Patent Application
20140053897
This disclosure relates to tandem photovoltaic cells, as well as related systems, methods, and components.
There is an increasing interest in the development of photovoltaic technology due primarily to a desire to reduce consumption of and dependency on fossil fuel-based energy sources. Photovoltaic technology is also viewed by many as being an environmentally friendly energy technology. However, for photovoltaic technology to be a commercially feasible energy technology, the material and manufacturing costs of a photovoltaic system (a system that uses one or more photovoltaic cells to convert light to electrical energy) should be recoverable over some reasonable time frame. But, in some instances, the cell performance and/or the costs of materials and manufacture associated with practically designed photovoltaic systems have restricted their availability and use.
This disclosure is based on the unexpected discovery that an interconnecting layer including an n-type semiconductor material (e.g., a substituted fullerene) and a cross-linked polyamine can be used to form a tandem photovoltaic cell having a large number of subcells (e.g., 10 subcells or more), while minimizing voltage loss between two neighboring subcells. As a result, the voltage output of the tandem photovoltaic cell thus formed is generally equal to the total voltages generated in the subcells.
In one aspect, this disclosure features a system that includes first and second electrodes; first and second photoactive layers between the first and second electrodes; and a recombination material between the first and second photoactive layers. The first photoactive layer is between the first electrode and the recombination material. The second photoactive layer is between the second electrode and the recombination material. The recombination material includes a first hole blocking layer and a first hole carrier layer. The first hole blocking layer includes an n-type semiconductor material and a polyamine, at least some molecules of the polyamine being cross-linked. The system is configured as a photovoltaic system.
In another aspect, this disclosure features a system that includes first and second electrodes; first and second photoactive layers between the first and second electrodes; and a recombination material between the first and second photoactive layers. The recombination material includes a first layer that comprises an n-type semiconductor material and a polyamine. The system is configured as a photovoltaic system.
In still another aspect, this disclosure features a method that includes disposing a composition containing an n-type semiconductor material, a polyamine, and a cross-linking agent on a substrate to form a layer supported by the substrate; and heating the layer to cross-link at least some molecules of the polyamine, thereby forming a first hole blocking layer.
Embodiments can include one or more of the following features.
In some embodiments, the n-type semiconductor material can include a fullerene, such as a substituted fullerene (e.g., C61-PCBM or C71-PCBM).
In some embodiments, the polyamine can be a polyethylenimine or a copolymer thereof.
In some embodiments, at least some molecules of the polyamine can be cross-linked by a cross-linking agent, such as an epoxy-containing compound (e.g., glycerol propoxylate triglycidyl ether or glycerol diglycidyl ether).
In some embodiments, the first hole blocking layer can have a thickness of from about 20 nm to about 200 nm (e.g., from about 30 nm to about 60 nm).
In some embodiments, the first hole blocking layer can have a work function of from about 3.5 eV to about 4.5 eV.
In some embodiments, the first hole carrier layer can include a p-type semiconductor material. For example, the p-type semiconductor material can include a polymer or a metal oxide. The polymer can be selected from the group consisting of polythiophenes (e.g., poly(3,4-ethylene dioxythiophene) or poly(thieno[3,4-b]thiophene)), polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, and copolymers thereof. The metal oxide can include an oxide selected from the group consisting of nickel oxides, vanadium oxides, tungsten oxides, molybdenum oxides, copper oxides, strontium copper oxides, and strontium titanium oxides. In some embodiments, the p-type semiconductor material can include a metal oxide dispersed in a polymer.
In some embodiments, the first hole carrier layer can have a work function of from about 4.8 eV to about 6.5 eV.
In some embodiments, the system can further include a second hole blocking layer between the first electrode and the first photoactive layer. In such embodiments, the first photoactive layer can be between the second hole blocking layer and the first hole carrier layer. In some embodiments, the second hole blocking layer can be made from a material different from the material used to make the first hole blocking layer. For example, the second hole blocking layer can include LiF, metal oxides, or amines.
In some embodiments, the system can further include a second hole carrier layer between the second electrode and the second photoactive layer. In such embodiments, the second photoactive layer can be between the first hole blocking layer and the second hole carrier layer. For example, the second hole carrier layer can include a polymer selected from the group consisting of polythiophenes, polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, and copolymers or mixtures thereof.
In some embodiments, the system can be configured as a tandem photovoltaic system.
In some embodiments, the method can further include disposing a first electrode, a first photoactive layer, and a first hole carrier layer sequentially onto the substrate prior to applying the composition to the substrate. In such embodiments, the method can further include disposing a second photoactive layer and a second electrode sequentially onto the first hole blocking layer. The method can further include disposing a second hole blocking layer on the first electrode prior to disposing the first photoactive layer and/or disposing a second hole carrier layer on the second photoactive layer prior to disposing the second electrode.
In some embodiments, each of the above disposing steps is carried out via a liquid-based coating process.
Other features, objects, and advantages of the subject matter in this disclosure will be apparent from the description and drawings, and from the claims.
Like reference symbols in the various drawings indicate like elements.
