HK1150285B - Organic photosensitive optoelectronic devices containing tetra-azaporphyrins - Google Patents

Description

Organic photosensitive optoelectronic devices containing porphyrazine

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based on and claims priority from U.S. provisional patent application serial No. 60/960,769, entitled "organic photosensitive optoelectronic devices containing porphyrazines," filed on 12/10/2007, the entire contents of which are incorporated herein by reference.

Joint research protocol

The claimed invention is made in conjunction with the parties on behalf of and/or under a university-corporation research agreement: university of southern California (The University of southern California), University of Michigan (The University of Michigan), and Global photon Energy Corporation (Global Photonic Energy Corporation). The agreement was made on and before the date the claimed invention was made as a result of activities undertaken within the scope of the agreement.

Technical Field

The present invention relates generally to organic photosensitive optoelectronic devices containing at least one porphyrazine compound

Background

Optoelectronic devices rely on the optical and electronic properties of materials to electronically generate or detect electromagnetic radiation or to generate electricity from ambient electromagnetic radiation.

Photosensitive optoelectronic devices convert electromagnetic radiation into electrical signals or power. Solar cells, also known as photovoltaic ("PV") devices, are a type of photosensitive optoelectronic device that is specifically used to generate electrical energy. A photoconductive cell is a type of photosensitive optoelectronic device that is used in conjunction with a signal detection circuit to monitor the resistance of the device to detect changes due to absorbed light. A photodetector, which can receive an applied bias voltage, is a type of photosensitive optoelectronic device that is used in conjunction with a current sensing circuit for measuring the current generated when the photodetector is exposed to electromagnetic radiation.

These three types of photosensitive optoelectronic devices can be distinguished based on the presence or absence of a rectifying junction, and also based on whether the device is operated by an externally applied voltage, also referred to as a bias voltage or bias voltage. The photoconductive cell has no rectifying junction and typically operates using a bias voltage. The PV device has at least one rectifying junction and operates without a bias voltage. The photodetector has at least one rectifying junction and is typically, but not always, operated using a bias voltage.

The term "rectifying" as used herein, especially means that the interface has asymmetric conductive properties, i.e. the interface supports charge transport preferably in one direction. The term "semiconductor" refers to a material that can conduct electricity when charge carriers are induced by thermal or electromagnetic excitation. The term "photoconductive" generally refers to a process in which electromagnetic radiant energy is absorbed, thereby converting to excitation energy of charge carriers, such that the carriers can conduct (i.e., transport) charge in a material. The term "photoconductive material" refers to semiconductor materials that take advantage of their property of absorbing electromagnetic radiation to generate charge carriers.

When electromagnetic radiation of appropriate energy is incident on the organic semiconductor material, photons may be absorbed to produce excited molecular states. In organic photoconductive materials, it is generally believed that the molecular states generated are "exciton excitons," i.e., electron-hole pairs in a bound state, which are transported as quasi-particles. Excitons may have an appreciable lifetime before they recombine in pairs ("quenching"), which refers to the recombination of the original electron and hole with each other (as opposed to recombination with holes or electrons from other pairs). To generate a photocurrent, the electron-hole forming the exciton are typically separated at a rectifying junction.

In the case of photosensitive devices, the rectifying junction is referred to as a photovoltaic heterojunction. Types of organic photovoltaic heterojunctions include donor-acceptor heterojunctions formed at the interface of a donor material and an acceptor material, and Schottky-barrier heterojunctions formed at the interface of a photoconductive material and a metal.

Figure 1 is an energy level diagram showing an exemplary donor-acceptor heterojunction. In the case of organic materials, the terms "donor" and "acceptor" refer to the relative positions of the highest occupied molecular orbital ("HOMO") and lowest unoccupied molecular orbital ("LUMO") energy levels of two contacting, but dissimilar, organic materials. A material is an acceptor if the LUMO energy level of one material in contact with another is lower. Otherwise it is a donor. In the absence of an external bias, it is energetically favorable for electrons at the donor-acceptor junction to move into the acceptor material.

As used herein, a first HOMO or LUMO energy level is "greater than" or "higher than" a second HOMO or LUMO energy level if the first energy level is closer to vacuum level 10. The ionization potential ("IP") corresponding to a higher HOMO energy level has a smaller absolute energy relative to the vacuum level. Likewise, a higher LUMO energy level corresponds to an electron affinity ("EA") having a smaller absolute energy relative to the vacuum level. On a conventional energy level diagram, with the vacuum level at the top, the LUMO level of a material is higher than the HOMO level of the same material.

Upon absorption of a photon 6 in the acceptor 152 or generation of an exciton 8 by the acceptor 154, the exciton 8 dissociates at the rectifying interface. The donor 152 transports holes (open circles) and the acceptor 154 transports electrons (closed circles).

An important property of organic semiconductors is carrier mobility. Mobility measures the ease with which charge carriers can move through a conductive material in response to an electric field. In the case of organic photosensitive devices, materials that conduct preferentially by electrons due to high electron mobility may be referred to as electron transport materials. Materials that conduct preferentially through holes due to high hole mobility may be referred to as hole transport materials. A layer that conducts preferentially by electrons due to mobility and/or position in the device may be referred to as an electron transport layer ("ETL"). A layer that conducts preferentially by holes due to mobility and/or position in the device may be referred to as a hole transport layer ("HTL"). Preferably, but not necessarily, the acceptor material is an electron transporting material and the donor material is a hole transporting material.

How to pair two organic photoconductive materials that act as donors and acceptors in photovoltaic heterojunctions based on carrier mobility and relative HOMO and LUMO energy levels is well known in the art and is not described herein.

One common feature of bulk semiconductors and insulators is the "band gap". The energy band gap is the energy difference between the highest energy level filled with electrons and the lowest energy level empty. In inorganic semiconductors or inorganic insulators, this energy difference is the difference between the valence band edge (top of the valence band) and the conduction band edge (bottom of the conduction band). In an organic semiconductor or an organic insulator, this energy difference is the difference between HOMO and LUMO. The energy band gap of a pure material has no energy states in which electrons and holes can exist. The only carriers available for conduction are electrons and holes that have sufficient energy to be excited through the band gap. Generally, semiconductors have a relatively small energy band gap compared to insulators.

According to the energy band model of an organic semiconductor, only electrons on the LUMO side of the energy band gap are charge carriers, and only holes on the HOMO side of the energy band gap are charge carriers.

Other background explanations and descriptions of the prior art relating to organic photosensitive devices, including their general structure, features, materials, and characteristics, may be found in U.S. Pat. No.6,657,378 to Forrest et al, U.S. Pat. No.6,580,027 to Forrest et al, and U.S. Pat. No.6,352,777 to Bulovic et al, the disclosures of which are incorporated herein by reference.

