1. Field of the Invention
The present invention relates to a solar cell, and particularly to a solar cell using a phenomenon that is unique to a strongly correlated electron system, the phenomenon being discovered in a transition process of a Mott insulator or a Mott semiconductor to a metal phase upon light irradiation is applied.
2. Description of the Related Art
Silicon element, gallium-arsenic compound semiconductors, and the like are presently used as a material exhibiting solar cell functions. The principle of photovoltaic energy conversion in these materials involves the use of single-electron excitation induced by photons as shown in
Materials in which the single-electron excitation occurs are solid materials so-called band semiconductors which accord with a single-electron band theory. Typical materials for such band semiconductors are silicon semiconductors, gallium arsenic, and the like. Currently manufactured or developed solar cells are based on such materials.
Meanwhile, there is a series of solid materials in which electrons show different behavior from those of the above band semiconductors. These solid materials are called Mott insulators or Mott semiconductors. The Mott insulators or Mott semiconductors refer to the following solid materials. Specifically, when the number of electrons at each lattice point in a crystal structure is an odd number, the solid materials are expected to have metal-like electrical properties on the basis of the Pauli exclusion principle, but exhibit insulating properties because of localization of electrons (generation of an energy gap) which is caused when strong Coulomb repulsion acting between electrons exceeds the ease of electron movement from one lattice point to another (electron conduction energy). The use of Mott insulators or Mott semiconductors having the conduction mechanism as solar cell materials has not been considered so far.
The above-described solid materials are not ordinarily called as Mott semiconductors but Mott insulators. However, as various applications, including solar cells, of Mott insulators are developed in future, Mott insulators having a low electrical resistance may be called as Mott semiconductors. Hence, the term “Mott semiconductor” is also used in this context.
Among Mott insulators or Mott semiconductors, transition metal oxides have been intensively studied in the course of searching for superconducting materials. The inventors of the present application have found that especially manganese oxide-based materials based on LnMnO3 (Ln: rare-earth metal element) undergo a metal-insulator phase transition upon receiving an external perturbation such as magnetic field and light. Based on the knowledge, the present inventors have proposed a light switching element utilizing photo-induced insulator-metal transition occurring upon light irradiation (see, for example, Japanese Patent Application Publication No. H10-261291).
The present inventors have invented a magneto resistive element made of a perovskite oxide material containing manganese (see, for example, Japanese Patent Application Publication No. 2001-257396). In the magneto resistive element, metal-insulator transition of a Mott insulator or a Mott semiconductor is employed as the principle of a magneto resistive effect. Application of such a phase transition phenomenon of a Mott insulator or a Mott semiconductor has been tried in various application fields of electronics such as light switching elements, magnetometric sensors and memory devices.
However, there are no detailed theoretical studies on the electron behavior during a metal-insulator phase transition induced by light irradiation in a Mott insulator or a Mott semiconductor. In addition, there have been no attempts to apply such electron behavior to a solar cell.
In order to achieve the above-described object, a solar cell according to the present invention is provided, which comprises solid material layers containing insulators or semiconductors of different types that are joined, and in which any one of the solid material layers contains a Mott insulator or a Mott semiconductor.
The solar cell of the present invention enables to dramatically improve the conversion efficiency per photon absorbed, in the following manner. Specifically, in the process of carriers having energy exceeding the Mott gap being relaxed to the band edge of the corresponding upper or lower energy band, carrier relaxation process undergoes carrier excitation as well as heat dissipation. By extracting these carriers through electrodes, the conversion efficiency can be improved.
Hereinafter, the present invention will be described in detail with reference to the drawings. The same components are denoted by the same numerals. Note that the present invention is not limited to embodiments to be described below. Embodiments of the present invention will be described below with reference to the drawings. However, the present invention is not limited to the following description. One skilled in the art can easily understand that the embodiments and details can be modified in various manners without departing from the gist of the present invention and from the scope of the present invention. Accordingly, one should understand that the technical scopes of the present invention are not limited to the following description of the embodiments. In the configurations of the present invention to be described below, reference numerals denoting the same components are used commonly among different drawings.
