JP5962503B2 - Substrate for photoelectric conversion element and photoelectric conversion element - Google Patents

Description

  The present invention relates to a photoelectric conversion element substrate and a photoelectric conversion element.

  The photoelectric conversion element includes an element that converts electricity into light and an element that converts light into electricity. Elements that convert electricity into light include light emitting diodes and semiconductor lasers, and elements that convert light into electricity include solar cells and photodiodes.

  In the case of a light emitting diode, for example, the photoelectric conversion element is configured by laminating an electrode (cathode or anode) layer, a light emitting layer, and an electrode (anode or cathode) layer on a substrate. Further, an intermediate layer such as an electron transport layer, an electron injection layer, a hole transport layer, or a hole injection layer may be provided between the layers.

  The light generated in the light emitting layer of the light emitting diode is extracted to the outside of the light emitting diode through the above-described intermediate layer and electrode layer (through the substrate when the substrate is transparent). At this time, light reflection occurs due to the difference in refractive index of the material constituting each layer at the layer interface of the light emitting layer, the intermediate layer, the electrode layer, and the substrate, and a phenomenon in which part of the light is confined in each layer occurs. Preventing light loss due to this phenomenon has been one of the problems of conventional light emitting diodes.

  In the solar cell, when sunlight enters the semiconductor layer through the electrode layer, part of the light is reflected by the difference in refractive index at the layer interface as in the case of the light emitting diode. Increasing the light transmittance at the layer interface and increasing the power generation efficiency has been one of the problems of conventional solar cells.

  In order to increase the light extraction efficiency, a light emitting diode has been proposed in which a light extraction layer is provided between the substrate and the transparent electrode so that the surface facing the electrode is uneven (Patent Document 1). The concavo-convex structure of Patent Document 1 is for extracting light that is generated in the light emitting layer and confined inside the light emitting layer or the transparent electrode by total reflection. Since the wavelength range of light that can be extracted is limited to the wavelength range of light determined by the period of the concavo-convex structure, the period of the concavo-convex structure is designed in accordance with the light having the central wavelength of light emission.

  On the other hand, in the case of a light emitting diode that extracts white light, which has been widely used in recent years for illumination, etc., it has a plurality of monochromatic light emitting layers with different emission peak wavelengths, and there are multiple emission peak wavelengths. In the concavo-convex structure described in 1, the light extraction efficiency could not be increased beyond a certain level.

JP 2006-269163 A

  The present invention relates to a substrate for a photoelectric conversion element, and provides a substrate for a photoelectric conversion element for obtaining a light-emitting element having a wide emission wavelength region and having a high light-emitting element luminous efficiency or a solar cell having a high power generation efficiency.

As means for solving the above problems, the present invention includes the following [1] to [5].
[1] A substrate for a photoelectric conversion element, which has an uneven structure on at least a part of at least one surface of the substrate, and the uneven structure includes two or more types of two-dimensional periodic structures having different periods. Of the two or more types of two-dimensional periodic structure portions, at least one type of two-dimensional periodic structure portion forms a micro area composed of two or more two-dimensional periodic units in the concavo-convex structure, and has a different period. A substrate characterized by existing in a mixed state with the two-dimensional periodic structure portion.
[2] The substrate according to (1), wherein the size of the minute area is a size that fits in a circle having a diameter of 50 μm.
[3] Of the two-dimensional periodic structure parts having different periods, the two types of two-dimensional periodic structure parts having the closest periods are compared, and the period of the two-dimensional periodic structure part having the smallest period is P1, and the period is Let P2 be the period of the large two-dimensional periodic structure part, compare the two types of two-dimensional periodic structure parts that are farthest apart, compare the period of the two-dimensional periodic structure part with the smallest period to P3, and the two-dimensional periodic structure with a large period The board | substrate as described in [1] or [2] in which P1, P2, P3, and P4 satisfy | fill Formula (1) and Formula (2) when the period of a part is set to P4.
Formula (1) P1 ≦ 0.90P2
Formula (2) P3 ≧ 0.10 P4
[4] A light emitting device in which at least a light emitting layer, a cathode layer, and an anode layer are laminated on the substrate according to any one of [1] to [3].
[5] A solar cell in which at least a semiconductor layer, a cathode layer, and an anode layer are stacked on the substrate according to any one of [1] to [3].

According to the present invention, a light emitting element having a wide emission wavelength region and high light emitting efficiency can be obtained. Alternatively, a solar cell with high power generation efficiency can be obtained.

Fig.1 (a) is a schematic diagram which shows an example of distribution of the micro area in the uneven structure provided in one surface of the substrate for photoelectric conversion elements of this invention. FIG. 1B is a cross-sectional view of the concavo-convex structure of FIG. 1A taken along line X1-X2. Fig.2 (a) is a schematic diagram which shows another example of distribution of the micro area in the uneven structure provided in one surface of the substrate for photoelectric conversion elements of this invention. FIG. 2B is a cross-sectional view of the concavo-convex structure of FIG. 2A taken along line X3-X4. FIG. 3 shows an example (light emitting element) of the embodiment of the present invention. FIG. 4 is another example (solar cell) of the embodiment of the present invention.

