# Patent

## Title
Low temperature interconnection of nanoparticles

## Abstract

A polymeric linking agent enables the manufacture of photovoltaic cells on flexible substrates, including, for example, polymeric substrates. Photovoltaic cells may be fabricated by a relatively simple continuous manufacturing process, for example, a roll-to-roll process, instead of a batch process.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 10/057,394 filed on Jan. 25, 2002, now U.S. Pat. No. 6,706,963 the entire disclosures of which are herein incorporated by reference. This application also claims the benefits of and priority to U.S. Provisional Patent Application Ser. No. 60/351,691 filed on Jan. 25, 2002, to U.S. Provisional Patent Application Ser. No. 60/368,832 filed on Mar. 29, 2002, and to U.S. Provisional Patent Application Ser. No. 60/400,289 filed on Jul. 31, 2002, all of which are owned by the assignee of the instant application and the disclosures of which are incorporated herein by reference in their entireties.


FIELD OF THE INVENTION
The invention relates generally to the field of photovoltaic devices, and more specifically to chemical structures and methods of interconnecting nanoparticles at low temperatures.
BACKGROUND OF THE INVENTION
Thin film solar cells composed of percolating networks of liquid electrolyte and dye-coated sintered titanium dioxide were developed by Dr. Michael Grätzel and coworkers at the Swiss Federal Institute of Technology. These photovoltaic devices fall within a general class of cells referred to as dye-sensitized solar cells (“DSSCs”). Conventionally, fabrication of DSSCs requires a high temperature sintering process (>about 400° C.) to achieve sufficient interconnectivity between the nanoparticles and enhanced adhesion between the nanoparticles and a transparent substrate. Although the photovoltaic cells of Grätzel are fabricated from relatively inexpensive raw materials, the high temperature sintering technique used to make these cells limits the cell substrate to rigid transparent materials, such as glass, and consequently limits the manufacturing to batch processes and the applications to those tolerant of the rigid structure. Furthermore, the high temperature sintering process increases the cost of manufacturing a photovoltaic cell due to the energy required to perform the sintering.
SUMMARY OF THE INVENTION
The invention in, one embodiment, addresses the deficiencies of the prior art by providing a polymeric linking agent that enables the fabrication of thin film solar cells at relatively low temperatures. This enables the manufacture of such cells on flexible substrates, including, for example, those substrates constructed from somewhat heat sensitive polymeric materials. In addition, the invention provides photovoltaic cells and methods of photovoltaic cell fabrication that facilitate their manufacture by a relatively simple, continuous manufacturing process. For example, a roll-to-roll process can be utilized instead of the batch processes that limited the prior art. More particularly, in one embodiment, the invention provides a method for interconnecting metal oxide nanoparticles in DSSCs, with reduced or no heating, using a polymeric linking agent. By way of example, metal oxide nanoparticles may be interconnected by contacting the nanoparticles with a suitable polymeric linking agent dispersed in a solvent, such as n-butanol, at about room temperature or at elevated temperatures below about 300° C.
In one aspect, therefore, the invention provides a method of interconnecting nanoparticles at low temperature that includes providing a solution having a polymeric linking agent and a solvent and contacting a plurality of metal oxide nanoparticles with the solution at a temperature below about 300° C., where the solution contains the polymeric linking agent in a concentration sufficient to interconnect at least a portion of the plurality of metal oxide nanoparticles. In various embodiments of the method, the temperature is below about 200° C., below about 100° C., or at about room temperature. In one embodiment, the polymeric linking agent includes a long chain macromolecule. The long chain macromolecule may have a backbone structure substantially similar to the chemical structure of the plurality of metal oxide nanoparticles, and one or more reactive groups chemically bonded to the backbone structure. In another embodiment, the plurality of metal oxide nanoparticles has a chemical structure of the form MxOy, where x and y are integers. By way of example, M can include Ti, Zr, W, Nb, Ta, Tb, or Sn.
In one embodiment, the polymeric linking agent is poly(n-butyl titanate). In another embodiment, the solvent of the solution is n-butanol. In various embodiments of the method, the mechanism for interconnecting at least a portion of the plurality of metal oxide nanoparticles is a mechanical or electrical bridge formed by the one or more reactive groups binding to the plurality of metal oxide nanoparticles. The plurality of metal oxide nanoparticles may be disposed, for example, as a thin film on a substrate. In various embodiments of the method, the metal oxide nanoparticles are disposed on the substrate by, for example, dipping the substrate into the solution including the polymeric linking agent, spraying the solution including the polymeric linking agent onto the substrate, or dispersing the solution including the polymeric linking agent on the substrate. In one embodiment, the plurality of metal oxide nanoparticles are dispersed onto the substrate, and then the solution including the polymeric linking agent is deposited onto the substrate. In another embodiment, the method includes the step of contacting the metal oxide nanoparticles with a modifier solution. In yet another embodiment, the plurality of metal oxide nanoparticles includes nanoparticles of titanium oxides, zirconium oxides, zinc oxides, tungsten oxides, niobium oxides, lanthanum oxides, tantalum oxides, tin oxides, terbium oxides, and one or more combinations thereof.
In another aspect, the invention provides a polymeric linking agent solution including (1) a polymeric linking agent of the formula —[O—M(OR)i—]m—; (2) a plurality of metal oxide nanoparticles that have the formula MxOy; and (3) a solvent; where i, m, x, and y are integers greater than zero. In one embodiment, M is Ti, Zr, Sn, W, Nb, Ta, or Tb. R may be a hydrogen atom, an alkyl, an alkene, an alkyne, an aromatic, or an acyl group. In this embodiment, the solution preferably contains the polymeric linking agent in a concentration sufficient to interconnect at least a portion of the plurality of metal oxide nanoparticles at a temperature below about 300° C. In another embodiment, the polymeric linking agent solution contains the polymeric linking agent in a concentration sufficient to interconnect at least a portion of the plurality of nanoparticles at a temperature below about 100° C. In one embodiment, for example, the polylinker solution is a 1% (by weight) poly(n-butyl titanate) in n-butanol.
In a further aspect, the invention provides a flexible photovoltaic cell including a photosensitized interconnected nanoparticle material and a charge carrier material, both of which are disposed between first and second flexible and significantly light transmitting substrates. The photosensitized interconnected nanoparticle material may include nanoparticles linked by a polymeric linking agent. In one embodiment of the photovoltaic cell, the photosensitized interconnected nanoparticle material includes particles with an average size substantially in the range of about 10 nm to about 40 nm. In another embodiment, the photosensitized interconnected nanoparticle material is interconnected titanium dioxide nanoparticles. The photosensitized interconnected nanoparticle material may be, for example, zirconium oxides, zinc oxides, tungsten oxides, niobium oxides, lanthanum oxides, tantalum oxides, tin oxides, terbium oxides, or one or more combinations thereof. The photosensitized interconnected nanoparticle material may include a photosensitizing agent such as a xanthine, cyanine, merocyanine, phthalocyanine, and/or pyrrole. The photosensitizing agent may include a metal ion, such as divalent or trivalent metals. The photosensitizing agent may also include at least one of a ruthenium transition metal complex, an osmium transition metal complex, and an iron transition metal complex. In one embodiment of the photovoltaic cell, the charge carrier material includes a redox electrolyte system. In another embodiment, the charge carrier media is a polymeric electrolyte. According to one feature, the charge carrier material transmits at least about 60% of incident visible light.
In one embodiment of the photovoltaic cell, at least one of the first and second flexible, significantly light transmitting substrates includes a transparent substrate (e.g., a polyethylene terephthalate material). In another embodiment, the photovoltaic cell includes a catalytic media layer disposed between the first and second flexible, significantly light transmitting substrates. The catalytic media layer is, for example, platinum. In another embodiment, the photovoltaic cell includes an electrical conductor material disposed on at least one of the first and second flexible, significantly light transmitting substrates. In another embodiment, the electrical conductor material is, for example, indium tin oxide.
Other aspects and advantages of the invention will become apparent from the following drawings, detailed description, and claims, all of which illustrate the principles of the invention, by way of example only.



BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other objects, features, and advantages of the invention described above will be more fully understood from the following description of various illustrative embodiments, when read together with the accompanying drawings. In the drawings, like reference characters generally refer to the same parts throughout the different views. The drawings are not necessarily to scale, and emphasis instead is generally placed upon illustrating the principles of the invention.
FIG. 1 depicts an exemplary chemical structure of an illustrative embodiment of a polylinker for nanoparticles of an oxide of metal M, in accordance with the invention;
FIG. 2 depicts another exemplary chemical structure of an illustrative embodiment of a polylinker, according to the invention, for nanoparticles of an oxide of metal M;
FIG. 3A shows an exemplary chemical structure for an interconnected nanoparticle film with a polylinker, according to an illustrative embodiment of the invention;
FIG. 3B shows the interconnected nanoparticle film of FIG. 3A attached to a substrate oxide layer, according to an illustrative embodiment of the invention;
FIG. 4 depicts the chemical structure of poly(n-butyl titanate);
FIG. 5A shows the chemical structure of a titanium dioxide nanoparticle film interconnected with poly(n-butyl titanate), according to the invention;
FIG. 5B shows the interconnected titanium dioxide nanoparticle film of FIG. 5A attached to a substrate oxide layer, according to an illustrative embodiment of the invention;
FIG. 6 is a cross-sectional view of a flexible photovoltaic cell, according to an illustrative embodiment of the invention;
FIG. 7 depicts an illustrative embodiment of a continuous manufacturing process that may be used to form the flexible photovoltaic cell shown in FIG. 6;
FIG. 8 depicts a current-voltage curve for an exemplary solar cell, according to the invention;
FIG. 9 shows a current-voltage curve for an exemplary solar cell, according to an illustrative embodiment of the invention;
FIG. 10 shows current-voltage curves for two additional exemplary solar cells, according to an illustrative embodiment of the invention;
FIG. 11 depicts the chemical structure of gelation induced by a complexing reaction of Li+ ions with complexable poly(4-vinyl pyridine) compounds, in accordance with an illustrative embodiment of the invention;
FIG. 12 shows the chemical structure of a lithium ion complexing with polyethylene oxide segments, according to another illustrative embodiment of the invention;
FIGS. 13A-13C depict chemical structures for exemplary co-sensitizers, according to illustrative embodiments of the invention;
FIGS. 14A-14B depict additional exemplary chemical structures of co-sensitizers, according to illustrative embodiments of the invention;
FIG. 15 shows a graph of the absorbance of the 455 nm cut-off filter (GC455) used to characterize photovoltaic cells according to the invention;
FIG. 16 shows a graph of the absorbance of diphenylaminobenzoic acid; and
FIG. 17 depicts an illustrative embodiment of the coating of a semiconductor primer layer coating, according to the invention.