Hereinafter, an embodiment of the present invention will be described in detail on the basis of the drawings.
In a mode shown in
When such a solar cell is employed, the state of electrons excited by sunlight is totally different from that of excited electrons in conventional cases. This is because almost all Mott insulators or Mott semiconductors are accompanied by ordered magnetic states. Moreover, excited electron spins interact closely with an ordered magnetic state (magnetic moment). As a result, the magnetic structure in the ground state is strongly influenced. Consequently, electrons in an excited state are strongly influenced by the changed magnetic structure.
The double-exchange model shown in the following formula well describes this feature:
where t represents the kinetic energy, JH represents the exchange energy, σ and σ′ represent electron spins, i and j represent the coordinates of a lattice point, and <ij> appearing in the sum represents a set of closest lattice points. The operator
ciσ↑ (cjσ)
represents a creation (annihilation) operator of an electron with a spin a at a lattice point i(j).
{right arrow over (σ)}
in the second term represents a Pauli matrix, and
{right arrow over (S)}i
represents a localized spin representing the magnetic moment at a lattice point i. The first term in the formula (1) represents the Hamiltonian for electrons in motion, and the second term represents the interaction between electron spins in motion and localized spins. The third term HS means the Hamiltonian of localized spins, into which the anisotropy in the magnetic interaction of the target substance can be incorporated.
When HS contained in the formula (1) takes the following form, an antiferromagnetic insulating state unstable due to a possible first-order transition to a ferromagnetic metallic state can be taken as the ground state:
As can be seen from this graph, an antiferromagnetic (insulator) state at θ=π is separated from the ferromagnetic (metal) state at θ=0 by an energy barrier having a height of about 0.02.
The electron system in the antiferromagnetic (insulator) state was excited, and the relaxation process thereof was quantitatively investigated in detail by conducting a numerical simulation. As a result, it has been found that a ferromagnetic metallic state appears as the final state. Here, the effect of energy dissipation of the entire system is incorporated into the Gilbert damping term of motion of localized spins. Specifically, when the effective magnetic field acting on a localized spin at a lattice point i is denoted by
{right arrow over (h)}i,
the equation of motion of
{right arrow over (S)}i
is represented by the following formula:
The term containing α is the Gilbert damping term, and a is a damping constant. On the basis of the Hellmann-Feynman theorem, the effective magnetic field
{right arrow over (h)}i
and the Hamiltonian have the following relationship:
From the initial stage to around the time 5000 in the relaxation process, the system takes an antiferromagnetic structure, and has an energy gap to which the antiferromagnetic structure is reflected. In addition, the number of electrons contained in the upper energy band is substantially constant. Between the time 5000 and the time 8000, the magnetic structure is reconstructed, and the energy gap characteristic of an antiferromagnetic structure is gradually closed. Moreover, it can be seen that there exists a period of time where the number of electrons contained in the upper energy band becomes greater than the initial value. This indicates the occurrence of a multiple-excitation phenomenon, which cannot occur in a single-electron band. Eventually, the number of electrons contained in the upper energy band starts to decrease, and the system shows a time development leading to the final state of a ferromagnetic metal phase. In the magnetic structure at around the time 15000, a long-period spiral magnetism appears which is locally substantially ferromagnetic as will be described below. Then, the magnetic structure transits toward a structure having metallic energy levels in the final state. The excited electrons contained in the upper energy band transit to the lower energy band, and the value becomes sufficiently small, as the state becomes closer to the final state. The sequential process strongly reflects the magnetic structure formed by localized spins.
In the initial state immediately after the light excitation, localized spins 32 in lattice points 31 are in an antiferromagnetic state as shown in Part (a) of
What is characteristic in this relaxation process is the dynamic relaxation between the time 5000 to the time 10000. This period involves a dynamic relaxation process showing the transition from an antiferromagnetic phase to a ferromagnetic phase. To further promote the phase transition and relaxation, a larger number of electron-hole pairs are generated in the electron system than those generated at the initial stage. In comparison with conventional electronic materials, the emergence of the generation process of multiple “electron-hole” pairs along with the relaxation is a marked characteristic of a system including strong Coulomb interaction acting between electrons. The present inventors first demonstrated an example of multiple-carrier generation in a Mott insulator or a Mott semiconductor.