The performance of small molecule solar cells was determined by studying their characteristic IV response under dark conditions and light. Power conversion efficiency η p, dependent on open circuit voltage (V)_OC) Short circuit current density (J)_SC) And a Fill Factor (FF) determined by¹：

Wherein P is_OIs the incident optical power. Here, FF depends on the series resistance, typically between 0.5 and 0.65 for high performance small molecular weight organic photovoltaic materials. Maximum J_SCOverlap between absorptions by organic substancesThe spectrum of the sunlight, the extinction coefficient and thickness of the absorbing layer, and other factors. However, the photocurrent is highly dependent on the charge transport properties of the material, since the resistivity to charge flow represents a significant challenge to cell performance². Another very important parameter to consider when relating to cell performance is exciton diffusion length. The exciton diffusion length of a material represents the distance that an exciton can travel before recombination. Thus, to obtain a high percentage of charge carriers relative to the number of excitons generated by absorption of a photon, the excitons are preferably about L at the heterojunction_DAnd (4) forming. Exciton diffusion length L_DBy expression ofAssociated with the exciton diffusion coefficient D and exciton lifetime τ. For organic semiconductors, the exciton diffusion length is typically shorter than the light absorption length L_AThe thickness of the organic layer used is therefore limited due to the relatively low ability of the exciton to reach the donor-acceptor interface for charge separation. This effect not only limits the amount of absorbing material, but also creates a resistive path for the separated charges, which is detrimental to efficient photoconversion¹。

V in organic solar cell_OCThe origin of^3，4. Some have suggested that it relies primarily on the energy difference between the Lowest Unoccupied Molecular Orbital (LUMO) of an acceptor-like material and the Highest Occupied Molecular Orbital (HOMO) of a donor-like material at the heterointerface (referred to as the interface gap Ig) in a bilayer cell⁵. However, this Ig has not been observed by others with the observed V_OCA clear correlation between them, and that such voltages are controlled by a chemical potential gradient that depends on the mobility of the carriers⁶. Furthermore, it has been shown that V_OCThe total energy of the absorbed photons is not reflected and energy is somehow lost during power conversion. These losses have not been explained so far, and care must be taken in evaluating the basis of the open circuit voltage.

Brief description of the invention

The present invention provides organic photosensitive optoelectronic devices comprising at least one tetraazaporphyrin compound of formula I having a trivalent or tetravalent metal atom M bonded to the center of the tetraazaporphyrin core, wherein M is (a) a trivalent metal atom having a monoanionic ligand X attached as shown in formula II, (b) a tetravalent metal atom having two monoanionic ligands X 'and X "attached as shown in formula III, or (c) a tetravalent metal atom having two monoanionic ligands X' and X" attached as shown in formula IV:

wherein

X is a monoanionic ligand;

x 'and X' are independently the same or different two monoanionic ligands; and is

R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Independently selected from the group consisting of a Cl atom, a Br atom, an I atom, an At atom, and a chemical group containing a valence atom attached to a beta carbon atom of the pyrrole or dihydropyrrole ring of the porphyrazine nucleus, wherein the valence atom is selected from the group consisting of B, C, N, O, Si, P, S, Ge, As, Se, In, Sn, Sb, Te, Ti, Pb, Bi, and Po, optionally two adjacent R atoms attached to two beta carbon atoms of the same pyrrole or dihydropyrrole ring₁-R₈The group together with the two beta carbon atoms forms a carbocyclic or heterocyclic group in which the carbocyclic or heterocyclic group is monocyclic or polycyclic, with the proviso that the tetraazaporphyrin compound of formula I is not aluminum phthalocyanine chloride(AlClPc)。

In formulas II and IV, the monoanionic ligands X, X 'and X "are drawn to lie above the porphyrazine nucleus, but one skilled in the art will readily appreciate that monoanionic ligands X, X' and X" may lie below the porphyrazine nucleus.

The present invention also provides a photosensitive optoelectronic device comprising at least one porphyrazine compound of formula I, wherein the at least one porphyrazine compound is at least one phthalocyanine compound having M defined in formula I above of formula V:

the present invention also provides a photosensitive optoelectronic device comprising at least one porphyrazine compound of formula I shown above, wherein the organic photosensitive optoelectronic device comprises

(i) A first electrode and a second electrode, wherein at least one of the first electrode and the second electrode is transparent;

(ii) an organic photoactive material disposed between a first electrode and a second electrode, comprising:

(a) a first organic semiconductor material; and

(b) a second type of organic semiconductor material, which is,

wherein the first organic semiconductor material comprises at least one donor material relative to the second organic semiconductor material and the second organic semiconductor material comprises at least one acceptor material, or the first organic semiconductor material comprises at least one acceptor material relative to the second organic semiconductor material and the second organic semiconductor material comprises at least one donor material, wherein the donor material comprises at least one tetraazaporphyrin compound of formula I, and

(iii) at least one exciton blocking layer between and adjacent to at least one of the two electrodes.

The invention also provides a method of making a photosensitive optoelectronic device of the invention, the method comprising

Providing a donor material and an acceptor material, wherein the donor material and/or the acceptor material comprises at least one tetraazaporphyrin compound of formula (I) of the present invention; and

fabricating a photosensitive optoelectronic device includes placing a donor material in contact with a receptor material,

wherein when both the donor material and the acceptor material comprise at least one porphyrazine compound of formula (I), the at least one porphyrazine compound in the donor material is different from the at least one porphyrazine compound in the acceptor material.

In addition, the present invention provides at least one porphyrazine compound of formula (I) that may be used as at least one component in some or all embodiments of the photosensitive optoelectronic devices of the present invention.

Brief Description of Drawings

Fig. 1 is a diagram showing the energy levels of a donor-acceptor heterojunction.

Detailed Description

The porphyrazine compounds described herein may be used in optoelectronic devices other than organic solar cells. For example, other optoelectronic devices such as organic photodetectors, organic photosensors, and organic photoconductors may use porphyrazine compounds.

The photosensitive optoelectronic device may be a solar cell.

The photosensitive optoelectronic device may be a photodetector.

The photosensitive optoelectronic device may be a light sensor.

The photosensitive optoelectronic device may be a photoconductor.

