PHOTOVOLTAIC ELEMENT

Abstract

The purpose of the present invention is to improve power generation efficiency of a photovoltaic element. In a tandem-type photovoltaic element that comprises titanium dioxide and silicon dioxide, silicon dioxide particles that constitute a first photovoltaic layer 24 composed of silicon dioxide are thinly dispersed on a charge exchange layer 23 that is composed of Pt and has a roughness on the surface and on a first conductive film 22 that is composed of FTO and also has a roughness on the surface. Due to this configuration, a photovoltaic element with high power generation efficiency can be obtained.

Claims

1. A photovoltaic element comprising a first photovoltaic layer, wherein the first photovoltaic layer is composed of a silicon dioxide particle that has an average major axis of 100 nm or smaller.

2. A photovoltaic element comprising a first photovoltaic layer, wherein the first photovoltaic layer is composed of a silicon dioxide particle, and a thickness of the first photovoltaic layer in a height direction is formed to be equal to or smaller than three times an average major axis of the silicon dioxide particle.

3. A photovoltaic element comprising a first photovoltaic layer, wherein the first photovoltaic layer is composed of a silicon dioxide particle, and the silicon dioxide particle is arranged on a charge exchange layer that has an roughness in a height direction.

4. A photovoltaic element comprising a first photovoltaic layer, wherein the first photovoltaic layer is composed of a silicon dioxide particle, and the silicon dioxide particle is formed on an upper surface of a first conductive film that has a roughness in a height direction and arranged on a first conductive film that has a roughness in the height direction.

5. The photovoltaic element according to claim 3, wherein the roughness of the charge exchange layer in the height direction is 50 nm or greater.

6. The photovoltaic element according to claim 4, wherein the roughness of the first conductive film in the height direction is 50 nm or greater.

7. A photovoltaic element comprising: a first substrate comprising a first conductive film on one surface and a second substrate comprising a second conductive film on one surface are arranged such that the first conductive film and the second conductive film face each other; a second photovoltaic layer arranged on the second conductive film; a charge exchange layer arranged on the first conductive film; a first photovoltaic layer arranged on the charge exchange layer; an electrolyte arranged between the second photovoltaic layer and the first photovoltaic layer; and the first photovoltaic layer is composed of a silicon dioxide particle that has an average major axis of 100 nm or smaller.

8. The photovoltaic element according to claim 7, wherein in the first photovoltaic layer, the silicon dioxide particle is arranged such that a thickness in a height direction is equal to or smaller than three times the average major axis of the silicon dioxide particle.

9. The photovoltaic element according to claim 7, wherein when the first substrate is viewed from the second substrate side, the silicon dioxide particle in the first photovoltaic layer is arranged such that the charge exchange layer is visible through a gap formed between the silicon dioxide particles.

10. The photovoltaic element according to claim 7, wherein the charge exchange layer and or the first conductive film has a roughness of 50 nm or greater in the height direction.

11. The photovoltaic element according to claim 1, wherein the silicon dioxide particle is silicon dioxide immersed in hydrogen halide.

12. The photovoltaic element according to claim 7, wherein the second photovoltaic layer is a substance selected from TiO.sub.2, SnO, ZnO, WO.sub.3, Nb.sub.2O.sub.5, In.sub.2O.sub.3, ZrO.sub.2, Ta.sub.2O.sub.5 and TiSrO.sub.3.

13. The photovoltaic element according to claim 7, wherein the second photovoltaic layer comprises sensitized dye carried thereon.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0022] FIG. 1 is a cross-sectional view of a tandem-type photovoltaic element according to a first embodiment.

[0023] FIG. 2 is a cross-sectional view of a tandem-type photovoltaic element according to a second embodiment.

[0024] FIG. 3 is an enlarged view of portion A of FIG. 2.

[0025] FIG. 4 is a cross-sectional view of a tandem-type photovoltaic element according to a third embodiment.

[0026] FIG. 5 is an enlarged view of portion B of FIG. 4.

[0027] FIG. 6 is a schematic diagram in which a first conductive film according to the third embodiment is illustrated from bird's eye view.

[0028] FIG. 7 is a cross-sectional view of a tandem-type photovoltaic element according to a comparative example.