The electron state of conventional electron materials is well understood by an electronic theory based on the one electron approximation. In the electron excitation and the relaxation process thereof in an insulator, a part of the excitation energy of electron-hole pairs exceeding the magnitude of the energy gap is simply dissipated. When the electrons reach the lower edge of the conduction band, and the holes reach the upper edge of the valence band, pair annihilation thereof occurs. In contrast, in a system including a strong Coulomb interaction, a part of the excitation energy of electron-hole pairs exceeding the magnitude of the energy gap is not only dissipated, but also causes a dynamic relaxation process, which consequently leads to the generation of further multiple “electron-hole” pairs as shown in
The model used in the present invention extremely well describes the electron states around transition metal compounds. For example, this model gives quantitatively good results in the cases of electronic properties of manganese oxides exhibiting a giant magneto resistive effect. Properties of individual actual substances can be reproduced by adjusting the parameters contained in the formula. A theoretical example of the electron excitation and the relaxation process thereof obtained by the present invention directly gives a leading principle for development of a highly-efficient solar cell based on a novel power generation mechanism using a Mott insulator or a Mott semiconductor.
The solar cell according to the present invention comprises a Mott insulator or a Mott semiconductor. The Mott insulator or the Mott semiconductor may be an inorganic compound or an organic compound. Typical Mott insulators are inorganic compounds containing a 3d transition metal element, a 4d transition metal element, or a 5d transition metal element, or organic compounds. The Mott gap attributable to the Coulomb repulsion of the Mott insulator is desirably 1 eV or less in order to effectively utilize the energy region of sunlight.
The Mott insulator or the Mott semiconductor of the inorganic compound is not particularly limited as long as the Mott insulator or the Mott semiconductor has a Mott gap. Accordingly, the Mott insulator or the Mott semiconductor is an insulator formed of one or more transition metal elements selected from the group consisting of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, molybdenum, ruthenium, rhodium, cadmium, indium, tin, rhenium, osmium, iridium, and platinum. In addition, the Mott insulator or the Mott semiconductor may be any one of the following general formulae (1) to (8):
LnxA1−xBO3 (1)
LnAB2O6 (2)
Ln1−xA1+xBO4 (3)
Ln2−2xA1+2xB2O7 (4)
Ln2−xAxBO4 (5)
A2BO3 (6)
A2BO4 (7)
A2BO2Cl2 (8)
Among these, a manganese oxide [LnxA1−xMnO3] having a perovskite-type crystal structure is preferably used. Here, a preferred upper limit of x may vary depending on the kind of the transition metal element used, and the like. Any lattice substitution (filling control) by ions having a different valence is allowed, as long as the manganese oxide has a Mott gap.
The Mott insulator or the Mott semiconductor which is the aforementioned inorganic compound may be any one of vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, and rhenium oxide.
The Mott insulator or Mott semiconductor is not limited to inorganic compounds. This is because organic compounds are generally Mott insulators or Mott semiconductors. The organic compounds are any of an aromatic amine compound, a carbazole derivative, an aromatic hydrocarbon, a polymer compound, and a charge transfer complex. The charge transfer complex may be any one of a quasi-one-dimensional halogen-bridged metal complex [MX complex], a quasi-one-dimensional halogen-bridged multinuclear metal complex [MMX complex], and an aromatic hydrocarbon which is a quasi-one-dimensional charge transfer complex including tetrathiafulvalene [TTF] and chloranil [CA]. The quasi-one-dimensional halogen-bridged metal complex is a chain material where a transition metal (M) and a halogen (X) are alternately arranged. Examples of the quasi-one-dimensional halogen-bridged metal complex and the quasi-one-dimensional halogen-bridged multinuclear metal complex include compounds represented by [Ni1-yPdy(chxn)2X1]X22 [where y represents a number not less than 0 but not more than 1, X1 and X2 are the same or different, and represent a halogen selected from F, Cl, Br, and I, and chxn represents cyclohexanediamine]; Pt2(EtCS2)4I; Pt2(n-BuCS2)4I; and the like.
