WO2011152460A1 - Élément convertisseur photoélectrique et son procédé de fabrication - Google Patents

Élément convertisseur photoélectrique et son procédé de fabrication Download PDF

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WO2011152460A1
WO2011152460A1 PCT/JP2011/062605 JP2011062605W WO2011152460A1 WO 2011152460 A1 WO2011152460 A1 WO 2011152460A1 JP 2011062605 W JP2011062605 W JP 2011062605W WO 2011152460 A1 WO2011152460 A1 WO 2011152460A1
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layer
convex
conductive layer
electrode
photoelectric conversion
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PCT/JP2011/062605
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Japanese (ja)
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穂世 ブリセニョ
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株式会社Si-Nano
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Priority to JP2012518436A priority Critical patent/JP5443602B2/ja
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    • 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
    • H01L31/02—Details
    • H01L31/0232—Optical elements or arrangements associated with the device
    • H01L31/02327—Optical elements or arrangements associated with the device the optical elements being integrated or being directly associated to the device, e.g. back reflectors
    • 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
    • H01L31/08—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 in which radiation controls flow of current through the device, e.g. photoresistors
    • H01L31/10—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 in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
    • H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
    • H01L31/102—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier
    • H01L31/108—Devices sensitive to infrared, visible or ultraviolet radiation characterised by only one potential barrier the potential barrier being of the Schottky type

Definitions

  • the present invention relates to a photoelectric conversion element applied to, for example, a photodiode or a solar cell and a method for manufacturing the photoelectric conversion element, and more particularly to a photoelectric conversion element using the Schottky effect and the surface plasmon effect synergistically and a method for manufacturing the photoelectric conversion element.
  • Patent Document 1 describes a photoelectric conversion element using surface plasmon resonance.
  • An uneven structure having a uniform period is formed on the surface of the metal layer of the element.
  • a semiconductor layer is laminated on the concavo-convex structure, and a transparent electrode is further laminated thereon.
  • Another electrode is laminated on the back surface of the metal layer.
  • Non-Patent Document 1 describes that near-infrared light of 1 ⁇ m to 2 ⁇ m can be detected by an optical sensor in which CoSi 2 is laminated on n-type Si.
  • Non-Patent Document 2 describes that infrared light of 1 ⁇ m to 5 ⁇ m can be detected by an optical sensor in which CoSi 2 is laminated on p-type SiGe.
  • Non-Patent Document 3 describes that infrared light of 1 ⁇ m to 6 ⁇ m can be detected by an optical sensor in which Pt is stacked on p-type Si.
  • Non-Patent Document 4 describes that light of 10 ⁇ m or less can be detected by an optical sensor in which Ir is laminated on Si.
  • the photoelectric conversion element is: An n-type or p-type semiconductor layer formed so that a convex layer protrudes from the surface; A conductive layer laminated on the surface and in contact with one side surface of the convex layer; A first electrode provided on the opposite side of the conductive layer across the convex layer on the surface and in contact with the opposite side surface of the convex layer; A second electrode provided on the conductive layer; A metal nanostructure including a plurality of (preferably many) periodic structures laminated on the convex layer or the conductive layer; Each periodic structure is composed of a plurality of first convex portions, and the arrangement interval of the first convex portions is different depending on the periodic structure.
  • the first Schottky junction is formed between the surface of the semiconductor layer and the conductive layer.
  • a second Schottky junction is formed between one side surface of the convex layer and the end surface of the conductive layer on the convex layer side.
  • the metal component constituting the conductive layer examples include Co, Fe, W, Ni, Al, and Ti. These metal elements listed have relatively high melting points and excellent mechanical properties at high temperatures.
  • the conductive layer may be a metal, or a mixture or alloy of a metal and a semiconductor. Examples of the metal or semiconductor mixture or alloy include metal silicide. When the semiconductor layer is made of silicon, the conductive layer may be a metal silicide formed by diffusing the metal component and the surface layer portion of the semiconductor layer. The diffusion and thus silicidation can be performed, for example, by annealing.
