PHOTOELECTRIC CONVERSION ELEMENT
20180248143 ยท 2018-08-30
Assignee
- National University Corporation Nagoya University (Nagoya-shi, Aichi-ken, JP)
- NISSHINBO HOLDINGS INC. (Chuo-ku, Tokyo, JP)
Inventors
- Kunio AWAGA (Nagoya-shi, JP)
- Simon DALGLEISH (Nagoya-shi, JP)
- Louisa REISSIG (Nagoya-shi, JP)
- Kanako Yuyama (Chiba-shi, JP)
Cpc classification
H10K30/82
ELECTRICITY
H10K30/353
ELECTRICITY
H10K30/451
ELECTRICITY
H10K30/354
ELECTRICITY
H01G9/2013
ELECTRICITY
H10K85/113
ELECTRICITY
H10K30/352
ELECTRICITY
Y02E10/549
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
International classification
Abstract
A photoelectric conversion element includes: a pair of electrodes including a first electrode and a second electrode; a first insulator having a first capacitance, and disposed to make contact with the first electrode; a second insulator having a second capacitance, which is smaller than the first capacitance of the first insulator, and disposed to make contact with the second electrode; and an organic semiconductor receiving a light to generate an electromotive force, and interposed between the first insulator and the second insulator to make contact with them.
Claims
1. A photoelectric conversion element comprising: a pair of electrodes including a first electrode and a second electrode; a first insulator having a first capacitance, and disposed to make contact with the first electrode; a second insulator having a second capacitance, which is smaller than the first capacitance of the first insulator, and disposed to make contact with the second electrode; and an organic semiconductor receiving a light to generate an electromotive force, and interposed between the first insulator and the second insulator to make contact therewith.
2. The photoelectric conversion element as set forth in claim 1, wherein the first insulator includes an ionic liquid whose major components are a positive ion and a negative ion, or a solid insulator shaped by a predetermined insulating material.
3. The photoelectric conversion element as set forth in claim 1, wherein the organic semiconductor includes a fine-particle-shaped electric conductor intermixed in a predetermined proportion.
4. The photoelectric conversion element as set forth in claim 1, wherein the light is at least one member selected from the group consisting of pulsed lights, chopped lights and modulated lights.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0022]
[0023]
[0024]
[0025]
[0026]
[0027]
[0028]
MODE FOR CARRYING OUT THE INVENTION
[0029] Forms for executing or implementing the present invention will be hereinafter described based on the drawings. Note that, unless otherwise specified explicitly, the word, connect, means to electrically connect members with each other when it is used. The respective drawings illustrate elements needed for describing the present invention, but do not necessarily illustrate all of the actual elements. When referring to directions, such as up, down, right and left, they are based on notes or designations implied or illustrate in the drawings.
First Embodiment
[0030] First Embodiment will be hereinafter described with reference to
[0031] The first electrode 11 and second electrode 15 correspond to the claimed a pair of electrodes. It is not necessarily needed to use a transparent electrode, which exhibits optical transparency, for the first electrode 11 and second electrode 15 as far as they have an elemental structure capable of optically exciting the organic semiconductor 13A directly. However, when exciting the organic semiconductor 13A by way of one of the electrodes, the electrode is required to exhibit transparency. The following are exemplary materials for transparent electrically conducting member: tin oxide with antimony or fluorine doped, such as ATO or FTO; and electrically conducting metallic oxides, such as tin oxide, zinc oxide, indium oxide, indium tin oxide (or ITO) and indium zinc oxide (or IZO). The first electrode 11 and second electrode 15 can even be a thin film made of metal, such as gold, silver, chromium or nickel. The first electrode 11 and second electrode 15 may also be made of a thin film including a mixture of an electric conducting metallic oxide and metal, or a laminated member including thin films made of an electric conducting metallic oxide and metal. The first electrode 11 and second electrode 15 can even be made of an inorganic electrically conducting substance, such as copper iodide or copper sulfide. The first electrode 11 and second electrode 15 may also be made of an organic electrically conducting substance, such as carbon nanotube, polypyrrole, polyaniline, polythiophene, polypyrrole, or polyethylenedioxythiophene. The first electrode 11 and second electrode 15 can even be a laminated substance which is formed by laminating indium tin oxide (or ITO) and at least one member selected from the group consisting of the metals, the inorganic electrically conducting substances and the organic electrically conducting substances. From the viewpoints, such as high electrically conducting property and transparency, the first electrode 11 and second electrode 15 are desirably made of a transparent and electrically conducting metallic oxide.
