Abstract
The present invention relates generally to the field of organic chemistry and particularly to the organic compound for organic photovoltaic devices. More specifically, the present invention is related to the organic compounds and the organic photovoltaic devices based on these compounds. In one preferred embodiment, this organic compound has the general structural formula
##STR00001##
where Het.sub.1 is a predominantly planar polycyclic molecular system of first type; Het.sub.2 is a predominantly planar polycyclic molecular system of second type; A is a bridging group providing a lateral bond of the molecular system Het.sub.1 with the molecular system Het.sub.2 via strong chemical bonds; n is 1, 2, 3, 4, 5, 6, 7 or 8; B1 and B2 are binding groups; i is 0, 1, 2, 3, 4, 5, 6, 7 or 8; j is 0, 1, 2, 3, 4, 5, 6, 7 or 8; S1 and S2 are groups providing solubility of the organic compound; k is 0, 1, 2, 3, 4, 5, 6, 7 or 8; m is 0, 1, 2, 3, 4, 5, 6, 7 or 8; D1 and D2 are substituents independently selected from a list comprising CH.sub.3, C.sub.2H.sub.5, NO.sub.2, Cl, Br, F, CF.sub.3, CN, OH, OCH.sub.3, OC.sub.2H.sub.5, OCOCH.sub.3, OCN, SCNNH.sub.2, NHCOCH.sub.3, C.sub.2Si(CH.sub.3).sub.3, and CONH.sub.2; y is 0, 1, 2, 3, 4, 5, 6, 7 or 8; and z is 0, 1, 2, 3, 4, 5, 6, 7 or 8. Said organic compound absorbs electromagnetic radiation in at least one predetermined spectral subrange within a wavelength range from 400 to 3000 nm and is capable to form supramolecules. The molecular system Het.sub.1, the bridging group A, and the molecular system Het.sub.2 are capable to form a donor-bridge-acceptor system providing dissociation of excited electron-hole pairs. A solution of the organic compound or its salt is capable of forming a solid photovoltaic layer on a substrate.
Claims
1-20. (canceled)
21. An organic photovoltaic device comprising a first and a second electrode and at least one solid organic photovoltaic layer, wherein said layer comprises at least one organic compound having the general structural formula II: ##STR00034## where Het.sub.1 is a predominantly planar polycyclic molecular system of a first type; Het.sub.2 is a predominantly planar polycyclic molecular system of a second type; A is a bridging group providing a lateral bond of the molecular system Het.sub.1 with the molecular system Het.sub.2 via strong chemical bonds; n is 2, 3, 4, 5, 6, 7 or 8; B1 and B2 are binding groups; i is 0, 1, 2, 3, 4, 5, 6, 7 or 8; j is 0, 1, 2, 3, 4, 5, 6, 7 or 8; S1 and S2 are groups providing solubility of the at least one organic compound; k is 0, 1, 2, 3, 4, 5, 6, 7 or 8; m is 0, 1, 2, 3, 4, 5, 6, 7 or 8; wherein k+m0, D1 and D2 are substituents independently selected from a list consisting of CH.sub.3, C.sub.2H.sub.5, C.sub.3H.sub.7, NO.sub.2, Cl, Br, F, CF.sub.3, CN, OH, OCH.sub.3, OC.sub.2H.sub.5, OCOCH.sub.3, OCN, SCN, NH.sub.2, NHCOCH.sub.3, C.sub.2Si(CH.sub.3).sub.3, and CONH.sub.2; and y is 0, 1, 2, 3, 4, 5, 6, 7 or 8; z is 0, 1, 2, 3, 4, 5, 6, 7 or 8; X is a counterion selected from a list consisting of H.sup.+, Li.sup.+, Na.sup.+, K.sup.+, NH.sub.4.sup.+, Ba.sup.++, Zn.sup.++, Sr.sup.++, Ca.sup.++, Mg.sup.++, and any combination thereof; t is the number of counterions providing for the electric neutrality of the at least one organic compound; wherein the photovoltaic layer is formed of column-like or planar supramolecules, wherein the photovoltaic layer has absorption of electromagnetic radiation in at least one predetermined spectral subrange within a wavelength range from 400 to 3000 nm, and wherein the molecular system Het.sub.1, the bridging group A, and the molecular system Het.sub.2 form a donor-bridge-acceptor system providing dissociation of excited electron-hole pairs.
22. The organic photovoltaic device according to claim 21, wherein at least one of the predominantly planar polycyclic molecular systems Het.sub.1 and Het.sub.2 is a heterocyclic molecular system.
