# Patent

## Title
Highly efficient dye-sensitized solar cells using microtextured electron collecting anode and nanoporous and interdigitated hole collecting cathode and method for making same

## Abstract

The present invention generally relates to the field of photovoltaic devices. Specifically, the present invention relates to the areas of dye sensitized solar cells (DSSCs).

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to the field of photovoltaic devices. Specifically, the present invention relates to the areas of dye sensitized solar cells (DSSCs).
2. Description of Related Art
As global climate change becomes an issue of increasing concern, cutting greenhouse gas emissions from energy production has become top priority. Solar energy is currently thought to hold immense potential as a reliable clean energy source. Effective utilization of solar energy relies on the development of efficient photovoltaic devices including dye sensitized solar cells (DSSCs).
Nanocrystalline dye-sensitized solar cells (DSSC) are appealing devices for solar-electric energy conversion because of their potentially low cost, and simple process in comparison to silicon-based photovoltaics. In a classic DSSC device configuration, the incident solar light first penetrates the device through a piece of transparent conducting oxide (TCO) glass, on which a thick layer of interconnected semiconducting nanoparticles (NP) such as TiO2 are coated to provide a large internal surface area for anchoring the light-harvesting dye molecules, whose lowest unoccupied molecular orbital matches the conduction band edge of the nanoparticles. The dye molecules are excited by the incident photons, leading to electron-hole pairs (excitons), of which the electrons are quickly injected into the conduction band of the semiconducting nanoparticles and subsequently collected by the TCO anode, while the holes in the highest unoccupied molecular orbital are refilled by electrons from the cathode via redox species, e.g. an I−/I3− couple in an electrolyte that interpenetrates the nanoparticle network.
The trap-limited electron transport in the nanoparticle network often leads to low electron-collection efficiency, thereby leading to low energy conversion efficiency, inherently due to the defect states at the particle-particle interface or in the bulk of the nanoparticles, where the congested electrons are recombined with the oxidized dye molecules or redox species such as I3−. On the other hand, the photocurrent is also influenced by the diffusion of the I−/I3− couple in electrolyte.
The overall efficiency (η) of a solar cell is calculated from η=(FF×|Jsc|×Voc)/I, where Jsc is the short circuit photocurrent density, Voc is the open-circuit photovoltage, FF is the fill factor of the cell and I is the light intensity (I=0.1 W/cm2 for one sun at AM 1.5 G). In addition to maximizing the overlap of the absorption window of dyes and the solar spectrum through the discovery of new dyes, Jsc can also be improved by thickening the TiO2 nanoparticle film for increased optical density. However, a dilemma arises in that the electron diffusion length, typically 10 μm in TiO2 nanoparticle networks, limits the useful TiO2 nanoparticle film thickness.
Many efforts are focused on improving the electron diffusion length by using nanostructured anodes with a higher degree of order than the random fractal-like assembly of nanoparticles. Those semiconducting nanostructures include nonporous channels, nanotubes, or even single-crystalline nanowires that are all aligned in parallel to each other and vertically with respect to the TCO glass.
For example, enhanced electron transfers have been reported in various n-type semiconducting layers consisting of arrays of one-dimensional (1-D) nanostructures including ZnO nanowires and nanotubes, TiO2 nanotubes, etc. These highly ordered 1-D semiconducting nanostructures provide an ordered pathway for electrons percolating to the collecting anode, in contrast to the highly disordered electron pathway found in a nanoparticulate layer that can lead to significant scattering of free electrons at the particle-particle interfaces. In addition, if the radius of the 1-D n-type semiconductors is large enough, an upward band bending at the semiconductor surface can form, which suppresses the adverse back electron transfers from the semiconductor to the electrolyte or to the oxidized dyes. This is because the Fermi level of an n-type semiconductor is typically higher than the redox potential of the electrolyte. To equilibrate the two electron levels, electrons flow from the semiconductor into the electrolyte. As a result, there is a built-in circular electric field from the surface of the semiconductor nanowires towards their centers. This internal electric field pulls the injected electrons towards the center of the wire and reduces the interception of the electrons by the electrolyte around the surface of the wire. The suppression of back electron transfer improves the current density of the cells.
