# Patent

## Title
Organic photovoltaic cells

## Abstract

Organic photovoltaic cells, as well as related components, photovoltaic systems, and methods, are disclosed.

## Background
CROSS REFERENCE TO RELATED APPLICATION
Pursuant to 35 U.S.C. §119(e), this application claims priority to U.S. Provisional Application Ser. No. 60/926,459, filed Apr. 27, 2007, the contents of which are hereby incorporated by reference.


TECHNICAL FIELD
This disclosure relates to organic photovoltaic cells, as well as related components, photovoltaic systems, and methods.
BACKGROUND
Photovoltaic cells are commonly used to transfer energy in the form of light into energy in the form of electricity. A typical photovoltaic cell includes a photoactive material disposed between two electrodes. Generally, light passes through one or both of the electrodes to interact with the photoactive material. As a result, the ability of one or both of the electrodes to transmit light (e.g., light at one or more wavelengths absorbed by a photoactive material) can limit the overall efficiency of a photovoltaic cell. In many photovoltaic cells, a film of semiconductive material (e.g., indium tin oxide) is used to form the electrode(s) through which light passes because, although the semiconductive material can have a lower electrical conductivity than electrically conductive materials, the semiconductive material can transmit more light than many electrically conductive materials.
SUMMARY
This disclosure relates to organic photovoltaic cells, as well as related components, photovoltaic systems, and methods.
In one aspect, this disclosure features an article that includes first and second electrodes, a photoactive layer between the first and second electrodes, and a second layer between the first electrode and the photoactive layer. The second layer includes a compound selected from the group consisting of nitrogen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds, and combinations thereof. The article is configured as a photovoltaic cell.
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 third layer between the first and second electrodes. The third layer includes a compound selected from the group consisting of nitrogen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds, and combinations thereof. The system is configured as a photovoltaic system.
Embodiments can include one or more of the following features.
In some embodiments, the second or third layer is a hole blocking layer.
In some embodiments, the compound is a nitrogen-containing compound. In certain embodiments, the nitrogen-containing compound includes at least one amino group, which can include a primary amino group, a secondary amino group, or a tertiary amino group. For example, the amino group can include NH2 or N(CH3)2.
In some embodiments, the compound can further include an alkoxylsilyl group, a chlorosilyl group, a carboxylic acid group, a carbonyl chloride group, a phosphonic acid group, a phosphoryl chloride group, or a thiol group.
In some embodiments, the compound can be of the formula R1—N(R2R3), in which each of R1, R2, and R3, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl; or R1 and R2, R2 and R3, or R1 and R3, together with the nitrogen atom to which they are attached, are heteroaryl or C3-C20 heterocycloalkyl. In certain embodiments, R1 is C1-C20 alkyl substituted with Si(OR)3 or NH(R), or aryl substituted with COOH or SH; in which each R, independently, is C1-C20 alkyl. For example, the compound can be 3-(2-aminoethyl)aminopropyl trimethoxy silane, (3-trimethoxysilylpropyl)-diethylenetriamine, 3-aminopropyl-trimethoxysilane, 3-(N,N-dimethylamino)propyl trimethoxysilane, 4-dimethylaminobenzoic acid, 4-aminobenzoic acid, or 4-aminothiophenol.
In some embodiments, at least some molecules of the compound are cross-linked.
In some embodiments, at least some molecules of the compound are adsorbed to a surface of the first electrode.
In some embodiments, the compound is a polymer, such as a polyamine (e.g., a polyethylenimine). In some embodiments, at least some molecules of the polymer are cross-linked by a cross-linking agent. For example, the cross-linking agent can include an epoxy-containing compound (e.g., glycerol propoxylate triglycidyl ether or glycerol diglycidyl ether).
In some embodiments, the second or third layer has a thickness of at most about 50 nm (e.g., at most about 30 nm or at most about 10 nm).
In some embodiments, the photoactive layer includes an electron donor material and an electron acceptor material.
In some embodiments, the electron donor material includes a polymer. The polymer can be selected from the group consisting of polythiophenes, polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, polycyclopentadithiophenes, polysilacyclopentadithiophenes, polycyclopentadithiazoles, polythiazolothiazoles, polythiazoles, polybenzothiadiazoles, poly(thiophene oxide)s, poly(cyclopentadithiophene oxide)s, polythiadiazoloquinoxaline, polybenzoisothiazole, polybenzothiazole, polythienothiophene, poly(thienothiophene oxide), polydithienothiophene, poly(dithienothiophene oxide)s, polytetrahydroisoindoles, and copolymers thereof. For example, the electron donor material can include a polymer selected from the group consisting of polythiophenes (e.g., poly(3-hexylthiophene) (P3HT)), polycyclopentadithiophenes (e.g., poly(cyclopentadithiophene-co-benzothiadiazole)), and copolymers thereof.
In some embodiments, the electron acceptor material includes a material selected from the group consisting of fullerenes, inorganic nanoparticles, oxadiazoles, discotic liquid crystals, carbon nanorods, inorganic nanorods, polymers containing CN groups, polymers containing CF3 groups, and combinations thereof. For example, the electron acceptor material can include a substituted fullerene (e.g., C61-phenyl-butyric acid methyl ester (C61-PCBM) or C71-phenyl-butyric acid methyl ester (C71-PCBM)).
In some embodiments, the article further includes a hole carrier layer between the second electrode and the photoactive layer. The hole carrier layer can include a polymer, which can be selected from the group consisting of polythiophenes (e.g., poly(3,4-ethylene dioxythiophene) (PEDOT)), polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, and copolymers thereof.
In some embodiments, the article further includes a hole blocking layer between the second layer and the first electrode. The hole blocking layer can include a material selected from the group consisting of LiF, metal oxides and combinations thereof.
In some embodiments, the first photoactive layer has a first band gap and the second photoactive layer has a second band gap different from the first band gap.
In some embodiments, the system further includes a recombination layer between the first and second photoactive layers. The recombination layer can include a p-type semiconductor material and an n-type semiconductor material. In certain embodiments, the p-type and n-type semiconductor materials are blended into one layer.
In some embodiments, the recombination layer includes two layers, one layer containing the p-type semiconductor material and the other layer containing the n-type semiconductor material. In certain embodiments, the layer containing the n-type semiconductor material is between the first photoactive layer and the layer containing the p-type semiconductor material. The n-type semiconductor material can include a metal oxide, such as an oxide selected from the group consisting of titanium oxides, zinc oxides, tungsten oxides, molybdenum oxides, and combinations thereof. In certain embodiments, the system can further include a fourth layer between the first photoactive layer and the layer containing the n-type semiconductor material, in which the fourth layer includes a second compound selected from the group consisting of nitrogen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds, and combinations thereof.
In some embodiments, the recombination layer includes two layers, one layer containing a p-type semiconductor material and the other layer containing a second compound selected from the group consisting of nitrogen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds, and combinations thereof. In certain embodiments, the layer containing the second compound can be disposed between the first photoactive layer and the layer containing the p-type semiconductor material.
In certain embodiments, the first photoactive layer can be between the first electrode and the recombination layer and/or the third layer can be between the second photoactive layer and the second electrode. In such embodiments, the system can further include a hole carrier layer between the first photoactive layer and the first electrode and/or a hole blocking layer between the third layer and the second electrode.
In some embodiments, the system includes a tandem photovoltaic cell.
Embodiments can provide one or more of the following advantages.
In some embodiments, the compounds described above can form ohmic contact with the photoactive layer and the electrode. Thus, when these compounds are used as a hole blocking material, they allow use of an electrode (e.g., indium tin oxide, a high work function metal such as silver or gold, or a low work function metal oxide such as titanium oxide) that does not form ohmic contact with the photoactive layer by itself. In particular, when such a hole blocking material is used in combination with titanium oxide, titanium oxide does not need to be exposed to UV light to establish ohmic contact with the photoactive layer, thereby reducing damages resulted from UV light exposure.
The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features and advantages of the invention will be apparent from the description, drawings, and claims.