Photovoltaic cell 100 includes two subcells. The first subcell includes electrode 120, optional hole blocking layer 130, photovoltaic layer 140, and recombination material 150. The second subcell includes recombination layer 150, photoactive layer 160, optional hole carrier layer 170, and electrode 180. The first and second subcells are electrically connected via electrodes 120 and 180 and share recombination layer 150 (which can be considered as a common electrode between the first and second subcells) such that they are electrically connected in series.
In general, during use, light can impinge on the surface of electrode 120 of the first subcell, and pass through electrode 120 and optional hole blocking layer 130. The light can then interact with photoactive layer 140. The residual light can further pass through recombination material 150, and interact with photoactive layer 160 of the second subcell. The interactions between the light and photoactive layers 120 and 160 can cause the electrons to be transferred from an electron donor material (e.g., poly(3-hexylthiophene) (P3HT)) to an electron acceptor material (e.g., C61-phenyl-butyric acid methyl ester (C61-PCBM)) within each photoactive layer. The electron acceptor materials in photoactive layers 140 and 160 can then transfer the electrons to electrode 120 and recombination material 150, respectively. The electron donor materials in photoactive layers 140 and 160 can transfer holes to recombination material 150 and electrode 180, respectively. As a result, the holes generated from the first subcell can recombine with the electrons generated from the second subcell in recombination material 150 (e.g., at the interface of layers 152 and 156). During use, electrodes 120 and 180 are electrically connected to an external load so that electrons pass from electrode 120 through the external load to electrode 180.
Referring to
Hole blocking layer 156 is generally formed of a material that, at the thickness used in photovoltaic cell 100, transports electrons to hole carrier layer 152 and substantially blocks the transport of holes to hole carrier layer 152. Hole blocking layer 156 generally includes an n-type semiconductor material and a polyamine. Examples of suitable n-type semiconductor materials include fullerenes, such as unsubstituted fullerenes or substituted fullerenes. Examples of unsubstituted fullerenes include C60, C70, C76, C78, C82, C84, and C92. Examples of substituted fullerenes include fullerene substituted with phenyl-butyric acid methyl esters (PCBMs, such as phenyl-C61-butyric acid methyl ester (C61-PCBM) or a phenyl-C71-butyric acid methyl ester (C71-PCBM)) or fullerenes substituted with C1-C20 alkoxy optionally further substituted with C1-C20 alkoxy and/or halo (e.g., (OCH2CH2)2OCH3 or OCH2CF2OCF2CF2OCF3). Other examples of fullerenes have been described in, e.g., commonly-owned U.S. Pat. No. 7,329,709 and International Application No. WO 2011/160021. In certain embodiments, a combination of n-type semiconductor materials can be used in hole blocking layer 156.
In some embodiments, hole blocking layer 156 can include at least about 20 wt % (e.g., at least about 30 wt %, at least about 40 wt %, at least about 50 wt %) and/or at most about 75 wt % (e.g., at most about 70 wt %, at most about 60%, or at most about 50 wt %) of the n-type semiconductor material.
In some embodiments, the n-type semiconductor material (e.g., a substituted fullerene) can be dissolved in the solvent (e.g., a mixture of an alcohol and a chlorinated solvent) used to dissolve other components used to prepare hole blocking layer 156. Without wishing to be bound by theory, it is believed that such an n-type semiconductor material can facilitate formation of a uniform hole blocking layer 156. In addition, without wishing to be bound by theory, it is believed that using such an n-type semiconductor material can facilitate formation of hole blocking layer 156 having a relative large thickness (e.g., from about 30 nm to about 60 nm), while still maintaining the electrical conductivity of layer 156. Layer 156 thus formed can minimize shunting between two neighboring subcells and minimize voltage loss caused by shunting, thereby forming a tandem photovoltaic cell having a voltage output that is generally equal to the sum of the total voltages of the subcells.
As used herein, the term “polyamine” refers to a polymer having two or more amino groups, including primary amino groups, secondary amino groups, and tertiary amino groups. Examples of suitable polyamines in hole blocking layer 156 include polyethylenimines or their copolymers. In certain embodiments, at least some (e.g., substantially all) of the molecules of the polyamine in hole blocking layer 156 can be cross-linked, e.g., via a cross-linking agent. Exemplary cross-linking agents include epoxy-containing compounds, such as glycerol propoxylate triglycidyl ether and glycerol diglycidyl ether. Without wishing to be bound by theory, it is believed that cross-linked the polyamine can result in a cross-linked hole blocking layer 156, which can function as a barrier for the solvent used to prepare photoactive layer 160 to prevent the solvent from reaching the layers (e.g., hole carrier layer 152 or photoactive layer 140) underneath hole blocking layer 156, thereby resulting in shunting between the first and second subcells in photovoltaic cell 100 and/or and disrupting the morphology of photoactive layer 140. In some embodiments, the weight ratio between the polyamine and the cross-linking agent can be between about 1:2 and about 2:1 (e.g., about 1:1).
