. The dog out degree of each of the i-th convex portions 13a is about 1 〇 ηιη to 20 nm or so. Each of the second convex portions 13b is disposed to be overlapped with a certain periodic structure 13c or disposed adjacent to the periodic structure 丨3c. The protruding height of the second convex portion 13b is higher than the protruding height of the first convex portion 13& and is about 50 nm to 200 nm. The dispersion interval of the second convex portion 13b is about 2 μηι to 3 μιη. [Industrial Applicability] The present invention is applicable to, for example, a photo sensor or a solar cell. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a schematic configuration of an optical power storage device according to a first embodiment of the present invention. Fig. 2 is a cross-sectional view showing a schematic configuration of a photovoltaic power storage device according to a second embodiment of the present invention 156673.doc -38 - 201230358. Fig. 3 is a cross-sectional view showing the schematic configuration of a photo-electrical device in the third embodiment of the present invention. Fig. 4 is a cross-sectional view showing a schematic configuration _ of the optical power storage device of the fourth embodiment of the present invention. Fig. 5 is a cross-sectional view showing a schematic configuration of an optical power storage device of a sixth embodiment of the present invention. Fig. 6 is a schematic view showing a schematic configuration of an optical power storage device according to a sixth embodiment of the present invention. Sectional view. Fig. 7U) is an image obtained by observing a part of the surface of the metal nanostructure of Example i by SEM (Scanning Electron Microscope). Fig. 7(b) shows an image obtained by observing a portion of the surface of the metal nanostructure of Example i which is different from Fig. 7(a) by SEM. Fig. 8 is a stereoscopic image obtained by observing the surface structure of the metal nanostructure of Example 1 by AFM (atomic force microscope). Figure 9 is an illustration of a stereoscopic image of Figure 8. [Description of main component symbols] 1 Optical power storage device 2 Photovoltaic power generation unit 3 Power storage unit 10 First photoelectric conversion element 11 n-type semiconductor layer, substrate 12 ' 22 Conductive layer 13 ' 23 Metal nanostructure 156673.doc -39- 201230358 13a, 23a First convex portion 13b, 23b Second convex portion 13c' 23c Periodic structure 14 and 24 First electrode (one electrode) 15 > 25 Second electrode (other electrode) 16 ' 26 Barrier layer (Polar Determining layer) 17, 27 convex layer (polarity determining layer) 20 second photoelectric conversion element 21 p-type semiconductor layer, substrate 23d random structure 31 negative electrode 31e ' 32e terminal 32 positive electrode 33 dielectric layer 41 zinc oxide nanostructure 42 Carbon nanostructure L incident light 156673.doc -40-

Claims (1)

201230358 VII. Patent application scope: l - A light storage device is characterized in that: a photovoltaic power generation unit 1 is used to generate electricity by light; and a power storage unit is connected to the photovoltaic power generation unit, and the power generated by the power generation is stored. The photo power generation unit includes a second photoelectric conversion element that is connected in series, in parallel, or in series and parallel, and the first and second photoelectric conversion elements each include a semiconductor layer and a conductive layer laminated on the above a semiconductor layer; and a metal nanostructure which is laminated on the conductive layer and includes a plurality of periodic structures; each of the periodic structures includes a plurality of first protrusions protruding in a direction of the laminate, and the first protrusions are disposed The interval differs depending on the periodic structure; the semiconductor layer of the first photoelectric conversion element is an n-type semiconductor layer, and the semiconductor layer of the second photoelectric conversion element is a p-type semiconductor layer. 2. The optical power storage device of claim 1, wherein at least one of the periodic structures has a configuration interval of 0 丨 to 丨 times the arbitrary wavelength in a certain wavelength range from the visible light region to the infrared region. 3. The optical power storage device according to claim 1, wherein the metal nanostructure further includes a plurality of second convex portions that protrude larger than the i-th convex portion, and the second convex portions are dispersed with each other and each of the second convex portions The optical power storage device according to any one of the preceding claims, wherein the first photoelectric conversion element is overlapped with the second photoelectric conversion element In the thickness direction of each other. 5. The optical power storage device according to any one of claims 1 to 3, wherein the first photoelectric conversion element and the second photoelectric conversion element are arranged in a direction orthogonal to a thickness direction of each other. The optical power storage device according to any one of claims 1 to 3, wherein the first photoelectric conversion element is provided with a nanostructure including an n-type semiconductor having sensitivity to an ultraviolet region. The optical power storage device according to any one of claims 1 to 3, wherein the second photoelectric conversion element is provided with a nanostructure including a germanium semiconductor having sensitivity to the infrared region. 156673.doc