DESCRIPTION OF DRAWINGS
FIG. 1 is a cross-sectional view of an embodiment of a photovoltaic cell.
FIG. 2 is a cross-sectional view of an embodiment of a tandem photovoltaic cell.
FIG. 3 is a schematic of a system containing multiple photovoltaic cells electrically connected in series.
FIG. 4 is a schematic of a system containing multiple photovoltaic cells electrically connected in parallel.



Like reference symbols in the various drawings indicate like elements.
DETAILED DESCRIPTION
FIG. 1 shows a cross-sectional view of a photovoltaic cell 100 that includes a substrate 110, an electrode 120, a hole carrier layer 130, a photoactive layer 140 (e.g., containing an electron acceptor material and an electron donor material), an intermediate layer 150, an electrode 160, and a substrate 170.
In general, during use, light can impinge on the surface of substrate 110, and pass through substrate 110, electrode 120, and hole carrier layer 130. The light then interacts with photoactive layer 140, causing electrons to be transferred from the electron donor material (e.g., a P3HT) to the electron acceptor material (e.g., a PCBM). The electron acceptor material then transmits the electrons through intermediate layer 150 to electrode 160, and the electron donor material transfers holes through hole carrier layer 130 to electrode 120. Electrodes 160 and 120 are in electrical connection via an external load so that electrons pass from electrode 160, through the load, and to electrode 120.
Intermediate layer 150, at the thickness used in photovoltaic cell 100, can generally serve as an electron injection layer (e.g., to facilitate electron transfer to electrode 160) and/or a hole blocking layer (e.g., to substantially block the transport of holes to electrode 160). In some embodiments, intermediate layer 150 includes an electron donating compound, such as a nitrogen-containing compound, a phosphorus-containing compound, and/or a sulfur-containing compound. The electron donating compound can be a small molecule compound or a polymer. A “small molecule compound” mentioned herein refers to a compound with a molecular weight of at most about 1,000 Daltons (e.g., at most about 500 Daltons or at most about 250 Daltons). A “polymer” mentioned herein refers to a compound with a weight average molecule weight of at least about 1,000 Daltons (e.g., at least about 10,000 Daltons, at least about 100,000 Daltons, or at least about 1,000,000 Daltons).
In some embodiments, the electron donating compound includes a nitrogen-containing compound, such as an amine compound. In certain embodiments, the amine compound can contain at least one amino group, such as a primary amino group (e.g., NH2), a secondary amino group (e.g., NH(CH3)), or a tertiary amino group (e.g., N(CH3)2). In some embodiments, the amine compound can further include an alkoxylsilyl group, a chlorosilyl group, a carboxylic acid group, a carbonyl chloride group, a phosphonic acid group, a phosphoryl chloride group, or a thiol group. In certain embodiments, the amine compound can include a cyclic moiety that contains a ring nitrogen atom, such as a pyridyl group, a piperidinyl group, a pyrrolyl group, a pyrrolidinyl group, a pyrimidinyl group, an imidazolyl group, or a thiazolyl group.
In some embodiments, the amine compound is of the formula R1—N(R2R3), in which each of R1, R2, and R3, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl; or R1 and R2, R2 and R3, or R1 and R3, together with the nitrogen atom to which they are attached, are heteroaryl or C3-C20 heterocycloalkyl. For example, R1 can be C1-C20 alkyl substituted with Si(OR)3 or NH(R), or aryl substituted with COOH or SH, in which each R, independently, is C1-C20 alkyl.
An alkyl can be saturated or unsaturated and branch or straight chained. A C1-C20 alkyl contains 1 to 20 carbon atoms (e.g., one, two, three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Examples of alkyl moieties include —CH3, —CH2—, —CH2═CH2—, —CH2—CH═CH2, and branched —C3H7. An alkoxy can be branch or straight chained and saturated or unsaturated. An C1-C20 alkoxy contains an oxygen radical and 1 to 20 carbon atoms (e.g., one, two, three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Examples of alkoxy moieties include —OCH3 and —OCH═CH—CH3. A cycloalkyl can be either saturated or unsaturated. A C3-C20 cycloalkyl contains 3 to 20 carbon atoms (e.g., three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Examples of cycloalkyl moieties include cyclohexyl and cyclohexen-3-yl. A heterocycloalkyl can also be either saturated or unsaturated. A C3-C20 heterocycloalkyl contains at least one ring heteroatom (e.g., O, N, and S) and 3 to 20 carbon atoms (e.g., three, four, five, six, seven, eight, nine, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Examples of heterocycloalkyl moieties include 4-tetrahydropyranyl and 4-pyranyl. An aryl can contain one or more aromatic rings. Examples of aryl moieties include phenyl, phenylene, naphthyl, naphthylene, pyrenyl, fluorenyl, anthryl, and phenanthryl. A heteroaryl can contain one or more aromatic rings, at least one of which contains at least one ring heteroatom (e.g., O, N, and S). Examples of heteroaryl moieties include furyl, furylene, pyrrolyl, thienyl, oxazolyl, imidazolyl, thiazolyl, pyridyl, pyrimidinyl, quinazolinyl, quinolyl, isoquinolyl, and indolyl.
Alkyl, alkoxy, cycloalkyl, heterocycloalkyl, aryl, and heteroaryl mentioned herein include both substituted and unsubstituted moieties, unless specified otherwise. Examples of substituents on cycloalkyl, heterocycloalkyl, aryl, and heteroaryl include C1-C20 alkyl, C3-C20 cycloalkyl, C1-C20 alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, amino, C1-C10 alkylamino, C1-C20 dialkylamino, arylamino, diarylamino, hydroxyl, halogen, thio, C1-C10 alkylthio, arylthio, C1-C10 alkylsulfonyl, arylsulfonyl, cyano, nitro, acyl, acyloxy, carboxyl, and carboxylic ester. Examples of substituents on alkyl and alkoxy include all of the above-recited substituents except C1-C20 alkyl. Cycloalkyl, heterocycloalkyl, aryl, and heteroaryl also include fused groups.
Exemplary amine compounds are shown below:




In some embodiments, at least some molecules of the amine compound are cross-linked. For example, when the amine compound contains an alkoxysilyl group, at least some molecules of the amine compound can be cross-linked with each other via reactions between the alkoxysilyl groups to form cross-linked polysiloxane molecules. Without wishing to be bound by theory, it is believed that intermediate layer 150 containing cross-linked molecules has improved adhesion with its neighboring layer (e.g., electrode 160).
In some embodiments, at least some molecules of the amine compound are adsorbed to a surface of its neighboring layer (e.g., electrode 160). For example, the adsorption can occur via a chemical reaction between a group on the molecules (e.g., an alkoxysilyl group or a carboxylic acid group) with a group (e.g., an hydroxyl group) on the surface of electrode 160 (e.g., an indium tin oxide electrode or a TiO2-coated indium tin oxide electrode). Without wishing to be bound by theory, it is believed that this adsorption can improve the adhesion between intermediate layer 150 and its neighboring layer.
In some embodiments, the electron donating compound includes a phosphorus-containing compound. In certain embodiments, the phosphorus-containing compound can further include an alkoxylsilyl group, a chlorosilyl group, a carboxylic acid group, a carbonyl chloride group, a phosphonic acid group, a phosphoryl chloride group, or a thiol group. In some embodiments, the phosphorus-containing compound is of the formula R1—P(R2R3) or O═P(R1R2R3), in which each of R1, R2, and R3, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl; or R1 and R2, R2 and R3, or R1 and R3, together with the phosphorous atom to which they are attached, are heteroaryl or C3-C20 heterocycloalkyl. For example, each of R1, R2, and R3 can be C1-C20 alkyl (e.g., butyl) or aryl (e.g., phenyl). Exemplary phosphorus-containing compounds include trialkylphosphines (e.g., tributylphosphine), triarylphosphines (e.g., triphenylphosphine), and phosphine oxides (e.g., tributylphosphine oxide or triphenylphosphine oxide).
In some embodiments, the electron donating compound includes a sulfur-containing compound. In certain embodiments, the sulfur-containing compound can further include an alkoxylsilyl group, a chlorosilyl group, a carboxylic acid group, a carbonyl chloride group, a phosphonic acid group, a phosphoryl chloride group, or a thiol group. In certain embodiments, the sulfur-containing compound can include a cyclic moiety that contains a ring sulfur atom, such as a thienyl group, a tetrahydrothienyl group, or a thiazolyl group. In some embodiments, the sulfur-containing compound is of the formula R1—S—R2, in which each of R1 and R2, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl; or R1 and R2, together with the sulfur atom to which they are attached, are heteroaryl or C3-C20 heterocycloalkyl. Exemplary sulfur-containing compounds include tetrathiafulvalene (i.e.,