In some embodiments, hole blocking layer 156 can include at least about 25 wt % (e.g., at least about 30 wt %, at least about 40 wt %, or at least about 50 wt %) and/or at most about 80 wt % (e.g., at most about 70 wt %, at most about 60%, or at most about 50 wt %) of the cross-linked polyamine.
In general, hole blocking layer 156 have a sufficiently large thickness such that it functions as a barrier for the solvent used to prepare photoactive layer 160 on top of layer 156. In some embodiments, hole blocking layer 156 can have a thickness of at least about 20 nm (e.g., at least about 30 nm, at least about 40 nm, or at least about 50 nm) and/or at most about 200 nm (e.g., at most about 150 nm, at most about 100 nm, at most about 80 nm, or at most about 60 nm). Without wishing to be bound by theory, it is believe that, if the thickness of hole blocking layer 156 is too small (e.g., smaller than about 20 nm), shunting between the first and second subcells in photovoltaic cell 100 can occur, which can cause voltage losses to cell 100. Without wishing to be bound by theory, it is believe that, if the thickness of hole blocking layer 156 is too large (e.g., larger than about 200 nm), light absorption by layer 156 may be too high such that the second subcell in photovoltaic cell 100 may not receive enough incident light to generate electricity with a sufficiently high voltage or current.
In some embodiments, hole blocking layer 156 can have a work function of at least about 3.5 eV (e.g., at least about 3.6 eV, at least about 3.8 eV, or at least about 4 eV) and/or at most about 4.5 eV (e.g., at most about 4.4 eV, at most about 4.2 eV, or at most about 4 eV). Without wishing to be bound by theory, it is believed that, when hole blocking layer 156 has a work function ranging from about 3.5 eV to about 4.5 eV, layer 156 can selectively transport electrons to hole carrier layer 152 and substantially block the transport of holes to hole carrier layer 152.
Without wishing to be bound by theory, it is believed that cross-linked hole blocking layer 156 containing an n-type semiconductor material and having a relatively large thickness (e.g., from about 30 nm to about 60 nm) can minimize shunting between two neighboring subcells while maintaining sufficient electrical conductivity between two neighboring subcells. As a result, a tandem photovoltaic cell formed from such a hole blocking layer in a recombination material can have a voltage output that is generally equal to the sum of the total voltages of the subcells.
In some embodiments, hole blocking layer 156 can be prepared by dissolving or dispersing an n-type semiconductor material (e.g., C61-PCBM), a polyamine (e.g., a polyethylenimine), and a cross-linking agent (e.g., glycerol diglycidyl ether) in a suitable solvent to form a composition (e.g., a dispersion or solution) and then coating the composition thus formed on a layer (e.g., hole carrier layer 152) in photovoltaic cell 100 using a liquid-based coating process. In general, solvents suitable for the above process do not dissolve the components in the underlying layer (e.g., hole carrier layer 152) and therefore do not adversely impact that layer. Examples of suitable solvents include chlorinated solvents (e.g., trichloroethylene, methylene chloride, ethylene chloride, tetrachloroethylene), ethers (diethylether, dimethylether, or tetrahydrofuran), dimethylformamide, dimethyl sulfoxide, or a mixture thereof. In some embodiments, the solvent can be a mixture containing a chlorinated solvent and one or more other solvents (e.g., an alcohol such as methanol, ethanol, propanol, or butanol). In some embodiments, the weight ratio between the amount of the n-type semiconductor material and the combined amount of the polyamine and the cross-linking agent in the above composition can be between about 1:3 and about 3:1 (e.g., about 1:1).
The term “liquid-based coating process” mentioned herein refers to a process that uses a liquid-based coating composition. Examples of the liquid-based coating composition can be a solution, a dispersion, or a suspension. The concentration of a liquid-based coating composition can generally be adjusted as desired. In some embodiments, the concentration can be adjusted to achieve a desired viscosity of the coating composition or a desired thickness of the coating. The liquid-based coating process can be carried out by using at least one of the following processes: solution coating, ink jet printing, spin coating, dip coating, knife coating, bar coating, spray coating, roller coating, slot coating, gravure coating, flexographic printing, or screen printing. Examples of liquid-based coating processes have been described in, for example, commonly-owned co-pending U.S. Application Publication No. 2008-0006324.
Hole carrier layer 152 is generally formed of a material that, at the thickness used in photovoltaic cell 100, transports holes to hole blocking layer 156 and substantially blocks the transport of electrons to hole blocking layer 156. In general, hole carrier layer 152 can include a p-type semiconductor material. Examples of suitable p-type semiconductor materials include polymers and/or metal oxides. Exemplary p-type semiconductor polymers include polythiophenes (e.g., poly(3,4-ethylene dioxythiophene) (PEDOT) or poly(thieno[3,4-b]thiophene)), polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, and copolymers thereof. Examples of commercially available polymers that can be used in layer 152 include the Air Products® HIL family of thiophene polymers and H.C. Starck Baytron® family of thiophene polymers. In some embodiments, layer 152 can also include a dopant for the polymer. For example, the dopant can include poly(styrene-sulfonate)s, polystyrene sulfonic acids, or sulfonated tetrafluorethylenes.