DESCRIPTION OF THE ILLUSTRATIVE EMBODIMENTS
A. Low Temperature Interconnection of Nanoparticles
As discussed in the summary above, the invention, in one embodiment, provides a polymeric linking agent (hereinafter a “polylinker”) that enables the fabrication of thin film solar cells at relatively low “sintering” temperatures (<about 300° C.). Although the term “sintering” conventionally refers to high temperature (>about 400° C.) processes, as used herein, the term “sintering” is not temperature specific, but instead refers generally to the process of interconnecting nanoparticles at any suitable temperature. In one illustrative embodiment, the invention provides a method for using polylinkers to interconnect nanoparticles in a thin film solar cells. According to another illustrative embodiment, the relatively low temperature sintering process enables the manufacture of such photovoltaic cells using flexible polymer substrates. By employing flexible substrates, the invention also enables a continuous roll-to-roll or web manufacturing process to be employed.
FIGS. 1 and 2 schematically depict chemical structures of illustrative polylinkers, according to the invention. The particular polylinker structures depicted are for use with nanoparticles of the formula MxOy where M may be, for example, titanium (Ti), zirconium (Zr), tungsten (W), niobium (Nb), lanthanum (La), tantalum (Ta), terbium (Tb), or tin (Sn) and x and y are integers greater than zero. According to the illustrative embodiment of FIG. 1, the polylinker 100 includes a backbone structure 102, which is similar in structure to the metal oxide nanoparticles, and (OR)i reactive groups, where R may be, for example, acetate, an alkyl, alkene, alkyne, aromatic, or acyl group; or a hydrogen atom and i is an integer greater than zero. Suitable alkyl groups include, but are not limited to, ethyl, propyl, butyl, and pentyl groups. Suitable alkenes include, but are not limited to, ethene, propene, butene, and pentene. Suitable alkynes include, but are not limited to, ethyne, propyne, butyne, and pentyne. Suitable aromatic group include, but are not limited to, phenyl, benzyl, and phenol. Suitable acyl groups include, but are not limited to, acetyl and benzoyl. In addition, a halogen including, for example, chlorine, bromine, and iodine may be substituted for the (OR)i reactive groups.
Referring to FIG. 2, the polylinker 110 has a branched backbone structure that includes two —M—O—M—O—M—O— backbone structures, which include (OR)i reactive groups and (OR)i+1 reactive groups, where R may be, for example, one of the atoms, molecules, or compounds listed above and i is an integer greater than zero. The two backbone structures have similar structures to the metal oxide nanoparticles. Collectively, the structure depicted in FIG. 2 can be represented by —M(OR)i—O—(M(OR)i—O)n—M(OR)i+1, where i and n are integers greater than zero.
FIG. 3A depicts schematically the chemical structure 300 resulting from interconnecting the MxOy nanoparticles 302 with a polylinker 304. In various embodiments, the polylinker 304 has the chemical structure of the polylinkers 100 and 110 depicted in FIGS. 1 and 2, respectively. According to the illustrative embodiment, the nanoparticles 302 are interconnected by contacting the nanoparticles 302 with a polylinker 304 at or below room temperature or at elevated temperatures that are less than about 300° C. Preferably, the polylinker 304 is dispersed in a solvent to facilitate contact with the nanoparticles 302. Suitable solvents include, but are not limited to, various alcohols, chlorohydrocarbons (e.g., chloroform), ketones, cyclic and linear chain ether derivatives, and aromatic solvents among others. It is believed that the reaction between surface hydroxyl groups of the nanoparticles 302 with alkoxy groups on the polymer chain of the polylinker 304 leads to bridging (or linking) the many nanoparticles 302 together through highly stable covalent links, and as a result, to interconnecting the nanoparticles 302. It also is believed that since the polylinker 304 is a polymeric material with a chemical structure similar to that of the nanoparticles 302, even a few binding (or linking) sites between the nanoparticles 302 and the polylinker 304 leads to a highly interconnected nanoparticle film with a combination of electrical and mechanical properties superior to those of a non-sintered or non-interconnected nanoparticle film. The electrical properties include, for example, electron and/or hole conducting properties that facilitate the transfer of electrons or holes from one nanoparticle to another through, for example, π-conjugation. The mechanical properties include, for example, improved flexibility.
Still referring to FIG. 3A, at low concentrations of the polylinker 304, a single polylinker 304 polymer can link many nanoparticles 302 forming a cross-linked nanoparticle network. However, by increasing the concentration of the polylinker 304 polymer, more polylinker 304 molecules may be attached to the surface of the nanoparticles 302 forming polymer-coated nanoparticles 300. Such polymer-coated nanoparticles 300 may be processed as thin films due to the flexibility of the polymer. It is believed that the electronic properties of the polymer-coated nanoparticles are not affected to a significant extent due to the similar electronic and structural properties between the polylinker polymer and the nanoparticles.
FIG. 3B depicts the chemical structure 306 of an illustrative embodiment of the interconnected nanoparticle film 300 from FIG. 3A formed on a flexible substrate 308 that includes an oxide layer coating 310, which is an electrical conductor. In particular, the polylinkers may be used to facilitate the formation of such nanoparticle films 300 on flexible, significantly light transmitting substrates 308. As used herein, the term “significantly light transmitting substrate” refers to a substrate that transmits at least about 60% of the visible light incident on the substrate in a wavelength range of operation. Examples of flexible substrates 308 include polyethylene terephthalates (PETs), polyimides, polyethylene naphthalates (PENs), polymeric hydrocarbons, cellulosics, combinations thereof, and the like. PET and PEN substrates may be coated with one or more electrical conducting, oxide layer coatings 310 of, for example, indium tin oxide (ITO), a fluorine-doped tin oxide, tin oxide, zinc oxide, and the like.
According to one preferred embodiment, by using the illustrative polylinkers, the methods of the invention interconnect nanoparticles 302 at temperatures significantly below 400° C., and preferably below about 300° C. Operating in such a temperature range enables the use of the flexible substrates 308, which would otherwise be destructively deformed by conventional high temperature sintering methods. In one illustrative embodiment, the exemplary structure 306 is formed by interconnecting the nanoparticles 302 using a polylinker 304 on a substrate 308 at temperatures below about 300° C. In another embodiment, the nanoparticles 302 are interconnected using a polylinker 304 at temperatures below about 100° C. In still another embodiment, the nanoparticles 302 are interconnected using a polylinker 304 at about room temperature and room pressure, from about 18 to about 22° C. and about 760 mm Hg, respectively.
In embodiments where the nanoparticles are deposited on a substrate, the reactive groups of the polylinker bind with the substrate, substrate coating and/or substrate oxide layers. The reactive groups may bind to the substrate, substrate coating and/or substrate oxide layers by, for example, covalent, ionic and/or hydrogen bonding. It is believed that reactions between the reactive groups of the polylinker with oxide layers on the substrate result in connecting nanoparticles to the substrate via the polylinker.
According to various embodiments of the invention, metal oxide nanoparticles are interconnected by contacting the nanoparticles with a suitable polylinker dispersed in a suitable solvent at or below room temperature or at elevated temperatures below about 300° C. The nanoparticles may be contacted with a polylinker solution in many ways. For example, a nanoparticle film may be formed on a substrate and then dipped into a polylinker solution. A nanoparticle film may be formed on a substrate and the polylinker solution sprayed on the film. The polylinker and nanoparticles may be dispersed together in a solution and the solution deposited on a substrate. To prepare nanoparticle dispersions, techniques such as, for example, microfluidizing, attritting, and ball milling may be used. Further, a polylinker solution may be deposited on a substrate and a nanoparticle film deposited on the polylinker.
In embodiments where the polylinker and nanoparticles are dispersed together in a solution, the resultant polylinker-nanoparticle solution may be used to form an interconnected nanoparticle film on a substrate in a single step. In various versions of this embodiment, the viscosity of the polylinker-nanoparticle solution may be selected to facilitate film deposition using printing techniques such as, for example, screen-printing and gravure-printing techniques. In embodiments where a polylinker solution is deposited on a substrate and a nanoparticle film deposited on the polylinker, the concentration of the polylinker can be adjusted to achieve a desired adhesive thickness. In addition, excess solvent may be removed from the deposited polylinker solution prior to deposition of the nanoparticle film.
The invention is not limited to interconnection of nanoparticles of a material of formula MxOy. Suitable nanoparticle materials include, but are not limited to, sulfides, selenides, tellurides, and oxides of titanium, zirconium, lanthanum, niobium, tin, tantalum, terbium, and tungsten, and combinations thereof. For example, TiO2, SrTiO3, CaTiO3, ZrO2, WO3, La2O3, Nb2O5, SnO2, sodium titanate, and potassium niobate are suitable nanoparticle materials.
The polylinker may contain more than one type of reactive group. For example, the illustrative embodiments of FIGS. 1-3B depict one type of reactive group OR. However, the polylinker may include several types of reactive groups, e.g., OR, OR′, OR′′, etc.; where R, R′ and R′′ are one or more of a hydrogen, alkyl, alkene, alkyne, aromatic, or acyl group or where one or more of OR, OR′, and OR′′ are a halide. For example, the polylinker may include polymer units of formulas such as, —[O—M(OR)i(OR′)j—]—, and —[O—M(OR)i(OR′)j(OR′′)k—]—, where i, j and k are integers greater than zero.
FIG. 4 depicts the chemical structure of a representative polylinker, poly(n-butyl titanate) 400 for use with titanium dioxide (TiO2) nanoparticles. Suitable solvents for poly(n-butyl titanate) 400 include, but are not limited to, various alcohols, chlorohydrocarbons (e.g., chloroform), ketones, cyclic and linear chain ether derivatives, and aromatic solvents among others. Preferably, the solvent is n-butanol. The poly(n-butyl titanate) polylinker 400 contains a branched —Ti—O—Ti—O—Ti—O— backbone structure with butoxy (OBu) reactive groups.
FIG. 5A depicts the chemical structure of a nanoparticle film 500, which is constructed from titanium dioxide nanoparticles 502 interconnected by poly(n-butyl titanate) polylinker molecules 504. It is believed that the reaction between surface hydroxyl groups of the TiO2 nanoparticles 502 with butoxy groups 506 (or other alkoxy groups) of the polylinker 504 leads to the bridging (or linking) of many nanoparticles 502 together through highly stable covalent links, and as a result, interconnecting the nanoparticles 502. Furthermore, it is believed that since the polylinker 504 is a polymeric material with a chemical structure similar to that of TiO2, even a few binding (or linking) sites between nanoparticles 502 and polylinker 504 will lead to a highly interconnected nanoparticle film 500, with electronic and mechanical properties superior to those of a non-sintered or non-interconnected nanoparticle film.
FIG. 5B depicts the chemical structure 508 of the nanoparticle film 500 from FIG. 5A formed on a substrate 510, which includes an electrically-conducting oxide layer coating 512, by applying the polylinker solution to the substrate 510 and then depositing the nanoparticles 502 on the polylinker 504. In the illustrative example using titanium dioxide nanoparticles 502, a polylinker solution including poly(n-butyl titanate) 504 is dissolved in n-butanol and applied to the substrate 510. The concentration of the polylinker 504 can be adjusted to achieve a desired adhesive thickness for the polylinker solution. A titanium dioxide nanoparticulate film 500 is then deposited on the polylinker coated substrate 510. Reaction between the surface hydroxyl groups of the TiO2 nanoparticles with reactive butoxy groups 506 (or other alkoxy groups) of poly(n-butyl titanate) 504 results in interconnecting the nanoparticles 502, as well as connecting nanoparticles 502 with the oxide layers 512 on the substrate 510.
FIG. 6 depicts a flexible photovoltaic cell 600, in accordance with the invention, that includes a photosensitized interconnected nanoparticle material 603 and a charge carrier material 606 disposed between a first flexible, significantly light transmitting substrate 609 and a second flexible, significantly light transmitting substrate 612. In one embodiment, the flexible photovoltaic cell further includes a catalytic media layer 615 disposed between the first substrate 609 and second substrate 612. Preferably, the photovoltaic cell 600 also includes an electrical conductor 618 deposited on one or both of the substrates 609 and 612. The methods of nanoparticle interconnection provided herein enable construction of the flexible photovoltaic cell 600 at temperatures and heating times compatible with such substrates 609 and 612.
The flexible, significantly light transmitting substrates 609 and 612 of the photovoltaic cell 600 preferably include polymeric materials. Suitable substrate materials include, but are not limited to, PET, polyimide, PEN, polymeric hydrocarbons, cellulosics, or combinations thereof. Further, the substrates 609 and 612 may include materials that facilitate the fabrication of photovoltaic cells by a continuous manufacturing process such as, for example, a roll-to-roll or web process. The substrate 609 and 612 may be colored or colorless. Preferably, the substrates 609 and 612 are clear and transparent. The substrates 609 and 612 may have one or more substantially planar surfaces or may be substantially non-planar. For example, a non-planar substrate may have a curved or stepped surface (e.g., to form a Fresnel lens) or be otherwise patterned.
According to the illustrative embodiment, an electrical conductor 618 is deposited on one or both of the substrates 609 and 612. Preferably, the electrical conductor 618 is a significantly light transmitting material such as, for example, ITO, a fluorine-doped tin oxide, tin oxide, zinc oxide, or the like. In one illustrative embodiment, the electrical conductor 618 is deposited as a layer between about 100 nm and about 500 nm thick. In another illustrative embodiment, the electrical conductor 618 is between about 150 nm and about 300 nm thick. According to a further feature of the illustrative embodiment, a wire or lead line may be connected to the electrical conductor 618 to electrically connect the photovoltaic cell 600 to an external load.
The photosensitized interconnected nanoparticle material 603 may include one or more types of metal oxide nanoparticles, as described in detail above. In one embodiment, the photosensitized interconnected nanoparticle material 603 includes nanoparticles with an average size of between about 2 nm and about 100 nm. In another embodiment, the photosensitized nanoparticle material 603 includes nanoparticles with an average size of between about 10 nm and about 40 nm. Preferably, the nanoparticles are titanium dioxide particles having an average particle size of about 20 nm.