  • the metals listed above (Co, Fe, W, Ni, Al, Ti) are suitable for silicidation.
  • the metal nanostructure is preferably an aggregate of nanosized metal fine particles. Plasmon resonance occurs when light enters the metal nanostructure. Thereby, the metal nanostructure contributes to the increase of the light-induced electric field.
  • the metal constituting the metal nanostructure Au, Ag, Pt, Cu, or Pd is preferably used. These listed metal elements have relatively high chemical stability, are not easily alloyed, and are not easily combined with a semiconductor such as Si. Therefore, surface plasmon can be formed reliably.
  • the metal nanostructure is provided on the convex layer or the conductive layer.
  • the metal nanostructure may be provided mainly on the convex layer, may be provided mainly on the conductive layer, or may be provided across the convex layer and the conductive layer. It is more preferable that the metal nanostructure is widely distributed on the convex layer or the conductive layer.
  • the carrier can be promoted to move to the side of the convex layer and thus to the side of the first electrode in the second Schottky junction. Therefore, the rectifying action of the second Schottky junction can be enhanced.
  • Providing the metal nanostructure on the conductive layer can promote the movement of carriers toward the semiconductor layer at the first Schottky junction. Therefore, the photo-induced current can be reliably increased.
  • the metal nanostructure further includes a plurality of second protrusions protruding larger than the first protrusions, the second protrusions are dispersed from each other, and each second protrusion is one of the periodic structures. It is preferable that they are arranged on top of each other or close to each other.
  • near-field light is generated around the second convex portion. Due to the synergistic effect of this near-field light and plasmon resonance due to the periodic structure, the photo-induced electric field can be amplified with high sensitivity and output (K. Kobayashi, et.al., Progress in Nano-Electro-Optecs I. ed. M See Ohtsu, p.119 (Sptinger-Verlag, Berlin, 2003). Even if the incident light is weak, the photovoltaic force can be generated with high sensitivity.
  • the dispersion interval of the second protrusions is preferably 1 ⁇ m or more, and more preferably about 2 ⁇ m to 3 ⁇ m.
  • the dispersion interval of the second protrusions is about 3 ⁇ m to 5 ⁇ m.
  • the upper limit of the dispersion interval of the second protrusions is preferably about 3 ⁇ m to 5 ⁇ m for the n-type, and preferably about 5 ⁇ m to 6 ⁇ m for the p-type.
  • the first electrode After the first electrode is coated on the surface, heat treatment is performed at a first temperature, and thereafter, after the metal component of the conductive layer is coated on the surface, heat treatment is performed at a second temperature lower than the first temperature. Is preferred. Thereby, it can prevent that the junction part of a conductive layer and a semiconductor layer is alloyed by the heat processing of the said electrode formation process, and can obtain a favorable Schottky junction part.
  • the electrode forming step it is not necessary to simultaneously form the first electrode and the second electrode.
  • another process such as a conductive layer forming process or a nanostructure forming process
  • the second electrode may be formed. It is preferable to heat-treat after coating the first electrode on the surface.
  • the base material is diffused so as to branch in multiple stages or multiple, and becomes an aggregate of a fractal structure.
  • the metal nanostructure can be naturally formed.
  • Sub-micron or nano-order irregularities are formed on the surface of the metal nanostructure.
  • the surface of the metal nanostructure includes a large number of protrusions protruding in the stacking direction and has a cluster shape.
  • the multiple convex portions include the first convex portion and the second convex portion.
  • Each of the periodic structures is constituted by a plurality of convex portions arranged at substantially equal intervals among the plurality of convex portions.
  • the temperature condition of the annealing process in the electrode forming step is preferably about 600 ° C. to 1000 ° C., for example, and more preferably about 800 ° C.
  • the annealing temperature condition in the conductive layer forming step is, for example, about 400 ° C. to 800 ° C., and more preferably about 600 ° C.