[0032] The first electrode 11 and second electrode 15 can also be made of a material which hardly makes their work functions different from one another, or can even be made of distinct materials to one another so as to make the work functions different. As set forth in Dictionary of Physics and Chemistry (5th Edition, Published by IWANAMI SHOTEN in 1998), the term, work function, means a minimum energy required for taking out an electron from the surface of substance (such as the crystal of metal or semiconductor) to the outside. In order to generate a current quickly and greatly, the first electrode 11 and second electrode 15 are made to exhibit work functions between which the difference falls in a predetermined range. For example, the difference between the work functions is set up desirably to fall in a range of from 1 eV to 3 eV. The first electrode 11 and second electrode 12 whose work functions are made different from one another augment or build up the charge separation within the organic semiconductor 13A. The first insulator 12, and the second insulator 14 as well help a charge separate, and then covey the polarization, which has occurred within the organic semiconductor 13A, to the first electrode 11 and second electrode 15. Accordingly, a transitional potential difference arises between the first electrode 11 and the second electrode 15. Consequently, the response characteristics of a photoelectric conversion element, for instance, a time required for the organic semiconductor 13A to output a transient current after receiving a light, are enhanced more than that of its predecessors. The result is a higher light/current conversion efficiency, and a shorter light/current conversion time.
[0033] The first insulator 12 and second insulator 14 have a function of electrically storing positive holes (or simply referred to as holes) and electrons which have been separated in the organic semiconductor 13A. The first insulator 12 is disposed to make contact with the first electrode 11, and has a first capacitance C1. The second insulator 14 is disposed to make contact with the second electrode 15, and has a second capacitance C2. The first insulator 12 and second insulator 14 are formed so that the first capacitance C1 is larger than the second capacitance C2 (namely, so that they satisfy C1>C2). Note however that both of the first insulator 12 and second insulator 14 are formed satisfactorily of an arbitrary or discretional material, which has both insulation and electric storage properties combinedly, such as a solid insulator or ionic liquid, for instance.
[0034] To the solid insulator, a fluorine-based plastic (or fluororesin) is applicable. Exemplary materials of the fluorine-based plastic are as follows: polyvinylidene difluoride (or PVDF); polyvinyl fluoride (or PVF); polytetrafluoroethyelene (or PTFE); tetrafluoroethylene-ethylene copolymers (or ETFE); tetrafluoroethyelene-hexafluoropropylene copolymers (or FEP); tetrafluoroethyelene-perfluoroalkyl-vinylether copolymers (or PFA); polychloro-trifluoroethylene (or PCTFE); and chlorotrifluoroethylene-ethylene copolymers (or ECTFE).
[0035] Instead of the above-described solid insulator, an ionic liquid including a positive ion and negative ion as the major components can also be applied to the first insulator 12. In general, an ionic liquid exerts extremely low vapor pressures, and exhibits inflammability or noncombustibility. Since the ionic liquid is sometimes referred to as an ordinary-temperature molten salt, many ionic liquids have a melting point which is present at around room temperature. The ionic liquid according to some of the present embodiments is preferably a liquid in the service temperature range.
[0036] The positive ion is not at all limited especially. The following are given however as some of the examples applicable to the positive ion: a cation of nitrogen-containing compound; a quaternary phosphonium cation; or a sulfonium cation. For example, the following are applicable to the cation of nitrogen-containing compound: a heterocyclic aromatic cation, such as an imidazolium cation or pyridinium cation; a heterocyclic aliphatic cation, such as a piperidinium cation, pyrrolidinium cation, pyrazolium cation, thiazolium cation or morpholinium cation; a quaternary ammonium cation; or a cation with a form to which an aromatic amine, aliphatic amine or alicyclic amine is added.