23. The organic photovoltaic device according to claim 21, wherein the predominantly planar polycyclic molecular system of first type (Het.sub.1) and at least one predominantly planar polycyclic molecular system of second type (Het.sub.2) absorb electromagnetic radiation in different predetermined spectral subranges within a wavelength range from 400 to 3000 nm.
24. The organic photovoltaic device according to claim 21, wherein the strong chemical bond is selected from the list consisting of covalent bond, coordination bond, ionic bond, and any combination thereof.
25. The organic photovoltaic device according to claim 21, wherein the photovoltaic layer has column-like supramolecules formed by means of --interaction of single-type polycyclic molecular systems and having longitudinal axes oriented predominantly in the layer plane, wherein the column-like supramolecules are positioned predominantly parallel to each other.
26. The organic photovoltaic device according to claim 5, wherein a number and a chain length of the substituents are selected to provide an electric isolation of the adjacent column-like supramolecules.
27. The organic photovoltaic device according to claim 21, wherein the photovoltaic layer comprises photovoltaic fibers oriented predominantly parallel to each other in the layer plane.
28. The organic photovoltaic device according to claim 21, comprising at least one woven photovoltaic layer comprising photovoltaic fibers, wherein the photovoltaic fibers are arranged predominantly parallel to each other.
29. The organic photovoltaic device according to claim 21, wherein the photovoltaic layer has planar supramolecules having polycyclic molecular systems with planes oriented predominantly parallel to the layer plane due to lateral interaction of binding groups by means of strong and weak chemical bonds, wherein at least one of said planar supramolecules has the form selected from the list consisting of disk, plate, lamella, ribbon or any combination thereof, and wherein the weak chemical bond is selected from the list consisting of single hydrogen bond, dipole-dipole interaction, cation- interaction, van der Waals interaction, - interaction, and any combination thereof.
30. The organic photovoltaic device according to claim 29, wherein the planar supramolecules form molecular stacks by means of --interaction of the single-type polycyclic molecular systems Het.sub.1 and Het.sub.2 providing different current-conducting-paths with electron and hole conductivity respectively, wherein said molecular stacks are electrically isolated among themselves due to the substituents or/and groups providing solubility of the organic compound, and wherein the molecular stacks are oriented predominantly perpendicular to the plane of the photovoltaic layer.
31. The organic photovoltaic device according to claim 21, wherein the predetermined spectral subrange is from 400 to 700 nm.
32. The organic photovoltaic device according to claim 21, wherein at least one of the predominantly planar polycyclic molecular systems Het.sub.1 and Het.sub.2 is partially or completely conjugated.
33. The organic photovoltaic device according to claim 2, wherein at least one of the predominantly planar polycyclic molecular systems Het.sub.1 and Het.sub.2 comprises the hetero-atoms selected from the list consisting of nitrogen, oxygen, sulfur, and any combination thereof.
34. The organic photovoltaic device according to claim 21, wherein at least one of the bridging groups A is independently selected from the list consisting of an imidazole; perylene-3,4-dicarboximide; a series of p-phenylene (Ph.sub.P) oligomers, where p is 1, 2, 3, 4 or 5; and a series of 2,7-oligofluorene (FL.sub.S) oligomers, where s is 1, 2, 3, or 4.
35. The organic photovoltaic device according to claim 21, wherein at least one of the predominantly planar polycyclic molecular systems Het.sub.1 and Het.sub.2 comprises tetrapirolic macrocyclic fragments and having a general structural formula selected from the group consisting of structures 1-6, where M denotes an atom of metal or two protons (2H): ##STR00035## ##STR00036##
36. The organic photovoltaic layer according to claim 21, wherein at least one of the predominantly planar polycyclic molecular systems Het.sub.1 and Het.sub.2 comprises rylene fragments and having a general structural formula selected from the group consisting of structures 7-27: ##STR00037## ##STR00038## ##STR00039##
37. The organic photovoltaic layer according to claim 21, wherein at least one of the predominantly planar polycyclic molecular systems Het.sub.1 and Het.sub.2 comprises naphthalene fragments having a general structural formula selected from the group consisting of structures 28-29: ##STR00040##
38. The organic photovoltaic layer according to claim 30, wherein the molecular stacks are oriented predominantly perpendicular to the plane of the photovoltaic layer.
39. The organic photovoltaic layer according to claim 25, comprising the parallel column-like supramolecules oriented predominantly in the plane of the photovoltaic layer.
40. The organic photovoltaic layer according to claim 27, comprising the parallel photovoltaic fibers oriented predominantly in the plane of the photovoltaic layer.