  • Either one or both of the pair of electrodes may be used as the metal raw material for the metal nanostructure.
  • the metal constituting the electrode may be diffused around the electrode in a cluster shape or a fractal shape by annealing. Then, the metal nanostructure can be formed in the vicinity of the electrode.
  • the electrode and the metal nanostructure include the same metal component.
  • the semiconductor layer is a p-type semiconductor
  • a semiconductor having sensitivity in the infrared region refers to a semiconductor having a property in which carriers are excited when irradiated with infrared light having a wavelength of, for example, 0.7 ⁇ m or more.
  • Examples of such a semiconductor include p-type gallium nitride (p-GaN) and carbon.
  • nanostructures include nanowires, nanotubes, nanoneedles, and nanorods. The nanostructure can increase the sensitivity of photoelectric conversion.
  • the photoelectric conversion sensitivity to incident light in the ultraviolet region can be increased.
  • the nanostructure is made of a semiconductor having sensitivity in the infrared region
  • the photoelectric conversion sensitivity to incident light in the infrared region can be increased.
  • FIG. 1 is a cross-sectional view showing a schematic structure of a photoelectric conversion element according to the first embodiment of the present invention.
  • FIG. 2 is a cross-sectional view showing a convex layer forming step in the method for manufacturing a photoelectric conversion element.
  • FIG. 3 is a cross-sectional view showing a step of forming an ohmic contact promoting layer of the first electrode in the method for manufacturing a photoelectric conversion element.
  • FIG. 4 is a cross-sectional view showing a process of coating the first electrode and the material of the metal nanostructure in the method for manufacturing a photoelectric conversion element.
  • FIG. 5 is a cross-sectional view showing a step of coating the metal component of the conductive layer in the method for manufacturing a photoelectric conversion element.
  • FIG. 6 is a cross-sectional view showing a step of forming a second electrode in the method for manufacturing a photoelectric conversion element.
  • FIG. 7 is a cross-sectional view showing a schematic configuration of a photoelectric conversion element according to the second embodiment of the present invention.
  • FIG. 8 is a cross-sectional view illustrating a schematic configuration of a photoelectric conversion element according to the third embodiment of the present invention.
  • FIG. 9 is a cross-sectional view showing a convex layer forming step in the method of manufacturing a photoelectric conversion element according to the third embodiment.
  • FIG. 10 is a cross-sectional view illustrating a process of coating the first electrode material in the method for manufacturing a photoelectric conversion element according to the third embodiment.
  • FIG. 1 shows a photoelectric conversion element 1 according to the first embodiment of the present invention.
  • the photoelectric conversion element 1 includes a semiconductor layer 10, a pair of electrodes 21 and 22, a metal nanostructure 30, and a conductive layer 40.
  • the semiconductor layer 10 also serves as a substrate for the photoelectric conversion element 1.
  • the semiconductor layer 10 is composed of a silicon substrate.
  • the silicon substrate is doped with n-type impurities.
  • a silicon wafer or the like can be used as the silicon substrate.
  • the silicon substrate ensures the shape retention and mechanical rigidity of the photoelectric conversion element 1.
  • the substrate may be provided separately from the semiconductor layer 10.
  • the n-type semiconductor layer 10 may be coated on a substrate made of glass or a resin film.
  • the n-type semiconductor layer 10 may be formed on the surface of the separate substrate by CVD or the like.
  • a convex layer 11 is formed on the surface of the semiconductor layer 10.
  • the convex layer 11 protrudes in the thickness direction of the semiconductor layer 10 (the stacking direction of the elements 1).
  • the convex layer 11 is constituted by a part of the semiconductor layer 10 and is integrated with the semiconductor layer 10. Both side surfaces of the convex layer 11 in the width direction (left and right in FIG. 1) are inclined with respect to the surface of the semiconductor layer 10. Note that the both side surfaces may be substantially vertical.
  • the protruding height of the convex layer 11 is, for example, about 1 nm to 10 nm, and preferably about several nm.