A wide variety of photosensitizing agents may be applied to and/or associated with the nanoparticles to produce the photosensitized interconnected nanoparticle material 603. The photosensitizing agent facilitates conversion of incident visible light into electricity to produce the desired photovoltaic effect. It is believed that the photosensitizing agent absorbs incident light resulting in the excitation of electrons in the photosensitizing agent. The energy of the excited electrons is then transferred from the excitation levels of the photosensitizing agent into a conduction band of the interconnected nanoparticles 603. This electron transfer results in an effective separation of charge and the desired photovoltaic effect. Accordingly, the electrons in the conduction band of the interconnected nanoparticles are made available to drive an external load electrically connected to the photovoltaic cell. In one illustrative embodiment, the photosensitizing agent is sorbed (e.g., chemisorbed and/or physisorbed) on the interconnected nanoparticles 603. The photosensitizing agent may be sorbed on the surfaces of the interconnected nanoparticles 603, throughout the interconnected nanoparticles 603, or both. The photosensitizing agent is selected, for example, based on its ability to absorb photons in a wavelength range of operation, its ability to produce free electrons (or electron holes) in a conduction band of the interconnected nanoparticles 603, and its effectiveness in complexing with or sorbing to the interconnected nanoparticles 603. Suitable photosensitizing agents may include, for example, dyes that include functional groups, such as carboxyl and/or hydroxyl groups, that can chelate to the nanoparticles, e.g., to Ti(IV) sites on a TiO2 surface. Examples of suitable dyes include, but are not limited to, anthocyanins, porphyrins, phthalocyanines, merocyanines, cyanines, squarates, eosins, and metal-containing dyes such as, for example, cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)-ruthenium(II) (“N3 dye”); tris(isothiocyanato)-ruthenium(II)-2,2′:6′,2′′-terpyridine-4,4′,4′′-tricarboxylic acid; cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)-ruthenium(II) bis-tetrabutylammonium; cis-bis(isocyanato) (2,2′-bipyridyl-4,4′ dicarboxylato) ruthenium (II); and tris(2,2′-bipyridyl-4,4′-dicarboxylato) ruthenium (II) dichloride, all of which are available from Solaronix.
The charge carrier material 606 portion of the photovoltaic cells may form a layer in the photovoltaic cell, be interspersed with the material that forms the photosensitized interconnected nanoparticle material 603, or be a combination of both. The charge carrier material 606 may be any material that facilitates the transfer of electrical charge from a ground potential or a current source to the interconnected nanoparticles 603 (and/or a photosensitizing agent associated therewith). A general class of suitable charge carrier materials can include, but are not limited to solvent based liquid electrolytes, polyelectrolytes, polymeric electrolytes, solid electrolytes, n-type and p-type transporting materials (e.g., conducting polymers), and gel electrolytes, which are described in more detail below.
Other choices for the charge carrier material 606 are possible. For example, the electrolyte composition may include a lithium salt that has the formula LiX, where X is an iodide, bromide, chloride, perchlorate, thiocyanate, trifluoromethyl sulfonate, or hexafluorophosphate. In one embodiment, the charge carrier material 606 includes a redox system. Suitable redox systems may include organic and/or inorganic redox systems. Examples of such systems include, but are not limited to, cerium(III) sulfate/cerium(IV), sodium bromide/bromine, lithium iodide/iodine, Fe2+/Fe3+, Co2+/Co3+, and viologens. Furthermore, an electrolyte solution may have the formula MiXj, where i and j are ≧1. X is an anion, and M is selected from the group consisting of Li, Cu, Ba, Zn, Ni, lanthanides, Co, Ca, Al, and Mg. Suitable anions include, but are not limited to, chloride, perchlorate, thiocyanate, trifluoromethyl sulfonate, and hexafluorophosphate.
In some illustrative embodiments the charge carrier material 606 includes a polymeric electrolyte. In one version, the polymeric electrolyte includes poly(vinyl imidazolium halide) and lithium iodide. In another version, the polymeric electrolyte includes poly(vinyl pyridinium salts). In still another embodiment, the charge carrier material 606 includes a solid electrolyte. In one version, the solid electrolyte includes lithium iodide and pyridinium iodide. In another version, the solid electrolyte includes substituted imidazolium iodide.
According to some illustrative embodiments, the charge carrier material 606 includes various types of polymeric polyelectrolytes. In one version, the polyelectrolyte includes between about 5% and about 100% (e.g., 5-60%, 5-40%, or 5-20%) by weight of a polymer, e.g., an ion-conducting polymer, about 5% to about 95%, e.g., about 35-95%, 60-95%, or 80-95%, by weight of a plasticizer and about 0.05 M to about 10 M of a redox electrolyte, e.g., about 0.05 M to about 10 M, e.g., 0.05-2 M, 0.05-1 M, or 0.05-0.5 M, of organic or inorganic iodides, and about 0.01 M to about 1 M, e.g., 0.05-5 M, 0.05-2 M, or 0.05-1 M, of iodine. The ion-conducting polymer may include, for example, polyethylene oxide (PEO), polyacrylonitrile (PAN), polymethylmethacrylate (acrylic) (PMMA), polyethers, and polyphenols. Examples of suitable plasticizers include, but are not limited to, ethyl carbonate, propylene carbonate, mixtures of carbonates, organic phosphates, butyrolactone, and dialkylphthalates.
Preferably, the flexible photovoltaic cell 600 also includes a catalytic media layer 615 disposed between the substrates 609 and 612. According to the illustrative embodiment, the catalytic media layer 615 is in electrical contact with the charge carrier material 606. The catalytic media 615 may include, for example, ruthenium, osmium, cobalt, rhodium, iridium, nickel, activated carbon, palladium, platinum, or hole transporting polymers (e.g., poly(3,4-ethylene dioxythiophene and polyaniline). Preferably, the catalytic media 615 further includes titanium, or some other suitable metal, to facilitate adhesion of the catalytic media to a substrate and/or substrate coating. Preferably, the titanium is deposited in regions or a layer about 10 Å thick. In one embodiment, the catalytic media 615 includes a platinum layer between about 13 Å and about 35 Å thick. In another embodiment, the catalytic media 615 includes a platinum layer between about 15 Å and about 50 Å thick. In another embodiment, the catalytic media 615 includes a platinum layer between about 50 Å and about 800 Å thick. Preferably, the catalytic media 615 includes a platinum layer about 25 Å thick.
In another aspect, the invention also provides methods of forming a layer of interconnected metal oxide nanoparticles on a substrate using a continuous manufacturing process, such as, for example, a roll-to-roll or web process. These methods may be used, for example, to produce DSSCs. The current processes for producing DSSCs in large numbers, for example using a continuous and cost effective assembly line process, are extremely difficult at best. The difficulties associated with a continuous assembly process for a DSSC may arise from the cell support or substrate, which is generally rigid and typically includes thermally resistant materials such as glass and metal. The primary reason for this is related to the high temperature sintering process for producing fused nanocrystals (typically about 400-500° C.). Rigid substrate materials, by their very nature, generally do not lend themselves to a continuous process for manufacture, but rather to a more expensive batch process.
FIG. 7 depicts an illustrative embodiment of a continuous manufacturing process 700 that may be used to form the photovoltaic cell shown in FIG. 6. According to the illustrative embodiment, an interconnected nanoparticle film is formed on an advancing substrate sheet 705, which may be continuously advanced, periodically advanced, and/or irregularly advanced during a manufacturing run using rollers 708. In this illustrative embodiment, the electrical conductor material 710, which serves as the basis for one electrode of a photovoltaic cell, is deposited on the advancing substrate 705. In various embodiments, the electrical conductor material 710 may be deposited on a target region of the substrate 705 by thermal evaporation or low temperature sputtering. In addition, the electrical conductor material 710 may be deposited, for example, by vacuum deposition.
According to the illustrative embodiment shown in FIG. 7, the photosensitized nanoparticle material 715 is then deposited. As described above, the photosensitized nanoparticle material 715 may be formed by applying a solution having a polylinker and metal oxide nanoparticles onto the advancing substrate sheet 705. The polylinker-nanoparticle solution may be applied by any suitable technique including, but not limited to, dip tanks, extrusion coating, spray coating, screen printing, and gravure printing. In other illustrative embodiments, the polylinker solution and metal oxide nanoparticles are separately applied to the advancing substrate sheet 705 to form the photosensitized nanoparticle material 715. In one illustrative embodiment, the polylinker solution is applied to the advancing substrate 705 and the metal oxide nanoparticles (preferably dispersed in a solvent) are disposed on the polylinker. In another illustrative embodiment, the metal oxide nanoparticles (preferably dispersed in a solvent) are applied to the advancing substrate 705 and the polylinker solution is applied to the nanoparticles to form the photosensitized nanoparticle material 715. As described above with regard to FIG. 6, a wide variety of photosensitizing agents may be applied to and/or associated with the nanoparticles to produce the photosensitized nanoparticle material 715.
After deposition of the photosensitized nanomatrix material 715, the substrate sheet 705 may proceed to further processing stations depending on the ultimate product desired. According to this illustrative embodiment, the charge carrier material 720, which facilitates the transfer of electrical charge from a ground potential or a current source to the photosensitized nanoparticle material 715, is deposited. The charge carrier material 720 may be applied by, for example, spray coating, roller coating, knife coating, or blade coating. The charge carrier media 720 may be prepared by forming a solution having an ion-conducting polymer, a plasticizer, and a mixture of iodides and iodine. The polymer provides mechanical and/or dimensional stability; the plasticizer helps the gel/liquid phase transition temperature; and the iodides and iodine act as redox electrolytes.
Still referring to FIG. 7, the catalytic media layer 725, which facilitates the transfer of electrons ejected by the photoexcited molecules within the photovoltaic cell, is then deposited. Subsequently, a second electrical conductor layer 730 is deposited. The second electrical conductor layer 730 serves as the basis for a second electrode of the photovoltaic cell. A second, flexible substrate 735 is then unwound and applied to the advancing sheet 705 to complete the photovoltaic cell using the continuous manufacturing process 700.
Further illustrative examples of the invention in the context of a DSSC including titanium dioxide nanoparticles are provided below. The following examples are illustrative and not intended to be limiting. Accordingly, it is to be understood that the invention may be applied to a wide range of nanoparticles including, but not limited to, SrTiO3, CaTiO3, ZrO2, WO3, La2O3, Nb2O5, sodium titanate, and potassium niobate nanoparticles. In addition, it should be realized that the invention is generally applicable to formation of interconnected nanoparticles for a wide variety of applications in addition to DSSC, such as, for example, metal oxide and semiconductor coatings.
EXAMPLE 1
Dip-Coating Application of Polylinker
In this illustrative example, a DSSC was formed as follows. A titanium dioxide nanoparticle film was coated on a SnO2:F coated glass slide. The polylinker solution was a 1% (by weight) solution of the poly(n-butyl titanate) in n-butanol. In this embodiment, the concentration of the polylinker in the solvent was preferably less than 5% by weight. To interconnect the particles, the nanoparticle film coated slide was dipped in the polylinker solution for 15 minutes and then heated at 150° C. for 30 minutes. The polylinker treated TiO2 film was then photosensitized with a 3×10−4 N3 dye solution for 1 hour. The polylinker treated TiO2 film coated slide was then fabricated into a 0.6 cm2 photovoltaic cell by sandwiching a triiodide based liquid redox electrolyte between the TiO2 film coated slide a platinum coated SnO2:F glass slide using 2 mil SURLYN 1702 hot melt adhesive available from DuPont. The platinum coating was approximately 60 nm thick. The cell exhibited a solar conversion efficiency of as high as 3.33% at AM 1.5 solar simulator conditions (i.e., irradiation with light having an intensity of 1000 W/m2). The completed solar cells exhibited an average solar conversion efficiency (“η”) of 3.02%; an average open circuit voltage (“Voc”) of 0.66 V; an average short circuit current (“Isc”) of 8.71 mA/cm2, and an average fill factor of 0.49 (0.48 to 0.52). FIG. 8 depicts a graph 800 that shows the current-voltage curve 802 for the dip-coated photovoltaic cell.
EXAMPLE 2
Polylinker-Nanoparticle Solution Application
In this illustrative example, a 5.0 mL suspension of titanium dioxide (P25, which is a titania that includes approximately 80% anatase and 20% rutile crystalline TiO2 nanoparticles and which is available from Degussa-Huls) in n-butanol was added to 0.25 g of poly(n-butyl titanate) in 1 mL of n-butanol. In this embodiment, the concentration of the polylinker in the polylinker-nanoparticle solution was preferably less than about 50% by weight. The viscosity of the suspension changed from milk-like to toothpaste-like with no apparent particle separation. The paste was spread on a patterned SnO2:F coated glass slide using a Gardner knife with a 60 μm thick tape determining the thickness of wet film thickness. The coatings were dried at room temperature forming the films. The air-dried films were subsequently heat treated at 150° C. for 30 minutes to remove solvent, and sensitized overnight with a 3×10−4 M N3 dye solution in ethanol. The sensitized photoelectrodes were cut into desired sizes and sandwiched between a platinum (60 nm thick) coated SnO2:F coated glass slide and a tri-iodide based liquid electrolyte. The completed solar cells exhibited an average η of 2.9% (2.57% to 3.38%) for six cells at AM 1.5 conditions. The average Voc was 0.68 V (0.66 to 0.71 V); the average Isc was 8.55 mA/cm2 (7.45 to 10.4 mA/cm2); and the average fill factor was 0.49 (0.48 to 0.52). FIG. 9 depicts a graph 900 showing the current-voltage curve 902 for the photovoltaic cell formed from the polylinker-nanoparticle solution.
EXAMPLE 3
DSSC Cells Formed Without Polylinker
In this illustrative example, an aqueous titanium dioxide suspension (P25) containing about 37.5% solid content was prepared using a microfluidizer and was spin coated on a fluorinated SnO2 conducting electrode (15 Ω/cm2) that was itself coated onto a coated glass slide. The titanium dioxide coated slides were air dried for about 15 minutes and heat treated at 150° C. for 15 minutes. The slides were removed from the oven, cooled to about 80° C., and dipped into 3×10−4 M N3 dye solution in ethanol for about 1 hour. The sensitized titanium dioxide photoelectrodes were removed from dye solution rinsed with ethanol and dried over a slide warmer at 40° C. The sensitized photoelectrodes were cut into small pieces (0.7 cm×0.5-1 cm active area) and sandwiched between platinum coated SnO2:F-transparent conducting glass slides. A liquid electrolyte containing 1 M LiI, 0.05 M iodine, and 1 M t-butyl pyridine in 3-methoxybutyronitrile was applied between the photoelectrode and platinized conducting electrode through capillary action. Thus constructed photocells exhibited an average solar conversion efficiency of about 3.83% at AM 1.5 conditions. The η at AM 1.5 conditions and the photovoltaic characteristics Isc, Voc, voltage at maximum power output (“Vm”), and current at maximum power output (“Im”) of these cells are listed in Table 1 under column A. FIG. 10 depicts a graph 1000 showing the current-voltage curve 1002 for the photovoltaic cell formed without the polylinker.