As used herein, the term "organic" includes polymeric materials as well as small molecule organic materials that may be used to fabricate organic photosensitive optoelectronic devices. By "small molecule" is meant any organic material that is not a polymer, and "small molecules" may in fact be quite large. In some cases the small molecule may comprise a repeat unit. For example, the use of long chain alkyl groups as substituents does not exclude molecules from the "small molecule" class. Small molecules may also be incorporated into polymers, for example as a pendant group on the polymer backbone or as part of the backbone. Small molecules can also be used as the core moiety of dendrimers, which are composed of a series of chemical shells built on the core moiety. The core moiety of the dendrimer may be a fluorescent or phosphorescent small molecule emitter. Dendrimers can be "small molecules". In general, small molecules have a defined chemical formula, with the molecular weight being the same between different molecules, while polymers have a defined chemical formula, but the molecular weight can vary between different molecules. As used herein, "organic" includes metal complexes of hydrocarbyl and heteroatom-substituted hydrocarbyl ligands.

Examples of "monoanionic ligand" include halides, pseudohalides, alkyls, aryls, alkoxys, alkenyloxy, alkynyloxy, aralkyloxy, aralkenyloxy, aralkynyloxy, cycloalkylalkoxy, cycloalkylalkenyloxy, cycloalkylalkynyloxy, acylamidos, cycloalkyls, heterocyclyls, heteroaryls, cycloalkoxy, heterocyclyloxy, heteroaryloxy, cycloalkenyloxy, cycloalkynyloxy, aralkyloxy, aralkynyloxy, aryloxy, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, hydroxycarbonyloxy or alkoxycarbonyloxy, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, N-alkyl-N' -arylamino, acyl, acyloxy, nitro, hydroxy, thiol, alkylthio, alkenylthio, alkynylthio, aralkylthio, aralkenylthio, aralkynylthio, cycloalkylalkylthio, cycloalkenylalkylthio, cycloalkynylalkylthio, cycloalkylthio, cycloalkenylthio, cycloalkynylthio and arylthio.

As used herein, "carbocyclic group" refers to a cyclic chemical group in which all of the ring atoms are carbon. A "carbocyclic group" is monocyclic or polycyclic. "carbocyclic groups" may be cycloalkyl, cycloalkenyl, cycloalkynyl, and aryl groups.

As used herein, "heterocyclic group" refers to a cyclic chemical group having at least one N, O or S ring atom, with the other ring atoms being C atoms. "heterocyclic group" is monocyclic or polycyclic. When a "heterocyclic group" is aromatic, it is referred to as a "heteroaryl group". The heterocyclic group may be a cyclic group containing a 4-, 5-, 6-, 7-or 8-membered ring, wherein the ring comprises at least one ring atom selected from N, O and S, the remaining ring atoms being C. Examples of heterocyclic groups include pyrrolidinyl, piperidinyl, piperazinyl, morpholino, thiomorpholino, homopiperidinyl, chromanyl, isochromanyl, chromenyl, pyrrolyl, furanyl, thienyl, pyrazolyl, imidazolyl, furazanyl (fin-azanyl), oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, pyranyl, indolyl, isoindolyl, indazolyl, purinyl, indolizinyl, quinolinyl, isoquinolinyl, quinazolinyl, pteridinyl, quinolizinyl, benzoxazinyl, carbazolyl, phenazinyl, phenothiazinyl, and phenanthridinyl.

As used herein, when the term "monocyclic" is used to modify a "carbocyclic group" or a "heterocyclic group," the carbocyclic or heterocyclic group contains only a single ring.

As used herein, when the term "polycyclic" is used to modify a "carbocyclic group" or a "heterocyclic group," the carbocyclic or heterocyclic group contains at least two rings. Examples of "polycyclic" rings include bicyclic, tricyclic and tetracyclic. Some or all of the rings in a "polycyclic" group may be peri-fused, ortho-fused, and/or bridged. A "polycyclic" group can be a spiro group.

As used herein, a "valence atom" of a chemical group refers to an atom to which the chemical group is attached to another chemical group or atom.

The term "hydrocarbyl" as used herein refers to a chemical group having carbon and hydrogen atoms.

The term "alkyl" as used herein refers to a straight or branched chain saturated hydrocarbon group. Preferably, "alkyl" is C₁-C₆. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and n-hexyl.

The term "alkenyl" as used herein refers to a hydrocarbon group containing at least one C ═ C double bond. Preferably, "alkenyl" is C₂-C₆. An example of an alkenyl group is vinyl.

The term "alkynyl" as used herein refers to a hydrocarbyl group containing at least one carbon-carbon triple bond. The term "alkynyl" includes chemical groups having at least one carbon-carbon triple bond and at least one C ═ C double bond. Preferably, "alkynyl" is C₂-C₆。

The term "cycloalkyl" as used herein refers to a saturated cyclic hydrocarbon group. "cycloalkyl" is monocyclic or polycyclic. "cycloalkyl" may be C₃-C₈. Examples of "cycloalkyl" include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclononyl.

The term "cycloalkenyl" as used herein refers to an unsaturated cyclic hydrocarbon group having at least one C ═ C double bond. "cycloalkenyl" is monocyclic or polycyclic. "cycloalkenyl" can be C₃-C₈。

The term "cycloalkynyl" as used herein refers to an unsaturated cyclic hydrocarbon group having at least one carbon-carbon triple bond. "cycloalkynyl" is monocyclic or polycyclic. "cycloalkynyl" may be C₃-C₈。

The term "aryl" as used herein refers to an aromatic hydrocarbon group. An "aryl" group is monocyclic or polycyclic. The "aryl" group may be C₆-C₁₀. Examples of "aryl" include phenyl and naphthyl.

The term "aralkyl" as used herein refers to an alkyl group substituted with at least one aryl group. The aryl moiety of "aralkyl" may be C₆-C₁₀. The alkyl moiety of "aralkyl" may be C₁-C₆. Examples of "aralkyl" are benzyl, i.e., phenylmethyl, and 2-phenylethyl.

As used herein, when a chemical group is modified by "substitution," it is meant that the chemical group has at least one hydrogen atom substituted with a substituent. Examples of the substituent include groups selected from: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclyl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkynyloxy, aryloxy, alkylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, cycloalkynylcarbonyloxy, arylcarbonyloxy, thiol, alkylthio, cycloalkylthio, cycloalkenylthio, cycloalkynylthio, arylthio, formyl, acyl, carbamoyl, amino substituted with at least one alkyl, alkenyl or alkynyl group, acylamino, N-acyl-N-alkylamino, N-acyl-N-alkenylamino, N-acyl-N-alkynylamino, N-acyl-N-cycloalkylamino, N-acyl-N-cycloalkenylamino group, N-acyl-N-arylamino, nitro, heterocyclic group and halogen atom.