  • the width dimension (left and right dimensions in FIG. 1) of the convex layer 11 is, for example, 0. It is several mm to several mm.
  • the width of the upper surface (projecting end surface) of the convex layer 11 is about 1 mm.
  • the protruding height (vertical dimension) of the convex layer 11 is exaggerated with respect to the width (horizontal dimension).
  • the conductive layer 40 is laminated on the surface portion of one side (left side in FIG. 1) of the convex layer 11 of the semiconductor layer 10.
  • the bottom surface (lower surface) of the conductive layer 40 and the semiconductor layer 10 are in Schottky contact.
  • a first Schottky junction 41 is formed between the conductive layer 40 and the semiconductor layer 10.
  • the right end surface (convex layer side end surface) of the conductive layer 40 is joined to the left side surface (one side surface) of the convex layer 11 and is in Schottky contact.
  • a second Schottky junction 42 is formed between the conductive layer 40 and the convex layer 11.
  • the conductive layer 40 is made of metal silicide and has conductivity.
  • the silicon of the surface layer of the semiconductor layer 10 is self-organized and constitutes the silicon component of the conductive layer 40.
  • the metal component constituting the conductive layer 40 include Co, Fe, W, Ni, Al, Ti, and the like. However, the metal component is not limited to these.
  • Co is used as the metal component of the conductive layer 40.
  • Conductive layer 40 is formed by CoSix, preferably are composed of CoSi 2. Thereby, good Schottky interfaces are formed between the conductive layer 40 and the semiconductor layer 10 and between the conductive layer 40 and the convex layer 11.
  • the conductive layer 40 may be composed of only a metal component.
  • the thickness of the conductive layer 40 is approximately the same as the protruding height of the convex layer 11.
  • the upper surface (front side surface) of the conductive layer 40 is substantially flush with the upper surface (projecting end surface) of the convex layer 11.
  • the upper surface of the conductive layer 40 may protrude from the convex layer 11 or may be recessed.
  • the thickness of the conductive layer 40 is about 1 nm to 10 nm, preferably about several nm.
  • the width dimension (lateral dimension) of the conductive layer 40 is, for example, about 3 mm to 5 mm. However, it is not restricted to this, The said width dimension may be 3 mm or less, and may be 5 mm or more.
  • the thickness of the conductive layer 40 and the protruding amount of the convex layer 11 are exaggerated with respect to the thickness of the semiconductor layer 10, the electrodes 21, 22, the metal nanostructure 30, and the like.
  • the first electrode 21 is arranged on the right side of the convex layer 11 on the surface of the semiconductor layer 10, that is, on the opposite side of the conductive layer 40 with the convex layer 11 in between.
  • the first electrode 21 is in contact with the surface of the semiconductor layer 10 and is also in contact with the right side surface (opposite side surface) of the convex layer 11.
  • the surface portion where the electrode 21 is disposed on the surface of the semiconductor layer 10 is slightly depressed downward (for example, about 1 nm or less) from the portion where the conductive layer 40 is disposed.
  • This recessed portion is continuous with the right side surface (opposite side surface) of the convex layer 11.
  • the bottom portion of the first electrode 21 is in ohmic contact with the recessed portion of the semiconductor layer 10. Further, the first electrode 21 is in ohmic contact with the right side surface (opposite side surface) of the convex layer 11.
  • the second electrode 22 is disposed on the conductive layer 40 so as to be separated from the convex layer 11 on the left side (one side).
  • the electrodes 21 and 22 are made of metal such as Au, Ag, Pt, Cu, and Pd.
  • Au is used as the metal constituting the electrodes 21 and 22.
  • the two electrodes 21 and 22 may be composed of different metal components.
  • the ohmic junction between the first electrode 21 and the semiconductor layer 10 is made of an alloy of Au, Co, and Si, and preferably made of an Au-rich alloy.
  • the metal nanostructure 30 is laminated on the upper surface of the convex layer 11.