TABLE 1








B
C
D
E



A
0.1%
0.4%
1%
2%



Untreated
polymer soln.
polymer soln.
polymer soln.
polymer soln.





















η (%)
Avg = 3.83 
Avg. = 4.30 
Avg = 4.55
Avg = 4.15
Avg = 4.15



(3.37-4.15)
(4.15-4.55)
 (4.4-4.82)
(3.48-4.46)
 (3.7-4.58)


Isc
Avg = 10.08
Avg = 10.96
 Avg = 10.60
 Avg = 11.00
 Avg = 11.24


(mA/cm2)
 (8.88-10.86)
(10.44-11.5) 
 (9.79-11.12)
 (10.7-11.28)
(10.82-11.51)


Voc (V)
Avg = 0.65 
Avg = 0.66 
Avg = 0.71
Avg = 0.7 
Avg = 0.69



(0.65-0.66)
(0.6-0.7)
(0.69-0.74)
(0.69-0.71)
(0.68-0.71)


Vm (V)
Avg = 0.454
Avg = 0.46 
Avg = 0.50
Avg = 0.45
Avg = 0.44



(0.43-0.49)
 (0.43-0.477)
(0.47-0.53)
 (0.4-0.47)
(0.42-0.46)


Im
Avg = 8.4 
Avg = 9.36 
Avg = 9.08
Avg = 9.14
Avg = 9.28


(mA/cm2)
 (7.5-8.96)
(8.75-9.71)
(8.31-9.57)
(8.70-9.55)
(8.66-9.97)









EXAMPLE 4
DSSC Cells Formed with Various Concentrations of Polylinker Solution
In this illustrative example, a P25 suspension containing about 37.5% solid content was prepared using a microfluidizer and was spin coated on fluorinated SnO2 conducting electrode (15 Ω/cm2) coated glass slide. The titanium dioxide coated slides were air dried for about 15 minutes and heat treated at 150° C. for 15 minutes. The titanium dioxide coated conducting glass slide were dipped into a polylinker solution including poly(n-butyl titanate) in n-butanol for 5 minutes in order to carry out interconnection (polylinking) of nanoparticles. The polylinker solutions used were 0.1 wt % poly(n-butyl titanate), 0.4 wt % poly(n-butyl titanate), 1 wt % poly(n-butyl titanate), and 2 wt % poly(n-butyl titanate). After 5 minutes, the slides were removed from the polylinker solution, air dried for about 15 minutes and heat treated in an oven at 150° C. for 15 minutes to remove solvent. The slides were removed from the oven, cooled to about 80° C., and dipped into 3×10−4 M N3 dye solution in ethanol for about 1 hour. The sensitized titanium dioxide photoelectrodes were removed from dye solution, rinsed with ethanol, and dried over a slide warmer at 40° C. The sensitized photoelectrodes were cut into small pieces (0.7 cm×0.5-1 cm active area) and sandwiched between platinum coated SnO2:F-transparent conducting glass slides. A liquid electrolyte containing 1 M LiI, 0.05 M iodine, and 1 M t-butyl pyridine in 3-methoxybutyronitrile was applied between the photoelectrode and platinized conducting electrode through capillary action. The η at AM 1.5 conditions and the photovoltaic characteristics Isc, Voc, Vm, and Im of the constructed cells are listed in Table 1 for the 0.1 wt % solution under column B, for the 0.4 wt % solution under column C, for the 1 wt % solution under column D, and for the 2 wt % solution under column E. FIG. 10 depicts the current-voltage curve 1008 for the photovoltaic cell formed with the polylinker.
EXAMPLE 5
Modifier Solutions
In this illustrative example, titanium dioxide coated transparent conducting oxide coated glass slides were prepared by spin coating process as described in Example 4. The titanium oxide coated conducting glass slides were treated with polylinker solution including a 0.01 M poly(n-butyl titanate) solution in n-butanol for 5 minutes to interconnect the nanoparticles. The slides were air dried for about 5 minutes after removing from the polylinker solution. The slides were later dipped into a modifier solution for about 1 minute. The modifier solutions used were 1:1 water/ethanol mixture, 1 M solution of t-butyl pyridine in 1:1 water/ethanol mixture, 0.05 M HCl solution in 1:1 water/ethanol mixture. One of the slides was treated with steam from humidifier for 15 seconds. The slides were air dried for 15 minutes and heat-treated at 150° C. for 15 minutes to remove solvent and then sensitized with a 3×10−4 M N3 dye solution for 1 hour. The sensitized photoelectrodes were sandwiched between platinized SnO2:F coated glass slides and studied for photovoltaic characteristics using a liquid electrolyte containing 1 M LiI, 0.05 M iodine, and 1 M t-butyl pyridine in 3-methoxybutyronitrile. Acid seems to help in increasing the photoconductivity and efficiency of these photocells. The η at AM 1.5 conditions and the photovoltaic characteristics of the cells of this example are listed in Table 2 as follows: slides not dipped into a modifier solution and not treated with polylinker solution (column A); slides not dipped into a modifier, but treated with polylinker solution (column B); slides were first treated with polylinker solution and then dipped in 1:1 water/ethanol mixture (column C); slides were first treated with polylinker solution and then dipped in 1 M solution of t-butyl pyridine in 1:1 water/ethanol mixture (column D); slides were first treated with polylinker solution and then dipped in 0.05 M HCl solution in 1:1 water/ethanol mixture (column E); and slides were first treated with polylinker solution and then treated with steam from humidifier (column F).














TABLE 2










Treated
Treated





Treated
Treated
with 1 m t-
with 0.05 M
Steam from




with 0.01 M
with 1:1
BuPy/1:1
HCl/1:1
Humidifier



Untreated
TiBut
EtOH/H2O
EtOH/H2O
EtOH/H2O
for 15 sec.






















η (%)
Avg = 3.92
Avg = 4.41
Avg = 4.11
Avg = 4.34
Avg = 4.67
Avg = 4.41



(3.75-4.15)
(4.12-4.74)
(4.06-4.15)
(4.27-4.38)
(4.61-4.73)
(4.38-4.45)


Voc (V)
Avg = 0.66
Avg = 0.66
Avg = 0.65
Avg = 0.65
Avg = 0.66
Avg = 0.66



(0.66-0.67)
(0.65-0.66)
(0.64-0.65)
(0.64-0.66)
(0.65-0.66)
(0.66-0.67)


Isc
Avg = 9.97
 Avg = 12.57
 Avg = 11.85
 Avg = 11.85
 Avg = 12.51
 Avg = 11.63


(mA/cm2)
 (9.48-10.56)
 (11.7-13.22)
(11.21-12.49)
(11.21-12.49)
(12.15-12.87)
(11.25-12.01)


Vm (V)
 Avg = 0.468
 Avg = 0.434
Avg = 0.44
Avg = 0.45
 Avg = 0.457
Avg = 0.45



(0.46-0.48)
 (0.4-0.457)
(0.43-0.45)
 (0.44-0.456)
(0.453-0.46) 
(0.44-0.46)


Im
Avg = 8.36
 Avg = 10.08
Avg = 9.27
Avg = 9.52
 Avg = 10.23
Avg = 9.67


(mA/cm2)
(7.85-8.89)
 (9.57-10.37)
(9.01-9.53)
(9.22-9.75)
(10.17-10.29)
(9.38-9.96)









EXAMPLE 6
Post-Interconnection Heating to 150° C.
In this illustrative example, a titanium-dioxide-coated, transparent-conducting-oxide-coated glass slide was prepared by a spin coating process as described in Example 4. The slide was dipped into 0.01 M poly(n-butyl titanate) in n-butanol for 30 seconds and was air-dried for 15 minutes. The slide was later heat treated at 150° C. for 10 minutes in an oven. The heat-treated titanium oxide layer was sensitized with N3 dye solution for 1 hour, washed with ethanol, and warmed on a slide warmer at 40° C. for 10 minutes. The sensitized photoelectrodes were cut into 0.7 cm×0.7 cm active area photocells and were sandwiched between platinized conducting electrodes. A liquid electrolyte containing 1 M LiI, 0.05 M iodine, and 1 M t-butyl pyridine in 3-methoxybutyronitrile was applied between the photoelectrode and platinized conducting electrode through capillary action. The photocells exhibited an average η of 3.88% (3.83, 3.9 and 3.92), an average Voc of 0.73 V (0.73, 0.74 and 0.73 V), and an average Isc of 9.6 mA/cm2 (9.88, 9.65 and 9.26), all at AM 1.5 conditions.
EXAMPLE 7
Post-Interconnection Heating to 70° C.
In this illustrative example, a titanium-dioxide-coated, transparent-conducting-oxide-coated glass slide was prepared by a spin coating process as described in Example 4. The slide was dipped into 0.01 M poly(n-butyl titanate) in n-butanol for 30 seconds and was air-dried for 15 minutes. The slide was later heat treated at 70° C. for 10 minutes in an oven. The heat-treated titanium oxide layer was sensitized with N3 dye solution for 1 hour, washed with ethanol, and warmed on a slide warmer at 40° C. for 10 minutes. The sensitized photoelectrodes were cut into 0.7 cm×0.7 cm active area photocells and were sandwiched between platinized conducting electrodes. A liquid electrolyte containing 1 M LiI, 0.05 M iodine, and 1 M t-butyl pyridine in 3-methoxybutyronitrile was applied between the photoelectrode and platinized conducting electrode through capillary action. The photocells exhibited an average η of 3.62% (3.55, 3.73 and 3.58), an average Voc of 0.75 V (0.74, 0.74 and 0.76 V), and average Isc of 7.96 mA/cm2 (7.69, 8.22 and 7.97), all at AM 1.5 conditions.
EXAMPLE 8
Formation on a Flexible, Transparent Substrate
In this illustrative example, a PET substrate about 200 μm thick and about 5 inches by 8 feet square was coated with ITO and loaded onto a loop coater. An 18.0 mL suspension of titanium dioxide (P25 with 25% solid content) in n-butanol and 0.5 g of poly(n-butyl titanate) in 10 mL of n-butanol were in-line blended and coated onto the ITO coated PET sheet. After deposition, the coating was heated at about 50° C. for about 1 minute. The interconnected nanoparticle layer was then dye-sensitized by coating with a 3×10−4 M solution of N3 dye in ethanol.
B. Gel Electrolytes for DSSCs
According to further illustrative embodiments, the invention provides electrolyte compositions that include multi-complexable molecules (i.e., molecules containing 2 or more ligands capable of complexing) and redox electrolyte solutions, which are gelled using metal ions, such as lithium ions. The multi-complexable compounds are typically organic compounds capable of complexing with a metal ion at a plurality of sites. The electrolyte composition can be a reversible redox species that may be liquid by itself or solid components dissolved in a non-redox active solvent, which serves as a solvent for the redox species and does not participate in reduction-oxidation reaction cycle. Examples include common organic solvents and molten salts that do not contain redox active ions. Examples of redox species include, for example, iodide/triiodide, Fe2+/Fe3+, Co2+/Co3+, and viologens, among others. The redox components are dissolved in non-aqueous solvents, which include all molten salts. Iodide based molten salts, e.g., methylpropylimidazolium iodide, methylbutylimidazolium iodide, methylhexylimidazolium iodide, etc., are themselves redox active and can be used as redox active liquids by themselves or diluted with non-redox active materials like common organic solvents or molten salts that do not undergo oxidation-reduction reaction cycles. Multi-dendate inorganic ligands may also be a source of gelling compounds.
FIG. 11 depicts an illustrative embodiment of an electrolyte gelled using metal ions. Lithium ions are shown complexed with poly(4-vinyl pyridine). The lithium ions and the organic compounds, in this instance poly(4-vinyl pyridine) molecules capable of complexing at a plurality of sites with the lithium ions, can be used to gel a suitable electrolyte solution. An electrolyte composition prepared in accordance with the invention may include small amounts of water, molten iodide salts, an organic polymer, and other suitable compound gels upon the addition of a metal ion such as lithium. Gelled electrolytes may be incorporated into individual flexible photovoltaic cells, traditional solar cells, photovoltaic fibers, interconnected photovoltaic modules, and other suitable devices. The dotted lines shown in FIG. 11 represent the type of bonding that occurs in a photovoltaic gel electrolyte when the constituent electrolyte solution and organic compounds gel after the introduction of a suitable metal ion.
A non-exhaustive list of organic compounds that are capable of complexing with the metal ion at a plurality of sites, and which are suitable for use in the invention, include various polymers, starburst/dendrimeric molecules, and other molecules containing multiple functional groups, e.g., urethanes, esters, ethylene/propylene oxide/imines segments, pyridines, pyrimidines, N-oxides, imidazoles, oxazoles, triazoles, bipyridines, quinolines, polyamines, polyamides, ureas, β-diketones, and β-hydroxy ketones.
More generally, the multi-complexable molecules employed in various embodiments may be polymeric or small organic molecules that possess two or more ligand or ligating groups capable of forming complexes. Ligating groups are functional groups that contain at least one donor atom rich in electron density, e.g., oxygen, nitrogen, sulfur, or phosphorous, among others and form monodentate or multidentate complexes with an appropriate metal ion. The ligating groups may be present in non-polymeric or polymeric material either in a side chain or part of the backbone, or as part of a dendrimer or starburst molecule. Examples of monodentate ligands include, for example, ethyleneoxy, alkyl-oxy groups, pyridine, and alkyl-imine compounds, among others. Examples of bi- and multidentate ligands include bipyridines, polypyridines, urethane groups, carboxylate groups, and amides.
According to various embodiments of the invention, dye-sensitized photovoltaic cells having a gel electrolyte 1100 including lithium ions are fabricated at or below room temperature or at elevated temperatures below about 300° C. The temperature may be below about 100° C., and preferably, the gelling of the electrolyte solution is performed at room temperature and at standard pressure. In various illustrative embodiments, the viscosity of the electrolyte solution may be adjusted to facilitate gel electrolyte deposition using printing techniques such as, for example, screen-printing and gravure-printing techniques. The complexing of lithium ions with various ligands can be broken at higher temperatures, thereby permitting the gel electrolyte compositions to be easily processed during DSSC based photovoltaic module fabrication. Other metal ions may also be used to form thermally reversible or irreversible gels. Examples of suitable metal ions include: Li+, Cu2+, Ba2+, Zn2+, Ni2+, Ln3+ (or other lanthanides), Co2+, Ca2+, Al3+, Mg2+, and any metal ion that complexes with a ligand.
FIG. 12 depicts a gel electrolyte 1200 formed by the complexing of an organic polymer, polyethylene oxide (PEO), by lithium ions. The PEO polymer segments are shown as being complexed about the lithium ions and crosslinked with each other. In another embodiment, the metal ion complexed with various polymer chains can be incorporated into a reversible redox electrolyte species to promote gelation. The gel electrolyte composition that results from the combination is suitable for use in various photovoltaic cell embodiments such as photovoltaic fibers, photovoltaic cells, and electrically interconnected photovoltaic modules.
Referring back to FIG. 6, the charge carrier material 606 can include an electrolyte composition having an organic compound capable of complexing with a metal ion at a plurality of sites; a metal ion such as lithium; and an electrolyte solution. These materials can be combined to produce a gelled electrolyte composition suitable for use in the charge carrier material 606 layer. In one embodiment, the charge carrier material 606 includes a redox system. Suitable redox systems may include organic and/or inorganic redox systems. Examples of such systems include, but are not limited to, cerium(III) sulfate/cerium(IV), sodium bromide/bromine, lithium iodide/iodine, Fe2+/Fe3+, Co2+/Co3+, and viologens.
Further illustrative examples of the invention in the context of a DSSC having a gel electrolyte composition are provided below. The photoelectrodes used in the following illustrative examples were prepared according to the following procedure. An aqueous, titania suspension (P25, which was prepared using a suspension preparation technique with total solid content in the range of 30-37%) was spun cast on SnO2:F coated glass slides (15 Ω/cm2). The typical thickness of the titanium oxide coatings was around 8 μm. The coated slides were air dried at room temperature and sintered at 450° C. for 30 minutes. After cooling the slides to about 80° C., the slides were immersed into 3×10−4 M N3 dye solution in ethanol for 1 hour. The slides were removed and rinsed with ethanol and dried over slide a warmer at 40° C. for about 10 minutes. The slides were cut into about 0.7 cm×0.7 cm square active area cells. The prepared gels were applied onto photoelectrodes using a glass rod and were sandwiched between platinum-coated, SnO2:F coated, conducting glass slides. The cell performance was measured at AM 1.5 solar simulator conditions (i.e., irradiation with light having an intensity of 1000 W/m2).
EXAMPLE 9
Effect of Lithium Iodide in Standard Ionic Liquid Based Electrolyte Composition
In this illustrative example, the standard, ionic, liquid-based redox electrolyte composition that was used contained a mixture containing 99% (by weight) imidazolium iodide based ionic liquid and 1% water (by weight), combined with 0.25 M iodine and 0.3 M methylbenzimidazole. In various experimental trials, electrolyte solutions with at least a 0.10 M iodine concentration exhibit the best solar conversion efficiency. In a standard composition, butylmethylimidazolium iodide (MeBuImI) was used as the ionic liquid. Photovoltage decreased with increases in iodine concentration, while photoconductivity and conversion efficiency increased at least up to 0.25 M iodine concentration. Adding lithium iodide to the standard composition enhanced the photovoltaic characteristics Voc and Isc and the η. Therefore, in addition to lithium's use as a gelling agent, it may serve to improve overall photovoltaic efficiency. Table 3 summarizes the effect of LiI on photovoltaic characteristics.













