WO2003038909A1 - Element de conversion photoelectrique et son procede de fabrication - Google Patents

Element de conversion photoelectrique et son procede de fabrication Download PDF

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Publication number
WO2003038909A1
WO2003038909A1 PCT/JP2001/009538 JP0109538W WO03038909A1 WO 2003038909 A1 WO2003038909 A1 WO 2003038909A1 JP 0109538 W JP0109538 W JP 0109538W WO 03038909 A1 WO03038909 A1 WO 03038909A1
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Prior art keywords
film
photoelectric conversion
conversion element
blocking
blocking film
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PCT/JP2001/009538
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English (en)
Japanese (ja)
Inventor
Kietsu Iwabuchi
Hirofumi Kondo
Akio Yasuda
Gabriele Nelles
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Sony Corporation
Sony International (Europe) G.M.B.H.
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Application filed by Sony Corporation, Sony International (Europe) G.M.B.H. filed Critical Sony Corporation
Priority to JP2003541065A priority Critical patent/JPWO2003038909A1/ja
Priority to DE10197130.3T priority patent/DE10197130B4/de
Priority to PCT/JP2001/009538 priority patent/WO2003038909A1/fr
Publication of WO2003038909A1 publication Critical patent/WO2003038909A1/fr

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H10K30/15—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2
    • H10K30/151—Sensitised wide-bandgap semiconductor devices, e.g. dye-sensitised TiO2 the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
    • H01G9/2009—Solid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the present invention relates to a method for manufacturing a photoelectric conversion element and a photoelectric conversion element, and more particularly to a method for manufacturing a photoelectric conversion element and a photoelectric conversion element that can be suitably used as a solid-state solar cell.
  • Photovoltaic conversion elements used as solar cells are: 1) low cost, 2) can be supplied on a global scale, and 3) can be obtained by a production method that is adaptable to the global environment and has resource constraints. It is required to meet the requirements of,, etc.
  • the solar cell 101 shown in this figure has a transparent electrode film 105 formed on the surface of a substrate 103 having optical transparency, and the transparent electrode film 105 and a power generation layer film 1 described below.
  • a blocking film 107 for preventing a short circuit with the hole transport material 109 c of No. 09 is formed.
  • the blocking film 107 is made of, for example, titanium oxide, and is formed by a spray pyrolysis method or the like. This method is a method of spraying an alcoholic solution of an organic complex salt of titanium (T i) on a substrate 103 heated to about 600 ° C.!
  • a power generation layer film 109 composed of electron transporting fine particles 109a having a sensitizing dye 109b adsorbed thereon and a hole transport material 109c is provided.
  • anatase type titanium oxide is used as the electron transporting fine particles 109 a constituting the power generation layer film 109.
  • the counter electrode film 1 is formed on the power generation layer film 109. 10 is provided.
  • the operation mechanism of the solar cell having such a configuration will be described using the energy diagram of FIG. 2 together with FIG. That is, when light (sunlight) H enters from the substrate 103 side, the light H excites the sensitizing dye 109 b in the power generation layer film 109, causing electrons e and holes h to form. Occurs. Then, the electron e is injected into the electron-transporting fine particles 109 a from the excitation level, moves inside the electron e, passes through the blocking film 107, is supplied to the transparent electrode film 105, and flows as a current. Taken out. On the other hand, the holes h move from the base level through the hole transport material 109 c by hobbing conduction.
  • the blocking film 107 is required to make physical contact between the hole transport material 109 c constituting the power generation layer film 109 and the transparent electrode film 105. It has the function of preventing For this reason, the blocking film 107 is required to have a dense film quality and a certain thickness. That is, when the hole transport layer 109 c and the transparent electrode film 105 come into contact with each other, holes h (indicated by a chain line in the figure) move from this contact portion to the transparent conductive film 105. Since the holes h combine with the electrons e in the transparent conductive film 105 and disappear, the battery performance deteriorates.
  • the blocking film 107 becomes a part of a conductive path for electrons e generated in the power generation layer film 109, when the film thickness is larger than necessary, the internal resistance of the battery is reduced. High, which causes deterioration of battery performance. Further, since the blocking film 107 also becomes a part of the optical path for the incident light H, the photoelectric conversion efficiency is deteriorated when the optical absorption is large.