However, so far, none of these ordered 1-D semiconductor-based DSSCs have achieved an efficiency exceeding that of conventional TiO2 nanoparticle-based DSSCs. This is because many other device parameters are often interlinked, which can offset or reduce the improvements available through the new features. One particular problem is the diametric opposing effect resulting from increasing the length of the ZnO nanowires. On one hand, longer wires exhibit higher short circuit current (Jsc) due to the increased surface area and thus higher dye loading. On the other hand, longer wires lead to higher series resistance, thus lowering the fill factor (FF). Narrower, thus denser nanowires appear as a potential approach to overcome this problem. However, if the Debye-Hückel screening length exceeds the wire radius, reducing the diameter of the wires can eliminate the upward band bending at the wire's surface, an advantage of 1-D semiconductor elucidated above. Typically, depending on the carrier density and the electrolyte, the width of the depletion layer can extend to tens of nanometers into the ZnO wires.
Another fundamental bottleneck that substantially impedes the advantages brought about by 1-D semiconductor photoanode is the slow hole transport that is carried by redox species through mass transport in electrolyte. In all DSSCs that are based on the I−/I3− as redox shuttle, the cathode is essentially a planar platinized TCO that is separated from the semiconductor layer by the electrolyte. Pt is an indispensable catalyst for efficient reduction of I3− to I−. The Pt cathode is typically 20 ̃40 μm apart from the top of the semiconductor layer, defined by a polymer spacer as sealer. The diffusion coefficient of I3− in the electrolyte is less than 10-4 cm2/s at room temperature, which is 2 ̃3 orders of magnitude slower than the electron diffusion coefficient in 1-D semiconductor nanowires (>10-2 cm2/s for ZnO nanowires, for example). Thus, the synchronism of charge carriers (both electrons and holes) transport can no longer be established. As a result, many adverse back electron transfers will take place including the recombination of the electron the semiconductors with dye+ and I3− as well as the formation of dye+−I3− complex.
These dilemmas make it especially necessary to explore further innovations to drastically improve this fascinating photovoltaic device. The aim is (1) to increase the effective semiconductor thickness in the conventional nanoparticle-based DSSC without exceeding the electron diffusion length, (2) to increase the surface roughness of 1-D nanostructured semiconductor without significantly increasing the length, and thus the series resistance; (3) to alter the route of I−/I3− diffusion pathways to catch up with the fast electron transport in the 1-D ordered semiconductor-based photoanode so that the electron/hole transport can be synchronized to exert the advantage of fast electron transport in 1-D photoanode; and (4) to enhance the interfacial rectifying effect to suppress the back electron transfer.
SUMMARY OF THE INVENTION
The present invention presents an improved dye-sensitized solar cell (DSSC) including microtextured TCO glass as an anode, thereby providing a greater surface area to accommodate more TiO2 nanoparticles without increasing the electron transport distance in the TiO2 nanoparticle layer, and resulting in significantly enhanced electron harvest in a traditional TiO2 nanoparticle (NP) DSSC. In addition, the present invention includes a Pt-coated nanoporous anodized aluminum oxide (AAO) placed directly on the TiO2 layer to serve as cathode in order to shorten the distance for hole transport.
The present invention further presents an improved dye-sensitized solar cell (DSSC) that uses a flat TCO as anode, on which an array of free-standing metallic micropillars are deposited to serve as shortcuts for electron diffusion in the nanoparticle network, thereby significantly enhancing the electron harvest beyond that of conventional TiO2 nanoparticle-based dye-sensitized solar cells.
The present invention further presents an improved dye-sensitized solar cell (DSSC) including a nanoscale interdigitated TCO anode and Pt cathode, thereby significantly enhancing the electron and hole transport beyond that of conventional TiO2 nanoparticle-based dye-sensitized solar cells.