Examples of substituted alkyl groups include aralkyl, cycloalkyl-substituted alkyl, cycloalkenyl-substituted alkyl, hydroxy-substituted alkyl, alkoxy-substituted alkyl, cycloalkoxy-substituted alkyl, aryloxy-substituted alkyl, alkylcarbonyloxy-substituted alkyl, cycloalkylcarbonyloxy-substituted alkyl, cycloalkenylcarbonyloxy-substituted alkyl, cycloalkynylcarbonyloxy-substituted alkyl, arylcarbonyloxy-substituted alkyl, thiol-substituted alkyl, alkylthio-substituted alkyl, cycloalkylthio-substituted alkyl, formyl-substituted alkyl, acylated alkyl, carbamoyl-substituted alkyl, amino-substituted alkyl, acylamino-substituted alkyl, nitro-substituted alkyl, halogen-substituted alkyl and heterocyclyl-substituted alkyl.

Examples of substituted alkenyl groups include aralkenyl, cycloalkenyl-substituted alkenyl, hydroxy-substituted alkenyl, alkoxy-substituted alkenyl, cycloalkoxy-substituted alkenyl, aryloxy-substituted alkenyl, alkylcarbonyloxy-substituted alkenyl, cycloalkylcarbonyloxy-substituted alkenyl, cycloalkenylcarbonyloxy-substituted alkenyl, cycloalkynylcarbonyloxy-substituted alkenyl, arylcarbonyloxy-substituted alkenyl, thiol-substituted alkenyl, alkylthio-substituted alkenyl, cycloalkylthio-substituted alkenyl, formyl-substituted alkenyl, acylated alkenyl, carbamoyl-substituted alkenyl, amino-substituted alkenyl, acylamino-substituted alkenyl, nitro-substituted alkenyl, halogen-substituted alkenyl, and heterocyclyl-substituted alkenyl.

Examples of substituted alkynyl groups include arylalkynyl, cycloalkyl-substituted alkynyl, cycloalkenyl-substituted alkynyl, hydroxy-substituted alkynyl, alkoxy-substituted alkynyl, cycloalkoxy-substituted alkynyl, aryloxy-substituted alkynyl, alkylcarbonyloxy-substituted alkynyl, cycloalkylcarbonyloxy-substituted alkynyl, cycloalkenylcarbonyloxy-substituted alkynyl, cycloalkynylcarbonyloxy-substituted alkynyl, arylcarbonyloxy-substituted alkynyl, thiol-substituted alkynyl, alkylthio-substituted alkynyl, cycloalkylthio-substituted alkynyl, formyl-substituted alkynyl, acylated alkynyl, carbamoyl-substituted alkynyl, amino-substituted alkynyl, acylamino-substituted alkynyl, nitro-substituted alkynyl, halogen-substituted alkynyl and heterocyclyl-substituted alkynyl.

Examples of substituted cycloalkyl groups include alkyl-substituted cycloalkyl groups, aryl-substituted cycloalkyl groups, cycloalkyl-substituted cycloalkyl groups, cycloalkenyl-substituted cycloalkyl groups, cycloalkynyl-substituted cycloalkyl groups, hydroxy-substituted cycloalkyl groups, alkoxy-substituted cycloalkyl groups, cycloalkoxy-substituted cycloalkyl groups, aryloxy-substituted cycloalkyl groups, alkylcarbonyloxy-substituted cycloalkyl groups, cycloalkylcarbonyloxy-substituted cycloalkyl groups, cycloalkenylcarbonyloxy-substituted cycloalkyl groups, cycloalkynylcarbonyloxy-substituted cycloalkyl groups, arylcarbonyloxy-substituted cycloalkyl groups, thiol-substituted cycloalkyl groups, alkylthio-substituted cycloalkyl groups, cycloalkylthio-substituted cycloalkyl groups, formyl-substituted cycloalkyl groups, acylated cycloalkyl groups, carbamoyl-substituted cycloalkyl groups, amino-substituted cycloalkyl groups, acylamino-substituted cycloalkyl groups, nitro-substituted cycloalkyl groups, halogen-substituted cycloalkyl and heterocyclyl-substituted cycloalkyl.

Examples of substituted cycloalkenyls include alkyl-substituted cycloalkenyls, aryl-substituted cycloalkenyls, cycloalkyl-substituted cycloalkenyls, cycloalkenyl-substituted cycloalkenyls, cycloalkynyl-substituted cycloalkenyls, hydroxy-substituted cycloalkenyls, alkoxy-substituted cycloalkenyls, cycloalkoxy-substituted cycloalkenyls, aryloxy-substituted cycloalkenyls, alkylcarbonyloxy-substituted cycloalkenyls, cycloalkylcarbonyloxy-substituted cycloalkenyls, cycloalkenylcarbonyloxy-substituted cycloalkenyls, cycloalkynylcarbonyloxy-substituted cycloalkenyls, arylcarbonyloxy-substituted cycloalkenyls, thiol-substituted cycloalkenyls, alkylthio-substituted cycloalkenyls, cycloalkylthio-substituted cycloalkenyls, formyl-substituted cycloalkenyls, acylated cycloalkenyls, carbamoyl-substituted cycloalkenyls, amino-substituted cycloalkenyls, acylamino-substituted cycloalkenyls, nitro-substituted cycloalkenyls, halogen substituted cycloalkenyl and heterocyclyl substituted cycloalkenyl.

Examples of substituted cycloalkynyl groups include alkyl-substituted cycloalkynyl, aryl-substituted cycloalkynyl, cycloalkyl-substituted cycloalkynyl, cycloalkenyl-substituted cycloalkynyl, cycloalkynyl-substituted cycloalkynyl, hydroxy-substituted cycloalkynyl, alkoxy-substituted cycloalkynyl, cycloalkoxy-substituted cycloalkynyl, aryloxy-substituted cycloalkynyl, alkylcarbonyloxy-substituted cycloalkynyl, cycloalkylcarbonyloxy-substituted cycloalkynyl, cycloalkenylcarbonyloxy-substituted cycloalkynyl, cycloalkynylcarbonyloxy-substituted cycloalkynyl, arylcarbonyloxy-substituted cycloalkynyl, thiol-substituted cycloalkynyl, alkylthio-substituted cycloalkynyl, cycloalkylthio-substituted cycloalkynyl, formyl-substituted cycloalkynyl, acylated cycloalkynyl, carbamoyl-substituted cycloalkynyl, amino-substituted cycloalkynyl, acylamino-substituted cycloalkynyl, nitro-substituted cycloalkynyl, halogen-substituted cycloalkynyl and heterocyclyl-substituted cycloalkynyl.