TABLE 3







Stan-
Standard +
Standard +
Standard +
Standard +



dard
1 wt % LiI
2 wt % LiI
3 wt % LiI
5 wt % LiI





















η (%)
2.9%
3.57
3.75
3.70
3.93


Voc (V)
0.59
0.61
0.6
0.6
0.61


Isc (mA/cm2)
10.08
11.4
11.75
11.79
12.62


Vm (V)
0.39
0.4
0.39
0.4
0.39


Im (mA/cm2)
7.44
9.02
9.64
9.0
10.23









The fill factor (“FF”) is referenced below and can be calculated from the ratio of the solar conversion efficiency to the product of the open circuit voltage and the short circuit current, i.e., FF=η/[Voc*Isc].
EXAMPLE 10
The Effect of Cations on the Enhancement in Photovoltaic Characteristics
In order to ascertain whether the enhancement in photovoltaic characteristics was due to the presence of lithium or iodide, controlled experimental trials using various iodides in conjunction with cations including lithium, potassium, cesium and tetrapropylammonium iodide were conducted. The iodide concentration was fixed at 376 μmols/gram of standard electrolyte composition. The standard composition used was a mixture containing 99% MeBuImI and 1% water, combined with 0.25 M iodine and 0.3 M methylbenzimidazole. 376 μmols of various iodide salts per gram of standard electrolyte composition were dissolved in the electrolyte. The complete dissolution of LiI was observed. The other salts took a long time to dissolve and did not dissolve completely over the course of the experimental trial. DSSC-based photovoltaic cells were fabricated using prepared electrolytes containing various cations. Table 4 shows the effect of the various cations on the photovoltaic characteristics. It is apparent from the second column of Table 4 that Li+ ion shows enhanced photovoltaic characteristics compared to the standard formula, while the other cations do not appear to contribute to the enhancement of the photovoltaic characteristics.













TABLE 4







Stan-
Standard +
Standard +
Standard +
Standard +



dard
LiI
NPR4I
KI
CsI





















η (%)
3.23
4.39
2.69
3.29
3.23


Voc (V)
0.58
0.65
0.55
0.58
0.6


Isc (mA/cm2)
10.96
12.03
9.8
9.91
10.14


Vm (V)
0.36
0.44
0.36
0.4
0.4


Im (mA/cm2)
8.96
9.86
7.49
8.25
8.32









EXAMPLE 11
Effect of Ionic Liquid Type
In one aspect of the invention, MeBuImI-based electrolyte compositions have been found to perform slightly better than MePrImI based electrolytes. In addition, experimental results demonstrate that a 1/1 blend of MeBuImI and MePrImI exhibit better performance than MeBuImI, as shown in Table 5.










TABLE 5







376 μmoles




of LiI per 1 gram of
376 μmoles of LiI per 1 gram of



MeBuImI based standard
MeBuImI/MePrImI based



electrolyte composition.
standard electrolyte composition.


















η (%)
3.64
3.99


Voc (V)
0.63
0.63


Isc (mA/cm2)
11.05
11.23


Vm (V)
0.42
0.42


Im (mA/cm2)
8.69
9.57









EXAMPLE 12
Using Li-induced Gelling in Composition a Instead of a Dibromocompound
In this illustrative example, a Composition A was prepared by dissolving 0.09 M of iodine in a mixed solvent consisting of 99.5% by weight of 1-methyl-3-propyl imidazolium iodide and 0.5% by weight of water. Then, 0.2 g of poly(4-vinylpyridine) (“P4VP”), a nitrogen-containing compound, was dissolved in 10 g of the Composition A Further, 0.2 g of 1,6-dibromohexane, an organic bromide, was dissolved in the resultant Composition A solution, so as to obtain an electrolyte composition, which was a precursor to a gel electrolyte.
Gelling occurred quickly when 5 wt % of lithium iodide (376 μmols of lithium salt per gram of standard electrolyte composition) was used as the gelling agent in an electrolyte composition containing (i) 2 wt % P4VP and (ii) a mixture containing 99.5% MePrImI and 0.5% water. The gel did not flow when a vial containing the Li-induced gel was tilted upside down. One approach using a dibromo compound produced a phase-segregated electrolyte with cross-linked regions suspended in a liquid, which flows (even after gelling at 100° C. for 30 minutes). A comparison of the photovoltaic characteristics of Composition A, with and without LiI, is presented in the following Tables 6 and 7. The results demonstrate that functional gels suitable for DSSC-based photovoltaic cell fabrication can be obtained using lithium ions, while also improving the photovoltaic characteristics.











TABLE 6







Composition
Composition A
MeBuImI based



A with
with 2
electrolyte + 2 wt. %



dibromohexane
wt. % P4VP
P4VP + 5 wt. % LiI



















η (%)
2.6
3.04
3.92


Voc (V)
0.59
0.58
0.65


Isc (mA/cm2)
9.73
10.0
11.45


Vm (V)
0.38
0.38
0.42


Im (mA/cm2)
6.82
8.04
9.27



















TABLE 7







(a) Composition A where




MePrImI:water is 99.5:0.5 and with 2%
(b) Same composition as (a), but with 5 wt



P4VP and 0.09 M Iodine
% of LiI


















Physical
Reddish fluid; flows well
Non-scattering Gel; does not flow; can be


Properties

thinned by applying force using a glass rod.


Efficiency
2.53%
3.63%


Voc
0.55 V
0.62 V


Isc
9.82 mA/cm2
12.29 mA/cm2


Vm
0.343 V
0.378 V


FF
0.47
0.47









EXAMPLE 13
Effect of Anions of Lithium Salts on the Efficiency and Photovoltage of DSSCs
Experiments were performed to study the effect of counter ions on lithium, given lithium's apparent role in enhancing the overall efficiency of DSSCs. 376 μmols of LiI, LiBr, and LiCl were used per gram of the electrolyte composition containing MePrImI, 1% water, 0.25 M iodine and 0.3 M methylbenzimidazole in order to study the photovoltaic characteristics of the cells. The photovoltaic characteristics of cells containing these electrolytes are presented in Table 8.











TABLE 8







Electrolyte composition
Electrolyte composition with
Electrolyte composition



with LiI
LiBr
with LiCl



















Efficiency
 3.26%
 3.64%
 3.71%


Voc
 0.59 V
 0.62 V
 0.65 V


Isc
10.98 mA/cm2
11.96 mA/cm2
11.55 mA/cm2


Vm
 0.385 V
 0.4 V
 0.40 V


FF
 0.5
 0.49
 0.49









EXAMPLE 14
Passivation and Improved Efficiency and Photovoltage of DSSCs
In the field of photovoltaic cells, the term passivation refers to the process of reducing electron transfer to species within the electrolyte of a solar cell. Passivation typically includes treating a nanoparticle layer by immersion in a solution of t-butylpyridine in methoxypropionitrile or other suitable compound. After the nanomatrix layer, such as a titania sponge, of a photovoltaic cell has been treated with a dye, regions in the nanomatrix layer where the dye has failed to adsorb may exist. A passivation process is typically performed on a DSSC to prevent the reversible electron transfer reaction from terminating as result of reducing agents existing at the undyed regions. The typical passivation process does not appear to be necessary when ionic liquid compositions containing various lithium salts and/or other alkali metal salts are used in the DSSCs. A photovoltage greater than 0.65 V was achieved using a chloride salt of lithium without a passivation process.
In this illustrative example, a DSSC was passivated by immersing it in a solution containing 10 wt % of t-butylpyridine in methoxypropionitrile for 15 minutes. After passivation, the DSSC was dried on a slide warmer maintained at 40° C. for about 10 minutes. Electrolyte compositions containing MePrImI, 1% water, 0.3 M methylbenzimidazole, and 0.25 M iodine were gelled using 376 μmoles of LiI, LiBr, and LiCl per gram of standard electrolyte composition used during this study. Adding a t-butylpyridine-based passivation agent to the electrolyte enhanced the DSSC's photovoltage, but decreased the efficiency of the DSSC by decreasing the photoconductivity. Table 9 summarizes the effects of passivation on photovoltaic characteristics of electrolytes containing various lithium halides.