The present invention additionally presents a method for manufacturing improved dye-sensitized solar cells (DSSC) including a microtextured TCO comprising the steps of: preparing a photolithographic pattern, applying a reactive ion etching, coating the TCO layer, preparing TiO2 nanocrystalline dye-sensitized solar cells, preparing and fabricating nanoporous platinized counter electrodes (cathode), and assembling a dye-sensitized solar cell.



DESCRIPTION OF THE DRAWINGS
Other advantages of the present invention will be readily appreciated, as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings wherein.
FIG. 1 depicts a Schematic diagram of a DSSC using TiO2 nanoparticles on a microgrooved TCO-coated glass as an anode and a Pt/TCO/AAO (AAO refers to nanoporous anodized aluminum oxide) as a cathode. The cathode is directly placed on the TiO2 nanoparticle layer in order to shorten the transport distance of holes, i.e. the I−/I3− redox shuttle.
FIG. 2 depicts: (a) a schematic diagram of a flat TCO, on which a square array of metallic micropillars are deposited; (b) a schematic diagram of dye-sensitized solar cells of the present invention imbedded on the TiO2 nanoparticle layer; (c) a scanning electron microscopy (SEM) topview image of the present invention's TCO, on which a square array of metallic micropillars are deposited as electron collectors (Inset shows the SEM cross-section image of the microtextured TCO), and (d) a cross-section SEM image of the Ni micropillars in a  ̃23 μm thick TiO2 nanoparticle layer;
FIG. 3 depicts the fabrication of a 1-D TiO2 nanotube DSSC using AAO as a template. The Pt cathode is interdigitated into the TiO2 nanotubes to drastically reduce the hole (redox species) transport distance, thereby synchronizing the hole transport with the fast electron transport in 1-D TiO2 nanotubes.



DETAILED DESCRIPTION OF THE INVENTION
The present invention presents an improved dye-sensitized solar cell (DSSC) including (A) a TCO-coated microtextured glass substrate (2) as an electron collecting anode, thereby accommodating more TiO2 nanoparticles per unit substrate area without exceeding the electron diffusion length in the TiO2 nanoparticle layer; (B) free-standing metallic micropillars on the TCO glass, which significantly enhance electron harvest in a traditional TiO2 nanoparticle (NP) DSSC. This array of free-standing metallic micropillars on the transparent conducting anode serve as shortcuts for electron diffusion in the nanoparticle network, thereby significantly enhancing the electron harvest beyond that of conventional TiO2 nanoparticle-based dye-sensitized solar cells; (C) a cathode (4) consisting of a TCO-coated nanoporous substrate by atomic layer deposition method. The TCO coating assures the conductivity of the cathode. Furthermore, scattered Pt nanoparticles are then coated on this TCO layer as catalysts. The cathode is directly placed onto the TiO2 nanoparticle layer as described in (A) and (B). In this way, the hole transport distance (mass flow of redox species) can be significantly shortened to catch up the fast electron transport in (A) and (B); (D) a nanoscale interdigitated anode and cathode, which consists of 1-D TCO and TiO2 concentric nanotubes as an anode; then, interdigitated Pt nanowires are interdigitated in the inner voids of the tubes by electrochemical deposition. This configuration significantly shortens the hole transport (mass flow of redox species) distance to catch up the fast electron transport in the Ti nanotubes.
The present invention additionally presents a method for manufacturing improved dye-sensitized solar cell (DSSC) including free-standing metallic pillars on the TCO comprising the steps of: preparing a photolithographic pattern, electrochemically depositing nickel micropillars, preparing TiO2 nanocrystalline dye-sensitized solar cells, preparing an anode|semiconductor, sensitizing the dye, fabricating platinized counter electrodes, and assembling a dye-sensitized solar cell.