and substituted tetrathiafulvalene (e.g.,





In some embodiments, at least some of the molecules of the phosphorous-containing compound or the sulfur-containing compound can be cross-linked or adsorbed to a surface of its neighboring layer in the same manner as that described with respect to the amine compound.
In some embodiments, the electron donating compound includes a polymer. An exemplary polymer is a polyamine (e.g., a polyethylenimine). 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. In certain embodiments, at least some of the molecules of the polymeric electron donating compound can be cross-linked via a cross-linking agent. Exemplary cross-linking agents include epoxy-containing compounds, such as glycerol propoxylate triglycidyl ether and glycerol diglycidyl ether. In some embodiments, at least some of the molecules of the polymeric electron donating compound can be adsorbed to a surface in the same manner as that described with respect the amine compound above.
In some embodiments, intermediate layer 150 has a thickness of at most about 50 nm (e.g., at most about 30 nm or at most about 10 nm) or at least about 1 nm (e.g., at least about 2 nm or at least about 5 nm. Without wishing to be bound by theory, it is believed that intermediate layer 150 having a suitable thickness facilitates electron transfer (e.g., through electron tunneling) from photoactive layer 140 to electrode 160. Further, without wishing to be bound by theory, it is believed that if intermediate layer 150 is too thick, its resistance would be too high and would hinder electron transfer, and if intermediate layer 150 is too thin, it would not form a desired ohmic contact with photoactive layer 140 and electrode 160.
Intermediate layer 150 can generally be prepared by any suitable methods. Examples of such methods include 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. In some embodiments, intermediate layer 150 can be prepared by mixing an electron donating compound (e.g., an amine compound) with an organic solvent (e.g., an alcohol) to form a solution, coating the solution on an electrode, and drying the coated solution.
Without wishing to be bound by theory, it is believed that the electron donating compound (e.g., an amine compound) in intermediate layer 150 facilitates formation of ohmic contact between photoactive layer 140 and electrode 160. Thus, such an intermediate layer allows use of an electrode or a layer (e.g., indium tin oxide, a high work function metal such as silver or gold, or a low work function metal oxide such as titanium oxide) that does not form ohmic contact with the photoactive layer by itself. For example, a conventional photovoltaic cell containing a hole blocking layer made of metal oxide (e.g., zinc oxide or titanium oxide) typically needs to be exposed to UV light to form ohmic contact between the metal oxide and photoactive layer 140. However, when such a hole blocking layer is used in combination with intermediate layer 150, intermediate layer 150 facilitates the formation of ohmic contact between the metal oxide and photoactive layer 140 without UV light exposure, thereby reducing damage to photovoltaic cell 100 resulted from such exposure.
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 5,00 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, 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, 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., 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 commonly owned co-pending U.S. Patent Application Publication Nos. 20040187911 and 20060090791, the contents of which are hereby incorporated by reference.
Hole carrier layer 130 is generally formed of a material that, at the thickness used in photovoltaic cell 100, transports holes to electrode 120 and substantially blocks the transport of electrons to electrode 120. Examples of materials from which layer 130 can be formed include polythiophenes (e.g., PEDOT), polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, and copolymers thereof. Examples of commercially available polymers that can be used in layer 130 include the Air Products® HIL family of thiophene polymers and H.C. Starck Baytron® family of thiophene polymers. In some embodiments, layer 130 can also include a dopant for the polymer. For example, the dopant can include poly(styrene-sulfonate)s, polystyrene sulfonic acids, or sulfonated tetrafluorethylenes. In some embodiments, hole carrier layer 130 can include combinations of hole carrier materials.
In general, the thickness of hole carrier layer 130 (i.e., the distance between the surface of hole carrier layer 130 in contact with photoactive layer 140 and the surface of electrode 120 in contact with hole carrier layer 130) can be varied as desired. Typically, the thickness of hole carrier layer 130 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 130 is from about 0.01 micron to about 0.5 micron.
In some embodiments, photoactive layer 140 contains 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.
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, 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.
In some embodiments, the electron donor materials or the electron acceptor materials can include a polymer having a first comonomer repeat unit and a second comonomer repeat unit different from the first comonomer repeat unit. The first comonomer repeat unit can include a cyclopentadithiophene moiety, a silacyclopentadithiophene moiety, a cyclopentadithiazole moiety, a thiazolothiazole moiety, a thiazole moiety, a benzothiadiazole moiety, a thiophene oxide moiety, a cyclopentadithiophene oxide moiety, a polythiadiazoloquinoxaline moiety, a benzoisothiazole moiety, a benzothiazole moiety, a thienothiophene moiety, a thienothiophene oxide moiety, a dithienothiophene moiety, a dithienothiophene oxide moiety, or a tetrahydroisoindoles moiety.
In some embodiments, the first comonomer repeat unit includes a cyclopentadithiophene moiety. In some embodiments, the cyclopentadithiophene moiety is substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C1-C20 heterocycloalkyl, aryl, heteroaryl, halo, CN, OR, C(O)R, C(O)OR, and SO2R; R being H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C1-C20 heterocycloalkyl. For example, the cyclopentadithiophene moiety can be substituted with hexyl, 2-ethylhexyl, or 3,7-dimethyloctyl. In certain embodiments, the cyclopentadithiophene moiety is substituted at 4-position. In some embodiments, the first comonomer repeat unit can include a cyclopentadithiophene moiety of formula (1):




In formula (1), each of R1, R2, R3, or R4, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C1-C20 heterocycloalkyl, aryl, heteroaryl, halo, CN, OR, C(O)R, C(O)OR, or SO2R; R being H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C1-C20 heterocycloalkyl. For example, each of R1 and R2, independently, can be hexyl, 2-ethylhexyl, or 3,7-dimethyloctyl.

The second comonomer repeat unit can include a benzothiadiazole moiety, a thiadiazoloquinoxaline moiety, a cyclopentadithiophene oxide moiety, a benzoisothiazole moiety, a benzothiazole moiety, a thiophene oxide moiety, a thienothiophene moiety, a thienothiophene oxide moiety, a dithienothiophene moiety, a dithienothiophene oxide moiety, a tetrahydroisoindole moiety, a fluorene moiety, a silole moiety, a cyclopentadithiophene moiety, a fluorenone moiety, a thiazole moiety, a selenophene moiety, a thiazolothiazole moiety, a cyclopentadithiazole moiety, a naphthothiadiazole moiety, a thienopyrazine moiety, a silacyclopentadithiophene moiety, an oxazole moiety, an imidazole moiety, a pyrimidine moiety, a benzoxazole moiety, or a benzimidazole moiety. In some embodiments, the second comonomer repeat unit is a 3,4-benzo-1,2,5-thiadiazole moiety.
In some embodiments, the second comonomer repeat unit can include a benzothiadiazole moiety of formula (2), a thiadiazoloquinoxaline moiety of formula (3), a cyclopentadithiophene dioxide moiety of formula (4), a cyclopentadithiophene monoxide moiety of formula (5), a benzoisothiazole moiety of formula (6), a benzothiazole moiety of formula (7), a thiophene dioxide moiety of formula (8), a cyclopentadithiophene dioxide moiety of formula (9), a cyclopentadithiophene tetraoxide moiety of formula (10), a thienothiophene moiety of formula (11), a thienothiophene tetraoxide moiety of formula (12), a dithienothiophene moiety of formula (13), a dithienothiophene dioxide moiety of formula (14), a dithienothiophene tetraoxide moiety of formula (15), a tetrahydroisoindole moiety of formula (16), a thienothiophene dioxide moiety of formula (17), a dithienothiophene dioxide moiety of formula (18), a fluorene moiety of formula (19), a silole moiety of formula (20), a cyclopentadithiophene moiety of formula (21), a fluorenone moiety of formula (22), a thiazole moiety of formula (23), a selenophene moiety of formula (24), a thiazolothiazole moiety of formula (25), a cyclopentadithiazole moiety of formula (26), a naphthothiadiazole moiety of formula (27), a thienopyrazine moiety of formula (28), a silacyclopentadithiophene moiety of formula (29), an oxazole moiety of formula (30), an imidazole moiety of formula (31), a pyrimidine moiety of formula (32), a benzoxazole moiety of formula (33), or a benzimidazole moiety of formula (34):













In the above formulas, each of X and Y, independently, is CH2, O, or S; each of R5 and R6, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, C3-C20 cycloalkyl, C1-C20 heterocycloalkyl, aryl, heteroaryl, halo, CN, OR, C(O)R, C(O)OR, or SO2R, in which R is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C1-C20 heterocycloalkyl; and each of R7 and R8, independently, is H, C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, or C3-C20 heterocycloalkyl. In some embodiments, the second comonomer repeat unit includes a benzothiadiazole moiety of formula (2), in which each of R5 and R6 is H.