TABLE 9







Electrolyte

Electrolyte



gelled with
Electrolyte gelled with
gelled with



LiI
LiBr
LiCl



















Efficiency
 3.5%
 3.65%
 3.85%


Voc
 0.61 V
 0.63 V
 0.65 V


Isc
10.96 mA/cm2
11.94 mA/cm2
11.75 mA/cm2


Vm
 0.395 V
 0.4 V
 0.405 V


FF
 0.52
 0.49
 0.5









EXAMPLE 15
Lithium's Role in Gelling the Electrolyte Compositions Containing Polyvinylpyridine and the Effect of Other Alkali Metal Ions on Gelability
Lithium cation appears to have a unique effect in gelling ionic liquid composition containing complexable polymers, e.g., P4VP, in as small an amount as 2 wt %. Other alkali metal ions such as sodium, potassium, and cesium were used to carry out gelling experiments. Alkali metal salts such as lithium iodide, sodium chloride, potassium iodide, cesium iodide were added to portions of electrolyte composition containing propylmethylimidazolium iodide (MePrImI), 1% water, 0.25 M iodine, and 0.3 M methylbenzimidazole. Only compositions containing lithium iodide gelled under the experimental conditions used. The remaining three compositions containing sodium, potassium, and cesium did not gel at the experimental conditions used. Divalent metal ions, such as calcium, magnesium, and zinc, or trivalent metals, such as aluminum or other transition metal ions, are other potential gelling salts.
EXAMPLE 16
Effect of Iodine and Lithium Concentration on Ionic Liquid Electrolyte Gels
In this illustrative example, gels were prepared by adding lithium salts to an electrolyte composition containing MeBuImI, iodine, and 2 wt % P4VP. The photovoltaic characteristics of the gels were tested using high-temperature sintered, N3 dye sensitized titanium-oxide photoelectrodes and platinized SnO2:F coated glass slides. Both LiI and LiCl gelled the ionic liquid-based compositions that contained small amounts (2% was sufficient) of complexable polymers like P4VP. In compositions lacking methylbenzimidazole, the lithium did not effect the photovoltage. 5 wt % corresponds to a composition including about 376 μmoles of lithium salt per gram of ionic liquid and a mixture of 99 wt % butylmethylimidazolium iodide, 1 wt % water, 0.3 M methyl benzimidazole, and 0.25 M iodine. Therefore, 1 wt % corresponds to a 376/5≅75 μmoles of lithium salt per gram of ionic liquid composition. The photovoltaic characteristics are summarized in Table 10.












TABLE 10







5% LiI
2.5% LiI
5% LiCl
2.5% LiCl
























0.05 M Iodine
η =
 1.6%
η =
 1.23%
η =
 0.64%
η =
 1.19%



Voc =
 0.6 V
Voc =
 0.59 V
Voc =
 0.59 V
Voc =
 0.58 V



Isc =
 4.89 mA
Isc =
 4.21 mA
Isc =
 2.95 mA
Isc =
 3.87 mA



FF =
 0.54
FF =
 0.495
FF =
 0.36
FF =
 0.53



Vm =
 0.445 V
Vm =
 0.415 V
Vm =
 0.4 V
Vm =
 0.426 V


 0.1 M Iodine
η =
 1.22%
η =
 1.29%
η =
 2.83%
η =
 2.06%



Voc =
 0.48 V
Voc =
 0.56 V
Voc =
 0.57
Voc =
 0.58



Isc =
 6.46 mA
Isc =
 5.12 mA
Isc =
 9.04 mA
Isc =
 7.14 mA



FF =
 0.39
FF =
 0.45
FF =
 0.55
FF =
 0.5



Vm =
 0.349 V
Vm =
 0.386 V
Vm =
 0.422 V
Vm =
 0.42 V


0.25 M Iodine
η =
 2.58%
η =
 3.06%
η =
 3.4%
η =
 2.6%



Voc =
 0.55 V
Voc =
 0.55 V
Voc =
 0.56 V
Voc =
 0.56 V



Isc =
11.49 mA
Isc =
10.78 mA
Isc =
11.32 mA
Isc =
10.18 mA



FF =
 0.41
FF =
 0.52
FF =
 0.54
FF =
 0.46



Vm =
 0.338 V
Vm =
 0.36 V
Vm =
 0.369 V
Vm =
 0.364 V









EXAMPLE 17
Effect of Polymer Concentration on Gelability and Photovoltaic Characteristics of Redox Electrolyte Gels
In this illustrative example, polymer concentration was varied to study its effect on gel viscosity and photovoltaic characteristics. The electrolyte composition used for this study was a mixture containing 99% MeBuImI, 1% water, 0.25 M iodine, 0.6 M LiI, and 0.3 M methylbenzimidazole. The concentration of the polymer, P4VP was varied from 1% to 5%. The electrolyte composition with 1% P4VP did flow slowly when the vial containing the gel was tilted down. The gels with 2%, 3%, and 5% did not flow. The gel with 5% P4VP appeared much more solid when compared to the 2% P4VP preparation. Table 11 summarizes the photovoltaic characteristics of the gels containing the various P4VP contents that were studied.
The results show that the photovoltaic characteristics do not vary with the increases in viscosity achieved by increasing the P4VP content. Therefore, the viscosity of the gel can be adjusted without causing degradation to the photovoltaic characteristics. Methylbenzimidazole may be necessary to achieve high η. Increasing the iodine concentration up to 0.25 M also increased the efficiency. Beyond 0.25 M, the photovoltage decreased drastically, reducing the overall efficiency. Other metal ions or cations like cesium, sodium, potassium or tetraalkylammonium ions were not found to contribute to the efficiency enhancement and did not cause gelling of the electrolyte solutions. Furthermore, chloride anion was found to enhance the efficiency along with lithium, by improving the photovoltage without causing decreased photoconductivity in compositions containing methylbenzimidazole.











TABLE 11





Photovoltaic






Characteristics
1% P4VP
2% P4VP
3% P4VP
5% P4VP



















η (%)
3.23
3.48
3.09
3.19


Isc (mA/cm2)
10.74
10.42
12.03
10.9


Voc (V)
0.59
0.59
0.6
0.61


Vm (V)
0.39
0.4
0.38
0.40


Im (mA/cm2)
8.27
8.69
8.07
8.03


FF
0.51
0.57
0.43
0.48









C. Co-sensitizers

According to one illustrative embodiment, the photosensitizing agent described above includes a first sensitizing dye and second electron donor species, the “co-sensitizer.” The first sensitizing dye and the co-sensitizer may be added together or separately to form the photosensitized interconnected nanoparticle material 603 shown in FIG. 6. As mentioned above with respect to FIG. 6, the sensitizing dye facilitates conversion of incident visible light into electricity to produce the desired photovoltaic effect. In one illustrative embodiment, the co-sensitizer donates electrons to an acceptor to form stable cation radicals, which improves the efficiency of charge transfer from the sensitizing dye to the semiconductor oxide nanoparticle material and reduces back electron transfer to the sensitizing dye or co-sensitizer. The co-sensitizer preferably includes (1) conjugation of the free electron pair on a nitrogen atom with the hybridized orbitals of the aromatic rings to which the nitrogen atom is bonded and, subsequent to electron transfer, the resulting resonance stabilization of the cation radicals by these hybridized orbitals; and (2) a coordinating group, such as a carboxy or a phosphate, the function of which is to anchor the co-sensitizer to the semiconductor oxide. Examples of suitable co-sensitizers include, but are not limited to, aromatic amines (e.g., such as triphenylamine and its derivatives), carbazoles, and other fused-ring analogues.
Once again referring back to FIG. 6, the co-sensitizer is electronically coupled to the conduction band of the photosensitized interconnected nanoparticle material 603. Suitable coordinating groups include, but are not limited to, carboxylate groups, phosphates groups, or chelating groups, such as, for example, oximes or alpha keto enolates.
Tables 12-18 below present results showing the increase in photovoltaic cell efficiency when co-sensitizers are co-adsorbed along with sensitizing dyes on the surface of high temperature sintered or low temperature interconnected titania. In Tables 12-18, characterization was conducted using AM 1.5 solar simulator conditions (i.e., irradiation with light having an intensity of 1000 W/m2). A liquid electrolyte including 1 M LiI, 1 M t-butylpyridine, 0.5 M I2 in 3-methoxypropanitrile was employed. The data shown in the tables indicates an enhancement of one or more operating cell parameters for both low-temperature-interconnected (Tables 15, 17 and 18) and high-temperature-sintered (Tables 12, 13, 14 and 16) titania nanoparticles. The solar cells characteristics listed include η, Voc, Isc, FF, Vm, and Im. The ratios of sensitizer to co-sensitizer are based on the concentrations of photosensitizing agents in the sensitizing solution.
In particular, it was discovered that aromatic amines enhance cell performance of dye sensitized titania solar cells if the concentration of the co-sensitizer is below about 50 mol % of the dye concentration. An example of the general molecular structure of the preferred aromatic amines is shown in FIGS. 13 and 14. Preferably, the concentration of the co-sensitizer is in the range of about 1 mol % to about 20 mol %, and more preferably in the range of about 1 mol % to about 5 mol %.
FIG. 13A depicts a chemical structure 1300 that may serve as a co-sensitizer. The molecule 1300 adsorbs to the surface of a nanoparticle layer via its coordinating group or chelating group, A. A may be a carboxylic acid group or derivative thereof, a phosphate group, an oxime or an alpha ketoenolate, as described above. FIG. 13B depicts a specific embodiment 1310 of the structure 1300, namely DPABA (diphenylaminobenzoic acid), where A=COOH. FIG. 13C depicts another specific amine 1320 referred to as DEAPA (N′,N-diphenylaminophenylpropionic acid), with A as the carboxy derivative COOH.
FIG. 14A shows a chemical structure 1330 that may serve as either a co-sensitizer, or a sensitizing dye. The molecule does not absorb radiation above 500 nm, and adsorbs to a surface of the nanoparticle layer via its coordinating or chelating groups, A. A may be a carboxylic acid group or derivative thereof, a phosphate group, an oxime or an alpha ketoenolate. R1 and R2 may each be a phenyl, alkyl, substituted phenyl, or benzyl group. Preferably, the alkyl may contain between 1 and 10 carbons. FIG. 14B depicts a specific embodiment 1340 of the structure 1330, namely DPACA (2,6 bis (4-benzoicacid)-4-(4-N,N-diphenylamino) phenylpyridine carboxylic acid), where R1 and R2 are phenyl and A is COOH.
DPACA 1340 may be synthesized as follows. 1.49 g (9.08 mmol) of 4-acetylbenzoic acid, 1.69 g (6.18 mmol) of 4-N,N-diphenylbenzaldehyde, and 5.8 g (75.2 mmol) of ammonium acetate were added to 60 ml of acetic acid in a 100 ml round bottom flask equipped with a condenser and stirring bar. The solution was heated to reflux with stirring under nitrogen for 5 hours. The reaction was cooled to room temperature and poured into 150 ml of water, which was extracted with 150 ml of dichloromethane. The dichloromethane was separated and evaporated with a rotary evaporator, resulting in a yellow oil. The oil was then eluted on a silica gel column with 4% methanol/dichloromethane to give the product, an orange solid. The solid was washed with methanol and vacuum dried to give 0.920 g of 2,6 bis (4-benzoicacid)-4-(4-N,N-diphenylamino)phenylpyridine (DPACA). The melting point was 199°-200° C., the λmax was 421 nm, and the molar extinction coefficient, E was 39,200 L mole−1 cm−1. The structure was confirmed by NMR spectroscopy.
Table 12 shows the results for high-temperature-sintered titania; photosensitized by overnight soaking in solutions of 1 mM N3 dye and three concentrations of DPABA. Table 12 also shows that the average η is greatest for the preferred 20/1 (dye/co-sensitizer) ratio.









TABLE 12









I-V CHARACTERIZATION


















Cell









General

area
Voc
Im
Vm
Isc

η



conditions
Conditions
cm2
V
mA/cm2
V
mA/cm2
FF
%
σ





Adsorption
1 mM
0.44
0.62
6.69
0.44
8.38
0.56
2.91



Temp.
N3/EtOH,
0.52
0.64
6.81
0.43
8.59
0.54
2.94



RT ° C.
Overnight
0.54
0.63
6.95
0.41
8.72
0.52
2.84




CONTROL


Solvent
Average
0.50
0.63
6.82
0.43
8.56
0.54
2.90
0.05


of Dye


EtOH


Dye Concen.
1 mM N3,
0.50
0.64
7.70
0.45
9.31
0.58
3.43




0.05 mM


N3, DPABA
DPABA in
0.53
0.64
7.40
0.45
9.30
0.56
3.31




EtOH for
0.50
0.64
7.70
0.45
9.38
0.57
3.44




Overnight;



20/1


Sintering
Average
0.51
0.64
7.60
0.45
9.33
0.57
3.39
0.07


Temp


450° C., 30


minutes


Thickness of
1 mM N3, 1
0.53
0.63
7.21
0.41
8.58
0.55
2.96



Film
mM DPABA
0.50
0.63
6.75
0.44
8.23
0.57
2.97



TiO2,  ̃10 μm
in EtOH for
0.42
0.63
7.11
0.44
8.67
0.57
3.13




Overnight;



1/1



Average
0.48
0.63
7.02
0.43
8.49
0.56
3.02
0.10


Electrolyte
1 mM N3, 10
0.33
0.58
4.95
0.42
6.02
0.60
2.08



AM 1.5D, l 1
mM DPABA
0.52
0.60
5.51
0.42
6.67
0.58
2.31



Sun
in EtOH for
0.49
0.60
5.53
0.42
6.72
0.58
2.32




Overnight;



1/10


Film
Average
0.45
0.59
5.33
0.42
6.47
0.58
2.24
0.14


pretreatment









Table 13 shows the results of using a cut-off filter (third and fourth entries) while irradiating a cell to test its I-V characteristics. Table 13 also shows that the efficiency of the cell still improves when DPABA is present, indicating that its effect when no filter is present is not simply due to absorption of UV light by DPABA followed by charge injection. FIG. 15 shows a plot 1400 of the absorbance versus wavelength for the cut-off filter used to characterize the photovoltaic cells, according to an illustrative embodiment of the invention. FIG. 16 shows a plot 1500 of the absorbance versus wavelength for DPABA, which absorbs below 400 nm. Because the absorbance of the cut-off is large, little light reaches the absorption bands of DPABA.