  • the metal nanostructure 30 is provided in the vicinity of the first electrode 21.
  • the metal nanostructure 30 is composed mainly of a metal such as Au, Ag, Pt, Cu, or Pd.
  • Au is used as the metal constituting the metal nanostructure 30.
  • the metal nanostructure 30 is an Au-rich structure. Therefore, the metal nanostructure 30 is composed of the same metal component as the electrode 21.
  • the metal nanostructure 30 is integrally connected to the first electrode 21.
  • the metal component constituting the metal nanostructure 30 and the metal component constituting the electrodes 21 and 22 may be different from each other.
  • An insulator such as a carbon compound may be mixed in the metal constituting the metal nanostructure 30, and the metal nanostructure 30 has a metal-insulator-metal (MIM: metal-insulator-metal) structure. It may be.
  • the metal nanostructure 30 has a structure in which metals (Au) are gathered in a cluster shape or a fractal shape (see FIGS. 13 and 14).
  • the aggregate of the metal nanostructures 30 includes a large number or innumerable protrusions protruding in the thickness direction (upward) of the element 1. These convex portions are gathered in a cluster. Alternatively, it has a fractal structure in which an aggregate of Au nanoparticles is diffused so as to branch multiple times.
  • the metal nanostructure 30 includes a large number of first protrusions 31 and second protrusions 32. A part of the many convex parts constitutes the first convex part 31, and the other part constitutes the second convex part 32.
  • the metal nanostructure 30 has at least one periodic structure 30.
  • the metal nanostructure 30 has a large number or innumerable (plural) periodic structures 33.
  • Each periodic structure 33 is constituted by several (plural) convex portions 31, 31... Adjacent to each other in the large number of convex portions of the metal nanostructure 30.
  • the first protrusions 31, 31... Constituting each periodic structure 33 are arranged at a certain interval (period) along the surface direction of the element 1 (direction orthogonal to the stacking direction). The arrangement interval (period) of the first convex portions 31 differs depending on the periodic structure 33.
  • a method for manufacturing the photoelectric conversion element 1 will be described.
  • a P (phosphorus) -doped n-type silicon substrate is prepared as the semiconductor layer 10.
  • the surface of the semiconductor layer 10 is etched to form the convex layer 11 (convex layer forming step).
  • the right side portion where the electrode 21 on the surface of the semiconductor layer 10 is to be disposed is etched so as to be slightly recessed (about 1 nm or less) from the left side portion of the convex layer 11. Etching may be performed by wet etching or dry etching.
  • a film 25 made of Co is coated on the recessed portion on the right side of the semiconductor layer 10.
  • the Co film 25 also coats the right side surface (one side surface) of the convex layer 11.
  • the coating of the Co film 25 can be performed by various film forming methods such as sputtering and vapor deposition.
  • the thickness of the Co film 25 is preferably 1 nm or less. It is preferable that the upper surface of the Co film 25 be substantially flush with the central portion of the surface of the semiconductor layer.
  • a film 26 made of Au serving as the first electrode and the metal nanostructure is laminated on the Co film 25.
  • the Au film 26 is in contact with the right side surface (one side surface) of the convex layer 11. Furthermore, the Au film 26 is also coated on at least a part of the upper surface of the convex layer 11.
  • the Au film 26 can be coated by various film forming methods such as sputtering and vapor deposition.
  • a film 43 made of Co is formed on the surface portion of the semiconductor layer 10 on the left side of the convex layer 11.
  • the coating of the Co film 43 can be performed by various film forming methods such as sputtering and vapor deposition.
  • the electrons of the photocarrier move to the semiconductor layer 10 side by the electric field of the depletion layer. Along with this, electrons flow from the second electrode 22 into the conductive layer 40.