[0037] The negative ion is not at all limited especially. The following are given however as some of the examples applicable to the negative ion: a halide anion, such as Cl.sup.?, Br.sup.? or I.sup.?; a boride anion, such as BF.sub.4.sup.?, B(CN).sub.4.sup.? or B(C.sub.2O.sub.4).sub.2.sup.?; an amide anion or imide anion, such as (CN).sub.2N.sup.?, [N(SO.sub.2F).sub.2].sup.?, [N(SO.sub.2CF.sub.3).sub.2].sup.? or [N(SO.sub.2C.sub.2F.sub.5).sub.2].sup.?; a sulfate anion or sulfonate anion, such as RSO.sub.3.sup.? (where R expresses an aliphatic hydrocarbon group or aromatic hydrocarbon group, and will signify the same hereinafter), RSO.sub.4.sup.?, RfSO.sub.3.sup.? (where Rf expresses a fluorine-containing halogenated hydrocarbon group, and will signify the same hereinafter) or RfSO.sub.4.sup.?; a phosphate anion, such as Rf.sub.2P(O)O.sup.?, PF.sub.6.sup.? or Rf.sub.3P.sub.3.sup.?; an antimony anion, such as SbF.sub.6.sup.?. In addition to the above, other various negative ions, such as lactate, a nitrate ion or trifluoroacetate, are also applicable to the negative ion.
[0038] The ionic liquid also comprises satisfactorily a combination of a cation and anion, each of which is one member selected from the group consisting of the above-described cations and anions. Moreover, the ionic liquid even comprises properly a cation and anion, one of which or both of which are two or more members selected from the group consisting of the above-described cations, and which coexist mixedly therein.
[0039] The organic semiconductor 13A is an example of the organic semiconductor 13. The organic semiconductor 13A is interposed between the first insulator 12 and the second insulator 14 to make contact with them, and has a function of receiving a light, which a light source sheds or casts, to generate an electromotive force by separating a charge. As far as the organic semiconductor 13A has the function, it comprises satisfactorily an n-type organic semiconductor, a p-type organic semiconductor, or an amphoteric semiconductor, or comprises properly a multi-laminated film or mixture of the semiconductors. The light source is an arbitrary or discretionary constituent which satisfactorily sheds or casts a light, like sunlight, including light components with multiple wavelengths, or which properly sheds or casts a light, like a laser light or LED light, including a light component with a single wave length. However, the light is needed to exhibit a modulated light or optical intensity. For example, the following are applicable to a light which the light source sheds or casts: pulsed lights, chopped lights, and modulated lights or radiations which are used for light or optical signal.
[0040] The n-type organic conductor is an acceptor organic semiconductor, and is an organic compound that is represented mainly by electron transporting organic compounds, and which is provided with such a property that it is likely to accept electrons. To be concrete, it is one of the two organic compounds that make contact with one another to be used, and one of which exhibits a larger electron affinity than that of the other.
[0041] To the acceptor organic semiconductor, an arbitrary or discretionary organic compound is applied satisfactorily as far as it is an organic compound having an electron-accepting property. Some of the applicable examples are as follows: fullerenes selected from the group 0 consisting of fullerene and fullerene derivatives; heterocyclic compounds containing nitrogen atom, oxygen atom or sulfur atom; polyarylene compounds; fluorene compounds; cyclopentadiene compounds; and silyl compounds. The acceptor organic semiconductor even comprises satisfactorily a metallic complex including a nitrogen-containing heterocyclic compound as one of the ligands.
[0042] The following are some of the examples applicable to the above-described heterocyclic compounds: pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, quinoxaline, quinazoline, phthalazine, cinnoline, isoquinoline, pteridine, acridine, phenazine, phenanthroline, tetrazole, pyrazole, imidazole, thiazole, oxazole, indazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, carbazole, purine, triazolopyridazine, triazolopyrimidine, tetrazaindene, oxadiazole, imidazopyridine, pyrrolidine, pyrrolopyridine, thiadiazolopyridine, dibenzazepine, and tribenzazepine.