Exemplary p-type semiconductor metal oxides include nickel oxides, vanadium oxides, tungsten oxides, molybdenum oxides, copper oxides, strontium copper oxides, and strontium titanium oxides. The metal oxides can be either undoped or doped with a dopant. Examples of dopants for metal oxides include salts or acids of fluoride, chloride, bromide, and iodide. In some embodiments, the hole carrier materials in layer 152 can be in the form of nanoparticles. The nanoparticles can have any suitable shape, such as a spherical, cylindrical, or rod-like shape.
In some embodiments, hole carrier layer 152 can include combinations of the above p-type semiconductor materials. For example, hole carrier layer 152 can include metal oxide nanoparticles dispersed or embedded in a polymer.
In general, the thickness of hole carrier layer 152 (i.e., the distance between the surface of hole carrier layer 152 in contact with photoactive layer 140 and the surface of hole blocking layer 156 in contact with hole carrier layer 152) can be varied as desired. Typically, the thickness of hole carrier layer 152 is at least 0.01 micron (e.g., at least about 0.05 micron, at least about 0.1 micron, at least about 0.2 micron, at least about 0.3 micron, or at least about 0.5 micron) and/or at most about five microns (e.g., at most about three microns, at most about two microns, or at most about one micron). In some embodiments, the thickness of hole carrier layer 152 is from about 0.01 micron to about 0.5 micron (e.g., about 0.1 micron).
In some embodiments, hole carrier layer 152 can have a work function of at least about 4.8 eV (e.g., at least about 5 eV, at least about 5.2 eV, or at least about 5.4 eV) and/or at most about 6.5 eV (e.g., at most about 6.4 eV, at most about 6.2 eV, or at most about 6 eV). Without wishing to be bound by theory, it is believed that, when hole carrier layer 152 has a work function ranging from about 4.8 eV to about 6.5 eV, layer 152 can selectively transport holes to hole blocking layer 156 and substantially block the transport of electrons to hole blocking layer 156.
Turning to other components of photovoltaic cell 100, substrate 110 is generally formed of a transparent material. As referred to herein, a transparent material is a material which, at the thickness used in a photovoltaic cell 100, transmits at least about 60% (e.g., at least about 70%, at least about 75%, at least about 80%, at least about 85%) of incident light at a wavelength or a range of wavelengths used during operation of the photovoltaic cell. Exemplary materials from which substrate 110 can be formed include polyethylene terephthalates, polyimides, polyethylene naphthalates, polymeric hydrocarbons, cellulosic polymers, polycarbonates, polyamides, polyethers, and polyether ketones. In certain embodiments, the polymer can be a fluorinated polymer. In some embodiments, combinations of polymeric materials are used. In certain embodiments, different regions of substrate 110 can be formed of different materials.
In general, substrate 110 can be flexible, semi-rigid or rigid (e.g., glass). In some embodiments, substrate 110 has a flexural modulus of less than about 5,000 megaPascals (e.g., less than about 1,000 megaPascals or less than about 500 megaPascals). In certain embodiments, different regions of substrate 110 can be flexible, semi-rigid, or inflexible (e.g., one or more regions flexible and one or more different regions semi-rigid, one or more regions flexible and one or more different regions inflexible).
Typically, substrate 110 is at least about one micron (e.g., at least about five microns or at least about 10 microns) thick and/or at most about 1,000 microns (e.g., at most about 500 microns thick, at most about 300 microns thick, at most about 200 microns thick, at most about 100 microns, or at most about 50 microns) thick.
Generally, substrate 110 can be colored or non-colored. In some embodiments, one or more portions of substrate 110 is/are colored while one or more different portions of substrate 110 is/are non-colored.
Substrate 110 can have one planar surface (e.g., the surface on which light impinges), two planar surfaces (e.g., the surface on which light impinges and the opposite surface), or no planar surfaces. A non-planar surface of substrate 110 can, for example, be curved or stepped. In some embodiments, a non-planar surface of substrate 110 is patterned (e.g., having patterned steps to form a Fresnel lens, a lenticular lens or a lenticular prism).
Electrode 120 is generally formed of an electrically conductive material. Exemplary electrically conductive materials include electrically conductive metals, electrically conductive alloys, electrically conductive polymers, and electrically conductive metal oxides. Exemplary electrically conductive metals include gold, silver, copper, aluminum, nickel, palladium, platinum, and titanium. Exemplary electrically conductive alloys include stainless steel (e.g., 332 stainless steel, 316 stainless steel), alloys of gold, alloys of silver, alloys of copper, alloys of aluminum, alloys of nickel, alloys of palladium, alloys of platinum, and alloys of titanium. Exemplary electrically conducting polymers include polythiophenes (e.g., doped poly(3,4-ethylenedioxythiophene) (doped PEDOT)), polyanilines (e.g., doped polyanilines), polypyrroles (e.g., doped polypyrroles). Exemplary electrically conducting metal oxides include indium tin oxide, fluorinated tin oxide, tin oxide and zinc oxide. In some embodiments, combinations of electrically conductive materials are used.