[0029] FIG. 8 is a view illustrating an example of a silicon dioxide particle.

[0030] FIG. 9 is a measurement chart of quantum efficiency of the photovoltaic element composed of TiO.sub.2 and the photovoltaic element including SiO.sub.2 in a light wavelength region.

DESCRIPTION OF EMBODIMENTS

[0031] Now, preferred embodiments of the present invention will be described with reference to the drawings. At first, matters common to the first, second and third embodiments are described.

[0032] FIG. 1 is a tandem-type photovoltaic element according to a first embodiment, FIG. 2 is a cross-sectional view of a tandem-type photovoltaic element according to a second embodiment, and FIG. 4 is a cross-sectional view of a tandem-type photovoltaic element according to a third embodiment, wherein matters described below are common to FIGS. 1, 2 and 4, so they are described with reference to FIG. 1 as the representative drawing.

[0033] FIGS. 1, 2 and 4 all illustrate a tandem-type photovoltaic element comprising two photovoltaic layers, which are a first photovoltaic layer and a second photovoltaic layer. In FIG. 1, among a first substrate 12 and a second substrate 11, at least the second substrate arranged on a side from which incident light enters is composed of a transparent material, and preferably, both substrates are composed of transparent material. Glass is a popular transparent material, but resin, such as plastic, can be used instead of glass.

[0034] A transparent second conductive film 13 is formed on the second substrate. The second conductive film 13 is preferably composed of FTO (fluorine-doped tin oxide), but other than the FTO layer, an indium-tin complex oxide (IOT) may be used, for example.

[0035] A second photovoltaic layer 16 is formed on the second conductive film 13. A typical example of the second photovoltaic layer 16 is an oxide semiconductor layer, and specifically, oxide semiconductors such as TiO.sub.2, SnO, ZnO, WOs, Nb.sub.2O.sub.5, In.sub.2O.sub.3, ZrO.sub.2, Ta.sub.2O.sub.5 and TiSrO.sub.3 are preferable. A porous titanium dioxide layer hardened by sintering is even further preferable.

[0036] Sulfide semiconductors such as CdS, ZnS, In.sub.2S, PbS, Mo.sub.2S, WS.sub.2, Sb.sub.2S.sub.3, Bi.sub.2S.sub.3, ZnCdS.sub.2 and CuS.sub.2 may be used. Moreover, metal chacogenide such as CdSe, In.sub.2Se.sub.2, WSe.sub.2, PbSe and CdTe are also applicable.

[0037] Even further, elemental semiconductors such as GaAs, Si, Se and InP may be used.

[0038] Further, a composite of two or more substances described above, such as a composite of SnO and ZnO or a composite of TiO.sub.2 and Nb.sub.2O.sub.5, may also be used.

[0039] The varieties of semiconductors are not restricted to those described above, and a mixture of two or more substances may also be used.

[0040] The thickness of the second photovoltaic layer 16 in the height direction should preferably be 3-30 m, and more preferably, 6-20 m.

[0041] Further, the above-described second photovoltaic layer 16 may carry sensitized dye. Various dyes that exert sensitization can be applied as the dye carried by the second photovoltaic layer 16, and for example, N3 complex, N719 complex (N719 dye), Ru complex such as Ru terpyrdine complex (black dye) and Ru diketonate complex, organic dyes such as coumarin dye, merocyanine dye and polyene dye, metal porphyrin dye and phthalocyanine dye are applicable. Among these dyes, the Ru complex is preferable, and specifically, N719 dye and black dye are especially preferable since they exert a wide absorption spectrum in the visible light range.

[0042] The dye can be used alone, or two or more dyes can be used in a mixture.

[0043] The above-described matters are common to the first, second and third embodiments and FIGS. 1, 2 and 4. In the following description, matters common to the first to third embodiments but have different reference numbers assigned in the drawings will be described by referring to the different reference numbers in the drawings.

[0044] A first conductive film (14 in FIGS. 1 and 2; 22 in FIG. 4) is formed on an upper surface of the first substrate 12. The first conductive film is preferably FTO (fluorine-doped tin oxide), but other than the FTO layer, for example, an indium-tin complex oxide (ITO) may be used.