TABLE 13









I-V CHARACTERIZATION
















Cell










area
Voc
Im
Vm
Isc

η



Conditions
cm2
V
mA/cm2
V
mA/cm2
FF
%
σ


















1 mM N3 in
0.49
0.70
8.62
0.46
11.02
0.51
3.97



EtOH


Overnight
0.49
0.70
8.13
0.45
10.20
0.51
3.66



control



0.49
0.73
7.93
0.51
9.69
0.57
4.04



Average
0.49
0.71
8.23
0.47
10.30
0.53
3.89
0.20


1 mM N3
0.49
0.71
9.05
0.46
11.53
0.51
4.16



0.05 mM


DPABA in
0.49
0.71
9.24
0.46
11.56
0.52
4.25



EtOH, 20/1


Overnight
0.49
0.71
9.39
0.46
11.50
0.53
4.32



Average
0.49
0.71
9.23
0.46
11.53
0.52
4.24
0.08


1 mM N3 in
0.49
0.69
6.35
0.47
7.83
0.55
4.26
455 nm cut


EtOH







off filter


Overnight
0.49
0.69
6.05
0.46
7.44
0.54
3.98
used,


control







70



0.49
0.72
5.74
0.52
6.94
0.60
4.27
mW/cm2


Average
0.49
0.70
6.05
0.48
7.40
0.56
4.17
0.17


1 mM N3
0.49
0.70
6.73
0.47
8.21
0.55
4.52
455 nm cut


0.05 mM







off filter


DPABA in
0.49
0.70
6.74
0.47
8.19
0.55
4.53
used,


EtOH, 20/1







70


Overnight
0.49
0.70
6.74
0.49
8.25
0.57
4.72
mW/cm2


Average
0.49
0.70
6.74
0.48
8.22
0.56
4.59
0.11









Table 14 shows that the addition of triphenylamine itself (i.e., no titania complexing groups such as carboxy) does not significantly enhance efficiency under the stated conditions.









TABLE 14









I-V CHARACTERIZATION
















Cell










area
Voc
Im
Vm
Isc

η



Conditions
cm2
V
mA/cm2
V
mA/cm2
FF
%
σ





0.5 mM N3
0.49
0.70
7.96
0.45
9.82
0.52
3.58



in EtOH,


Overnight
0.49
0.71
8.09
0.48
9.58
0.57
3.88




0.49
0.70
7.47
0.48
8.83
0.58
3.59



Average
0.49
0.70
7.84
0.47
9.41
0.56
3.68
0.17


0.5 mM N3,
0.49
0.69
7.44
0.45
9.21
0.53
3.35



0.025 mM


TPA in
0.49
0.69
7.61
0.47
9.75
0.53
3.58



EtOH


Overnight
0.49
0.69
6.98
0.45
8.56
0.53
3.14



20/1


Average
0.49
0.69
7.34
0.46
9.17
0.53
3.36
0.22


0.5 mM N3,
0.49
0.68
4.62
0.44
5.66
0.53
2.03



2.0 mM


TPA in
0.49
0.66
4.18
0.45
5.38
0.53
1.88



EtOH


Overnight
0.49
0.66
4.51
0.45
5.82
0.53
2.03



1⁄4


Average
0.49
0.67
4.44
0.45
5.62
0.53
1.98
0.09









Table 15 shows that the effect is present using low temperature interconnected titania and that the 20/1 (dye/co-sensitizer) ratio is preferred.









TABLE 15









I-V CHARACTERIZATION
















Cell area
Voc
Im
Vm
Isc

η



Conditions
cm2
V
mA/cm2
V
mA/cm2
FF
%
σ


















0.5 mM
0.49
0.73
8.32
0.50
10.56
0.54
4.16



N3/EtOH,


overnight,
0.51
0.72
8.13
0.49
10.30
0.54
3.98



control
0.50
0.72
8.56
0.47
10.65
0.52
4.02



Average
0.50
0.72
8.34
0.49
10.50
0.53
4.06
0.09


0.5 mM N3,
0.49
0.73
8.55
0.51
10.48
0.57
4.36



0.0125 mM


DPABA in
0.53
0.72
8.53
0.50
11.00
0.54
4.27



EtOH, 40/1,


overnight
0.49
0.74
8.08
0.54
10.96
0.54
4.36



Average
0.50
0.73
8.39
0.52
10.81
0.55
4.33
0.06


0.5 mM N3,
0.49
0.73
9.07
0.49
11.31
0.54
4.44



0.017 mM


DPABA in
0.49
0.75
8.64
0.52
10.97
0.55
4.49



EtOH, 30/1,


overnight
0.52
0.73
8.19
0.52
10.88
0.54
4.26



Average
0.50
0.74
8.63
0.51
11.05
0.54
4.40
0.12


0.5 mM N3,
0.50
0.75
8.57
0.52
11.56
0.51
4.46



0.025 mM


DPABA in
0.49
0.74
8.88
0.52
11.45
0.54
4.62



EtOH, 20/1,


overnight
0.53
0.74
9.01
0.51
12.08
0.51
4.60



Average
0.51
0.74
8.82
0.52
11.70
0.52
4.56
0.09


0.5 mM N3,
0.49
0.72
8.85
0.48
10.78
0.55
4.25



0.5 mM


DPABA in
0.51
0.74
8.62
0.47
10.37
0.53
4.05



EtOH, 1/1,


overnight
0.50
0.75
8.38
0.49
10.02
0.55
4.11



Average
0.50
0.74
8.62
0.48
10.39
0.54
4.14
0.10


0.5 mM N3,
0.49
0.68
7.56
0.44
9.09
0.54
3.33



5 mM


DPABA in
0.51
0.69
7.62
0.46
9.34
0.54
3.51



EtOH, 1/10,


overnight
0.49
0.67
7.25
0.45
8.84
0.55
3.26



Average
0.50
0.68
7.48
0.45
9.09
0.54
3.36
0.13









Table 16 shows results for high-temperature-sintered titania sensitized with a high concentration of N3 dye while maintaining a 20/1 ratio of dye to co-sensitizer. Entries 1 and 2 show the increase in cell performance due to co-sensitizer. Entry 3 shows the effect of DPABA alone as a sensitizer, demonstrating that this material acts as a sensitizer by itself when irradiated with the full solar spectrum, which includes low-intensity UV radiation.









TABLE 16









I-V CHARACTERIZATION
















General

Cell area
Voc
Im
Vm
Isc

η



Conditions
Conditions
cm2
V
mA/cm2
V
mA/cm2
FF
%
σ



















Adsorption
8 mM
0.49
0.68
8.51
0.44
10.07
0.55
3.74



Temp.
N3/aprotic
0.49
0.67
8.28
0.44
9.75
0.56
3.64



RT ° C.
polar solvent,


Solvent of Dye
1 hour
0.49
0.68
9.16
0.42
10.80
0.52
3.85




CONTROL


Aprotic polar
average
0.49
0.68
8.65
0.43
10.21
0.54
3.74
0.10


solvent



8 mM N3, 0.4
0.49
0.68
9.52
0.44
11.18
0.55
4.19




mM DPABA



in aprotic polar
0.49
0.68
9.96
0.44
11.59
0.56
4.38




solvent,



20/1
0.49
0.65
9.81
0.42
12.13
0.52
4.12




1 hour



average
0.49
0.67
9.76
0.43
11.63
0.54
4.23
0.14



5 mM DPABA
0.49
0.55
1.02
0.42
1.22
0.64
0.43




in aprotic polar
0.49
0.55
0.94
0.41
1.13
0.62
0.39




solvent



Overnight
0.49
0.58
0.89
0.44
1.07
0.63
0.39





0.49
0.56
0.95
0.42
1.14
0.63
0.40
0.02









Table 17 shows results for low-temperature-interconnected titania. Entry 5 shows the affect of DPACA alone as a sensitizer, demonstrating that this material acts as a sensitizer by itself when irradiated with the full solar spectrum, which includes low-intensity UV radiation.









TABLE 17









I-V CHARACTERIZATION
















Cell










area
Voc
Im
Vm
Isc

η



Conditions
cm2
V
mA/cm2
V
mA/cm2
FF
%
σ


















0.5 mM
0.51
0.73
8.40
0.50
10.84
0.53
4.20



N3/EtOH,


overnight,
0.53
0.72
8.13
0.49
10.30
0.54
3.98



control
0.50
0.72
8.77
0.47
10.87
0.53
4.12



average
0.51
0.72
8.43
0.49
10.67
0.53
4.10
0.11


0.5 mM N3,
0.49
0.73
8.10
0.51
10.39
0.54
4.13



0.01 mM


DPACA in
0.50
0.74
7.95
0.50
10.01
0.54
3.98



EtOH, 50/1,


overnight
0.49
0.72
8.10
0.50
9.85
0.57
4.05



average
0.49
0.73
8.05
0.50
10.08
0.55
4.05
0.08


0.5 mM N3,
0.49
0.74
8.38
0.50
10.48
0.54
4.19



0.02 mM


DPACA in
0.52
0.73
8.18
0.48
9.74
0.55
3.93



EtOH, 25/1,


overnight
0.49
0.76
8.08
0.54
9.45
0.61
4.36



average
0.50
0.74
8.21
0.51
9.89
0.57
4.16
0.22


0.5 mM N3,
0.49
0.73
9.07
0.46
11.31
0.51
4.17



0.5 mM


DPACA in
0.49
0.75
7.41
0.53
9.24
0.57
3.93



EtOH, 1/1,


overnight
0.52
0.76
7.93
0.52
9.12
0.59
4.12



average
0.50
0.75
8.14
0.50
9.89
0.56
4.07
0.13


0.5 mM N3,
0.56
0.73
6.36
0.49
7.59
0.56
3.12



5.0 mM


DPACA in
0.52
0.73
6.63
0.49
7.84
0.57
3.25



EtOH, 1/10,


overnight
0.50
0.72
6.53
0.49
7.59
0.59
3.20



average
0.53
0.73
6.51
0.49
7.67
0.57
3.19
0.07


5.0 mM
0.43
0.65
3.12
0.49
3.77
0.62
1.53



DPACA in
0.45
0.65
2.93
0.49
3.51
0.63
1.44



EtOH,


overnight
0.49
0.66
2.83
0.49
3.40
0.62
1.39



average
0.46
0.65
2.96
0.49
3.56
0.62
1.45
0.07









Table 18 shows results for low-temperature-interconnected titania. Entry 6 shows the affect of DEAPA alone as a sensitizer, demonstrating that this material acts as a sensitizer by itself when irradiated with the full solar spectrum, which includes low-intensity UV radiation.