In some embodiments, electrode 120 can include a mesh electrode. Examples of mesh electrodes are described in co-pending U.S. Patent Application Publication Nos. 20040187911 and 20060090791.
In some embodiments, a combination of the materials described above can be used to form electrode 120.
Optionally, photovoltaic cell 100 can include a hole blocking layer 130. Hole blocking layer 130 is generally formed of a material that, at the thickness used in photovoltaic cell 100, transports electrons to electrode 120 and substantially blocks the transport of holes to electrode 120. Hole blocking layer 130 can be made from materials different from or the same as the materials used to make hole blocking layer 156. Examples of materials from which hole blocking layer 130 can be formed include LiF, metal oxides (e.g., zinc oxide, titanium oxide), and amines (e.g., primary, secondary, tertiary amines, or polyamines). Examples of amines suitable for use in a hole blocking layer have been described, for example, in co-pending U.S. Application Publication No. 2008-0264488. In some embodiments, hole blocking layer 130 can be formed from the same materials used to prepare hole blocking layer 156 except that layer 130 does not include an n-type semiconductor material (e.g., C61-PCBM).
Without wishing to be bound by theory, it is believed that when photovoltaic cell 100 includes a hole blocking layer made of amines, the hole blocking layer can facilitate the formation of ohmic contact between two neighboring layers (e.g., photoactive layer 140 and electrode 120) without being exposed to UV light, thereby reducing damage to photovoltaic cell 100 resulted from UV exposure.
Typically, hole blocking layer 130 is at least about 1 nm (e.g., at least about 2 nm, at least about 5 nm, at least about 10 nm, at least about 20 nm, at least about 30 nm, or at least about 40 nm) thick and/or at most about 50 nm (e.g., at most about 40 nm, at most about 30 nm, at most about 20 nm, at most about 10 nm, at most about 5 nm, or at most about 2 nm) thick.
In some embodiments, each of photoactive layers 140 and 160 can contain an electron acceptor material (e.g., an organic electron acceptor material) and an electron donor material (e.g., an organic electron donor material).
Examples of electron acceptor materials include fullerenes, inorganic nanoparticles, oxadiazoles, discotic liquid crystals, carbon nanorods, inorganic nanorods, polymers containing moieties capable of accepting electrons or forming stable anions (e.g., polymers containing CN groups or polymers containing CF3 groups), and combinations thereof. In some embodiments, the electron acceptor material is a substituted fullerene (e.g., a PCBM). In some embodiments, a combination of electron acceptor materials can be used in photoactive layer 140 or 160.
Examples of electron donor materials include conjugated polymers, such as polythiophenes, polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, polycyclopentadithiophenes, polysilacyclopentadithiophenes, polycyclopentadithiazoles, polythiazolothiazoles, polythiazoles, polybenzothiadiazoles, poly(thiophene oxide)s, poly(cyclopentadithiophene oxide)s, polythiadiazoloquinoxalines, polybenzoisothiazoles, polybenzothiazoles, polythienothiophenes, poly(thienothiophene oxide)s, polydithienothiophenes, poly(dithienothiophene oxide)s, polytetrahydroisoindoles, polybenzodithiophenes, poly(pyrrolopyrroledione)s, and copolymers thereof. In some embodiments, the electron donor material can be polythiophenes (e.g., poly(3-hexylthiophene)), polycyclopentadithiophenes, and copolymers thereof. In certain embodiments, a combination of electron donor materials can be used in photoactive layer 140 or 160.
Examples of other photoactive polymers suitable for use in photoactive layer 140 or 160 have been described in, e.g., U.S. Pat. Nos. 8,058,550, 7,781,673 and 7,772,485, WO 2011/085004, PCT/US2012/035254, and U.S. Application Publication Nos. 2010-0224252, 2010-0032018, 2008-0121281, 2008-0087324, and 2007-0020526.
In some embodiments, photoactive layer 140 can include the same electron donor and acceptor materials as those in photoactive layer 160. In certain embodiments, photoactive layer 140 can include an electron donor or acceptor material that is different from the electron donor or acceptor material in photoactive layer 160.
Optionally, photovoltaic cell 100 can include a hole carrier layer 170. Hole carrier layer 170 is generally formed of a material that, at the thickness used in photovoltaic cell 100, transports holes to electrode 180 and substantially blocks the transport of electrons to electrode 180. In general, hole carrier layer 170 can be made from a p-type semiconductor material, such as one of the p-type semiconductor materials described above with respect to hole carrier layer 152. In some embodiments, hole carrier layer 170 is formed of a combination of p-type semiconductor materials. In some embodiments, hole carrier layer 170 can have substantially the same characteristics or properties as those of hole carrier layer 152. In some embodiments, hole carrier layer 170 can be made from a p-type semiconductor material different from that used in hole carrier layer 152.
Electrode 180 is generally formed of an electrically conductive material, such as one or more of the electrically conductive materials described above with respect to electrode 120. In some embodiments, electrode 180 is formed of a combination of electrically conductive materials. In certain embodiments, electrode 180 can be formed of a mesh electrode. In some embodiments, each of electrodes 120 and 180 can be formed of a mesh electrode described herein.