  • the electrons of carriers move to the convex layer 11 side and thus to the first electrode 21 side. Thereby, electrons flow along the conductive layer 40 toward the first electrode 21. Accordingly, the first electrode 21 becomes a cathode and the second electrode 22 becomes an anode. In this way, the electrode 22 that becomes the anode and the electrode 21 that becomes the cathode can be determined, and the direction of the photoinduced current can be controlled. Therefore, the current-voltage characteristic can be reliably asymmetrical between the positive side and the negative side, and a clean diode characteristic can be obtained.
  • the action of the metal nanostructure 30 will be described in detail. Plasmons are localized on the surface of the Au nanoparticle constituting the metal nanostructure 30. The surface plasmon and incident light resonate to generate a large electric field.
  • the periodic structure 33 of the metal nanostructure 30 enhances the sensitivity of photoelectric conversion with respect to incident light having a wavelength corresponding to the period (the arrangement interval of the first protrusions 31). That is, the periodic structure 33 causes plasmon resonance in a sensitive manner with respect to incident light having a wavelength of about 1 to 10 times, particularly about 10 times the period. Since the period of the 1st convex part 31 changes according to the periodic structure 33, the wavelength range which the metal nanostructure 30 can respond can be widened.
  • the existence density of the second protrusions 32 can be maintained high, and the number of the periodic structures 33 that can cause interaction with the second protrusions 32 is reduced. Can be secured, and the sensitive band can be reliably widened.
  • FIG. 7 shows a second embodiment of the present invention.
  • a photoelectric conversion element 1A according to the second embodiment includes a p-type semiconductor layer 10A instead of the n-type semiconductor layer 10 of the first embodiment.
  • the p-type semiconductor layer 10A is made of p-type silicon doped with a p-type impurity such as B (boron).
  • B boron
  • the arrangement interval (period) of the first protrusions 31 in the periodic structure 33 of the p-type element 1 ⁇ / b> A is slightly larger than that of the n-type element 1.
  • the arrangement interval (period) is more preferably about 60 nm to 150 nm.
  • the dispersion interval of the second convex portions 32 in the periodic structure 33 of the p-type element 1A is preferably slightly larger than that of the n-type element 1.
  • the dispersion interval is preferably about 3 ⁇ m to 5 ⁇ m, and the upper limit is preferably about 5 ⁇ m to 6 ⁇ m.
  • photocarriers are also generated by photoelectric conversion at the second Schottky junction 42 between the right end surface (convex layer side end surface) of the conductive layer 40 and the left side surface (one side surface) of the convex layer 11. appear.
  • the holes of the photocarrier move to the semiconductor layer 10 side by the electric field of the depletion layer. Along with this, holes flow from the second electrode 22 into the conductive layer 40. In the second Schottky junction 42, the carrier holes move toward the convex layer 11 and thus toward the first electrode 21. As a result, holes flow along the conductive layer 40 toward the first electrode 21. Therefore, the 1st electrode 21 becomes an anode and the 2nd electrode 22 becomes a cathode. In this way, the electrode 21 serving as the anode and the electrode 22 serving as the cathode can be determined, and the direction of the photoinduced current can be controlled. Therefore, the current-voltage characteristic can be reliably asymmetrical between the positive side and the negative side, and a clean diode characteristic can be obtained.
  • FIG. 8 shows a photoelectric conversion element 1B according to the third embodiment of the present invention.
  • the metal nanostructure 30 extends from the convex layer 11 to the conductive layer 40 and is widely distributed not only on the upper surface of the convex layer 11 but also on the surface of the conductive layer 40.
  • the electrode 21 arrangement portion on the right side of the surface of the semiconductor layer 10 is flush with the conductive layer 40 arrangement portion (same height), but may be slightly recessed (about 1 nm) as in the first embodiment. Good.
  • a method for manufacturing the photoelectric conversion element 1B of the third embodiment will be described.
  • Convex layer forming process As shown in FIG. 9, the surface of the semiconductor layer 10 is etched to form the convex layer 11. In the third embodiment, there is no need to further etch the right side portion of the convex layer 11 on the surface of the semiconductor layer 10.