The second comonomer repeat unit can include at least three thiophene moieties. In some embodiments, at least one of the thiophene moieties is substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, and C3-C20 heterocycloalkyl. In certain embodiments, the second comonomer repeat unit includes five thiophene moieties.
The polymer can further include a third comonomer repeat unit that contains a thiophene moiety or a fluorene moiety. In some embodiments, the thiophene or fluorene moiety is substituted with at least one substituent selected from the group consisting of C1-C20 alkyl, C1-C20 alkoxy, aryl, heteroaryl, C3-C20 cycloalkyl, and C3-C20 heterocycloalkyl.
In some embodiments, the polymer can be formed by any combination of the first, second, and third comonomer repeat units. In certain embodiments, the polymer can be a homopolymer containing any of the first, second, and third comonomer repeat units.
In some embodiments, the polymer can be







in which n can be an integer greater than 1.

The monomers for preparing the polymers mentioned herein may contain a non-aromatic double bond and one or more asymmetric centers. Thus, they can occur as racemates and racemic mixtures, single enantiomers, individual diastereomers, diastereomeric mixtures, and cis- or trans-isomeric forms. All such isomeric forms are contemplated.
The polymers described above can be prepared by methods known in the art, such as those described in commonly owned co-pending U.S. application Ser. No. 11/601,374, the contents of which are hereby incorporated by reference. For example, a copolymer can be prepared by a cross-coupling reaction between one or more comonomers containing two alkylstannyl groups and one or more comonomers containing two halo groups in the presence of a transition metal catalyst. As another example, a copolymer can be prepared by a cross-coupling reaction between one or more comonomers containing two borate groups and one or more comonomers containing two halo groups in the presence of a transition metal catalyst. The comonomers can be prepared by the methods know in the art, such as those described in U.S. patent application Ser. No. 11/486,536, Coppo et al., Macromolecules 2003, 36, 2705-2711, and Kurt et al., J. Heterocycl. Chem. 1970, 6, 629, the contents of which are hereby incorporated by reference.
Without wishing to be bound by theory, it is believed that an advantage of the polymers described above is that their absorption wavelengths shift toward the red and near IR regions (e.g., 650-800 nm) of the electromagnetic spectrum, which is not accessible by most other conventional polymers. When such a polymer is incorporated into a photovoltaic cell together with a conventional polymer, it enables the cell to absorb the light in this region of the spectrum, thereby increasing the current and efficiency of the cell.
In some embodiments, photoactive layer 140 can contain an inorganic semiconductor material. In some embodiments, the inorganic semiconductor material includes group IV semiconductor materials, group III-V semiconductor materials, group II-VI semiconductor materials, chalcogen semiconductor materials, and semiconductor metal oxides. Examples of group IV semiconductor materials include amorphous silicon, crystalline silicon (e.g., microcrystalline silicon or polycrystalline silicon), and germanium. Examples of group III-V semiconductor materials include gallium arsenide and indium phosphide. Examples of group II-VI semiconductor materials include cadmium selenide and cadmium telluride. Examples of chalcogen semiconductor materials include copper indium selenide (CIS) and copper indium gallium selenide (CIGS). Examples of semiconductor metal oxides include copper oxides, titanium oxides, zinc oxides, tungsten oxides, molybdenum oxides, strontium copper oxides, or strontium titanium oxides. In certain embodiments, the bandgap of the semiconductor can be adjusted via doping. In some embodiments, the inorganic semiconductor material can include inorganic nanoparticles.
Generally, photoactive layer 140 is sufficiently thick to be relatively efficient at absorbing photons impinging thereon to form corresponding electrons and holes, and sufficiently thin to be relatively efficient at transporting the holes and electrons. In certain embodiments, photoactive layer 140 is at least 0.05 micron (e.g., at least about 0.1 micron, at least about 0.2 micron, at least about 0.3 micron) thick and/or at most about one micron (e.g., at most about 0.5 micron, at most about 0.4 micron) thick. In some embodiments, photoactive layer 140 is from about 0.1 micron to about 0.2 micron thick.
Electrode 160 is generally formed of an electrically conductive material, such as one or more of the electrically conductive materials described above. In some embodiments, electrode 160 is formed of a combination of electrically conductive materials. In certain embodiments, electrode 160 can be formed of a mesh electrode.
Optionally, photovoltaic cell 100 can include a hole blocking layer (not shown in FIG. 1) between intermediate layer 150 and electrode 160. The hole blocking layer is generally formed of a material that, at the thickness used in photovoltaic cell 100, transports electrons to electrode 160 and substantially blocks the transport of holes to electrode 160. Examples of materials from which the hole blocking layer can be formed include LiF and metal oxides (e.g., zinc oxide, titanium oxide).
Typically, the hole blocking layer is at least 0.02 micron (e.g., at least about 0.03 micron, at least about 0.04 micron, at least about 0.05 micron) thick and/or at most about 0.5 micron (e.g., at most about 0.4 micron, at most about 0.3 micron, at most about 0.2 micron, at most about 0.1 micron) thick.
Without wishing to be bound by theory, it is believed that when photovoltaic cell 100 includes a hole blocking layer made of metal oxides (such as zinc oxide or titanium oxide), intermediate layer 150 can facilitate the formation of ohmic contact between the metal oxide and photoactive layer 140 without UV light exposure, thereby reducing damage to photovoltaic cell 100 resulted from such exposure.
Substrate 170 can be identical to or different from substrate 110. In some embodiments, substrate 170 can be formed of one or more suitable polymers, such as those described above.
In general, each of hole carrier layer 130, photoactive layer 140, intermediate layer 150, and the optional hole blocking layer described above can be prepared by a liquid-based coating process. 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. Without wishing to bound by theory, it is believed that the liquid-based coating process can be readily used in a continuous manufacturing process, such as a roll-to-roll process, thereby significantly reducing the cost of preparing a photovoltaic cell. Examples of roll-to-roll processes have been described in, for example, commonly-owned co-pending U.S. Application Publication No. 2005-0263179, the contents of which are hereby incorporated by reference.
In some embodiments, when a layer (e.g., layer 130, 140, or 150) includes inorganic semiconductor nanoparticles, the liquid-based coating process can be carried out by (1) mixing the nanoparticles (e.g., CIS or CIGS 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 photoactive layer, (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.
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, when a layer (e.g., layer 130, 140, or 150) 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. For example, an organic photoactive layer can be prepared by mixing an electron donor material (e.g., a P3HT) and an electron acceptor material (e.g., a PCBM) in a suitable solvent (e.g., xylene) to form a dispersion, coating the dispersion onto a substrate, and drying the coated dispersion.
The liquid-based coating process can be carried out at an elevated temperature (e.g., at least about 50° C., at least about 100° C., at least about 200° C., or at least about 300° C.). The temperature can be adjusted depending on various factors, such as the coating process and the coating composition used. For example, when preparing a layer containing inorganic nanoparticles, the nanoparticles can be sintered at a high temperature (e.g., at least about 300° C.) to form interconnected nanoparticles. On the other hand, when a polymeric linking agent (e.g., poly(n-butyl titanate)) is added to the inorganic nanoparticles, the sintering process can be carried out at a lower temperature (e.g., below about 300° C.).