Substrate 190 can be identical to or different from substrate 110. In some embodiments, substrate 190 can be formed of one or more suitable polymers, such as the polymers used in substrate 110 described above. Substrate 190 can be placed on top of electrode 180 by a method known in the art (e.g., by attaching to electrode 180 using an adhesive).
In some embodiments, a tandem cell can include more than two subcells (e.g., three, four, five, six, seven, eight, nine, ten, or more subcells). In certain embodiments, some subcells can be electrically interconnected in series and some subcells can be electrically interconnected in parallel.
In general, the methods of preparing each layer (e.g., layers 120-180) in photovoltaic cells described in
In some embodiments, when a layer includes inorganic semiconductor nanoparticles, the liquid-based coating process can be carried out by (1) mixing the nanoparticles with a solvent (e.g., an aqueous solvent or an anhydrous alcohol) to form a dispersion, (2) coating the dispersion onto a substrate, and (3) drying the coated dispersion. In certain embodiments, a liquid-based coating process for preparing a layer containing inorganic metal oxide nanoparticles can be carried out by (1) dispersing a precursor (e.g., a titanium salt) in a suitable solvent (e.g., an anhydrous alcohol) to form a dispersion, (2) coating the dispersion on a substrate, (3) hydrolyzing the dispersion to form an inorganic semiconductor nanoparticles layer (e.g., a titanium oxide nanoparticles layer), and (4) drying the inorganic semiconductor material layer. In certain embodiments, the liquid-based coating process can be carried out by a sol-gel process (e.g., by forming metal oxide nanoparticles as a sol-gel in a dispersion before coating the dispersion on a substrate).
In general, the liquid-based coating process used to prepare a layer containing an organic semiconductor material can be the same as or different from that used to prepare a layer containing an inorganic semiconductor material. In some embodiments, to prepare a layer that includes an organic semiconductor material, the liquid-based coating process can be carried out by mixing the organic semiconductor material with a solvent (e.g., an organic solvent) to form a solution or a dispersion, coating the solution or dispersion on a substrate, and drying the coated solution or dispersion.
In some embodiments, photovoltaic cell 100 can be prepared by a method that includes (1) applying a composition (e.g., a solution or a dispersion) containing an n-type semiconductor material, a polyamine, and a cross-linking agent on a substrate (e.g., substrate 110) to form a layer supported by the substrate; and (2) heating the layer to cross-link at least some molecules of the polyamine, thereby forming a first hole blocking layer (e.g., layer 156). In such embodiments, the method can further include disposing a first electrode (e.g., electrode 120), a first photoactive layer (e.g., layer 140), and a first hole carrier layer (e.g., layer 152) sequentially onto the substrate (e.g., substrate 110) prior to applying the composition to the substrate. In addition, the method can further include disposing a second photoactive layer (e.g., layer 160) and a second electrode (e.g., electrode 180) sequentially onto the first hole blocking layer (e.g., layer 156). In some embodiments, the method can further include disposing a second hole blocking layer (e.g., layer 130) on the first electrode (e.g., electrode 120) prior to disposing the first photoactive layer (e.g., layer 140). In some embodiments, the method can further include disposing a second hole carrier layer (e.g., layer 170) on the second photoactive layer (e.g., layer 160) prior to disposing the second electrode (e.g., electrode 180). In some embodiments, each disposing step described above can be carried out via a liquid-based coating process.
In some embodiments, the tandem photovoltaic cell described in
While certain embodiments have been disclosed, other embodiments are also possible.
In some embodiments, photovoltaic cell 100 includes a cathode as a bottom electrode and an anode as a top electrode. In some embodiments, photovoltaic cell 100 can include an anode as a bottom electrode and a cathode as a top electrode.
In some embodiments, photovoltaic cell 100 can include the layers shown in
In some embodiments, one of substrates 110 and 190 can be transparent. In other embodiments, both of substrates 110 and 190 can be transparent. In some embodiments, multiple photovoltaic cells can be electrically connected to form a photovoltaic system. As an example,
In some embodiments, recombination material 150 can be used in tandem photovoltaic cells other than that described in
While organic tandem photovoltaic cells have been described, other photovoltaic cells can also incorporate recombination material 150 described herein. Examples of such tandem photovoltaic cells include those in which one or more subcells are dye sensitized photovoltaic cells and/or inorganic photoactive cells with a photoactive material formed of amorphous silicon, cadmium selenide, cadmium telluride, copper indium selenide, and copper indium gallium selenide.
While photovoltaic cells have been described above, in some embodiments, recombination material 150 described herein can be used in other devices and systems. For example, recombination material 150 can be used in suitable organic semiconductive devices, such as field effect transistors, photodetectors (e.g., IR detectors), photovoltaic detectors, imaging devices (e.g., RGB imaging devices for cameras or medical imaging systems), light emitting diodes (LEDs) (e.g., organic LEDs (OLEDs) or IR or near IR LEDs), lasing devices, conversion layers (e.g., layers that convert visible emission into IR emission), amplifiers and emitters for telecommunication (e.g., dopants for fibers), storage elements (e.g., holographic storage elements), and electrochromic devices (e.g., electrochromic displays).