  • the blocking film 107 has a dense film quality and can prevent a short circuit with the power generation layer film 109, but does not hinder the transport of the electron e and has an optical property. It is desired that the film is thinned so that the absorption is suppressed as small as possible.
  • a film forming method such as the spray decomposition method described above has an advantage that a relatively transparent film can be obtained, the controllability of the film thickness is poor, and the thickness of the blocking film is reduced. Is difficult. Further, since the substrate 103 needs to be heated to a high temperature, the process load increases. Further, there is a problem that a foreign substance force is easily mixed into the film, and a blocking film having stable film quality cannot be obtained. Disclosure of the invention
  • the present invention for solving such a problem is to form a blocking film for preventing short circuit on a transparent electrode film, and to provide a sensitizing dye-adsorbed electron transporting fine particle and a hole transport material on the blocking film.
  • the formation of the blocking film is performed by vacuum film formation.
  • the present invention is also a photoelectric conversion element obtained by such a method.
  • FIG. 1 is a cross-sectional view for explaining the configuration of a conventional photoelectric conversion element and its problems.
  • FIG. 2 is a diagram for explaining the operation of the photoelectric conversion element.
  • FIG. 3 is a configuration diagram of the photoelectric conversion element of the present invention.
  • FIG. 4 is an enlarged sectional view of a main part of the photoelectric conversion element of the present invention.
  • FIG. 5 is a cross-sectional view illustrating an example of an end configuration of the photoelectric conversion element. '
  • FIG. 6 is a cross-sectional view for explaining another example of the end configuration of the photoelectric conversion element.
  • FIG. 7 is a cross-sectional view for explaining still another example of the end configuration of the photoelectric conversion element.
  • FIG. 3 is a configuration diagram of the photoelectric conversion element of the present invention
  • FIG. 4 is a cross-sectional view of a main part of the photoelectric conversion element.
  • the photoelectric conversion element 1 shown in these figures is suitably used as a solid-state solar cell.
  • a substrate 3, a transparent electrode film 5, a blocking film 7, a power generation layer film 9, and a counter electrode film 11 are laminated in this order from the bottom of the drawing.
  • the power generation layer film 9 is formed by filling the hole transporting material 9 c between the electron transporting fine particles 9 a to which the sensitizing dye 9 b is adsorbed, thereby forming the dye-sensitized photoelectric conversion element 1. Have been. In the following, details of each of these It will be described in order.
  • a substrate 3 made of a material capable of transmitting light (sunlight) H is prepared.
  • a substrate 3 is made of, for example, plastics such as glass, PET (polyethylene terephthalate), PEN, polyimide, polyamide, and polyproponate.
  • the substrate 3 does not need to be able to transmit the light H, and may be made of ceramic such as zirconia, or a metal such as steel or copper.
  • an insulating process such as covering the surface of the substrate 3 with a silicon oxide film is performed.
  • a transparent electrode film 5 serving as a negative electrode of the solar cell is formed on such a substrate 3.
  • the transparent electrode film 5 must have low resistance in order to form a series resistance in the battery, and must have a small optical absorption because it serves as an optical path of light H. Furthermore, the transparent electrode film 5 has poor weather resistance and chemical resistance. It is desirable to be excellent.
  • Examples of such a transparent electrode film 5, ZnO, Sn0 2, I n 2 ⁇ 3, I TO (S n de one flop ln 2 0: i), I FO (F -doped I n 2 0 3), ATO ( 313 de one flop 311_Rei 2), FT_ ⁇ (F-doped Sn_ ⁇ 2), CTO (Cd de one flop Sn0 2) use a layer consisting of such a single layer or a composite layer.
  • Sn0 2 ZI TO can be exemplified by ZnO / I TO like.
  • IT ⁇ , FTO, S ⁇ IT ⁇ , and Zn nIT ⁇ can be preferably used.
  • a sputtering method As a method for forming the transparent conductive film 5, a sputtering method, a vacuum evaporation method, a CVD (chemical vapor deposition) method, an IP (Ion Plating) method, a spray film forming method, a dip film forming method, or the like is applied. Can be.