In some embodiments, photovoltaic cell 100 can be prepared as follows: An ITO coated glass substrate can be cleaned by sonicating in an organic solvent (e.g., acetone and/or isopropanol) for a certain amount of time (e.g., 5-15 minutes). The substrate can then be treated with UV/ozone. A thin layer of an amine compound (e.g., 3-(2-aminoethyl)aminopropyl trimethoxy silane) can subsequently be blade-coated from a solution containing this compound in an organic solvent (e.g., an alcohol) at a certain temperature (e.g., 50-80° C.). After the film is dried, a semiconductor blend of a P3HT and a PCBM with a suitable weight ratio (e.g., 1-1.5:1) in an organic solvent (e.g., an aromatic solvent) can be blade-coated at a certain temperature (e.g., 50-80° C.) onto the film and then dried. A layer of PEDOT can be blade-coated on top of the semiconductor blend. The device can then be annealed (e.g., in a glove box) at a suitable temperature (e.g., 150-200° C.) for a certain amount of time (e.g., 3-10 minutes), followed by thermal evaporation of silver as the top metal electrode (e.g., having a thickness of 50-150 nm) to form photovoltaic cell 100.
FIG. 2 shows a tandem photovoltaic cell 200 having two semi-cells 202 and 204. Semi-cell 202 includes an electrode 220, a hole carrier layer 230, a first photoactive layer 240, and a recombination layer 242. Semi-cell 204 includes a recombination layer 242, a second photoactive layer 244, an intermediate layer 250, and an electrode 260. An external load is connected to photovoltaic cell 200 via electrodes 220 and 260. Depending on the production process and the desired device architecture, the current flow in a semi-cell can be reversed by changing the electron/hole conductivity of a certain layer (e.g., changing hole carrier layer 230 to a hole blocking layer). By doing so, a tandem cell can be designed such that the semi-cells in the tandem cells can be electrically interconnected either in series or in parallel.
In general, intermediate layer 250 can be formed of the same materials, or have the same physical characteristics (e.g., the same thickness or electron injection properties), as noted above regarding intermediate layer 150. In some embodiments, intermediate layer 250 can be disposed at locations other than that shown in FIG. 2. For example, when recombination layer 242 includes a layer containing a p-type semiconductor material, intermediate layer 250 can be disposed between the first or second photoactive layer and the layer containing the p-type semiconductor material to facilitate ohmic contact between these layers. In some embodiments, tandem cell 200 can include two or more intermediate layers 250. In certain embodiments, each semi-cell of tandem cell 200 can include an intermediate layer 250.
A recombination layer refers to a layer in a tandem cell where the electrons generated from a first semi-cell recombine with the holes generated from a second semi-cell. Recombination layer 242 typically includes a p-type semiconductor material and an n-type semiconductor material. In general, n-type semiconductor materials selectively transport electrons and p-type semiconductor materials selectively transport holes. As a result, electrons generated from the first semi-cell recombine with holes generated from the second semi-cell at the interface of the n-type and p-type semiconductor materials.
In some embodiments, the p-type semiconductor material includes a polymer and/or a metal oxide. Examples p-type semiconductor polymers include polythiophenes (e.g., poly(3,4-ethylene dioxythiophene) (PEDOT)), polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, polycyclopentadithiophenes, polysilacyclopentadithiophenes, polycyclopentadithiazoles, polythiazolothiazoles, polythiazoles, polybenzothiadiazoles, poly(thiophene oxide)s, poly(cyclopentadithiophene oxide)s, polythiadiazoloquinoxaline, polybenzoisothiazole, polybenzothiazole, polythienothiophene, poly(thienothiophene oxide), polydithienothiophene, poly(dithienothiophene oxide)s, polytetrahydroisoindoles, and copolymers thereof. The metal oxide can be an intrinsic p-type semiconductor (e.g., copper oxides, strontium copper oxides, or strontium titanium oxides) or a metal oxide that forms a p-type semiconductor after doping with a dopant (e.g., p-doped zinc oxides or p-doped titanium oxides). Examples of dopants includes salts or acids of fluoride, chloride, bromide, and iodide. In some embodiments, the metal oxide can be used in the form of nanoparticles.
In some embodiments, the n-type semiconductor material includes a metal oxide, such as a titanium oxide, a zinc oxide, a tungsten oxide, a molybdenum oxide, and a combination thereof. The metal oxide can be used in the form of nanoparticles. In other embodiments, the n-type semiconductor material includes a material selected from the group consisting of fullerenes, inorganic nanoparticles, oxadiazoles, discotic liquid crystals, carbon nanorods, inorganic nanorods, polymers containing CN groups, polymers containing CF3 groups, and combinations thereof.
In some embodiments, the p-type and n-type semiconductor materials are blended into one layer. In certain embodiments, the recombination layer includes two layers, one layer including the p-type semiconductor material and the other layer including the n-type semiconductor material. In such embodiments, recombination layer 242 can also include a layer of mixed n-type and p-type semiconductor material at the interface of the two layers.
In some embodiments, recombination layer 242 includes at least about 30 wt % (e.g., at least about 40 wt % or at least about 50 wt %) and/or at most about 70 wt % (e.g., at most about 60 wt % or at most about 50 wt %) of the p-type semiconductor material. In some embodiments, recombination layer 242 includes at least about 30 wt % (e.g., at least about 40 wt % or at least about 50 wt %) and/or at most about 70 wt % (e.g., at most about 60 wt % or at most about 50 wt %) of the n-type semiconductor material.
Recombination layer 242 generally has a sufficient thickness so that the layers underneath are protected from any solvent applied onto recombination layer 242. In some embodiments, recombination layer 242 can have a thickness at least about 10 nm (e.g., at least about 20 nm, at least about 50 nm, or at least about 100 nm) and/or at most about 500 nm (e.g., at most about 200 nm, at most about 150 nm, or at most about 100 nm).
In general, recombination layer 242 is substantially transparent. For example, at the thickness used in a tandem photovoltaic cell 200, recombination layer 242 can transmit at least about 70% (e.g., at least about 75%, at least about 80%, at least about 85%, or at least about 90%) of incident light at a wavelength or a range of wavelengths (e.g., from about 350 nm to about 1,000 nm) used during operation of the photovoltaic cell.
Recombination layer 242 generally has a sufficiently low surface resistivity. In some embodiments, recombination layer 242 has a resistivity of at most about 1×106 ohm/square (e.g., at most about 5×105 ohm/square, at most about 2×105 ohm/square, or at most about 1×105 ohm/square).
Without wishing to be bound by theory, it is believed that recombination layer 242 can be considered as a common electrode between two semi-cells (e.g., one including electrode 220, hole carrier layer 230, photoactive layer 240, and recombination layer 242, and the other include recombination layer 242, photoactive layer 244, intermediate layer 250, and electrode 260) in photovoltaic cells 200. In some embodiments, recombination layer 242 can include an electrically conductive mesh material, such as those described above. An electrically conductive mesh material can provide a selective contact of the same polarity (either p-type or n-type) to the semi-cells and provide a highly conductive but transparent layer to transport electrons to a load.
In some embodiments, recombination layer 242 can be prepared by applying a blend of an n-type semiconductor material and a p-type semiconductor material on a photoactive layer. For example, an n-type semiconductor and a p-type semiconductor can be first dispersed and/or dissolved in a solvent together to form a dispersion or solution, which can then be coated on a photoactive layer to form a recombination layer.