The contents of all publications cited herein (e.g., patents, patent application publications, and articles) are hereby incorporated by reference in their entirety.
The following examples are illustrative and not intended to be limiting.
Two sets of tandem photovoltaic cells were prepared using the procedures described below.
The first set of four tandem photovoltaic cells were prepared as follows: A transparent conducting oxide (TCO) coated plastic substrate was patterned of to form bottom electrodes and then sonicated for 5 minutes in isopropanol. A thin hole blocking layer is coated on the cleaned substrate using either 1 wt % sol-gel TiO2 (titanium tetrabutoxide solution in n-butanol) or 0.5 wt % polyethylenimine (PEI) and 0.5 wt % glycerol diglycidyl ether DEG (1:1 weight ratio in butanol). The typical thickness of the hole blocking layer was about 10 nm. The substrate thus formed was annealed at 100° C. for 2 minutes. A first photoactive layer including a poly(pyrrolopyrroledione) copolymer (available from Ciba Specialty Chemicals, Basel, Switzerland; referred to hereinafter as “Ciba”) and C61-PCBM in 1:2 weight ratio was deposited on the hole blocking layer and its thickness was controlled to achieve a light absorbance of about 0.4 to 0.5. A 100 nm thick hole carrier layer containing a HIL thiophene polymer (Air Products and Chemicals, Inc., Allentown, Pa.) was deposited on the first photoactive layer using blade coating technique and dried under ambient conditions for a few minutes. A 30 nm thick of a hole blocking layer was formed by applying a solution containing 1 wt % C61-PCBM, 0.5 wt % PEI, and 0.5 wt % DEG in 1/9 butanol/dichloroethylene on top of the hole carrier layer. This hole blocking layer was cross-linked by annealing at 140° C. for 10 minutes. A second photoactive layer was then formed by applying a solution containing 1:1 P3HT/PCBM in o-dichlorobenzene on top of the cross-linked hole blocking layer, which was followed by deposition of 50 nm another hole carrier layer of containing the HIL thiophene polymer mentioned above. A double junction tandem cell (i.e., having two subcells) was then formed by evaporation of a silver layer (80 nm) on the hole carrier layer as a top electrode.
A second set of four tandem photovoltaic cells were fabricated using the steps described in the preceding paragraph except that the cross-linked hole blocking layer was replaced with a 20 nm cross-linked hole blocking layer formed from a solution containing 0.5 wt % PEI and 0.5 wt % DEG in n-butanol. The second set of tandem photovoltaic cells were used as a control.
The performance of the tandem photovoltaic cells thus formed was measured using a solar simulator under AM 1.5 conditions. The results are summarized in Table 1.
As shown in Table 1, the first set of tandem cells (which included an interconnecting hole blocking layer containing C61-PCBM) exhibited open circuit Voc of over 1.0 V, which was generally equal to the sum of the voltages of the two subcells (i.e., about 0.6 V for the subcell containing Ciba and about 0.54 V for the subcell containing P3HT). On the other hand, the second set of tandem photovoltaic cells (which included an interconnecting hole blocking layer without C61-PCBM) exhibited Voc of less than 0.5 less than the Voc of each subcell. In addition, the first set of tandem cells exhibited significantly higher efficiencies than the second set of tandem cells.
A third set of seven tandem photovoltaic cells were made in the same manner as the first set of tandem photovoltaic cells described in Example 1 except that the first photoactive layer contained a polybenzodithiophene copolymer (available from Polyera Corporation, Skokie, Ill.; referred to hereinafter as “OPV6”) and C61-PCBM in 1:2 weight ratio and the second photoactive layer contained a polythiazolothiazole copolymer KP143 (available from Konarka Technologies, Inc., Lowell, Mass.) and C61-PCBM in 1:2 weight ratio.
The performance of the third set of tandem photovoltaic cells was measured using a solar simulator under AM 1.5 conditions. The results are summarized in Table 2 below.
As shown in Table 2, all seven tandem photovoltaic cells exhibited high Voc and efficiencies. In particular, each of the seven tandem photovoltaic cells exhibited Voc that was generally equal to the sum of the Voc values of the two subcells (i.e., about 0.66 V for the subcell containing OPV6 and about 0.78 V for the subcell containing KP143) in the tandem cells.
A fourth set of tandem photovoltaic cells containing two subcells, three subcells, four subcells, and five subcells were prepared as follows:
The tandem cells containing two subcells were prepared in the same manner as the first set of tandem cells described in Example 1 except that the first photoactive layer was formed by using a 1 wt % solution of OPV6 and C61-PCBM in a 1:2 weight ratio in o-dichlorobenzene (ODCB) at a blade speed of 5 mm/sec at 65° C. and the second photoactive layer was formed by using a 1 wt % solution of OPV6 and C61-PCBM in a 1:2 weight ratio in ODCB at a blade speed of 7.5 mm/sec at 65° C.