Examples of substituted aryl groups include alkyl-substituted aryl groups, aryl-substituted aryl groups, cycloalkyl-substituted aryl groups, cycloalkenyl-substituted aryl groups, cycloalkynyl-substituted aryl groups, hydroxyl-substituted aryl groups, alkoxy-substituted aryl groups, cycloalkyloxy-substituted aryl groups, aryloxy-substituted aryl groups, alkylcarbonyloxy-substituted aryl groups, cycloalkylcarbonyloxy-substituted aryl groups, cycloalkenylcarbonyloxy-substituted aryl groups, cycloalkynylcarbonyloxy-substituted aryl groups, arylcarbonyloxy-substituted aryl groups, thiol-substituted aryl groups, alkylthio-substituted aryl groups, cycloalkylthio-substituted aryl groups, formyl-substituted aryl groups, acylated aryl groups, carbamoyl-substituted aryl groups, amino-substituted aryl groups, acylamino-substituted aryl groups, nitro-substituted aryl groups, halogen-substituted aryl groups and heterocyclyl-substituted aryl groups.

Examples of the substituted heterocyclic group include an alkyl-substituted heterocyclic group, an aryl-substituted heterocyclic group, a cycloalkyl-substituted heterocyclic group, a cycloalkenyl-substituted heterocyclic group, a cycloalkynyl-substituted heterocyclic group, a hydroxyl-substituted heterocyclic group, an alkoxy-substituted heterocyclic group, a cycloalkyloxy-substituted heterocyclic group, an aryloxy-substituted heterocyclic group, an alkylcarbonyloxy-substituted heterocyclic group, a cycloalkylcarbonyloxy-substituted heterocyclic group, a cycloalkenylcarbonyloxy-substituted heterocyclic group, a cycloalkynylcarbonyloxy-substituted heterocyclic group, an arylcarbonyloxy-substituted heterocyclic group, a thiol-substituted heterocyclic group, an alkylthio-substituted heterocyclic group, a cycloalkylthio-substituted heterocyclic group, a formyl-substituted heterocyclic group, an acylated heterocyclic group, a carbamoyl-substituted heterocyclic group, an amino-substituted heterocyclic group, an acylamino-substituted heterocyclic group, a nitro-substituted heterocyclic group, halogen-substituted heterocyclic groups and heterocyclic-substituted heterocyclic groups.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atoms in the group are carbon atoms.

In bookIn certain embodiments of the inventive photosensitive optoelectronic devices, at least one R₁-R₈The valence atoms in the radical being carbon atoms, in which at least one R₁-R₈The groups are independently selected from the group consisting of alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, cycloalkynyl, substituted cycloalkynyl, aryl, substituted aryl, heterocyclic and substituted heterocyclic.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atoms in the radical being carbon atoms, in which at least one R₁-R₈The groups are independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl and heterocyclyl.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atoms in the radical being carbon atoms, in which at least one R₁-R₈The groups are independently selected from alkyl, substituted alkyl, aryl or substituted aryl.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atoms in the radical being carbon atoms, in which at least one R₁-R₈The groups are independently selected from phenyl, tolyl, xylyl, mesityl, methyl, ethyl, n-propyl, and isopropyl.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, two adjacent R's of at least one pyrrole ring₁-R₈The valence atoms in the group being carbon atoms, and wherein two adjacent R of at least one pyrrole ring₁-R₈The groups, together with the two beta carbon atoms of at least one pyrrole ring, form a carbocyclic group or a substituted carbocyclic group.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, two adjacent R's of at least one pyrrole ring₁-R₈The valence atoms in the radical being carbon atomsAnd wherein two adjacent R of at least one pyrrole ring are₁-R₈The groups, together with the two beta carbon atoms of at least one pyrrole ring, form a heterocyclic group or a substituted heterocyclic group.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, two adjacent R's of at least one pyrrole ring₁-R₈The valence atoms in the group being carbon atoms, wherein two adjacent R's of at least one pyrrole ring₁-R₈The group together with the two beta carbon atoms of at least one pyrrole ring forms a carbocyclic group or a substituted carbocyclic group, and the carbocyclic group or substituted carbocyclic group is a macrocycle or a benzo (benzanulated) pi-system.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, two adjacent R's of at least one pyrrole ring₁-R₈The valence atoms in the group being carbon atoms, wherein two adjacent R's of at least one pyrrole ring₁-R₈The groups, together with the two beta carbon atoms of at least one pyrrole ring, form a carbocyclic group or a substituted carbocyclic group, and the carbocyclic group or the substituted carbocyclic group is aromatic.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, two adjacent R's of at least one pyrrole ring₁-R₈The groups, together with the two beta carbon atoms of at least one pyrrole ring, form a heterocyclic group or a substituted heterocyclic group.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atom in the group is an oxygen atom.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atoms in the group being oxygen atoms, at least one of R having O as the valence atom₁-R₈The radical is hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkynyloxy, aralkyloxy, aralkenyloxy, aralkynyloxy, aryloxy, alkylcarbonylOxy, alkenylcarbonyloxy, alkynylcarbonyloxy, hydroxycarbonyloxy or alkoxycarbonyloxy.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atoms in the group being oxygen atoms, at least one of R having O as the valence atom₁-R₈The group is a hydroxyl group or an alkoxy group.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atoms in the group being oxygen atoms, at least one of R having O as the valence atom₁-R₈The radical is hydroxy, methoxy, ethoxy, n-propoxy or isopropoxy.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The group is a Cl atom, a Br atom, an I atom or an At atom.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atom in the group is a nitrogen atom.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atoms in the group being nitrogen atoms, at least one of R having N as the valence atom₁-R₈The group is selected from the group consisting of amino, alkylamino, dialkylamino, alkenylamino, dienylamino, alkynylamino, dialkynylamino, N-alkyl-N-alkenylamino, N-alkyl-N-alkynylamino, N-alkenyl-N-alkynylamino, acylamino, N-acyl-N-alkylamino, N-acyl-N-alkenylamino, N-acyl-N-alkynylamino, N-acyl-N-cycloalkylamino, N-acyl-N-cycloalkenylamino, N-acyl-N-arylamino, nitro, heterocyclic groups containing a nitrogen atom and substituted heterocyclic groups containing a nitrogen atom.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atom in the group is a sulfur atom.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, at least one R is₁-R₈The valence atom in the radical being a sulfur atom, at least one R₁-R₈The group is selected from thiol, alkylthio, alkenylthio, alkynylthio, aralkylthio, aralkenylthio, aralkynylthio, cycloalkylalkylthio, cycloalkenylalkylthio, cycloalkynylalkylthio, cycloalkylthio, cycloalkenylthio, cycloalkynylthio and arylthio.