In some embodiments, recombination layer 242 can include two or more layers with required electronic and optical properties for tandem cell functionality. For example, recombination layer 242 can include a layer that contains an n-type semiconductor material and a layer that contains a p-type semiconductor material. In some embodiments, the layer containing an n-type semiconductor material is disposed between photoactive layer 240 and the layer that contains a p-type semiconductor material. In some embodiments, when the n-type semiconductor material includes a metal oxide (e.g., zinc oxide or titanium oxide), an intermediate layer that includes a nitrogen-containing compound, a phosphorus-containing compound, or a sulfur-containing compound can be disposed between photoactive layer 240 and the layer containing the n-type semiconductor material to facilitate formation of ohmic contact between these two layers. The intermediate layer can be formed of the same material, or having the same characteristics, as intermediate layer 250. In certain embodiments, the layer containing an n-type semiconductor material can be replaced by the just-mentioned intermediate layer. In such embodiments, the intermediate layer can serve both as an electron injection layer and a hole blocking layer. In such embodiments, semi-cell 202 (e.g., including electrode 220, hole carrier layer 230, first photoactive layer 240, and an intermediate layer) can have the layers with the same function arranged in the same order as those in semi-cell 204 (e.g., including a layer containing a p-type semiconductor material that can serve as a hole carrier layer, second photoactive layer 244, intermediate layer 250, and electrode 260).
In some embodiments, a two-layer recombination layer can be prepared by applying a layer of an n-type semiconductor material and a layer of a p-type semiconductor material separately. For example, when titanium oxide nanoparticles are used as an n-type semiconductor material, a layer of titanium oxide nanoparticles can be formed by (1) dispersing a precursor (e.g., a titanium salt) in a solvent (e.g., an anhydrous alcohol) to form a dispersion, (2) coating the dispersion on a photoactive layer, (3) hydrolyzing the dispersion to form a titanium oxide layer, and (4) drying the titanium oxide layer. As another example, when a polymer (e.g., PEDOT) is used a p-type semiconductor, a polymer layer can be formed by first dissolving the polymer in a solvent (e.g., an anhydrous alcohol) to form a solution and then coating the solution on a photoactive layer.
Other components in tandem cell 200 can be identical to the corresponding components described with respect to photovoltaic cell 100. For example, tandem cell 200 can include a hole blocking layer (not shown in FIG. 2) between intermediate layer 250 and electrode 260. This hole block layer can be formed of the same materials, or have the same physical characteristics (e.g., the same thickness or hole blocking properties), as noted above regarding the hole blocking layer in photovoltaic cell 100.
In some embodiments, the semi-cells in a tandem cell are electrically interconnected in series. When connected in series, in general, the layers can be in the order shown in FIG. 2. In certain embodiments, the semi-cells in a tandem cell are electrically interconnected in parallel. When interconnected in parallel, a tandem cell having two semi-cells can include the following layers: a first cathode, a first hole carrier layer, a first photoactive layer, a first hole blocking layer (which can serve as an anode), a second hole blocking layer (which can serve as an anode), a second photoactive layer, a second hole carrier layer, and a second cathode. In such embodiments, the first and second hole blocking layers can be either two separate layers or can be one single layer. In case the conductivity of the first and second hole blocking layer is not sufficient, an additional layer (e.g., an electrically conductive mesh layer) providing the required conductivity may be inserted.
In some embodiments, a tandem cell can include more than two semi-cells (e.g., three, four, five, six, seven, eight, nine, ten or more semi-cells). In certain embodiments, some semi-cells can be electrically interconnected in series and some semi-cells can be electrically interconnected in parallel.
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 also 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 FIG. 1 in a reverse order. In other words, photovoltaic cell 100 can include these layers from the bottom to the top in the following sequence: substrate 170, an electrode 160, an intermediate layer 150, a photoactive layer 140, a hole carrier layer 130, an electrode 120, and a substrate 110.
In some embodiments, multiple photovoltaic cells can be electrically connected to form a photovoltaic system. As an example, FIG. 3 is a schematic of a photovoltaic system 300 having a module 310 containing photovoltaic cells 320. Cells 320 are electrically connected in series, and system 300 is electrically connected to a load 330. As another example, FIG. 4 is a schematic of a photovoltaic system 400 having a module 410 that contains photovoltaic cells 420. Cells 420 are electrically connected in parallel, and system 400 is electrically connected to a load 430. In some embodiments, some (e.g., all) of the photovoltaic cells in a photovoltaic system can have one or more common substrates. In certain embodiments, some photovoltaic cells in a photovoltaic system are electrically connected in series, and some of the photovoltaic cells in the photovoltaic system are electrically connected in parallel.
While photovoltaic cells have been described above, in some embodiments, the intermediate layer described herein can be used in other devices and systems. For example, the intermediate layer 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 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 following examples are illustrative and not intended to be limiting.
Example 1
An ITO coated glass substrate was cleaned by sonicating in acetone and isopropanol, respectively. The substrate was then treated with UV/ozone. A thin layer of 3-(2-aminoethyl)aminopropyl trimethoxy silane (AEAP-TMOS) was then blade coated from a solution in 2-methoxyethanol. The film thus formed was allowed to dry on the hot plate. A semiconductor blend of P3HT and C61-PCBM in o-xylene was blade coated onto the film and then dried. A layer of PEDOT (BAYTRON PH with a 0.2 wt % DYNOL surfactant) was blade coated on top of the semiconductor blend. The device was then annealed in a glove box, followed by thermal evaporation of silver as the top metal electrode (100 nm) to form a photovoltaic cell. Another photovoltaic cell was prepared in a similar manner except that AEAP-TMOS was not used.
The performance of both photovoltaic cells were measured. The results showed that the photovoltaic cell without AEAP-TMOS had Voc of 0.26 V, a Jsc of 8.39 mA/cm2, a fill factor of 0.35, and an efficiency of 0.78%. By contrast, the photovoltaic with AEAP-TMOS had a much better performance. Specifically, it had a Voc of 0.56 V, a Jsc of 11.03 mA/cm2, a fill factor of 0.53, and an efficiency as high as 3.30%
Further, the results showed that the photovoltaic cell with AEAP-TMOS exhibited much higher injection current under positive voltage than the photovoltaic cell without AEAP-TMOS, indicating that AEAP-TMOS possesses effective electron injection capability. The results also showed that the photovoltaic cell with AEAP-TMOS exhibited much lower leakage current under negative voltage than the photovoltaic cell without AEAP-TMOS, indicating that AEAP-TMOS possesses effective hole blocking capability.
Example 2
An ITO coated glass substrate was cleaned by sonicating in isopropanol, respectively. A thin layer of polyethylenimine and glycerol propoxylate triglycidyl ether (GPTGE) was then blade coated from a solution in isopropanol. The film thus formed was allowed to cure on the hot plate. A semiconductor blend of P3HT and C61-PCBM in o-xylene was blade coated onto the film and then dried. A hole injecting layer of PEDOT (BAYTRON PH) was blade coated on top of the semiconductor blend. The device was then annealed in a glove box, followed by thermal evaporation of silver as the top metal electrode to form a photovoltaic cell.
The performance of the photovoltaic cell formed above was measured under AM 1.5 conditions. The results showed that the photovoltaic cell had Voc of 0.57 V, a Jsc of 9.05 mA/cm2, a fill factor of 0.61, and an efficiency of as high as 3.14%.
Other embodiments are in the claims.