  • a blocking film 7 for preventing short-circuit between the transparent electrode film 5 and the hole transport material 9c of the power generation layer film 9 is formed on the transparent electrode film 5.
  • the electron transporting fine particles 9a made of titanium oxide in the power generation layer film 9 described below are deposited on the blocking film ⁇ , the electron transporting fine particles 9a It is preferable that the blocking film 7 is made of titanium oxide in consideration of securing the bonding with the insulating film 7.
  • the blocking film 7 is for preventing a short circuit (contact) between the transparent electrode film 5 and the hole transport material 9c, and therefore needs to have a dense film quality. For this reason, when using titanium oxide as the blocking film 7, it is preferable to form the film as titanium oxide having an amorphous (amorphous) or fine crystal structure. When the crystal grain size of titanium oxide is large, a large grain boundary is formed in the blocking film 7, so that the hole transport material 9c, which is a low-viscosity amorphous organic substance having a three-dimensional size of about 1 nm, is used. Then, it passes through the grain boundary and comes into contact with the transparent electrode film 5.
  • the blocking film 7 grows because the blocking film 7 crystal grows. It is preferable to form the film as an amorphous or fine crystal structure at the time of film formation. In the case of a fine crystal structure, for example, it is an anatase crystal.
  • the blocking film 7 since the blocking film 7 has a high resistance in its function, if the film thickness is large, the internal resistance of the battery increases, which causes deterioration of the battery performance. For this reason, the blocking film 7 is preferably a thin film.
  • the thickness when the blocking film 7 is made of titanium oxide, the thickness is preferably 100 nm or less.
  • the thickness in order to reliably obtain the effect of preventing the blocking electrode 7 from physically contacting the transparent electrode film 5 and the hole transport material 9c, when the layer is made of titanium oxide, the thickness is 15 nm or more, preferably 20 nm. The film thickness is set to the above value.
  • the blocking film 7 when the blocking film 7 is in the optical path of the light (sunlight) H irradiated from the substrate 3 side, the blocking film 7 has a film quality that minimizes optical absorption and is thinned. Is desired. For this reason, when the blocking film 7 is made of titanium oxide, it is preferable to form titanium oxide having a composition ratio of oxygen to titanium (OZTi composition ratio) of at least 0.8.
  • the blocking film 7 reliably separates the transparent electrode film 5 and the hole transport material 9c. It is preferable that the transparent electrode film 5 is formed in such a shape as to securely cover the surface of the transparent electrode film 5 to the edge portion. For this reason, as shown in FIG. 5, it is preferable to provide the blocking (3) in a state of covering not only the surface of the transparent electrode film 5 but also the entire exposed surface including the portion exposed at the end. .
  • the blocking film 7 having such a configuration is formed by a vacuum film forming method such as a sputtering method, a vacuum evaporation method, an IP method, and a CVD method.
  • a vacuum film forming method such as a sputtering method, a vacuum evaporation method, an IP method, and a CVD method.
  • a sputtering method because the quality of the formed film is easily controlled.
  • an RF sputtering method targeting titanium oxide or a sputtering method in an oxygen atmosphere targeting titanium is applied.
  • the film forming conditions for obtaining an amorphous or dense film of titanium oxide having a fine crystal structure include input power. 0-01 to 0.1 OW / mm 2 , film formation temperature (substrate temperature) 350 or less, oxygen partial pressure in film formation atmosphere 5.3 X 10 • 3 Pa or more.
  • the film formation temperature is set to 200 ° C. to 35 O a C.
  • the film formation rate becomes higher as the oxygen partial pressure in the film formation atmosphere increases, it is preferable to set the upper limit of the oxygen partial pressure in the film formation atmosphere to 8.0 ⁇ 10 3 ⁇ a. Therefore, the oxygen partial pressure in the film formation atmosphere, 5. 3X 10- 3 P a ⁇ 8. 0 XI 0- 3 P is preferably set to a.
  • the power generation layer film 9 is formed on the blocking film 7.
  • the electron transporting fine particles 9a are attached to the blocking film 7.