[0045] A charge exchange layer (15 in FIGS. 1 and 2; 23 in FIG. 4) is formed on the first conductive film. A platinum (Pt) film is preferable as the charge exchange layer, but carbon electrode and conductive polymer may also be used instead of the platinum (Pt) film.

[0046] A first photovoltaic layer (21 in FIG. 1; 17 in FIG. 2; 24 in FIG. 4) is formed on the charge exchange layer.

[0047] In any of the first to third embodiments, a first photovoltaic layer is composed by dispersing silicon dioxide particles 10 as a first photovoltaic layer (21 in FIG. 1; 17 in FIG. 2; 24 in FIG. 4) on the charge exchange layer (15 in FIGS. 1 and 2; 23 in FIG. 4).

[0048] The silicon dioxide particles 10 that constitute the first photovoltaic layer (21 in FIG. 1; 17 in FIG. 2; 24 in FIG. 4) use glass particles formed for example of synthetic quartz, fused quartz glass, soda-lime glass, non-alkali glass or borosilicate glass, which are immersed in a solution of 5-10% hydrofluoric acid or hydrochloric acid, washed with water and dried, and pulverized so that a major axis L of the particles is 20 to 100 nm. The first to third embodiments use synthetic quartz particles, which are crystalline of silicon dioxide, which are immersed in 10% hydrofluoric solution, washed with water and dried, and pulverized so that a major axis L of the particles is 20-100 nm.

[0049] Electrolyte 19 is enclosed between the first photovoltaic layer (21 in FIG. 1; 17 in FIG. 2; 24 in FIG. 4) and the second photovoltaic layer 16, in a space that is surrounded by a sealing member 18 on four sides. The electrolyte 19 is used in the prior-art dye-sensitized solar cells, and it can be of any of the following states; liquid, solid, coagulated and ordinary temperature molten salt.

[0050] The electrolyte can be, for example, a combination of metal iodide, such as lithium iodide, sodium iodide, potassium iodide and cesium iodide, and iodine; a combination dc iodine salt of quaternary ammonium compound, such as tetraalkylammonium iodide, pyridinium iodide and imidazolium iodide, and iodine; a combination of bromine compound-bromine instead of the aforementioned iodine and iodine compound; or a combination of cobalt complex.

[0051] If the electrolyte is an ionic liquid, there is no need to use a solvent. The electrolyte may be a gel electrolyte, a high polymer electrolyte or a solid electrolyte, and an organic charge transport material may be used instead of the electrolyte.

[0052] If the electrolyte 19 is in a state of a solution, the solvent may be, for example, nitrile-based solvent such as acetonitrile, methoxyacetonitrile and propionitrile, carbonate-based solvent such as ethylene carbonate, and ether-based solvent.

[0053] Specifically, the electrolyte 19 used in the first to third embodiments is formed by adding 0.1 mol LiI, 0.05 mol I.sub.2, 0.5 mol 4-tetra-butylpyridine and 0.5 mol tetrabutylammonium iodide in acetonitrile solvent.

[0054] The distance between the first photovoltaic layer (21 in FIG. 1; 17 in FIG. 2; 24 in FIG. 4) and the second photovoltaic layer 16 in the height direction should preferably be as short as possible, since transfer of charge becomes easier if the distance is shorter.

[0055] In the first to third embodiments, the thickness of the electrolyte 19 portion in the height direction, that is, the distance between the first photovoltaic layer (21 in FIG. 1; 17 in FIG. 2; 24 in FIG. 4) and the second photovoltaic layer 16 in the height direction, is 200 m or smaller.

[0056] Method for evaluating the maximum output value per unit area according to the present specification is as described below.

[0057] An LED light (manufactured by Cosmotechno Co., Ltd.) was used to irradiate light from the second substrate side, and light corresponding to 1000 lux by illuminometer DT-1309 manufactured by CEM Corporation was irradiated to the photovoltaic element being the target for measurement A digital multimeter was used to measure the I-V characteristics of the photovoltaic element as the target for measurement, by which values of short circuit current, open circuit voltage and form factor ff were acquired, and the maximum output value per unit area was derived.

[0058] Hereafter, characteristics of the present embodiments will be described with reference to the drawings. The other portions are similar to the description regarding the matters common to the first to third embodiments described above.