Description
[0059] A more complete assessment of the present invention and its advantages will be readily achieved as the same becomes better understood by reference to the following detailed description, considered in connection with the accompanying drawings and detailed specification, all of which forms a part of the disclosure. Embodiments of the invention are illustrated, by way of example only, in the following Figures, of which:
[0060] FIG. 1 schematically shows one embodiment of an organic compound according present invention, wherein n=4, i=2, k=1, y=1, j=1, m=1 and z=1.
[0061] FIG. 2 schematically shows column-like supramolecules formed by means of --interaction of single-type polycyclic molecular systems Het.sub.1 and Het.sub.2 shown in FIG. 1 (for simplicity the groups of A, B, S and D type are not shown in FIG. 2).
[0062] FIG. 3 schematically shows another embodiment of an organic compound according present invention, wherein n=1, i=3, k=0, y=0, j=1, m=0 and z=0.
[0063] FIG. 4 schematically shows a fragment of disk-like planar supramolecule made of the organic compound shown in FIG. 3 and formed by means of strong and weak chemical bonds.
[0064] FIG. 5 schematically shows a fragment of ribbon-like planar supramolecule formed by means of strong chemical bonds.
[0065] FIG. 6 shows first embodiment of an organic compound according to present invention.
[0066] FIG. 7 shows second embodiment of an organic compound according to present invention.
[0067] FIG. 8 shows third embodiment of an organic compound according to present invention.
[0068] FIG. 9 shows fourth embodiment of an organic compound according to present invention.
[0069] FIG. 10 shows fifth embodiment of an organic compound according to present invention.
[0070] FIG. 11 shows the cross section of an organic photovoltaic device according to present invention.
[0071] FIG. 12 is an energy band diagram of non-irradiated donor-bridge-acceptor system formed by p- and n-type molecular stacks connected by bridging groups.
[0072] FIG. 13 is an energy band diagram of irradiated donor-bridge-acceptor system formed by p- and n-type molecular stacks connected by bridging groups.
[0073] FIG. 14 is an energy band diagram of hole-harvesting contact.
[0074] FIG. 15 is an energy band diagram of barrier contact for electron.
[0075] FIG. 16 is an energy band diagram of electron-harvesting contact.
[0076] FIG. 17 is an energy band diagram of barrier contact for holes.
[0077] FIG. 18 is a schematic diagram of an organic photovoltaic device based on a structure with a photovoltaic organic layer with two contacts, which are located on the opposite surfaces of the photovoltaic layer.
[0078] FIG. 19 schematically shows a top view of the molecular stack.
[0079] FIG. 20 schematically shows the disclosed organic photovoltaic device, based on photovoltaic layer comprising the molecular stacks oriented predominantly perpendicular to the its plane and located between the front electrode and the rear electrode.
[0080] FIG. 21 schematically shows another embodiment of organic photovoltaic device with reflective electrode according present invention.
[0081] FIG. 22 schematically shows an organic photovoltaic device based on a single organic photovoltaic layer.
[0082] FIG. 23 shows an exemplary embodiment of the disclosed photovoltaic device with an interdigitated system of electrodes.
[0083] FIGS. 24a and 24b show schematically two embodiments of photovoltaic fibers according to present invention.
[0084] FIG. 25 shows a cell of disclosed photovoltaic device with an interdigitated system of electrodes shown in FIG. 23.
[0085] FIG. 26 shows a woven photovoltaic layer comprising photovoltaic fibers, wherein the photovoltaic fibers are arranged parallel to each other.
[0086] FIG. 27 shows another embodiment of cell of photovoltaic device.
[0087] FIG. 28 shows yet another embodiment of disclosed organic photosensitive optoelectronic device with an additional reflective a retarder layers.
[0088] FIG. 1 presents a schematic diagram of the disclosed organic compound based on one predominantly planar polycyclic molecular system of first type Het.sub.1 and four predominantly planar polycyclic molecular systems of second type Het.sub.2. The bridging groups A provide lateral bonds of the molecular system Het.sub.1 with the molecular systems Het.sub.2 via strong chemical bonds and form donor-bridge-acceptor systems. The molecular system Het.sub.1 comprises two binding groups (B1), one group providing solubility of the organic compound (S1) and one substituent (D1). The molecular systems Het.sub.2 comprise one binding group (B2), one group providing solubility of the organic compound (S2) and one substituent (D2).