  • the electron transporting fine particles 9a may be fine particles of an anatase-type titanium oxide doped with a different element or subjected to a surface treatment.
  • the particle diameter of the electron transporting fine particles 9a is set to 5 to 50 nm, and preferably set to 10 to 30 nm in consideration of photoelectric conversion efficiency.
  • the sensitizing dye 9b is adsorbed on the surface of the electron transporting fine particles 9a, so that there are many gaps between the electron transporting fine particles 9a, that is, the porosity.
  • the electron transporting fine particles 9 a are adhered onto the blocking film 7 while keeping the value large. Further, the thickness of the electron transporting fine particle 9a layer on the blocking film 7 is preferably about 0.1 to 40 m.
  • the electron transporting fine particles 9a can be attached to the blocking film 7 by, for example, any one of the following methods (1) to (4).
  • the electron transporting fine particles 9a are dispersed in a binder or a thickener and sprayed or applied onto the blocking film 7, dried, and then fired at 150 to 60 (TC temperature).
  • Titanium oxide particles obtained by hydrolyzing a titanium compound in the presence of nuclear seeds are sprayed or applied onto the blocking film 7 and then dried, and then dried as needed. Bake at a temperature of 0.
  • the sensitizing dye 9b is adsorbed on the electron transporting fine particles 9a attached on the blocking film 7.
  • the sensitizing dye 9b is a dye having an absorption in the visible light region, and a metal complex or an organic dye can be used.
  • Metal complexes include metal phthalocyanines such as copper phthalocyanine and titanyl phthalocyanine. Examples include metal complexes such as russian cyanine, chlorophyll or derivatives thereof, hemin, and ruthenium, osmium, iron, and zinc described in JP-A-1-220380 and JP-A-5-504023.
  • organic dye metal-free phthalocyanine, merocyanine dye, xanthene dye, and triphenylmethane dye can be used as the cyanine dye.
  • the sensitizing dye 9b it is preferable to use a metal complex as the sensitizing dye 9b from the viewpoint of sensitizing performance.
  • the adsorption of the sensitizing dye 9b to the electron transporting fine particles 9a adhered on the blocking film 7 is performed by removing the layer of the electron transporting fine particles 9a that have been well dried in the solution of the sensitizing dye 9b.
  • a method of immersing or applying a solution of the sensitizing dye 9b on the layer of the electron transporting fine particles 9a can be used.
  • the hole transporting material 9c is filled in the layer of the electron transporting fine particles 9a having the sensitizing dye 9b adsorbed thereon.
  • the hole transport material 9 c is, for example, an arylamine-based positive charge transport material such as N, N′-diphenyl 1 -N, N, — di-(3 -methy 1 heny 1 ) -4, 4'-bi pheny lamine (TPD) or amorphous 2, 2 ', 7 with a higher dislocation point (Tg) for longer and stable positive charge transport function , 7 '— tetr ak is [ ⁇ , ⁇ ' — di (4 -me th oxypheny l) ami ne ”— 9, 9 — spir ob ifluor en e: OMe TAD.
  • tri (bromo ⁇ ) is used as a dopant to improve the efficiency of electron injection from the sensitizing dye 9b into the electron transporting fine particles 9a and to compensate for the space charge effect.
  • heny 1) am ine and salts of S b C 1 6, L i [(CF 3 S0 2) 2 N] and, L i C 10 4, C aC 1_Rei 4 may be added.
  • the hole transporting material 9c is filled between the electron transporting fine particles 9a having the sensitizing dye 9b adsorbed thereon, for example, by spin coating.
  • a power generation layer film 9 composed of the electron transporting fine particles 9a having the sensitizing dye 9b adsorbed thereon and the hole transporting material 9c is formed.
  • the edge of the power generation layer film 9 is blocked by a blocking film so that the power generation layer film 9 and the transparent electrode film 5 are surely separated by the blocking film 7. 7 may be set inside the edge.
  • the above-described series of the power generation layer film 9 is formed while the periphery of the blocking film 7 is masked.
  • a counter electrode film 11 serving as a positive electrode of the solar cell when the photoelectric conversion element 1 is a solar cell is formed on the power generation layer film 9.