The objective of the present invention is to accelerate both electron and hole collections in a DSSC in a synchronized manner. In particular, for the TiO2 nanoparticle based DSSC, the objective is to utilize a microtextured TCO substrate to increase the effect volume of TiO2 nanoparticle layer and thus the dye-loading amount without increasing the electron transport distance in the TiO2 nanoparticle layer. In addition, the present invention allows for the shortening of the hole transport (mass flow of I−/I3− redox species) distance using a Pt and TCO coated nanoporous substrate (e.g. nanoporous anodized aluminum oxide) that is directly placed on the TiO2 nanoparticle layer, while the nanochannels in AAO are used for the mass flow of I−/I3− redox species. For the 1-D semiconductor-based DSSC, the objective of the present invention is to retain the state-of-the-art strategy of enhancing the electron transfer afforded in ordered 1-D semiconductor structures, while simultaneously reducing the series resistance of the semiconductor without a significant loss of surface roughness compared to 1-D nanowires. Instead of placing all the roughness onto the semiconductor layer, the present invention allocates part of the roughness onto the collecting anode. A rough collecting anode provides a larger surface area to accommodate more individual 1-D nanoscale semiconductors. Therefore, for the same level of surface roughness factor (SRF, defined as the ratio of the total semiconductor surface area to the nominal planar substrate area), the length of the 1-D semiconductor on a coarsened electron-collecting anode can be relatively shorter than that of conventional 1-D semiconductors supported on a planar anode. Additionally, the present invention allows for the simultaneous shortening of the hole transport distance by interdigitating Pt nanowires in the inner voids of semiconducting nanotubes as shown in FIG. 3.
As illustrated in FIG. 1, the preferred embodiment of the present invention constitutes a microgrooved glass substrate (2). This substrate is fabricated using conventional photolithography methods. In the preferred embodiment the grooves (6) are  ̃3 μm in width and 3 μm in depth. This configuration provides a 200% increase of the surface area in comparison to a flat glass substrate. The TCO layer (4) is created by sputtering 200 nm indium doped tin oxide (ITO) onto the microgrooved glass substrate. In order to ensure uniform deposition of TCO on all surfaces, the substrate is preferably rotated in a manner known to those of skill in the art. In the preferred embodiment the measure sheet resistance is  ̃20 Ω/sq.
As illustrated in FIGS. 2 (a) and (b), the preferred embodiment of the present invention constitutes a square array (12) of metallic micropillars (10) of 5 μm in height h, 3 μm in diameter d and 10 μm in edge-to-edge distance I. It should be noted that while in the preferred embodiment the micropillars of the present invention are arranged in a square array, in alternate embodiments the micropillars may be arranged in any other shape. Additionally, alternate embodiments of the present invention may call for different sized/shaped micropillars. For a 20 μm-thick TiO2 nanoparticle layer, nearly 75% of the nanoparticles will be in 10 μm proximity of the micropillars (10), as indicated by the region under the line (18) in FIG. 2(b). (Area covered by a 10 μm diameter circle with its center moving on the surface of the Ni micropillars). In contrast, only 50% of the nanoparticles are within 10 μm vicinity of the planar TCO (2) (region under the black dashed line). In the preferred embodiment the metallic Ni-micropillar array occupies only  ̃4.3% of the total TCO area, thereby causing only negligible loss in the optical transparency of the TCO anode.
FIG. 2(c) shows the scanning electron microscopy (SEM) top-view and cross-section images of the prepared nickel micropillars on F:SnO2 (FTO) conductive glass. Though the preferred embodiment utilizes nickel as the micropillar material (for its favorable electric contact to TCO), other materials with similar conductive properties (such as Zinc) could be used as well. The Ni-micropillars are fabricated using electronchemical deposition into a photoresist pattern consisting of a square array of circular wells, 3 μm in diameter and 10 μm from edge to edge, and  ̃3.5 μm in thickness. A small overgrowth out of the well provides an extra  ̃1.5 μm in height, resulting in the hemispherical heads (22) shown in the inset to FIG. 2(c). TiO2 nanoparticles are dip-coated onto the array using methods known to those of skill in the art. FIG. 2(d) shows SEM cross-section images of Ni micropillars (10) buried in a  ̃23 μm thick TiO2 nanoparticle layer. The cell is constructed by anchoring Ru N719 dye molecules on the TiO2 nanoparticles, followed by the assembly of spacer, electrolyte and Pt—FTO as cathode using such methods as are known to those of skill in the art.