[0089] FIG. 2 schematically shows column-like supramolecules formed by means of --interaction of single-type polycyclic molecular systems Het.sub.1 and Het.sub.2 shown in FIG. 1 (for simplicity the groups of A, B, S and D type are not shown in FIG. 2). In one embodiment the molecular system Het.sub.1 is donor of electrons and molecular system Het.sub.2 is acceptor of electrons. In this embodiment the molecular systems Het.sub.1 form molecular stack providing hole transport path and the molecular systems Het.sub.2 form four molecular stacks providing electron transport paths. In another embodiment of organic compound, the column-like supramolecules may comprise intra-binding groups. In this case said intra-binding groups reduce vibrating fluctuations of polycyclic molecular systems that lead to increasing of rigidity and therefore electrical conductivity of molecular stacks. In still another embodiment of organic compound, the column-like supramolecules may comprise inter-binding groups. In this case said inter-binding groups can connect the adjacent supramolecules forming three dimension networks.
[0090] FIG. 3 schematically shows another embodiment of an organic compound according present invention, wherein n=1, i=3, k=0, y=0, j=1, m=0 and z=0. In one embodiment of organic compound, the bridging group A provides a lateral bond of the molecular system Het.sub.1 with the molecular system Het.sub.2 via covalent chemical bonds. In another embodiment of organic compound, the bridging group A provides a lateral bond of the molecular system Het.sub.1 with the molecular system Het.sub.2 via coordination chemical bonds.
[0091] FIG. 4 schematically shows a fragment of disk-like planar suprarnolecule made of the organic compound shown in FIG. 3 and formed due to lateral interaction of binding groups by means of strong and weak chemical bonds. In one embodiment these disk-like planar supramolecules may be arranged one above another. In this embodiment the single-type polycyclic molecular systems of the adjacent planar supramolecules form molecular stacks by means of --interaction.
[0092] FIG. 5 schematically shows a fragment of ribbon-like planar supramolecule. In one embodiment of organic compound, the bridging group A provides a lateral bond of the molecular system Het.sub.1 with the molecular system Het.sub.2 via covalent chemical bonds. In another embodiment of organic compound, the bridging group A provides a lateral bond of the molecular system Het.sub.1 with the molecular system Het.sub.2 via coordination chemical bonds. In this embodiment of invention, the binding groups B1 provides a lateral bond of the molecular systems Het.sub.1 with each other via strong chemical bonds. In turn, the binding groups B2 provides a lateral bond of the molecular systems Het.sub.2 with each other via strong chemical bonds too. The strong chemical bonds create chains -B1-Het.sub.1-B1-B1-Het.sub.1-B1-B1-Het.sub.1-B1- and -B2-Het.sub.2-B2-B2-Het.sub.2-B2-B2-Het.sub.2-B2- with high electrical conductivity.
[0093] Figures from 6 to 10 show several embodiments of an organic compound according to present invention. FIG. 6 shows a Tetrakis(N-Alkyl-5,12-bis(trimethylsilylethynyl)-anthra[2,1,9-def:6,5,10-def]diisoquinoline-1,3,8,10-tetrone-N-phenylen-4-yl) porphyrin, FIG. 7 shows a Tetrakis(N-Alkyl-5,12-bis(trimethylsilylethynyl)-anthra[2,1,9-def:6,5,10-def]diisoquinoline-1,3,8,10-tetrone-N-biphenylen-4-ylimide) of octacarboxyphthalocyanine, FIG. 8 shows a Tetrakis(BenzoirnidazoPeryleneTetraCarboxlmid-p-PhenylenePyrrol-dion) Copper Phthalocyanine (TBIPTCl-p-PP-CuPc), FIG. 9 shows a Tetrakis(DiPhenyllmidePeryleneTetraCarboxylicAcid) Copper Phthalocyanine (TDPIPTCA-CuPc), and FIG. 10 shows a 2,9-Bis(tris(N,N,N-alkyl)-octacarboxyphthalocyanine-N-4-phenylenyl)-5,12-bis(trimethylsilylethynyl)-anthra[2,1,9-def:6,5,10-def]diisoquinoline-1,3,8,10-tetrone.