  • the counter electrode film 11 is preferably formed using Au, Pt ;, Pd, or the like, which have a work function of about 5. O eV and a high catalytic activity. Since the counter electrode film 11 forms an internal resistance in a solar cell using the photoelectric conversion element 1, it is preferable that the counter electrode film 11 be thicker for the purpose of reducing the resistance. In the case of a photoelectric conversion element in which light is incident from the counter electrode film 11 side, light absorption is suppressed by reducing the thickness of the counter electrode film 11 so that battery performance can be obtained. become. For this reason, for example, when the counter electrode 11 is made of Au, Pt, Pd, or the like, it is preferable that the thickness of the counter electrode film 11 be 30 Onm or less, and that the thickness be 200 nm or less.
  • This counter electrode film 11 is preferably formed by a vacuum film forming method such as a sputtering method, a vacuum evaporation method, an IP method, and a CVD method. Further, the substrate temperature at the time of film formation is set to be equal to or lower than the decomposition temperature of the hole transport material 9 c constituting the power generation layer film 9.
  • This photoelectric conversion element 1 Is used as a solar cell in a state where the transparent electrode film 5 and the counter electrode film 11 are connected to an external circuit 20.
  • the blocking film 7 is formed by vacuum film formation, the controllability of the film thickness and the film quality is good, and the blocking film 7 free of foreign matter or the like can be obtained. For this reason, it is possible to form the blocking film 7 which is dense and thin. That is, since the dense blocking film 7 can be made thinner, light absorption in the blocking film 7 is suppressed, and the power generation layer film 9 and the transparent electrode film 5 are reliably separated by the bracket blocking film. 1 is obtained. As a result, a photoelectric conversion element 1 having high conversion efficiency can be obtained, and a solid-state solar cell having good battery performance can be realized using the photoelectric conversion element 1.
  • the configuration of the dye-sensitized photoelectric conversion element in which the sensitizing dye 9b is adsorbed on the electron transporting fine particles 9a in the power generation layer film 9 has been described.
  • the power generation layer film 9 is composed of the electron transporting fine particles 9a and the hole transport material 9c.
  • the present invention can be widely applied to solid-state photoelectric conversion elements provided with a blocking film 7 between them.
  • a photoelectric conversion element there is an element using titanium oxide having a long-wavelength absorption-excitation type oxygen defect as the electron transporting fine particles 9a.
  • This photoelectric conversion element can be configured without adsorbing the sensitizing dye on the electron transporting fine particles 9a. Even in this case, the properties required for the blocking film are the same as those having the sensitizing dye. Therefore, a similar effect can be obtained by applying the present invention.
  • specific Examples 1 to 4 and Comparative Examples of the present invention, and the evaluation results thereof will be described.
  • the photoelectric conversion element was manufactured by changing the forming conditions of the blocking film 7) and changing the film thickness of the blocking film 7 under each forming condition. Then, the photoelectric conversion efficiency, the composition of the blocking film 7, and the crystal structure of the manufactured photoelectric conversion element were measured. ⁇ Preparation procedure>
  • the photoelectric conversion elements in Examples 1 to 4 and Comparative Example were manufactured in the following procedure. First, a transparent electrode film 5 made of ITO was formed on the entire surface of a substrate 3 made of 25 mm ⁇ 25 mm glass by sputtering.
  • a blocking film 7 made of titanium oxide was formed in a region of 2 mm ⁇ 25 mm on the transparent electrode film 5.
  • each embodiment 5 and 5 evaluation samples were prepared for each of the comparative examples, and in each evaluation sample, a 10 nm,
  • Blocking films were formed at five different thicknesses: 20 nm, 60 nm, 100 nm, and 150 nm.
  • Deposition of these flops locking film 7 is carried out by RF sputtering evening method to set the oxygen (0 2) partial pressure and the substrate temperature during the deposition as shown below display 1. Also this film, using a T i 0 2 (99. 99% ) to the target, as a common film formation conditions, the input power 0. 44WZmm 2, the partial pressure of A r used as sputtering evening gas 13.
  • the electron transporting fine particles 9a were printed and applied on the blocking film 7 by screen printing.