  • the coating of the Co film 25 (see FIG. 3) on the left side of the convex layer 11 on the surface of the semiconductor layer 10 can be omitted.
  • an Au film 26 is directly laminated on the right portion of the semiconductor layer 10 by sputtering, vapor deposition, or the like.
  • the Au film 26 may be coated so as to be in contact with the right side portion of the surface of the semiconductor layer 10 and the right side surface of the convex layer 11, and does not have to cover the upper surface of the convex layer 11.
  • the substrate 10 is placed in an annealing bath and annealed (heat treatment).
  • the annealing temperature condition (first temperature) is about 800 ° C.
  • Other conditions for the annealing treatment are the same as those in the first embodiment.
  • the Au film 26 is in ohmic contact with the semiconductor layer 10 (including the convex layer 11) and becomes the first electrode 21.
  • Au and Si can be diffused and alloyed with each other, so that the electrode 21 and the semiconductor layer 10 (including the convex layer 11) can be reliably connected. Can make ohmic contact.
  • a Co film 43 serving as a metal component of the conductive layer 40 is coated on the left side of the convex layer 11 on the surface of the semiconductor layer 10 by sputtering, vapor deposition, or the like.
  • the base material 34 (Au) to be the metal nanostructure 30 is disposed on the convex layer 11 and the Co film 43.
  • the shape or property of the active material 34 (Au) is not particularly limited, and may be any of a thin film shape, a small piece shape, a small lump shape, a granular shape, a powder shape, a colloidal shape, a fiber shape, a wire shape, and a dot shape. The shape or property may be used.
  • the base body 34 is preferably arranged so as to be dispersed and interspersed in a portion between the first electrode 21 and the second electrode 22 on the upper surface of the convex layer 11 and the Co film 43.
  • the width W of each original material 24 is preferably about several hundred nm to 1 mm.
  • the height H of each original material 24 is preferably about several hundred nm to 1 mm.
  • the width D of the gap between the adjacent original materials 34 is preferably about several hundred nm to 1 mm.
  • the coating of the original material 34 can be performed by various film forming methods such as sputtering and vapor deposition.
  • the second electrode 22 and the original material 34 may be formed simultaneously.
  • the annealing process is performed in two steps, so that the first annealing process is performed at a temperature suitable for ohmic contact between the first electrode 21 and the semiconductor layer 10 (including the convex layer 11).
  • the temperature can be set to a temperature suitable for making the Schottky contact between the conductive layer 40 and the semiconductor layer 10 and the temperature suitable for obtaining the cluster-like or fractal-like metal nanostructure 30.
  • the metal nanostructure 30 may be provided only on the surface of the conductive layer 40.
  • the metal nanostructure 30 may be stacked only on a part of the conductive layer 40.
  • a semiconductor nanostructure may be provided on the metal nanostructure 30.
  • the semiconductor layer 10 of the element 1 is n-type
  • the semiconductor nanostructure is preferably n-type, and more preferably a semiconductor nanostructure having sensitivity in the ultraviolet region.
  • Examples of the component of the semiconductor nanostructure include ZnO, and other examples include n-type GaN.
  • the metal component constituting the metal nanostructure 30 is not limited to Au, and may be Ag, Pt, Cu, Pd, or the like.
  • the metal component constituting the conductive layer 40 is not limited to Co, but may be Fe, W, Ni, Al, Ti, or the like.
  • a plurality of embodiments may be combined with each other.
  • a p-type semiconductor layer 10A similar to the second embodiment may be used instead of the n-type semiconductor layer 10.
  • a Co layer 43 that promotes ohmic junction may be interposed at the junction between the electrodes 21 and 22 and the semiconductor layer 10 as in the first embodiment.
  • the manufacturing steps of the photoelectric conversion elements 1 and 1A may be changed or changed as appropriate.
  • Example 1 fabrication and observation of metal nanostructures were performed.
  • the metal nanostructure was produced as follows.