TABLE 18









I-V CHARACTERIZATION
















General

Cell area
Voc
Im
Vm
Isc

η



conditions
Conditions
cm2
V
mA/cm2
V
mA/cm2
FF
%
σ



















Adsorption
0.5 mM
0.51
0.72
8.67
0.49
10.60
0.56
4.25



Temp.
N3/EtOH,


RT ° C.
overnight,
0.49
0.75
8.15
0.47
10.50
0.49
3.83




control
0.49
0.74
8.74
0.44
10.63
0.49
3.85



Solvent of
average
0.50
0.74
8.52
0.47
10.58
0.51
3.97
0.24


Dye


EtOH


Dye Concen.
0.5 mM N3,
0.49
0.70
8.68
0.44
11.00
0.50
3.82




0.01 mM


N3, DEAPA
DEAPA in
0.52
0.71
8.57
0.45
11.11
0.49
3.86




EtOH, 50/1,



overnight
0.50
0.72
8.40
0.45
10.61
0.49
3.78



Sintering
average
0.50
0.71
8.55
0.45
10.91
0.49
3.82
0.04


Temp


120° C., 10


minutes


Thickness of
0.5 mM N3,
0.51
0.74
8.90
0.44
10.92
0.48
3.92



Film
0.02 mM


TiO2,  ̃7 μm
DEAPA in
0.53
0.73
8.76
0.44
10.51
0.50
3.85




EtOH, 25/1,



overnight
0.49
0.73
8.40
0.45
10.21
0.51
3.78



Liquid
average
0.51
0.73
8.69
0.44
10.55
0.50
3.85
0.07


Electrolyte
0.5 mM N3,
0.49
0.71
8.94
0.43
10.78
0.50
3.84




0.5 mM


AM 1.5D, 1
DEAPA in
0.51
0.71
8.83
0.44
10.37
0.53
3.89



Sun
EtOH, 1/1,



overnight
0.50
0.70
8.18
0.42
9.71
0.51
3.44



Film
average
0.50
0.71
8.65
0.43
10.29
0.51
3.72
0.25


pretreatment



0.5 mM N3,
0.52
0.60
0.88
0.45
1.08
0.61
0.40




5.0 mM



DEAPA in
0.49
0.59
0.71
0.44
0.85
0.62
0.31




EtOH, 1/10,



overnight
0.49
0.59
0.75
0.44
0.91
0.61
0.33




average
0.50
0.59
0.78
0.44
0.95
0.62
0.35
0.04



5.0 mM
0.49
0.54
0.41
0.42
0.49
0.65
0.17




DEAPA in
0.49
0.54
0.35
0.39
0.46
0.55
0.14




CHCl3,



overnight
0.51
0.52
0.45
0.40
0.52
0.67
0.18




average
0.50
0.53
0.40
0.40
0.49
0.62
0.16
0.02









D. Semiconductor Oxide Formulations

In a further illustrative embodiment, the invention provides semiconductor oxide formulations for use with DSSCs formed using a low temperature semiconductor oxide nanoparticle interconnection, as described above. The semiconductor oxide formulations may be coated at room temperature and, upon drying at temperatures between about 50° C. and about 150° C., yield mechanically stable semiconductor nanoparticle films with good adhesion to the transparent conducting oxide (TCO) coated plastic substrates. In one embodiment, the nanoparticle semiconductor of the photosensitized interconnected nanoparticle material 603 is formed from a dispersion of commercially available TiO2 nanoparticles in water, a polymer binder, with or without acetic acid. The polymer binders used include, but are not limited to, polyvinylpyrrolidone (PVP), polyethylene oxide (PEO), hydroxyethyl cellulose (HOEC), hydroxypropyl cellulose, polyvinyl alcohol (PVA) and other water-soluble polymers. The ratio of semiconductor oxide particles, e.g., TiO2, to polymer can be between about 100:0.1 to 100:20 by weight, and preferably is between about 100:1 to 100:10 by weight. The presence of acetic acid in the formulation helps to improve the adhesion of the coating to the TCO coated substrate. However, acetic acid is not essential to this aspect of the invention and semiconductor oxide dispersions without acetic acid perform satisfactorily. In another embodiment, the TiO2 nanoparticles are dispersed in an organic solvent, such as, e.g., isopropyl alcohol, with polymeric binders such as, e.g., PVP, butvar, ethylcellulose, etc.
In another illustrative embodiment, the mechanical integrity of the semiconductor oxide coatings and the photovoltaic performance of the dye sensitized cells based on these coatings can be further improved by using a crosslinking agent to interconnect the semiconductor nanoparticles. The polylinkers described above may be used for this purpose. These crosslinking agents can be applied, e.g., in the titania coating formulation directly or in a step subsequent to drying the titania coating as a solution in an organic solvent such as ethanol, isopropanol or butanol. For example, subsequent heating of the films to temperatures in the range of about 70° C. to about 140° C. leads to the formation of TiO2 bridges between the TiO2 nanoparticles. Preferably, the concentration of the polylinker in this example ranges from about 0.01 to about 20 weight % based on titania.
E. Semiconductor Primer Layer Coatings
In another illustrative embodiment, the invention provides semiconductor oxide materials and methods of coating semiconductor oxide nanoparticle layers on a base material to form DSSCs. FIG. 17 depicts an illustrative embodiment 1600 of the coating process, according to the invention. In this illustrative embodiment, a base material 1610 is coated with a first primer layer 1620 of a semiconductor oxide, and then a suspension of nanoparticles 1630 of the semiconductor oxide is coated over the primer layer 1620. The primer layer 1620 may include a vacuum-coated semiconductor oxide film (e.g., a TiO2 film). Alternatively, the primer layer 1620 may include a thin coating with fine particles of a semiconductor oxide (e.g. TiO2, SnO2). The primer layer 1620 may also include a thin layer of a polylinker or precursor solution, one example of which is the Ti (IV) butoxide polymer 400 shown in FIG. 4 above. According to one illustrative embodiment of the invention, the base material 1610 is the first flexible, significantly light transmitting substrate 609 referred to in FIG. 6. Additionally, the base material 1610 is a transparent, conducting, plastic substrate. According to this illustrative embodiment, the suspension of nanoparticles 1630 is the photosensitized interconnected nanoparticle material 603 of FIG. 6. Numerous semiconducting metal oxides, including SnO2, TiO2, Ta2O5, Nb2O5, and ZnO, among others, in the form of thin films, fine particles, or precursor solutions may be used as primer layer coatings using vacuum coating, spin coating, blade coating or other coating methods.
The primer layer 1620 improves the adhesion of nano-structured semiconductor oxide films, like layer 1630, to the base material 1610. Enhancements in the performance of DSSCs with such primer layers have been observed and will be described below. The enhancement arises from an increase in the adhesion between the semiconductor oxide nanoparticles (or photoelectrodes) and the transparent conducting oxide coated plastic substrates, as well as from higher shunt resistance.
Examples of various illustrative embodiments of this aspect of the invention, in the context of a DSSC including a titanium dioxide nanoparticle layer, are as follows.
EXAMPLE 18
Vacuum Coated TiO2 as Prime Layers for Nanoparticle TiO2 Photoelectrodes
In this illustrative example, thin TiO2 films with thicknesses ranging from 2.5 nm to 100 nm were sputter-coated under vacuum on an ITO layer coated on a polyester (here, PET) substrate. A water based TiO2 (P25, with an average particle size of 21 nm) slurry was spin-coated on both the ITO/PET with sputter-coated thin TiO2 and on the plain ITO/PET (i.e., the portion without sputter-coated thin TiO2). The coated films were soaked in poly [Ti(OBu)4] solution in butanol and then heat treated at 120° C. for 2 minutes. The low-temperature reactively interconnected films were placed into an aprotic, polar solvent-based N3 dye solution (8 mM) for 2 minutes. Photovoltaic cells were made with platinum (Pt) counter-electrodes, an I−/I3− liquid electrolyte, 2 mil SURLYN, and copper conducting tapes. I-V characterization measurements were performed with a solar simulator.
Adhesion of nanostructured TiO2 films from the P25 slurry coated on the ITO/PET with sputter-coated, thin TiO2 was superior to films on the plain ITO/PET. Better photovoltaic performance was also observed from the PV cells prepared on the ITO/PET with sputter-coated, thin TiO2 as compared to those on the plain ITO/PET. Improvement on the fill-factor was achieved as well. A FF as high as 0.67 was measured for the photovoltaic cells made on the ITO/PETs with sputter-coated, thin TiO2. For the photovoltaic cells made on the plain ITO/PET, the FF observed was not greater than 0.60. Higher photovoltaic conversion efficiencies (about 17% higher than the photoelectrodes made from the plain ITO/PET) were measured for the photoelectrodes prepared on the ITO/PET with thin sputter-coated TiO2. Improvement in shunt resistance was also observed for the photovoltaic cells made on the ITO/PET with thin sputter-coated TiO2.
EXAMPLE 19
Fine Particles of TiO2 as Primer Layer for TiO2 Suspensions
In this illustrative example, fine particles of TiO2, small enough such that they would stick in the valleys between spikes of ITO on the PET substrate, were prepared by hydrolyzing titanium (IV) isopropoxide. The fine particles were then spin coated at 800 rpm onto the ITO layer. A 37% TiO2 (P25) suspension of approximately 21 nm average particle size was then spin coated at 800 rpm onto the fine particle layer. The coated TiO2 was low temperature interconnected by dipping in 0.01 molar Ti (IV) butoxide polymer in butanol for 15 minutes followed drying on a slide warmer at 50° C. before heating at 120° C. for 2 minutes. The interconnected coating was dyed with N3 dye by dipping into an 8 mM aprotic polar solvent solution for 2 minutes, then rinsed with ethanol and dried on a slide warmer at 50° C. for 2 minutes. Control coatings were prepared in the same way, except without the fine particle prime coat. The cells' performance characteristics were measured using a solar simulator. Results for test and control are listed below in Table 19. Fine particles of tin oxide as primer coating for TiO2 suspensions yielded similar improvements.












TABLE 19







Voc
Isc
η
FF






















Control
0.64
4.86
1.67%
0.54



Invention
0.66
6.27
2.36%
0.57










EXAMPLE 20
Titanium (IV) Butoxide Polymer in Butanol (Precursor Solution) as Primer Layer for TiO2 
In another test, titanium (IV) butoxide polymer in butanol at 0.01 molar was spin coated on an ITO/PET plastic base at 800 rpm. A 43% TiO2 (P25) suspension of approximately 21 nm average particle size was spin coated at 800 rpm. The coated TiO2 was interconnected at low temperature by dipping in 0.01 M titanium (IV) butoxide polymer in butanol for 15 minutes and then drying on a slide warmer at 50° C. before heating at 120° C. for 2 minutes. The sintered coating was dyed with N3 dye by dipping into an 8 mM aprotic, polar solvent solution for 2 minutes, then rinsed with ethanol and dried on a slide warmer at 50° C. for 2 minutes. Control coatings were prepared in the same way only without the primer layer coating. The I-V properties of the cells were measured with a solar simulator. Results for test and control are listed below in Table 20.












TABLE 20







Voc
Isc
η
FF






















Control
0.66
7.17
2.62%
0.56



Invention
0.70
8.11
3.38%
0.59










While the invention has been particularly shown and described with reference to specific illustrative embodiments, it should be understood that various changes in form and detail may be made without departing from the spirit and scope of the invention as defined by the appended claims. By way of example, any of the disclosed features may be combined with any of the other disclosed features to form a photovoltaic cell or module.

## Claims

1. A polymeric linking agent mixture comprising:
a polymeric linking agent of the formula —[O—M(OR)i—]m—; 
a plurality of metal oxide nanoparticles comprised of one or more compounds having the formula MxOy; and 
a solvent, 

wherein (i) i, x, and y are integers greater than zero, (ii) m is an integer greater than one, (iii) M is selected from the group consisting of Ti, Zr, Sn, W, Nb, La, Ta, and Tb, (iv) R is from the group consisting of hydrogen, alkyls, alkenes, alkynes, aromatics, and acyls, and (v) the mixture contains the polymeric linking agent in a concentration sufficient to interconnect at least a portion of the plurality of metal oxide nanoparticles at a temperature below about 300° C.

2. The polymeric linking agent mixture of claim 1, wherein the mixture contains the polymeric linking agent in a concentration sufficient to interconnect at least a portion of the plurality of nanoparticles at a temperature below about 100° C.

3. The polymeric linking agent mixture of claim 1, wherein the mixture contains the polymeric linking agent in a concentration sufficient to interconnect at least a portion of the plurality of metal oxide nanoparticles at a temperature below about 200° C.

4. The polymeric linking agent mixture of claim 1, wherein the mixture contains the polymeric linking agent in a concentration sufficient to interconnect at least a portion of the plurality of metal oxide nanoparticles at a temperature of about room temperature.

5. The polymeric linking agent mixture of claim 1, wherein at least one reactive group of the polymeric linking agent having the formula —[O—M(OR)i—]m— bonds to the plurality of metal oxide nanoparticles.

6. The polymeric linking agent mixture of claim 1, wherein the polymeric linking agent comprises poly(n-butyl titanate).

7. The polymeric linking agent mixture of claim 1, wherein the solvent comprises n-butanol.

8. The polymeric linking agent mixture of claim 5, wherein at least a portion of the plurality of metal oxide nanoparticles are interconnected via a mechanical bridge formed by the at least one reactive group binding with the plurality of metal oxide nanoparticles.

9. The polymeric linking agent mixture of claim 5, wherein at least a portion of the plurality of metal oxide nanoparticles are interconnected via an electrical bridge formed by the at least one reactive group binding with the plurality of metal oxide nanoparticles.

10. The polymeric linking agent mixture of claim 1, further comprising a modifier contacting at least a portion of the plurality of metal oxide nanoparticles.

11. The polymeric linking agent mixture of claim 1, wherein the plurality of metal oxide nanoparticles comprises nanoparticles of materials selected from the group consisting of titanium oxides, zirconium oxides, tungsten oxides, niobium oxides, lanthanum oxides, tin oxides, terbium oxides, tantalum oxides, and one or more combinations thereof.

12. The polymeric linking agent mixture of claim 1, wherein the plurality of metal oxide nanoparticles comprises particles with an average size in the range of 10 nm to 40 nm.

13. The polymeric linking agent mixture of claim 1, wherein the plurality of metal oxide nanoparticles comprises a photosensitizing agent.

14. The polymeric linking agent mixture of claim 13, wherein the photosensitizing agent comprises a molecule selected from the group consisting of xanthines, cyanines, merocyanines, phthalocyanines, and pyrroles.

15. The polymeric linking agent mixture of claim 13, wherein the photosensitizing agent comprises a metal ion selected from the group consisting of divalent and trivalent metals.

16. The polymeric linking agent mixture of claim 13, wherein the photosensitizing agent comprises at least one of a ruthenium transition metal complex, an osmium transition metal complex, and an iron transition metal complex.

17. The polymeric linking agent mixture of claim 11, wherein the plurality of metal oxide nanoparticles further comprises zinc oxides.