[0043] The p-type organic semiconductor is a donor organic semiconductor, and is an organic compound that is represented mainly by hole transporting organic compounds, and which is provided with such a property that it is likely to donate electrons. To be concrete, it is one of the two organic compounds that make contact with one another to be used, and one of which exhibits a smaller ionization potential than that of the other.
[0044] To the donor organic semiconductor, an arbitrary or discretionary organic compound is applied satisfactorily as far as it is an organic compound having an electron donating property. Some of the applicable examples are as follows: triaryl amine compounds; benzidine compounds; pyrazoline compounds; styryl amine compounds; hydrazone compounds; triphenylmethane compounds; carbazole compounds; polysilane compounds; thiophene compounds; phthalocyanine compounds; subphthalocyanine compounds; quinacridone compounds; porphyrin compounds; cyanine compounds; merocyanine compounds; oxonol compounds; polyamine compounds; indole compounds; pyrrole compounds; diketo-pyrrolo-pyrrole compounds; pyrazole compounds; polyarylene compounds; condensed aromatic cyclic hydrocarbon compounds; homopolymers, such as polythiophene, polyfluorene and polypyrole; and donor/accepter-type copolymers. The donor organic semiconductor even comprises satisfactorily a metallic complex including a nitrogen-containing heterocyclic compound as one of the ligands.
[0045] The following are some of the examples applicable to the above-described condensed aromatic cyclic hydrocarbon compounds: naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, tetracene derivatives, pyrene derivatives, perylene derivatives, and fluoranthene derivatives.
[0046] The amphoteric organic semiconductor is also called as a bipolar organic semiconductor, and shows the characteristics of both n-type organic semiconductor and p-type organic semiconductor. For example, bis(4-dimethylaminodithiobenzil) nickel (II), or 1,3,6,8-tetraphenylpyrene, and the like, is applicable to the amphoteric organic semiconductor.
[0047] The first insulator 12, which is interposed between the first electrode 11 and the organic semiconductor 13A, and the second insulator 14, which is interposed between the organic semiconductor 13A and the second electrode 15, keep a dark current from generating as less as possible, even if a pin hole should have occurred during a manufacturing process of the photoelectric conversion element 10A. It is because the first insulator 12 and second insulator 14 inhibit both of the positive holes and electrons from moving, even if a charge, which is separated at the organic semiconductor 13A, tries to move toward one of the first electrode 11 and second electrode 14.
[0048] The photoelectric conversion element 10A is manufactured arbitrarily or discretionarily. For example, the photoelectric conversion element 10A, which has a structure illustrated in
[0049] The principle how the photoelectric conversion element 10A constructed as described above operates will be hereinafter described with reference to
[0050] The first capacitance C1, and the second capacitance C2 are made to satisfy an inequality, namely, C1>C2. The second insulator 14 has the second capacitance C2, namely, a smaller capacitance, to bring about a high-speed response. Accordingly, the second insulator 14 desirably has the thickness T3 that is made thick adequately in order to give the second insulator 14 an insulating property sufficiently. For example, the thickness T3 falls desirably in a range of from 50 nm to 1,000 nm. Moreover, the first insulator 12 has the first capacitance C1, namely, a larger capacitance, to bring about a large current. Accordingly, the first insulator desirably has the thickness T1 that is made thin adequately in order to make the first capacitance C1 larger when the first insulator 12 is made up of a solid dielectric substance or ferroelectric substance. For example, the thickness T1 falls desirably in a range of from 10 nm to 200 nm. Note that, when the first insulator 12 is made of an electrolyte like an ionic liquid, the thickness T1 falls satisfactorily in a range of from 10 nm to 1 mm, because the formation of solid-liquid interface electric double layer does not depend on the thickness T1 at all.