Examples of M include aluminum, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zirconium, hafnium, molybdenum, tungsten, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, and gold.

In certain embodiments of the photosensitive optoelectronic device of the present invention, M is not Al.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, M is P, Pd or Ir. Preferably, M is Pt or Pd. More preferably, M is Pt.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, the devices are organic photovoltaic cells.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, the devices are photoconductive cells.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, the devices are photosensors.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, the device is a photodetector.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, the devices comprise a donor material and an acceptor material, wherein the donor material or the acceptor material comprises at least one porphyrazine compound of formula (I). Preferably, the donor material comprises at least one porphyrazine compound of formula (I).

In certain embodiments of the photosensitive optoelectronic devices of the present disclosure, the devices comprise a donor material and an acceptor material, wherein both the donor material and the acceptor material comprise at least one porphyrazine compound of formula (I), the at least one porphyrazine compound in the donor material being different from the at least one porphyrazine compound in the acceptor material.

In certain embodiments of the photosensitive optoelectronic devices of the present invention, the devices comprise a donor material and an acceptor material, wherein the donor material comprises at least one porphyrazine compound of formula (I) and the acceptor material comprises C₆₀A compound is provided.

The organic photosensitive optoelectronic devices of the present invention can comprise an exciton blocking layer ("EBL"). The exciton blocking properties of the material are not an intrinsic property (see US 6,451,415). Whether a given material will function as an exciton barrier depends on the relative HOMO and LUMO energy levels of the adjacent organic photoactive materials. Thus, it is not possible to identify a class of compounds in isolation as exciton blockers for the environment in which the device may be used. However, one skilled in the art will be able to identify whether a given material will function as an exciton blocker when used with a selected group of materials to construct an organic photosensitive optoelectronic device. Examples of EBLs are described in U.S. patent application Ser. No.11/150,143 and U.S. patent No.6,451,415 to Forrest et al, the disclosures of which in connection with EBLs are incorporated herein by reference. For example, the exciton blocking layer may comprise 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 4, 4', 4 "-tris { N- (3-methylphenyl) -N-phenylamino } triphenylamine (m-MTDATA) or Polyethylenedioxythiophene (PEDOT). Other background explanations for EBLs have also been found in Peumans et al, "Efficient photon harvesting in ultra thin organic double heterostructure photovoltaics" under high light intensities, Applied Physics letters 76, 2650-52 (2000). EBLs reduce quenching by preventing excitons from migrating out of the donor and/or acceptor material.

The invention provides a method for fabricating a photosensitive optoelectronic device of the invention, the method comprising

Providing a donor material and an acceptor material, wherein the donor material and/or the acceptor material comprises at least one tetraazaporphyrin compound of formula (I) of the present invention; and

fabricating a photosensitive optoelectronic device includes placing a donor material in contact with a receptor material,

wherein when both the donor material and the acceptor material comprise at least one porphyrazine compound of formula (I), the at least one porphyrazine compound in the donor material is different from the at least one porphyrazine compound in the acceptor material.

One aspect of the present invention relates to a method of fabricating a photosensitive optoelectronic device of the present invention, wherein the photosensitive optoelectronic device is fabricated using any known method of fabricating a photosensitive optoelectronic device, the improvement comprising:

providing a donor material and an acceptor material, wherein the donor material and/or the acceptor material comprises at least one tetraazaporphyrin compound of formula (I) of the present invention; and

the donor material is placed in contact with the receptor material,

wherein when both the donor material and the acceptor material comprise at least one porphyrazine compound of formula (I), the at least one porphyrazine compound in the donor material is different from the at least one porphyrazine compound in the acceptor material.

In any of the methods of making photosensitive optoelectronic devices of the present invention, the at least one porphyrazine compound used in the donor material and/or the acceptor material may be any of the porphyrazine compounds of formula (I) disclosed herein.

In certain embodiments of the methods of fabricating a photosensitive optoelectronic device of the present invention, the photosensitive optoelectronic device is a solar cell.

In certain embodiments of the methods of making photosensitive optoelectronic devices of the present invention, the photosensitive optoelectronic device is a photodetector.

In certain embodiments of the methods of making photosensitive optoelectronic devices of the present invention, the photosensitive optoelectronic device is a photosensor.

In certain embodiments of the methods of the present invention for fabricating a photosensitive optoelectronic device, the photosensitive optoelectronic device is a photoconductive cell.

The porphyrazine compounds of formula (I) can be prepared using known chemical synthesis methods. For example, the tetraazaporphyrin compounds can be synthesized as shown in the following reaction scheme, wherein R is₁-R₈Represented by the general R group.

The synthesis of tetraazaporphyrins involves the reaction of a metal salt (listed above) with fumaronitrile (E) or maleonitrile (Z) derivatives (various R groups), which, depending on the R group and the metal salt, can be carried out as a pure reaction or in butanol. The precipitate is then digested in acetic acid and washed, or washed with solvent only. The phthalocyanine compound is synthesized under the same conditions starting from a dicyanobenzene derivative. See, e.g., Mashenkov, V.A., et al, ZhurnalPrikladnoi Spektroskopii, 1974, 21(1), 73-81; fitzgerald, Jeffery et al, Synthesis, 1991, 9, 686-688; chizhova, n.v.; khelevina, o.g.; berezin, B.D. Russian Journal of General Chemistry 2003, 73(10), 1645-1647.

Reference to the literature

Peamans, p., a.yakimov and s.r.forrest, Small molecular weight organic thin film photodetectors and solar cells (Small molecular weight organic thin-film detectors and solar cells.), Journal of Applied Physics, 2003.93 (7): p.3693-3723.

Singh, v.p., r.s.singh, b.parthasarathy, a.agilelera, j.anthony, and m.payne, copper phthalocyanine-based organic solar cells with high open circuit voltage (copperphtalocyanine-based organic solar cells with high selectivity-circuit), Applied Physics Letters, 2005.86 (8): p.082106.

Brabec, cj, a.cravidio, d.meissner, n.s.saricifici, t.fromherz, mt.rispens, l.sanchez and j.c.hummelen, Origin of open circuit voltage of plastic solar cells (Origin of the open circuit voltage of plastic solar cells), Advanced Functional Materials, 2001.11 (5): p.374-380.

Gledhill, s.e., b.scott and b.a.gregg, organic and nanostructured composite photovoltaic materials: review (Organic and nano-structured composite photovoltiaics: Anoverview), Journal of Materials Research, 2005.20 (12): p.3167-3179.