[0094] FIG. 11 schematically shows the cross section of an organic photovoltaic device according to present invention. In one embodiment of an organic photovoltaic device, the photovoltaic layer is located between two electrodes (3) and (4). Said photovoltaic layer is formed by an organic compound, comprising the predominantly planar polycyclic molecular system Het.sub.1 with p-type conductivity and the predominantly planar polycyclic molecular systems Het.sub.2 with n-type conductivity. The organic compound comprises bridging groups. The bridging groups provide a lateral bond of the molecular system Het.sub.1 with the molecular system Het.sub.2 via strong chemical bonds. The organic compound absorbs electromagnetic radiation in at least one predetermined spectral subrange within a wavelength range from 400 to 3000 nm and is capable to form planar supramolecules. The molecular system Het.sub.1, the bridging groups, and the molecular system Het.sub.2 are capable to form a donor-bridge-acceptor system providing dissociation of excited electron-hole pairs. The planar supramolecules have polycyclic molecular systems with planes oriented predominantly parallel to the planes of electrodes due to lateral interaction of binding groups by means of strong and weak chemical bonds. The single-type polycyclic molecular systems of the adjacent planar supramolecules form molecular stacks (1) and (2) by means of --interaction. In one embodiment the molecular stacks (1) are conductors of electrons (marked by white arrows) and the molecular stacks (2) are conductors of holes (marked by black arrows). Under action of light hv a photocurrent is formed in the organic photovoltaic device. This photocurrent flows through resistive load (5).
[0095] FIG. 12 is an energy band diagram of non-irradiated donor bridge acceptor system in equilibrium state formed by said p- and n-type molecular stacks connected by the bridging groups. In this Figure the following designations are used: AEp, IPp and EGp are electron affinity, ionization potential and gap energy of the p-type polycyclic molecular system and AEn, IPn and EGn are electron affinity, ionization potential and gap energy of the n-type polycyclic molecular system. Fermi's level (F-level) is identical to the molecular systems of p- and n-type.
[0096] FIG. 13 is an energy band diagram of irradiated donor bridge acceptor system formed by p- and n-type molecular stacks connected by bridging groups. The Vac is open-circuit voltage; Vbi is built-in potential; .sub.N is potential barrier for electrons; .sub.P is potential barrier for holes. The excited electron-hole pairs (excitons) are dissociated on border between molecular systems. The FIG. 13 shows that an electron excited in the molecular system of p-type is passed into the molecular system of n-type and hole excited in the molecular system of p-type is reflected from potential barrier .sub.P. For effective exciton dissociation it is necessary that the potential barrier .sub.P obeys the following condition: .sub.P>3 kT, where k is the Boltzmann constant, T is the absolute temperature in K. On the other hand, an electron excited in the molecular system of n-type is reflected from potential barrier .sub.N and hole excited in the molecular system of n-type is passed into the molecular system of p-type. It is necessary that the potential barrier .sub.N obeys the following condition: .sub.N>3 kT. The electrode (4) (shown in FIG. 11) provides a hole-harvesting contact with energy band diagram shown in FIG. 14 and barrier contact for electrons with energy band diagram shown in FIG. 15. On the other hand, the electrode (3) (shown in FIG. 11) provides an electron-harvesting contact with energy band diagram shown in FIG. 16 and barrier contact for holes with energy band diagram shown in FIG. 17.
[0097] FIG. 18 presents a schematic diagram of the disclosed organic photovoltaic device, based on photovoltaic layer (6) located between the front electrode (3) and the rear electrode (4). At least one of said electrodes is transparent for the incident electromagnetic radiation to which said photovoltaic organic layer is sensitive. The front electrode shown in FIG. 18 is transparent. Said photovoltaic layer (6) comprises the molecular stacks oriented predominantly perpendicular to the plane of the photovoltaic layer. The molecular stacks of planar supramolecules are formed by means of --interaction of the single-type polycyclic molecular systems providing different current-conducting-paths with electron and hole conductivity respectively. These current-conducting-paths are electrically isolated among themselves due to the groups providing solubility of the organic compound. The entire structure is formed on a substrate (7) and the electrodes are connected to a resistive load (5).
[0098] FIG. 19 schematically shows a top view of the molecular stack formed by planar supramolecules comprising predominantly planar polycyclic molecular systems (Het.sub.1 and Het.sub.1) connected by bridging groups (A). In one embodiment, the polycyclic molecular systems (Het.sub.1) form current-conducting-path with electron conductivity, the other polycyclic molecular systems (Het.sub.1) form current-conducting-path with hole conductivity. These current-conducting-paths are surrounded with the groups providing solubility of the organic compound (S1 and S2). These groups electrically isolate adjacent molecular stacks from each other.
[0099] FIG. 20 schematically shows the disclosed organic photovoltaic device, based on photovoltaic layer (6) located between the front electrode (3) made of aluminium and the rear electrode (4) made of ITO. The photovoltaic layer (6) comprises the molecular stacks oriented predominantly perpendicular to the plane of the photovoltaic layer. The disclosed organic photovoltaic device further comprises resistive load (5), an electron acceptor layer (8) and electron donor layer (9).