  • Ana-ose type titania sol particle size: 13 nm, specific surface area: 12 OmV g
  • So1a1-oni X was used.
  • 30 By baking at 0 ° C., a layer of electron transporting fine particles 9a made of anatase type crystal titanium oxide having a thickness of about 5 m was obtained.
  • the sample having the electron-transporting fine particles 9a attached thereto is immersed in a sensitizing dye solution (the above-mentioned Ruthenium 53-bis TBA solution), and the sensitizing dye 9b is added to the electron-transporting fine particles 9a. Adsorbed. Thereafter, a hole transport material solution (the above-mentioned ⁇ Me TAD solution) was applied by a spin coating method, and the gap between the electron transporting fine particles 9a was filled with the hole transport material 9c. Then, the hole transporting material 9 c attached to the transparent electrode film 5 was sufficiently wiped off with a cotton swab, and the solvent in the hole transporting material 9 c was evaporated to obtain a power generation layer film 9.
  • a sensitizing dye solution the above-mentioned Ruthenium 53-bis TBA solution
  • a hole transport material solution the above-mentioned ⁇ Me TAD solution
  • the conversion element 1 was produced as a solar cell.
  • the photoelectric conversion efficiency was measured as a battery characteristic.
  • the composition ratio of titanium oxide was measured using an X-ray microanalyzer (XMA), and the crystal structure was analyzed using an X-ray diffractometer (MRD).
  • XMA X-ray microanalyzer
  • MRD X-ray diffractometer
  • the light absorptivity for nm light was measured.
  • the measurement of the light absorptance was performed on a blocking film having a thickness of 100 nm.
  • Table 2 shows the evaluation results of the comparative examples.
  • the light absorption of the blocking film (100 nm thick) of the comparative example was 11%. ' Table 2
  • Example 3 shows the evaluation results of Example 1 above. Further, the light absorption of the blocking film (film thickness l O Onm) of Example 1 was 1%.
  • Example 2 shows the results of the above evaluations for Example 2.
  • the light absorption of the blocking film (film thickness 100 nm) of Example 2 was 1%.
  • Example 3 150 nm 0.187 1.8 Amorphous Table 5 below shows the results of the above evaluations for Example 3. The light absorption of the blocking film (thickness: 100 nm) of Example 3 was 1%.
  • Example 6 shows the results of the evaluation of Example 4 above.
  • the light absorption of the blocking film (film thickness of 10 O nm) of Example 4 was 1%.
  • the crystalline form of the blocking film 7 is in the range of 2 O nm to 10 O nm if it is amorphous or anatase crystal. In the above, it was confirmed that the above-described conversion efficiency and light absorption were obtained.
  • the blocking film between the power generation layer film and the transparent electrode film is formed by vacuum film formation, so that the dense film quality of the blocking film can be reduced. Therefore, a photoelectric conversion element with high conversion efficiency can be obtained, and a solid-state solar cell having good battery performance can be realized using the photoelectric conversion element.

Abstract

L'invention concerne un élément de conversion photoélectrique pouvant atteindre une efficacité de conversion élevée par amélioration de la contrôlabilité de la qualité et de l'épaisseur d'un film de blocage formé entre un film à couche de génération de puissance et un film d'électrode transparent. Ledit élément de conversion (1) photoélectrique comprend un film (9) à couche de génération de puissance contenant des microparticules (9a) transportant des électrons; un matériau (9c) portant un alésage pris en sandwich entre le film d'électrode (5) transparent; un film de contre-électrode (11); et un film de blocage (7) permettant d'empêcher un court-circuit, interposé entre le film d'électrode (5) transparent et le film (9) à couche de génération de puissance et caractérisé en ce qu'il est formé par formation d'un film sous vide.