[0051] The light is shed or cast satisfactorily onto the organic semiconductor 13A from any of directions as far as the irradiated organic semiconductor 13A is excited. The shedding or casting directions shown by the graphic arrows in
[0052] The organic semiconductor 13A, which receives the light, undergoes an energy excited state so that the charge is separated therein, as illustrated in
[0053] When the light illuminates the second electrode 15, the first insulator 12 and second insulator 14 electrically store electrons which are separated at the organic semiconductor 13A. When the light does not illuminate the second electrode 15, the first insulator 12 and second insulator 14 electrically discharge the stored electrons. The first insulator 12 having the larger capacitance facilitates the charge separation within the organic semiconductor 13A to securely enlarge the current intensity of a transient current flowing in the conducting wiring W. On the other hand, the second insulator 14 having the smaller capacitance makes the response speed of a current flowing in the conducting wiring W greater securely. Hence, the photoelectric conversion element 10A makes the current intensity and response speed compatible with one another.
[0054] Next, operations of the photoelectric conversion element 10A, which is repetitively illuminated by the light and then is not illuminated by it, will be hereinafter described with reference to
[0055] The photoelectric conversion element 10A, which served as one of the constituents of the gauging circuit illustrated in
[0056] In
[0057] At the lower half in
[0058] The characteristic curves L1 and L2 are identical with one another in that the current I flowed in a certain direction (e.g., in the direction of the current I shown in
[0059] Moreover, the characteristic curves L1 and L3 indicate that the current intensity was saturated within the half cycle because the current increased fast as shown in
[0060] Note that
Second Embodiment
[0061] A photoelectric conversion element 10B according to Second Embodiment of the present invention will be hereinafter described with reference to
[0062] The photoelectric conversion element 10B illustrated in
[0063] The organic semiconductor 13B is one of the examples of the organic semiconductor 13. The organic semiconductor 13B is interposed between the first insulator 12 and the second insulator 14 to make contact with them, and has a function of receiving a light, which an external light source sheds or casts, to separate a charge in the manner as the organic semiconductor 13A. The organic semiconductor 13B differs from the organic semiconductor 13A in that it includes a fine-particle-shaped electric conductor intermingled or intermixed therein in a predetermined proportion.
[0064] To the fine-particle-shaped electric conductor, any of the following is applied, for instance: metals, electrically-conductive resins (or referred to as electrically-conductive plastics as well), and nanometer-size conducting substances. The metals involve copper, silver, and aluminum. The electrically-conductive resins involve polyacethylene, polypyrrole, polythiophene, and polyaniline. The nanometer-size conducting substances involve nanotube, graphene, and nanocarbon. The predetermined proportion is set up preferably in such a range as the electric conductor does not at all hinder the photoexcitation of the organic semiconductor 13B while decreasing the electric resistance of the organic semiconductor 13B to enhance the response characteristics; and moreover as the electric conductor does not at all shield the organic semiconductor 13B electromagnetically. For example, an applicable predetermined proportion is to intermingle or intermix the electric conductor in the organic semiconductor 13B in a proportion of 50% by volume or less.
[0065] Next, how the photoelectric conversion element 10B, which is illuminated by the light and then is not illuminated by it repetitively, operates will be hereinafter described with reference to
[0066] As illustrated in
[0067] In
[0068] At the lower half in
[0069] The characteristic curves L4 and L5 are identical with one another in that the current I flowed in a certain direction (e.g., in the direction of the current I shown in
[0070] Comparing the characteristic curve L4 with the characteristic curve L5, the photoelectric conversion element 10B was found to exhibit a current intensity that rose faster than that of the photoelectric conversion element 10A. The advantage was produced by the electric conductor which was intermingled or intermixed with the organic semiconductor 13B to decrease the electric resistance of the entire circuit. As illustrated in
[0071] Note that
Other Embodiments
[0072] Although modes for executing or implementing the present invention have been described so far in accordance with First and Second Embodiments, the present invention is not at all limited to the embodiments. In other words, the present invention is executed or implemented variously in other modes within a range not departing from the gist or spirit of the present invention. For example, the present invention is materialized satisfactorily by each of modes described below.