[0100] FIG. 21 schematically shows another embodiment of organic photovoltaic device according present invention. The photovoltaic layer (6) is located between the electron acceptor layer (8) and the electron donor layer (9). The photovoltaic layer (6) comprises the molecular stacks oriented predominantly perpendicular to the plane of the photovoltaic layer. The front electrode (3) is transparent and made of aluminium. The reflective electrode (10) is required to provide that the incident radiation would be doubly transmitted through the photovoltaic layer (6), thus increasing the conversion efficiency of the organic photovoltaic device. The disclosed photovoltaic device further comprises resistive load (5) and substrate (7).
[0101] Another embodiment of the present invention, illustrated in FIG. 22, is based on a single organic photovoltaic layer (6). The photovoltaic layer has column-like supramolecules formed by means of --interaction of single-type polycyclic molecular systems and having longitudinal axes oriented predominantly in the layer plane. At least a part of the front surface of said photovoltaic organic layer contacts with the first electrode (3) and at least a part of the same surface is in contact with the second electrode (4) as shown in FIG. 22. The column-like supramolecules arrange in photovoltaic layer (6) are predominantly aligned in direction from one electrode (3) to another one (4). The photovoltaic organic layer (6) is formed on substrate (7) and the electrodes are connected to a resistive load (5).
[0102] FIG. 23 shows an exemplary embodiment of the disclosed photovoltaic device with an interdigitated system of electrodes. This device comprises a photovoltaic layer (6) and two transparent electrodes (3) and (4). The photovoltaic layer (6) has the parallel column-like supramolecules oriented predominantly in the plane of the photovoltaic layer, the first electrode (3) is formed in grooves made on a part of one of the surfaces of said photovoltaic layer and the second electrode (4) is formed in grooves made on another part of the same surface of said photovoltaic layer. The photovoltaic layer is formed on a substrate (7) and the electrodes are connected to a resistive load (5).
[0103] FIGS. 24a and 24b show schematically two embodiments of photovoltaic fibers according to present invention. The fibers comprise predominantly planar polycyclic molecular systems (Het.sub.1) of first type (16), predominantly planar polycyclic molecular systems (Het.sub.2) of second type (18) and bridging groups A (17) providing a lateral bond of the molecular systems Het.sub.1 with the molecular systems Het.sub.2 via strong chemical bonds. In one embodiment of the invention, the molecular systems Het.sub.1 may be as electron acceptors, and the molecular systems Het.sub.2 may be as electron donors. In another embodiment of the invention, the molecular systems Het.sub.2 may be as electron acceptors, and the molecular systems Het.sub.1 may be as electron donors. The donor-bridge-acceptor systems (Het.sub.1-A-Het.sub.2) form molecular stacks by means of --interaction of the single-type polycyclic molecular systems providing current-conducting-paths with electron and hole conductivity. These stacks form a core of the photovoltaic fiber. Substituents and groups providing solubility of the organic compound (20) form an envelope (19) around the core. These envelopes electrically isolate the cores of the adjacent fibers.
[0104] FIG. 25 shows a cell of disclosed photovoltaic device with an interdigitated system of electrodes shown in FIG. 23. In this embodiment of invention, the cell of disclosed device comprises a photovoltaic layer (11) made of photovoltaic fibers (12). Finger-like metal electrodes (3 and 4) are formed in grooves made in the photovoltaic layer. The grooves may be made with the help of chemical etching, ion-plasma etching, pressing, forcing, scratching, or by any other method known in prior art. Longitudinal axes of fibres and direction of electrodes are perpendicular each other. An electron acceptor layer (8) and an electron donor layer (9) are located in the grooves between the photovoltaic layer (11) and electrodes (3 and 4), respectively. The photovoltaic layer (11) is formed on a substrate (7) and the electrodes are connected to a resistive load (5). In another embodiment of the disclosed device, the photovoltaic layer is a woven photovoltaic layer comprising photovoltaic fibers, wherein the photovoltaic fibers (12) according to the present invention are arranged predominantly parallel to each other and the photovoltiac fibers are fixed in place with the non-photovoltaic fibers (13) (see FIG. 26).
[0105] FIG. 27 shows another embodiment of cell of photovoltaic device. In this embodiment of invention, the cell of disclosed device comprises a photovoltaic layer (6) and finger-like metal electrodes (3 and 4). These electrodes are forced down into the photovoltaic layer. The first electrode (3) is made of material with a work function providing a hole-harvesting contact and a barrier contact for electrons and the second electrode (4) is made of material with a work function providing a barrier contact for holes and an electron-harvesting contact. The photovoltaic layer (6) is formed so that longitudinal axes of column-like supramolecules were perpendicular to a direction of the electrodes. The photovoltaic layer (6) is formed on a substrate (7) and the electrodes are connected to a resistive load (5). The black arrow shows an alignment direction of the organic compound on the substrate.