Mutolo, k.l, e.i.mayo, b.p.rand, s.r.forrest and m.e.thompson, increased open circuit voltage in subphthalocyanine/C-60 organic photovoltaic cells (enhanced-circuit voltage in subphthalocyanine/C-60 organic photovoltaic cells), Journal of the American Chemical Society, 2006.128 (25): p.8108-8109.

Terao, y., h.sasabe and c.adachi, Correlation between hole mobility in phthalocyanine/fullerene organic solar cells, exciton diffusion length and solar cell characteristics (Correlation of hole mobility, exciton diffusion length, and solar cell in phthalocyanine/fullerene organic solar cells), applied physics Letters, 2007.90 (10): p.103515.

Claims (33)

1. An organic photosensitive optoelectronic device comprising at least one tetraazaporphyrin compound of formula I having a trivalent or tetravalent metal atom M bonded to the center of the tetraazaporphyrin core, wherein M is (a) a trivalent metal atom having a monoanionic ligand X attached as shown in formula II, (b) a tetravalent metal atom having two monoanionic ligands X 'and X "attached as shown in formula III, or (c) a tetravalent metal atom having two monoanionic ligands X' and X" attached as shown in formula IV:

wherein

X is a monoanionic ligand;

x 'and X' are independently the same or different two monoanionic ligands; and is

R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Independently selected from the group consisting of alkyl, substituted alkyl, alkenyl, substituted alkenyl, alkynyl, substituted alkynyl, cycloalkyl, substituted cycloalkyl, cycloalkenyl, substituted cycloalkenyl, cycloalkynyl, substituted cycloalkynyl, aryl, substituted aryl, heterocyclic and substituted heterocyclic.

2. The device of claim 1, wherein R₁-R₈The valence atom in at least one of the groups is C.

3. The apparatus of claim 1, wherein

Substituted alkyl is alkyl substituted with at least one group independently selected from: cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclyl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkynyloxy, aryloxy, alkylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, cycloalkynylcarbonyloxy, arylcarbonyloxy, thiol, alkylthio, cycloalkylthio, cycloalkenylthio, cycloalkynylthio, arylthio, formyl, acyl, carbamoyl, amino substituted with at least one alkyl, alkenyl or alkynyl group, acylamino, N-acyl-N-alkylamino, N-acyl-N-alkenylamino, N-acyl-N-alkynylamino, N-acyl-N-cycloalkylamino, N-acyl-N-cycloalkenylamino, N-acyl-N-arylamino, nitro, heterocyclic and halogen atoms;

substituted alkenyl is alkenyl substituted with at least one group independently selected from: cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclyl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkynyloxy, aryloxy, alkylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, cycloalkynylcarbonyloxy, arylcarbonyloxy, thiol, alkylthio, cycloalkylthio, cycloalkenylthio, cycloalkynylthio, arylthio, formyl, acyl, carbamoyl, amino substituted with at least one alkyl, alkenyl or alkynyl group, acylamino, N-acyl-N-alkylamino, N-acyl-N-alkenylamino, N-acyl-N-alkynylamino, N-acyl-N-cycloalkylamino, N-acyl-N-cycloalkenylamino, N-acyl-N-arylamino, nitro, heterocyclic group and halogen atom;

substituted alkynyl is alkynyl substituted with at least one group independently selected from: cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclyl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkynyloxy, aryloxy, alkylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, cycloalkynylcarbonyloxy, arylcarbonyloxy, thiol, alkylthio, cycloalkylthio, cycloalkenylthio, cycloalkynylthio, arylthio, formyl, acyl, carbamoyl, amino substituted with at least one alkyl, alkenyl or alkynyl group, acylamino, N-acyl-N-alkylamino, N-acyl-N-alkenylamino, N-acyl-N-alkynylamino, N-acyl-N-cycloalkylamino, N-acyl-N-cycloalkenylamino, N-acyl-N-arylamino, nitro, heterocyclic and halogen atoms;

substituted cycloalkyl is cycloalkyl substituted with at least one group independently selected from: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclyl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkynyloxy, aryloxy, alkylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, cycloalkynylcarbonyloxy, arylcarbonyloxy, thiol, alkylthio, cycloalkylthio, cycloalkenylthio, cycloalkynylthio, arylthio, formyl, acyl, carbamoyl, amino substituted with at least one alkyl, alkenyl or alkynyl group, acylamino, N-acyl-N-alkylamino, N-acyl-N-alkenylamino, N-acyl-N-alkynylamino, N-acyl-N-cycloalkylamino, N-acyl-N-cycloalkenylamino group, N-acyl-N-arylamino, nitro, heterocyclic group and halogen atom;

substituted cycloalkenyl is cycloalkenyl substituted with at least one group independently selected from: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclyl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkynyloxy, aryloxy, alkylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, cycloalkynylcarbonyloxy, arylcarbonyloxy, thiol, alkylthio, cycloalkylthio, cycloalkenylthio, cycloalkynylthio, arylthio, formyl, acyl, carbamoyl, amino substituted with at least one alkyl, alkenyl or alkynyl group, acylamino, N-acyl-N-alkylamino, N-acyl-N-alkenylamino, N-acyl-N-alkynylamino, N-acyl-N-cycloalkylamino, N-acyl-N-cycloalkenylamino group, N-acyl-N-arylamino, nitro, heterocyclic group and halogen atom;

substituted cycloalkynyl is cycloalkynyl substituted with at least one group independently selected from: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclyl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkynyloxy, aryloxy, alkylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, cycloalkynylcarbonyloxy, arylcarbonyloxy, thiol, alkylthio, cycloalkylthio, cycloalkenylthio, cycloalkynylthio, arylthio, formyl, acyl, carbamoyl, amino substituted with at least one alkyl, alkenyl or alkynyl group, acylamino, N-acyl-N-alkylamino, N-acyl-N-alkenylamino, N-acyl-N-alkynylamino, N-acyl-N-cycloalkylamino, N-acyl-N-cycloalkenylamino group, N-acyl-N-arylamino, nitro, heterocyclic group and halogen atom;

substituted aryl is aryl substituted with at least one group independently selected from: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclyl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkynyloxy, aryloxy, alkylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, cycloalkynylcarbonyloxy, arylcarbonyloxy, thiol, alkylthio, cycloalkylthio, cycloalkenylthio, cycloalkynylthio, arylthio, formyl, acyl, carbamoyl, amino substituted with at least one alkyl, alkenyl or alkynyl group, acylamino, N-acyl-N-alkylamino, N-acyl-N-alkenylamino, N-acyl-N-alkynylamino, N-acyl-N-cycloalkylamino, N-acyl-N-cycloalkenylamino group, N-acyl-N-arylamino, nitro, heterocyclic group and halogen atom; and

a substituted heterocyclyl is a heterocyclyl substituted with at least one group independently selected from: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heterocyclyl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkynyloxy, aryloxy, alkylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkenylcarbonyloxy, cycloalkynylcarbonyloxy, arylcarbonyloxy, thiol, alkylthio, cycloalkylthio, cycloalkenylthio, cycloalkynylthio, arylthio, formyl, acyl, carbamoyl, amino substituted with at least one alkyl, alkenyl or alkynyl group, acylamino, N-acyl-N-alkylamino, N-acyl-N-alkenylamino, N-acyl-N-alkynylamino, N-acyl-N-cycloalkylamino, N-acyl-N-cycloalkenylamino group, N-acyl-N-arylamino, nitro, heterocyclic group and halogen atom.