First Embodiment

[0059] FIG. 1 is a view illustrating a first embodiment. In the first embodiment, silicon dioxide particles having an average major axis L of 20-100 nm are used as the silicon dioxide particles 10 used in the first photovoltaic layer 21. These silicon dioxide particles 10 are dispersed in an overlapped manner on a flat first conductive film 14 (FTO layer) and a similarly flat charge exchange layer 15 (Pt layer) formed thereon, by which the first photovoltaic layer 21 having a thickness of 300 to 500 nm in the height direction is composed.

[0060] Other conditions are as described as matters common to the first to third embodiments.

[0061] As a result, the embodiment realizes a significant improvement of photovoltaic efficiency compared to the prior art example described in the background art.

TABLE-US-00001 FTO layer Maximum output L t roughness per unit area Prior Art 500~800 nm 0.15~0.20 mm Very little surface 28.00 W/cm.sup.2 height difference First 20~100 nm 300~500 nm Very little surface 35.00 W/cm.sup.2 Embodiment height difference L: Average major axis of silicon dioxide particles t: Silicon dioxide layer thickness

[0062] In the first embodiment, the average major axis of the silicon dioxide particles 10 is small compared to the prior art, which is considered effective in increasing the surface area of the silicon dioxide particles 10 in the first photovoltaic layer 21 and raising the photovoltaic efficiency.

Second Embodiment

[0063] FIG. 2 is a view illustrating a second embodiment. The second embodiment uses the same materials and the like used in the first embodiment. However, in the second embodiment, a first photovoltaic layer 17 is composed so that the silicon dioxide particles 10 are arranged on a flat first conducive film 14 and a similarly flat charge exchange layer 15 disposed thereon, so that the thickness thereof in the height direction is 300 nm or smaller.

[0064] That is, the thickness of the first photovoltaic layer in the height direction is reduced compared to the first embodiment.

[0065] FIG. 3 is an enlarged view of portion A of FIG. 2, wherein the silicon dioxide particles 10 constituting the first photovoltaic layer 17 are dispersed on the flat first conductive film 14 (FTO layer) and the similarly flat charge exchange layer 14 (Pt layer) formed thereon, in a state where there is small overlap of particles.

[0066] As a result, the embodiment realizes a significant improvement of photovoltaic efficiency compared to the prior art example described in the background art.

TABLE-US-00002 FTO layer Maximum output L t roughness per unit area Prior Art 500~800 nm 0.15~0.20 mm Very little surface 28.00 W/cm.sup.2 height difference Second 20~100 nm 300 nm or less Very little surface 45.48 W/cm.sup.2 Embodiment height difference L: Average major axis of silicon dioxide particles t: Silicon dioxide layer thickness

[0067] In the second embodiment, the overlapping of the silicon dioxide particles 10 in the first photovoltaic layer 17 is reduced, according to which the property of charge transfer near the first photovoltaic layer 17 is enhanced, by which the photovoltaic efficiency is considered to be increased.

[0068] Therefore, it is important not to arrange too much silicon dioxide particles 10 on the upper surface of the charge exchange layer 15 in order to improve the photovoltaic efficiency. That is, it has been confirmed that the photovoltaic amount is increased if the silicon dioxide particles 10 are not excessively overlapped and sufficient space is formed therebetween.

[0069] Therefore, the thickness of the first photovoltaic layer 17 in the height direction should preferably be equal to or smaller than three times the average major axis L of the silicon dioxide particles.

[0070] The silicon dioxide particles 10 should preferably be arranged on the surface of an upper layer of the charge exchange layer 15 in a dispersed manner with spaces formed therebetween. This arrangement is to prevent the silicon dioxide particles 10 from being arranged in an overcrowded manner and hindering conductivity between the charge exchange layer 15, the silicon dioxide particles 10 and the electrolyte 19. It is preferable that the charge exchange layer 15, the silicon dioxide particles 10 and the electrolyte 19 are arranged with sufficient allowance, so that the total sum of contact surface areas of the charge exchange layer 15, the silicon dioxide particles 10 and the electrolyte 19 that perform charge exchange is maximized.

[0071] Therefore, the photovoltaic amount can be increased by arranging the silicon dioxide particles 10 in the first photovoltaic layer 17 such that the charge exchange layer 15 is visible through the spaces between the silicon dioxide particles 10 when the first substrate 12 is viewed from the second substrate 11 side.