The tandem cells containing three subcells were prepared in the same manner as those described in the preceding paragraph except that, prior to forming a silver top electrode, a cross-linked hole blocking layer, a third photoactive layer, and a hole carrier layer were sequentially formed. The cross-linked hole blocking layer and the hole carrier layer were formed in the same manner as those in the first set of tandem cells described in Example 1. The third photoactive layer was formed by using a 1 wt % solution of OPV6 and C61-PCBM in a 1:2 weight ratio in ODCB at a blade speed of 10 mm/sec at 65° C.
The tandem cells containing four subcells were prepared in the same manner as those described in the preceding paragraph except that, prior to forming a silver top electrode, a cross-linked hole blocking layer, a fourth photoactive layer, and a hole carrier layer were sequentially formed. The cross-linked hole blocking layer and the hole carrier layer were formed in the same manner as those in the first set of tandem cells described in Example 1. The fourth photoactive layer was formed by using a 1 wt % solution of OPV6 and C61-PCBM in a 1:2 weight ratio in ODCB at a blade speed of 15 mm/sec at 65° C.
The tandem cells containing five subcells were prepared in the same manner as those described in the preceding paragraph except that, prior to forming a silver top electrode, a cross-linked hole blocking layer, a fifth photoactive layer, and a hole carrier layer were sequentially formed. The cross-linked hole blocking layer and the hole carrier layer were formed in the same manner as those in the first set of tandem cells described in Example 1. The fifth photoactive layer was formed by using a 1 wt % solution of OPV6 and C61-PCBM in a 1:2 weight ratio in ODCB at a blade speed of 30 mm/sec at 65° C.
The performance of the photovoltaic cells formed above was measured using a solar simulator under AM 1.5 conditions. The results are summarized in Table 3. The values listed in Table 3 are average results based on measurements from 5 cells.
As shown in Table 3, the tandem photovoltaic cells containing two, three, four, and five subcells formed above exhibited Voc values that were generally equal to the sum of Voc of the subcells (i.e., 0.65 V for each subcell), respectively.
A set of tandem photovoltaic cells made in the same manner as the first set of tandem photovoltaic cells described in Example 1 were packaged using a proprietary plastic packaging techniques developed by Konarka Technologies, Inc. The packaged cells were tested using accelerated ageing processes under light soaking conditions (using AM 1.5 conditions) and damp heat ageing conditions (65° C. and 85% relative humidity).
The results of the above tests are shown in
Eight tandem photovoltaic cells were made in the same manner as the first set of tandem photovoltaic cells described in Example 1 except that tandem cells (1)-(4) included an interconnecting hole blocking layer containing C61-PCBM/PEI/DEG and having a thickness of 15 nm and tandem cells (5)-(8) included an interconnecting hole blocking layer containing C61-PCBM/PEI/DEG and having a thickness of 60 nm. In each of these tandem cells, the first photoactive layer contained OPV6/C61-PCBM and the second photoactive layer contained P3HT/C61-PCBM. The cells were packaged using proprietary plastic packaging techniques developed by Konarka Technologies, Inc. The packaged cells were tested under damp heat ageing conditions (65° C. and 85% relative humidity) for 120 hours. The results are summarized in Table 4.
As shown in Table 4, tandem cells (1)-(4) (which contained an interconnecting hole blocking-layer having a thickness of 15 nm) exhibited significant reduction in Voc, Jsc, and fill factor after the above damp heat ageing process. By contrast, tandem cells (5)-(8) (which contained an interconnecting hole blocking layer having a thickness of 60 nm) essentially maintained the same Voc, Jsc, and fill factor after the above damp heat ageing process.
A tandem photovoltaic module was prepared in a manner similar to the tandem cells prepared in Example 1 in a continuous roll-to-roll process except that the photovoltaic module contained 10 serially interconnected tandem cells, each of which included two subcells. All layers except the silver top electrode were deposited using procedures described in Example 1. A printed silver layer was deposited as a top electrode using a nanosilver based ink. All of the adjacent tandem cells were serially interconnected on the roll-to-roll coater.
The results showed that the tandem photovoltaic module thus formed exhibited a Voc of 10.55 V, a Jsc of 3.13 mA/cm2, a fill factor of 55.6%, and an efficiency of 1.84%. In particular, the Voc of the tandem photovoltaic module is generally equal to the sum of the Voc of each tandem cell (i.e., about 1.1 V), which suggested that the 10 tandem cells were interconnected in series with minimal voltage loss.
Other embodiments are within the scope of the following claims.
This application is a continuation of and claims benefit of co-pending international patent application PCT/US2012/036508, filed May 18, 2012, and claims the benefit of U.S. Provisional Application Ser. No. 61/483,825, filed May 9, 2011, under 35 U.S.C. §119(e); the contents of both applications are hereby incorporated by reference.
| Number | Date | Country | |
|---|---|---|---|
| 61483825 | May 2011 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/US2012/036508 | May 2012 | US |
| Child | 14050814 | US |