[0106] In yet another embodiment of disclosed organic photosensitive optoelectronic device is illustrated in FIG. 28. This device comprises a photovoltaic layer (6) and two electrodes (3) and (4) formed on one surface of the photovoltaic layer. First electrode (3) is made of material with work function providing a hole-harvesting contact and a barrier contact for electrons and the second electrode (4) is made of material with work function providing a barrier contact for holes and an electron-harvesting contact, while a retarder layer (15) and an additional reflective layer (14) with a reflection coefficient of not less than 95% for the incident radiation are formed on the another surface of the photoelectric layer. The entire multilayer structure is formed on a substrate (7) and the electrodes are connected to a resistive load (5). In this structure, the incident electromagnetic radiation doubly passes through the active photoelectric layer of the device structure thus increasing the efficiency of conversion. While the electromagnetic radiation incident on layer (6) is nonpolarized, the radiation transmitter through photovoltaic layer in one direction will be partly polarized. Being reflected from the reflective layer, the radiation polarized parallel to the transmission axis of the photovoltaic layer (6) will not be repeatedly absorbed in this layer on the second passage. In order to avoid this and increase the conversion efficiency of said device, it is necessary to rotate the polarization vector 90. To this end, an additional retarder layer (15) is introduced between a photovoltaic layer (6) and a reflective layer (14). The thickness and optical anisotropy of this retarder are selected so as to ensure a 45-rotation of the polarization vector of the transmitted radiation. Since the electromagnetic radiation double-passes through this layer, the resulting polarization rotation amounts to 90. Thus, the combination of retarder and reflective layer provides for a more complete use of the incident electromagnetic radiation and ensures an increase in the photovoltaic conversion efficiency of this embodiment.
[0107] The solid photovoltaic layer may be produced by the following method, which involves application on a substrate of a solution of one organic compound, or a combination of such organic compounds, with the general structural formula
##STR00033##
and drying with the formation of a photovoltaic layer. Here, Het.sub.1 is a predominantly planar polycyclic molecular system of first type; Het.sub.2 is a predominantly planar polycyclic molecular system of second type; A is a bridging group providing a lateral bond of the molecular system Het.sub.1 with the molecular system Het.sub.2 via strong chemical bonds; n is 1, 2, 3, 4, 5, 6, 7 or 8; B1 and B2 are binding groups; i is 0, 1, 2, 3, 4, 5, 6, 7 or 8; j is 0, 1, 2, 3, 4, 5, 6, 7 or 8; S1 and S2 are groups providing solubility of the organic compound; k is 0, 1, 2, 3, 4, 5, 6, 7 or 8; m is 0, 1, 2, 3, 4, 5, 6, 7 or 8; D1 and D2 are substituents independently selected from a list comprising CH.sub.3, C.sub.2H.sub.5, NO.sub.2, Cl, Br, F, CF.sub.3, CN, OH, OCH.sub.3, OC.sub.2H.sub.5, OCOCH.sub.3, OCN, SCNNH.sub.2, NHCOCH.sub.3, C.sub.2Si(CH.sub.3).sub.3, and CONH.sub.2; y is 0, 1, 2, 3, 4, 5, 6, 7 or 8; and z is 0, 1, 2, 3, 4, 5, 6, 7 or 8. Said organic compound is capable of forming supramolecules. The molecular system Het.sub.1, the bridging group A, and the molecular system Het.sub.2 are capable of forming a donor-bridge-acceptor system providing dissociation of excited electron-hole pairs. The solution may absorb electromagnetic radiation only in a part of wavelength range from 400 to 3000 nm. This part of spectral range will be called as subrange. This subrange may be determined experimentally for each particular solution. Thus, such subrange of absorption of the electromagnetic radiation can be considered as the predetermined subrange. In one embodiment of the disclosed method, said solution is based on water and/or water-miscible solvents. In another embodiment of the disclosed method, at least one of the groups providing a solubility of the organic compound in water and/or water-miscible solvents is selected from the list comprising COO.sup., SO.sub.3.sup., HPO.sub.3.sup., and PO.sub.3.sup.2 and any combination thereof. In yet another embodiment of the disclosed method, the photovoltaic layer produced from water solutions has polycyclic molecular systems with planes oriented predominantly perpendicularly to the substrate plane.