  Various known materials used as the substrate for photoelectric conversion elements can be used for the substrate for photoelectric conversion elements of the present invention. The material may be any of inorganic, organic, and inorganic-organic composites, and a visible light transmissive material such as glass or resin can also be used.

  An uneven structure is provided on at least a part of at least one surface of the substrate for photoelectric conversion elements of the present invention. The concavo-convex structure may be a structure in which convex portions are arranged with respect to the substrate plane, a structure in which concave portions are arranged with respect to the substrate plane, or a concavo-convex structure in a plane perpendicular to the substrate plane. A structure in which the cross-section taken off is a sine wave shape, a square wave shape, or a composite shape of a sine wave and a square wave. Examples of the shape of the convex portion or the concave portion include a columnar shape, a conical shape, a truncated cone shape, a bullet shape, or a composite shape thereof.

  As shown in FIG. 1, the concavo-convex structure is composed of two or more types of two-dimensional periodic structures having different periods. Of the two or more types of two-dimensional periodic structure portions, at least one type of two-dimensional periodic structure portion forms a micro area. Since the minute area is mixed with other two-dimensional periodic structure parts having different periods, the concavo-convex structure has a uniform ratio of two or more types of two-dimensional periodic structure parts having different periods.

  FIG. 2 is an example in which a minute area of a two-dimensional periodic structure portion B having a different period from the two-dimensional periodic structure portion A exists in an island shape in the two-dimensional periodic structure portion A.

  FIG. 3 shows an example in which the two-dimensional periodic structure portion A, the two-dimensional periodic structure portion B, and the two-dimensional periodic structure portion C having different periods exist as minute areas.

  The minute area has a structure in which two or more periodic structural units are repeated, preferably four or more, more preferably six or more.

  In the present invention, a figure formed by a line connecting the centers of the convex portions or concave portions of the two-dimensional periodic structure is applied to either a square lattice or a triangular lattice, and a fitted square or triangle is applied. A periodic structural unit.

  Note that there may be a portion having no concavo-convex structure inside the two-dimensional periodic structure portion or between two-dimensional periodic structure portions having different periods, and there is a concavo-convex structure portion having no periodicity. May be. It is preferable that the area of the concavo-convex structure part having no concavo-convex structure and the non-periodic concavo-convex structure part between the two-dimensional periodic structure parts having different periods is less than 50% of the area of the concavo-convex structure.

  The size of the minute area is preferably a size that fits in a circle having a diameter of 50 μm. When the size of the minute area exceeds a circle having a diameter of 50 μm, color tone unevenness may occur when the substrate of the present invention is used for a light emitting element, and when the substrate of the present invention is used for a solar cell. In some cases, the increase in power generation efficiency is not noticeable.

  Here, when the shape of the minute area is strain, if a circle having a size that can accommodate 75% or more of the area of the strained minute area is within a circle having a diameter of 50 μm, The size is considered to be a size that fits in a circle with a diameter of 50 μm.

  The method for forming the concavo-convex structure used in the photoelectric conversion element substrate of the present invention may be any method as long as the characteristics of the concavo-convex structure of the photoelectric conversion element substrate of the present invention can be reproduced, and various known methods can be applied. As an example of the method for forming a concavo-convex structure according to the present invention, a method for producing a concavo-convex structure by cutting a substrate surface with a laser beam, a photosensitive material is applied on the substrate, and a light-shielding mask pattern is applied, followed by exposure and development. A method for producing a concavo-convex structure by dry etching a substrate masked by a pattern, and a method for producing a concavo-convex structure by arranging a film made of particles on the substrate and dry-etching the substrate masked by the film made of particles Etc.

  When a substrate is prepared using a film made of the particles, a particle film is formed from two or more kinds of particles having different average particle diameters. By adjusting the mixing and dispersing conditions (for example, stirring intensity and time) of two or more types of particles with different average particle sizes and placing them on the substrate, particles with similar particle sizes form clusters and are placed on the substrate. By etching this, the concavo-convex structure used for the photoelectric conversion element substrate of the present invention is formed.

  When a substrate is prepared using a film made of the above particles, the Langmuir-Brochette method is adopted, and when forming a particle monolayer film on the liquid surface, two or more kinds of particles having different average particle diameters from different dropping ports A particle monolayer film in which particles having a similar particle diameter form a cluster can be produced by a method such as dripping. By arranging this on the substrate and etching, the concavo-convex structure used for the photoelectric conversion element substrate of the present invention is formed.

FIG. 3 is a schematic view showing a cross section of an example of a light emitting element using the substrate of the present invention.
The example of FIG. 3 is a light emitting device in which an anode layer, a light emitting layer, and a cathode layer are stacked on the substrate of the present invention. The interface of each layer formed on the substrate has the same uneven structure as the uneven structure on the substrate. A light-emitting element in which the interface of each layer has the same concavo-convex structure as that on the substrate can be produced by forming a thin film of each layer on the substrate of the present invention by vacuum deposition, sputtering, or the like.