  • a Co film was formed on the entire surface of a substantially square n-type Si substrate by sputtering.
  • the thickness of the Co film was 8 nm.
  • the thickness of the Au film was about 10 nm.
  • annealing treatment was performed.
  • the atmosphere gas for the annealing treatment was He 100%.
  • the annealing temperature was 600 ° C.
  • the annealing time was 3 minutes.
  • FIGS. 13A and 13B show the images. It was confirmed that the fine particles of the Au film diffused along the surface of the CoSix film, and a metal nanostructure was naturally formed around the Au film. The morphology of the metal nanostructure was different depending on the location. As shown in FIG. 2B, a fractal structure was formed in the metal nanostructure depending on the location.
  • FIG. 14 shows the image.
  • FIG. 15 duplicates and explains the image of FIG. Sub-order or nano-order irregularities were formed on the surface of the metal nanostructure, and a cluster structure or fractal structure was confirmed. Furthermore, a large number of periodic structures 33 and a large number of second convex portions 32 were confirmed in the above-described uneven shape.
  • Each periodic structure 33 includes a plurality of first protrusions 31, and the first protrusions 31 are arranged at a period (arrangement interval) according to the periodic structure 33.
  • the period of the periodic structure 33 was approximately 100 nm or less.
  • the protrusion height of each first protrusion 31 was about 10 nm to 20 nm.
  • Each of the second convex portions 32 is disposed so as to overlap with a certain periodic structure 33 or is disposed in the vicinity of the periodic structure 33.
  • the protrusion height of the second protrusion 32 is larger than the protrusion height of the first protrusion 31 and is about 50 nm to 200 nm.
  • the dispersion interval of the second protrusions 32 was about 2 ⁇ m to 3 ⁇ m.

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  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Light Receiving Elements (AREA)
  • Photovoltaic Devices (AREA)

Abstract

L'invention concerne un élément convertisseur photoélectrique capable de garantir qu'une électrode sera une anode et qu'une autre électrode sera une cathode. Une couche en saillie (11) est formée sur une couche semi-conductrice (10) d'un élément convertisseur photoélectrique (1). Une couche conductrice (40) est empilée sur la face opposée de la couche semi-conductrice (10) afin d'entrer en contact avec une face latérale de la couche en saillie (11). Une première électrode (21) est disposée sur la face opposée de la couche semi-conductrice (10) afin d'entrer en contact avec la face latérale opposée de la couche en saillie (11). Une seconde électrode (22) est disposée sur la couche conductrice (40). Une nanostructure métallique (30), comprenant une pluralité de structures périodiques (33), est stratifiée soit sur la couche en saillie (11), soit sur la couche conductrice (40). Chaque structure périodique (33) comprend en outre une pluralité de premières parties en saillie (31) et l'espacement du positionnement des premières parties en saillie (31) est différent selon les structures périodiques (33).
PCT/JP2011/062605 2010-06-03 2011-06-01 Élément convertisseur photoélectrique et son procédé de fabrication WO2011152460A1 (fr)

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JP5525047B2 (ja) * 2010-06-10 2014-06-18 ｎｕｓｏｌａ株式会社 光発電装置
WO2014136691A1 (fr) * 2013-03-04 2014-09-12 Ozaki Yoriyasu Dispositif de conversion photoélectrique et procédé de fabrication de dispositif de conversion photoélectrique

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KR102597565B1 (ko) 2021-05-03 2023-11-06 성균관대학교산학협력단 Ｐｃｒ 장치

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JP5525047B2 (ja) * 2010-06-10 2014-06-18 ｎｕｓｏｌａ株式会社 光発電装置
WO2014136691A1 (fr) * 2013-03-04 2014-09-12 Ozaki Yoriyasu Dispositif de conversion photoélectrique et procédé de fabrication de dispositif de conversion photoélectrique
JP2014170852A (ja) * 2013-03-04 2014-09-18 Yoriyasu Ozaki 光電変換装置及び同装置の製造方法

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