## Claims

1. An article, comprising:
first and second electrodes;
a photoactive layer between the first and second electrodes; and
a hole blocking layer between the first electrode and the photoactive layer, the hole blocking layer comprising a polyethylenimine;
wherein the article is configured as a photovoltaic cell.

2. The article of claim 1, wherein the polyethylenimine comprises at least one primary amino group or at least one secondary amino group.

3. The article of claim 1, wherein the polyethylenimine comprises a primary amino group, a secondary amino group, or a tertiary amino group.

4. The article of claim 3, wherein the polyethylenimine comprises NH2 or N(CH3)2.

5. The article of claim 2, wherein the polyethylenimine further comprises an alkoxylsilyl group, a chlorosilyl group, a carboxylic acid group, a carbonyl chloride group, a phosphonic acid group, a phosphoryl chloride group, or a thiol group.

6. The article of claim 1, wherein at least some molecules of the polyethylenimine are cross-linked.

7. The article of claim 1, wherein at least some molecules of the polyethylenimine are adsorbed to a surface of the first electrode.

8. The article of claim 6, wherein at least some molecules of the polyethylenimine are cross-linked by a cross-linking agent.

9. The article of claim 8, wherein the cross-linking agent comprises an epoxy-containing compound.

10. The article of claim 9, wherein the cross-linking agent comprises glycerol propoxylate triglycidyl ether or glycerol diglycidyl ether.

11. The article of claim 1, wherein the hole blocking layer has a thickness of at most about 50 nm.

12. The article of claim 1, wherein the hole blocking layer has a thickness of at most about 30 nm.

13. The article of claim 1, wherein the hole blocking layer has a thickness of at most about 10 nm.

14. The article of claim 1, wherein the photoactive layer comprises an electron donor material and an electron acceptor material.

15. The article of claim 14, wherein the electron donor material comprises a polymer.

16. The article of claim 15, wherein the polymer is selected from the group consisting of polythiophenes, polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, polycyclopentadithiophenes, polysilacyclopentadithiophenes, polycyclopentadithiazoles, polythiazolothiazoles, polythiazoles, polybenzothiadiazoles, poly(thiophene oxide)s, poly(cyclopentadithiophene oxide)s, polythiadiazoloquinoxaline, polybenzoisothiazole, polybenzothiazole, polythienothiophene, poly(thienothiophene oxide), polydithienothiophene, poly(dithienothiophene oxide)s, polytetrahydroisoindoles, and copolymers thereof.

17. The article of claim 16, wherein the electron donor material comprises a polymer selected from the group consisting of polythiophenes, polycyclopentadithiophenes, and copolymers thereof.

18. The article of claim 14, wherein the electron donor material comprises poly(3-hexylthiophene) or poly(cyclopentadithiophene-co-benzothiadiazole).

19. The article of claim 14, wherein the electron acceptor material comprises a material selected from the group consisting of fullerenes, inorganic nanoparticles, oxadiazoles, discotic liquid crystals, carbon nanorods, inorganic nanorods, polymers containing CN groups, polymers containing CF3 groups, and combinations thereof.

20. The article of claim 19, wherein the electron acceptor material comprises a substituted fullerene.

21. The article of claim 20, wherein the substituted fullerene comprises C61-PCBM or C71-PCBM.

22. The article of claim 1, further comprising a hole carrier layer between the second electrode and the photoactive layer.

23. The article of claim 22, wherein the hole carrier layer comprises a polymer.

24. The article of claim 23, wherein the polymer is selected from the group consisting of polythiophenes, polyanilines, polycarbazoles, polyvinylcarbazoles, polyphenylenes, polyphenylvinylenes, polysilanes, polythienylenevinylenes, polyisothianaphthanenes, and copolymers thereof.

25. The article of claim 24, wherein the polymer comprises poly(3,4-ethylene dioxythiophene).

26. The article of claim 1, wherein the first electrode is a cathode.