  A light-emitting element obtained by laminating at least a light-emitting layer, a cathode layer, and an anode layer on the substrate of the present invention has a luminous efficiency at the interface of each layer through which light generated in the light-emitting layer passes before exiting the light-emitting element. It has a concavo-convex structure to be enhanced. The concavo-convex structure at the interface of each layer has the same two-dimensional periodic structure as that of the substrate, and the period is designed to increase the light emission efficiency. The concavo-convex structure of the substrate of the present invention includes two or more types of two-dimensional periodic structure portions having different periods, and the period of each two-dimensional periodic structure portion is adjusted to the wavelength of the light whose intensity is desired to be increased in the emitted light. It is designed appropriately. The two-dimensional periodic structure portion and its period may be any principle as long as it is for increasing the luminous efficiency.

In the example of FIG. 3, an example of a light-emitting element that emits light through a substrate using a light-transmitting material is used. However, a light-emitting element that emits light from the light-emitting layer to the opposite side of the substrate may be used.
In the example of FIG. 3, only the anode layer, the light emitting layer, and the cathode layer are displayed. However, a hole transport layer, a hole injection layer, and the like may be provided between the anode layer and the light emitting layer, and between the cathode layer and the light emitting layer. May be provided with an electron injection layer, an electron transport layer, or the like.
Moreover, the light emitting element laminated | stacked in order of the cathode layer, the electron injection layer, the electron carrying layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode layer on the board | substrate of this invention may be sufficient.

  Note that the uneven structure of the interface is not necessarily formed in all layers, and for example, a light emitting element having an uneven structure only at the interface of each layer existing between the substrate and the light emitting layer may be used.

  FIG. 4 is a schematic view showing a cross section of an example of a solar cell using the substrate of the present invention. A solar cell can also be manufactured by forming a thin film of an electrode layer or a semiconductor layer on a substrate by a vacuum deposition method, a sputtering method, or the like.

The solar cell obtained by laminating at least the electrode layer and the semiconductor layer on the substrate of the present invention has a concavo-convex structure at the interface of each layer through which the sunlight incident on the solar cell passes before entering the semiconductor layer. is there. The concavo-convex structure at the interface of each layer has the same two-dimensional periodic structure as that of the substrate, and the period is designed to increase the power generation efficiency. The concavo-convex structure of the substrate of the present invention includes two or more types of two-dimensional periodic structure parts having different periods. The period of each two-dimensional periodic structure part amplifies light having a wavelength with high power generation efficiency in the semiconductor layer. It is designed appropriately. The two-dimensional periodic structure portion and its period may be any principle as long as it is for increasing power generation efficiency.

  The photoelectric conversion element substrate of the present invention makes it possible to provide a light emitting element with high luminous efficiency. Moreover, the photoelectric conversion element substrate of the present invention can provide a solar cell with high power generation efficiency.

Claims (6)

A photoelectric conversion element substrate having an uneven structure on at least a part of at least one surface of the substrate;
The concavo-convex structure includes two or more types of two-dimensional periodic structures having different periods.
Of the two or more types of two-dimensional periodic structure portions, at least one type of two-dimensional periodic structure portion is formed by a line connecting the centers of the convex portions or concave portions of the two-dimensional periodic structure in the concave-convex structure. A substrate characterized in that a minute area composed of two or more two-dimensional periodic units having a square or triangle as a periodic structure unit is formed, and the minute area exists in an island shape . A substrate for a photoelectric conversion element;
Having an uneven structure on at least a part of at least one surface of the substrate;
The concavo-convex structure includes two or more types of two-dimensional periodic structures having different periods.
The two or more types of two-dimensional periodic structure portions are two-dimensional with a square or a triangle formed by a line connecting the centers of the convex portions or concave portions of the two-dimensional periodic structure in the concavo-convex structure as a periodic structural unit. A substrate characterized in that a minute area composed of two or more periodic units is formed, and two-dimensional periodic structures having different periods are present as minute areas. The substrate according to claim 1 or 2 , wherein a size of the minute area is a size that fits in a circle having a diameter of 50 µm. Of the two-dimensional periodic structure parts having different periods, the two types of two-dimensional periodic structure parts having the closest period are compared, and the period of the two-dimensional periodic structure part having the smaller period is P1, and the two-dimensional period is large. Let P2 be the period of the periodic structure part, compare two types of two-dimensional periodic structure part periods that are farthest apart, compare P2 for the two-dimensional periodic structure part with a small period, and the period for the two-dimensional periodic structure part with a large period The board | substrate in any one of Claims 1-3 in which P1, P2, P3, and P4 satisfy | fill Formula (1) and Formula (2), when letting be P4.
Formula (1) P1 ≦ 0.90P2
Formula (2) P3 ≧ 0.10 P4
At least a light-emitting layer on a substrate according to any one of claims 1-4, the cathode layer, the light-emitting element formed by laminating an anode layer. The solar cell which laminated | stacked the semiconductor layer, the cathode layer, and the anode layer at least on the board | substrate in any one of Claims 1-4 .

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