[0108] In one embodiment of the disclosed method, said solution is based on organic solvent. In this embodiment of the disclosed method, the organic solvent is selected from the list comprising benzol, toluene, xylenes, acetone, acetic acid, methylethylketone, hydrocarbons, chloroform, carbontetrachloride, dichlorethane, methylenechloride, chlorobenzol, alcohols, nitrornethan, acetonitrile, dimethylforamide, 1,4-dioxane or any combination thereof. In another embodiment of the disclosed method, at least one of the groups providing a solubility of the organic compound in organic solvent is amide of acid residue independently selected from the list comprising CONR.sub.1R.sub.2, CONHCONH.sub.2, SO.sub.2NR.sub.1R.sub.2, and any combination thereof, were R.sub.1,R.sub.2 independently selected from H, alkyl or aryl. The alkyls may be selected from the list comprising methyl, ethyl, propyl, butyl, i-butyl, t-butyl and aryls may be selected from the list comprising phenyl, benzyl, naphthyl. The examples of alkyls and aryls serve to illustrate the invention without limiting it. In yet another embodiment of the disclosed method, at least one of the groups providing a solubility of the organic compound in organic solvent is alkyl. In still another embodiment of the disclosed method, the photovoltaic layer produced from organic solutions has polycyclic molecular systems with planes oriented predominantly parallel to the substrate plane.
[0109] In one embodiment of the disclosed method, said solution absorbs electromagnetic radiation within a wavelength range from 400 to 700 nm. In one embodiment of the disclosed method, said predominantly planar polycyclic molecular system is a partially or completely conjugated. In still another embodiment of the disclosed method, said polycyclic molecular system comprises the hetero-atoms selected from the list comprising nitrogen, oxygen, sulfur, and any combination thereof. In yet another embodiment of the disclosed method, at least one of the binding group is selected from the list comprising the hetero-atoms, COOH, SO.sub.3H, H.sub.2PO.sub.3, NH, NH.sub.2, NHR, NR.sub.2, and any combination thereof, where radical R is alkyl or aryl.
[0110] The examples of polycyclic molecular systems of a general structural formula corresponding to structures 1-28 shown above in Tables 1-3 serve to illustrate the disclosed method without limiting it. In still another embodiment of the disclosed method for obtaining semiconductor crystal films, the planar polycyclic molecular system comprises phthalocyanine fragments. Some examples of such planar polycyclic molecular systems comprising phthalocyanine fragments having a general structural formula from the group comprising structures 1-5 are given in Table 1. In another embodiment of the disclosed method, the planar polycyclic molecular system comprises rylene fragments. Some examples of such planar polycyclic molecular systems comprising rylene fragments having a general structural formula from the group comprising structures 6-26 are given in Table 2. In another embodiment of the disclosed method, the planar polycyclic molecular system comprises naphthalene fragments. Some examples of such polycyclic molecular systems having a general structural formula from the group comprising structures 27-28 are given in Table 3.
[0111] In one another embodiment of the disclosed method, the applied solution layer is dried in airflow. In another embodiment of the disclosed method, the substrate is pretreated to provide surface hydrophilization before application of said solution layer. In yet another embodiment of the present invention, the disclosed method further comprises the stage of treatment of the photovoltaic layer with a solution of any water-soluble inorganic salt with a cation selected from the group including Ba.sup.++, Zn.sup.++, Sr.sup.++, Ca.sup.++, Mg.sup.++, and any combination thereof. The polyvalent counterions (Ba.sup.++, Ca.sup.++, Mg.sup.++, Sr.sup.++, Zn.sup.++) are used for stabilization of the organic compounds and provide their insolubility. In one embodiment of the disclosed method, said photovoltaic layer is formed by planar polycyclic molecular systems of two or more types ensuring the absorption of electromagnetic radiation in different subranges within a wavelength range from 400 to 3000 nm.
[0112] In one embodiment of the disclosed method, said applied solution is isotropic. In another embodiment of the disclosed method, said solution is a lyotropic liquid crystal solution. In one embodiment of the method, the application of said lyotropic liquid crystal solution on the substrate is accompanied or followed by an orienting action upon this solution. In another embodiment of the method, the application stage is carried out using a spray-coating. In yet another embodiment of the disclosed method, the cycle of the technological operations of solution application and drying is repeated two or more times, and sequential photovoltaic layers are formed using solutions absorbing electromagnetic radiation in predefined spectral subranges, which can be either the same or different for various photovoltaic layers.