Third Embodiment

[0072] FIG. 4 is a view illustrating a third embodiment. The third embodiment uses the same materials and the like as the first embodiment. However, in the third embodiment, a first conductive film 22 (FTO layer) and a charge exchange layer 23 (Pt layer) that constitute a base on which the silicon dioxide particles 10 are arranged are not flat. As illustrated in FIG. 4, the first conductive film 22 has an uneven surface (roughness or asperity), with a height difference of approximately 50 nm formed on the surface. The charge exchange layer 23 formed on the first conductive film 22 also has a roughness on the surface, influenced by the height difference formed on the first conductive film 22.

[0073] FIG. 5 is an enlarged view of portion B of FIG. 4. The silicon dioxide particles 10 constituting the first photovoltaic layer 24 are dispersed on the first conductive film 22 that has a roughness on the surface and the charge exchange layer 23 formed thereon and having a similar roughness, in a state where there is small overlap of particles.

[0074] The difference of height of the surface roughness of the first conductive film 22 should be 50 nm or greater, and more preferably, 100 nm or greater. Further, it is preferable that the charge exchange layer 23 formed on the first conductive film 22 is formed in a manner maintaining the shape of the roughness on the surface of the first conductive film 22 without burying the surface roughness of the first conductive film 22.

[0075] As a result, the embodiment realizes an even further significant improvement of photovoltaic efficiency compared to the prior art example described in the background art

TABLE-US-00003 FTO layer Maximum output L t roughness per unit area Prior Art 500~800 nm 0.15~0.20 mm Very little surface 28.00 W/cm.sup.2 height difference Third 20~100 nm 300 nm or less Surface height 70.8 W/cm.sup.2 Embodiment difference approx. 50 nm L: Average major axis of silicon dioxide particles t: Silicon dioxide layer thickness

[0076] The arrangement of the silicon dioxide particles 10 dispersed on the charge exchange layer 23 formed on the first conductive film 22 is influenced by the surface roughness of the first conductive film 22 and charge exchange layer 23 as base layers.

[0077] Thanks to the surface roughness of the base layers, the silicon dioxide particles 10 are arranged in a thinly dispersed manner. Thereby, the silicon dioxide particles 10 are arranged with appropriate spatial allowance without excessive overlap, and therefore, the increase of photovoltaic amount is confirmed.

[0078] FIG. 6 is a schematic diagram in which the first conductive film 22 is illustrated from bird's eye view. The shape of the surface roughness of the first conductive film 22 is not only risen steeply, as illustrated in FIG. 5, but may also include a structure 25 where the surface is somewhat rounded, as illustrated in FIG. 6. Further, the roughness does not have to be random, as illustrated in FIGS. 5 and 6, and the roughness can be regularly arranged shapes, such as structural cones, trigonal pyramids, quadrangular pyramids and other pyramid shapes.

[0079] The present invention is not restricted to the above-described first to third embodiments, and various modifications are possible. For example, the optimum average major axis of the silicon dioxide particles 10 may vary according to the distribution of size and shape of the silicon dioxide particles 10 constituting the first photovoltaic layer. Similarly, the optimum value of thickness of the first conductive film in the height direction may vary according to the distribution of size and shape of the silicon dioxide particles 10.

[0080] Further, various optimum combinations of height difference of unevenness in the height direction of the first conductive film and/or the charge exchange layer, the shape of the roughness, and the distribution of the roughness in a direction parallel to the first substrate may be adopted in response to the distribution of size and shape of the silicon dioxide particles 10.

[0081] Of course, a portion of the respective embodiments may be added to, deleted from or replaced with other materials and configurations.

REFERENCE SIGNS LIST

[0082] 10 silicon dioxide particle [0083] 11 second substrate [0084] 12 first substrate [0085] 13 second conductive film [0086] 14 first conductive film [0087] 15 charge exchange layer [0088] 16 second photovoltaic layer [0089] 17 first photovoltaic layer [0090] 18 sealing member [0091] 19 electrolyte [0092] 21 first photovoltaic layer [0093] 22 first conductive film [0094] 23 charge exchange layer [0095] 24 first photovoltaic layer