In the solar cell according to the present invention, solid material layers containing different types of insulators or semiconductors are joined, and at least one of the solid material layers contains a Mott insulator or a Mott semiconductor.
In this description, “an insulator or a semiconductor” includes not only Mott insulators and Mott semiconductors, but also conventionally known band semiconductors in which electrons are excited by photons on a one-to-one basis.
Accordingly, examples of the junction structure between the insulators or the semiconductors of different types include combinations of an n-type Mott insulator and a p-type band semiconductor; an n-type Mott insulator and a p-type Mott insulator; a p-type Mott insulator and an n-type band semiconductor; a p-type Mott insulator and an n-type Mott insulator; and other combinations.
The n-type Mott insulator is not particularly limited, and examples thereof include SrMnO3, CaMnO3, Ln2CuO4 (Ln=a rare-earth element such as lanthanum, cerium, or praseodymium), tungsten oxide (WO3), and the like.
Examples of the p-type Mott insulator include oxygen-excess or Ln-deficient LnMnO3, Ln1−xAxMnO3 (A represents a divalent alkaline earth metal element), La2CuO4, vanadium oxide (VO2), chromium oxide (Cr2O3), and the like.
Examples of the n-type band semiconductor include Si:As, Si:Sb, SrTiO3:Nb, TiO2, ZnO, ZnO:Al, ZnO:I, ZnS, ZnSe, CdS, CdSe, and the like.
Examples of the p-type band semiconductor include Cu—In—Se systems such as Si;B, Si;Al, ZnTe, Cu2O, Cu2S, Cu2Te, CuO, and Cu(In, Ga)3Se5, InP, and the like.
Incidentally, GaAs and CdTe can be any of the n-type and p-type band semiconductors.
The transition metal elements used in the insulators or semiconductors forming the p-n junction may be different or the same.
The solar cell of the present invention can be obtained by forming on a substrate a multi-layered structure at least one layer of which comprises the Mott insulator or the Mott semiconductor. The substrate may be the second solid material layer 5 itself as shown in
In a method of forming the multi-layered structure, for example, the first solid material layer 3 is formed on the second solid material layer 5 serving also as the substrate for the solar cell as shown in
A method of forming the film for each layer is not particularly limited, and, for example, the pulsed laser deposition method (PLD) method, the laser ablation method, the molecular beam epitaxy method (MBE method), the sputtering method, the plasma CVD method, the metal organic chemical vapor deposition method (MOCVD method), the spin coating method, the inkjet method, or the like may be employed as the method.
When the first solid material layer comprises a Mott insulator or a Mott semiconductor, the thickness of the layer is generally 4 A (A represents ångström) to 10000 A, from the viewpoint of the balance between the absorption coefficient of the Mott insulator or the Mott semiconductor and the effective thickness thereof defined as the sum of the depletion layer width and the diffusion length. For a case where sunlight, particularly light with wavelengths in the visible region, is transmitted and reaches the second solid material layer, the thickness can be about several A to 100 A, for example.
In a second mode shown in
The solar cell of the present invention may include two or more of the p-n junction structures each formed of the first solid material layer and the second solid material layer. For example, the solar cell may be such that two or more of the p-n junction structures are connected in series.
Moreover, the solar cell may be provided with an irregular surface structure for the purpose of enhancing the effect of collecting light on the light-receiving surface.
Specific examples of the layer structure of the solar cell of the present invention include, for example, Au/La2CuO4/SrTiO3:Nb, Au/Pr0.7Ca0.3MnO3/SrTiO3:Nb, Au/LaMnO3/SrTiO3:Nb, and the like.
On the basis of the above-described simulation example, a solar cell as shown in
Note that the p-n junction structure containing a Mott insulator or a Mott semiconductor has been described as a solar cell in the present invention, but can also be applied to photo detectors (photo diodes).
Number | Date | Country | Kind |
---|---|---|---|
2010-094361 | Apr 2010 | JP | national |