4. The device of claim 1, wherein at least two adjacent R's are attached to the same pyrrole or dihydropyrrole ring₁-R₈Radicals, with two beta-carbon atoms of the pyrrole or dihydropyrrole ringTogether, the atoms form an optionally substituted carbocyclic or heterocyclic group.

5. The device of claim 4, wherein at least two adjacent R's are attached to the same pyrrole or dihydropyrrole ring₁-R₈The group, together with the two beta carbon atoms of the pyrrole or dihydropyrrole ring, forms an optionally substituted carbocyclic group.

6. The device of claim 5, wherein the optionally substituted carbocyclic group is an optionally substituted aryl group.

7. The device of claim 6, wherein the optionally substituted aryl is phenyl or substituted phenyl.

8. The device of claim 7, wherein the at least one porphyrazine compound is at least one phthalocyanine compound of formula V having M bonded at the center of the porphyrazine core:

。

9. the device of claim 4, wherein at least two adjacent R's are attached to the same pyrrole or dihydropyrrole ring₁-R₈The group, together with the two beta carbon atoms of the pyrrole or dihydropyrrole ring, forms a heterocyclic group.

10. The device of claim 5, wherein the optionally substituted carbocyclic group is an optionally substituted macrocycle or a benzo pi-system.

11. The device of claim 2, wherein R₁-R₈At least one of the groups is an alkyl, substituted alkyl, aryl or substituted aryl group.

12. The device of claim 1, wherein R₁-R₈The valence atom of at least one of the groups is O.

13. The device of claim 12, wherein at least one R having O as a valence atom₁-R₈The radical is hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkenyloxy, cycloalkynyloxy, aralkyloxy, aralkenyloxy, aralkynyloxy, aryloxy, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, hydroxycarbonyloxy or alkoxycarbonyloxy.

14. The device of claim 13, wherein at least one R having O as a valence atom₁-R₈The group is a hydroxyl group or an alkoxy group.

15. The device of claim 1, wherein R₁-R₈At least one of the groups is independently selected from a Cl atom, a Br atom, an I atom, and an At atom.

16. The device of claim 1, wherein R₁-R₈At least one of the groups has N as a valence atom.

17. The device of claim 1, wherein R₁-R₈At least one of the groups has S as a valence atom.

18. The device of claim 1, wherein X, X 'or X "is independently selected from the group consisting of halide, pseudohalide, alkyl, aryl, alkoxy, alkenyloxy, alkynyloxy, aralkyloxy, aralkenyloxy, aralkynyloxy, cycloalkylalkoxy, cycloalkylalkenyloxy, cycloalkylalkynyloxy, amide, cycloalkyl, heterocyclyl, heteroaryl, cycloalkoxy, heterocyclyloxy, heteroaralkyloxy, cycloalkenyloxy, cycloalkynyloxy, aralkyloxy, aryloxy, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, hydroxycarbonyloxy or alkoxycarbonyloxy, amino, monoalkylamino, dialkylamino, monoarylamino, diarylamino, N-alkyl-N' -arylamino, acyl, acyloxy, nitro, hydroxyl, thiol, alkylthio, alkenylthio, alkynylthio, aralkylthio, aralkenylthio, aralkynylthio, cycloalkylalkylthio, cycloalkenylalkylthio, cycloalkynylalkylthio, cycloalkylthio, cycloalkynylthio and arylthio.

19. The device of claim 18, wherein X, X' or X "is independently selected from the group consisting of halide, pseudohalide, alkyl, aryl, alkoxy, and amide groups.

20. The device of claim 1, wherein M is selected from the group consisting of aluminum, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zirconium, hafnium, molybdenum, tungsten, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, and gold.

21. The device of claim 20, wherein M is selected from the group consisting of gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, zirconium, hafnium, molybdenum, tungsten, ruthenium, osmium, rhodium, iridium, palladium, platinum, silver, and gold.

22. The apparatus of claim 21, wherein M is Pt, Pd or Ir.

23. The device of claim 1, wherein M is a trivalent metal atom.

24. The device of claim 1, wherein M is a tetravalent metal atom.

25. The apparatus of claim 1 comprising

(i) A first electrode and a second electrode, wherein at least one of the first electrode and the second electrode is transparent;

(ii) an organic photoactive material positioned between a first electrode and a second electrode, comprising:

(a) a first organic semiconductor material; and

(b) a second type of organic semiconductor material, which is,

wherein the first organic semiconductor material comprises at least one donor material relative to the second organic semiconductor material and the second organic semiconductor material comprises at least one acceptor material, or the first organic semiconductor material comprises at least one acceptor material relative to the second organic semiconductor material and the second organic semiconductor material comprises at least one donor material, wherein the donor material comprises at least one tetraazaporphyrin compound of formula I, and wherein the first organic semiconductor material is in direct contact with the second organic semiconductor material; and

(iii) at least one exciton blocking layer between and adjacent to at least one of the two electrodes.

26. The device of claim 1, wherein the device comprises a donor material and an acceptor material, and wherein the donor material comprises at least one porphyrazine compound of formula (I).

27. The device of claim 26, wherein the receptor material comprises C₆₀。

28. The device of claim 1, wherein the device comprises a donor material and an acceptor material, and wherein the donor material comprises a tetraazaporphyrin compound of formula (I), and the acceptor material comprises another tetraazaporphyrin compound of formula (I).

29. The device of claim 1, wherein the device is an organic photovoltaic cell.

30. The device of claim 1, wherein the device is a photoconductive cell.

31. The device of claim 1, wherein the device is a photodetector.

32. The device of claim 1, wherein the device is a light sensor.

33. A method for making the organic photosensitive device of claim 26, comprising

Providing a donor material and an acceptor material, wherein the donor material comprises at least one porphyrazine compound of formula (I); and

fabricating an organic photosensitive optoelectronic device includes contacting a donor material with an acceptor material.