PCT/JP2001/009538 2001-10-31 2001-10-31 Element de conversion photoelectrique et son procede de fabrication WO2003038909A1 (fr)

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Application Number Priority Date Filing Date Title
JP2003541065A JPWO2003038909A1 (ja) 2001-10-31 2001-10-31 光電変換素子の製造方法および光電変換素子
DE10197130.3T DE10197130B4 (de) 2001-10-31 2001-10-31 Verfahren zum Herstellen eines fotoelektrischen Umwandlers sowie fotoelektrischer Umwandler
PCT/JP2001/009538 WO2003038909A1 (fr) 2001-10-31 2001-10-31 Element de conversion photoelectrique et son procede de fabrication

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WO2010050575A1 (fr) 2008-10-29 2010-05-06 富士フイルム株式会社 Colorant, élément de conversion photoélectrique et cellule photoélectrochimique comprenant chacun le colorant, et procédé de fabrication du colorant
EP2302650A2 (fr) 2009-09-28 2011-03-30 Fujifilm Corporation Procédé de production d'un élément de conversion photoélectrique, élément de conversion photoélectrique et cellule photoélectricochimique
EP2306479A2 (fr) 2009-09-28 2011-04-06 Fujifilm Corporation Procédé de production d'un élément de conversion photoélectrique, élément de conversion photoélectrique et cellule photoélectricochimique
JP2011119696A (ja) * 2009-10-30 2011-06-16 Sumitomo Chemical Co Ltd 有機薄膜太陽電池及びその製造方法
JP2012509579A (ja) * 2008-11-18 2012-04-19 コナルカ テクノロジーズ インコーポレイテッド 色素増感光電セル
CN102522438A (zh) * 2011-12-15 2012-06-27 东南大学 一种利用氧化铟锡纳米颗粒增效的近红外光电探测器
JP2016082003A (ja) * 2014-10-14 2016-05-16 積水化学工業株式会社 薄膜太陽電池の製造方法
JP2018170382A (ja) * 2017-03-29 2018-11-01 積水化学工業株式会社 太陽電池
JP2020145226A (ja) * 2019-03-04 2020-09-10 シャープ株式会社 ハイブリッド粒子、光電変換素子、感光体及び画像形成装置

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JP2000231943A (ja) * 1998-12-08 2000-08-22 Toyota Central Res & Dev Lab Inc 半導体電極およびその製造方法
JP2000285974A (ja) * 1999-03-30 2000-10-13 Toshiba Corp 光増感型太陽光発電素子
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010050575A1 (fr) 2008-10-29 2010-05-06 富士フイルム株式会社 Colorant, élément de conversion photoélectrique et cellule photoélectrochimique comprenant chacun le colorant, et procédé de fabrication du colorant
EP2845882A2 (fr) 2008-10-29 2015-03-11 Fujifilm Corporation Colorant, élément de conversion photoélectrique et cellule photoélectrochimique
JP2012509579A (ja) * 2008-11-18 2012-04-19 コナルカ テクノロジーズ インコーポレイテッド 色素増感光電セル
EP2302650A2 (fr) 2009-09-28 2011-03-30 Fujifilm Corporation Procédé de production d'un élément de conversion photoélectrique, élément de conversion photoélectrique et cellule photoélectricochimique
EP2306479A2 (fr) 2009-09-28 2011-04-06 Fujifilm Corporation Procédé de production d'un élément de conversion photoélectrique, élément de conversion photoélectrique et cellule photoélectricochimique
JP2011119696A (ja) * 2009-10-30 2011-06-16 Sumitomo Chemical Co Ltd 有機薄膜太陽電池及びその製造方法
CN102522438A (zh) * 2011-12-15 2012-06-27 东南大学 一种利用氧化铟锡纳米颗粒增效的近红外光电探测器
JP2016082003A (ja) * 2014-10-14 2016-05-16 積水化学工業株式会社 薄膜太陽電池の製造方法
JP2018170382A (ja) * 2017-03-29 2018-11-01 積水化学工業株式会社 太陽電池
JP2020145226A (ja) * 2019-03-04 2020-09-10 シャープ株式会社 ハイブリッド粒子、光電変換素子、感光体及び画像形成装置
CN111653674A (zh) * 2019-03-04 2020-09-11 夏普株式会社 混合粒子、光电转换元件、感光体及图像形成装置
JP7198688B2 (ja) 2019-03-04 2023-01-11 シャープ株式会社 ハイブリッド粒子、光電変換素子、感光体及び画像形成装置

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