[0073] In First and Second Embodiments described above, the organic semiconductor 13 is sandwiched by the first insulator 12 and second insulator 14 to construct the photoelectric conversion element 10 (see
[0074] Above-described First and Second Embodiments comprise an ionic liquid which is applied to the first insulator 12. The ionic liquid is made to work as a liquid at ordinary or room temperature. Instead of the embodiments, a gelled ionic liquid is applied satisfactorily to the first insulator 12 in order to prevent the ionic liquid from leaking. In addition to the ionic liquids described above, the following may also be applied to the first insulator 12: polyoxometalates, ionic conductors, and protonic conductors. A polyoxometalate is a molecule whose chemical formula is expressed by [M.sub.xO.sub.y].sup.n? (where M is at least one member selected from the group consisting of Mo, V, W, Ti, Al and Nb, for instance), and is a condensed oxyacid, which is generated by condensing an oxyacid made of an earlier-cycle transition metal element belonging to a group other than Group 3, (i.e., an anionic metallic polynuclear oxygen complex). The ionic conductor is a conductor in which the displacement of ions makes a charge. The protonic conductor is a conductor in which protons (e.g., hydrogen ions) function as the most dominant charge carrier within the crystal. Whichever one of the aforementioned materials is applied to the first insulator 12, an electric double layer is formed readily at the interface between a solid and a liquid. Accordingly, positive holes and electrons, which result from a charge, are donated and accepted securely. Consequently, the first insulator 12 modified as described above provides the same operations and advantageous effects as the first insulator 12 according to First and Second Embodiments does.
[0075] Above-described First and Second Embodiments are constructed by applying the organic semiconductor 13, which comprises an n-type organic semiconductor or p-type organic semiconductor, to a charge separating member, which separates a charge into positive holes and electrons (see
Operations and Advantageous Effects
[0076] Above-described First and Second Embodiments, as well as the other embodiments, produce advantageous effects as described below, respectively.
[0077] (1) As illustrated in
[0078] (2) The first insulator 12 is constructed to include anionic liquid whose major components are a positive ion and negative ion, or a solid insulator shaped by a predetermined insulating material. Whichever one of the ionic liquid and solid insulator the thus constructed first insulator 12 includes, the first insulator 12 has such a large capacitance that it polarizes to facilitate the charge separation in the intermediate layer of the organic semiconductor 13. Accordingly, the first insulator 12 makes the current I greater. Consequently, the first insulator 12 provides the photoelectric conversion element 10 yielding a current intensity which is upgraded securely to be better than that of the conventional predecessors.
[0079] (3) The organic semiconductor 13B is constructed to include a fine-particle-shaped electric conductor intermingled or intermixed in a predetermined proportion (see
[0080] (4) The light is constructed to be at least one member selected from the group consisting of pulsed lights, chopped lights and modulated lights or radiations. The photoelectric conversion element 10 constructed as described above yields a strengthened current intensity and quickened response speed to a light whose light intensity is modulated.
INDUSTRIAL APPLICABILITY
[0081] A photoelectric conversion element according to the present invention has a function of receiving a light to generate an electromotive force. Parts or apparatuses, to which the present photoelectric conversion element is applicable and which make good use of the function, are as follows: light-current conversion elements, light sensors involving photodiodes, luminosity sensors, and so on. A light-current conversion element converts at an ultrafast rate a pulse of infrared beam, which propagates through an optical fiber, into a current. A luminosity sensor detects the intensity of a light.
EXPLANATION ON REFERENCE NUMERALS
[0082] 10 (e.g., 10A, 10B, or 10C): Photoelectric Conversion Element; [0083] 11: First Electrode; [0084] 12: First Insulator (e.g., Ionic Liquid, or Solid Insulator); [0085] 13 (e.g., 13A, or 13B): Organic Semiconductor; [0086] 14: Second Insulator (e.g., Solid Insulator); and [0087] 15: Second Electrode