FIG. 3 shows the fabrication procedures of a one dimensional (1-D) TiO2 nanotube DSSC using nanoporous anodized aluminum oxide (AAO) as a template. The Pt nanowires cathode is interdigitated into the inner voids of the TiO2 nanotubes to drastically reduce the hole (redox species) transport distance, thereby synchronizing the fast electron transport in one dimensional TiO2 nanotubes.
Method and Process of Manufacturing the Present Invention
A. For DSSCs Using Either Microtextured TCO-Coated Glass and/or the Micropillar Array-Deposited TCO (e.g. FTO) Glass as the Electron Collecting Anode and the Nanoporous Membrane as Cathode
In the preferred embodiment, the process begins with the preparation of the photolithographic pattern as follows: The FTO glass (e.g., Solaronix) is cleaned in acetone under ultrasonication prior to the spin-coating of photoresist, preferably at 2500 rpm for 30 sec to form a  ̃3.5 um thick film. The photoresist-coated FTO glass is then soft-baked at 110 degrees C. for 1 minute to drive off excess solvent. After prebaking, the desired photolithographic pattern (area=0.7 cm×0.7 cm) is obtained using a laser writer and developed in developer (Shipley 351:DI water, 1v:3v) for 50 seconds.
The Electrochemical deposition of nickel micropillars then occurs as follows: The growth of Ni miropillars is preferably guided by two-electrode electrochemical deposition. The FTO glass with photolithographic pattern is used as a cathode and a graphite plate is used as counter electrode. Electrodeposition is preferably carried out under room temperature at a cathodic potential of −1.8V in Watts solution (a mixture of 300 g/L NiSO4.6H2O, 45 g/L NiCl2.6H2O, 45 g/L H3BO3, pH=4.5). The micropillars formed are generally approximately 5 μm tall when filling up the 3.5 μm deep microwells followed by a small overgrowth out of the well to gain an extra  ̃1.5 μm height, which led to the formation of hemispherical heads at the top. Lift-off is accomplished by immersing the sample in acetone for 5 minutes. The resulting slightly conic shape is ascribed to the inevitable intensity gradient of UV light in the photoresist during the exposure.
The microtextured glass is fabricated using conventional photolithography method. The photomask is customer-designed. The microgrooves were etched by reactive ion etching. A TCO layer is coated by sputtering method.
The TiO2 nanoparticle film and assembly of the TiO2 nanocrystalline dye-sensitized solar cells are then preferably prepared as follows: A slurry solution of TiO2 nanoparticle is preferably prepared by grinding a mixture of 50 mg TiO2 (anatase nanopowder,  ̃25 nm), 1.25 ml water, 0.6 μl acetylacetone and 3 μl Triton X-100. Tape is used to define the area on the microgrooved TCO-coated glass, or the micropillar-deposited FTO glass to be coated with TiO2 film. A doctor blade is used to define the thickness of the applied slurry thickness which is typically 25 μm. The sample is then dried at room temperature for 30 minutes prior to sintering at 450 degrees C. for 30 minutes. This process generally yields a 20 ̃25 μm thick TiO2 with good filling in the microgrooves. After cooling the sample, the sample is soaked overnight under dark in a 0.5 mM solution of cis-bis(isothiocyanato)bis(2,2′-bipyridyl-4,4′-dicarboxylato)-ruthenium(Π) bis-tetrabutylammonium (N719) in absolute ethanol. In darkness, the sample is then rinsed with ethanol for 30 minutes to remove non-chemisorbed dye molecules.
The cathode is prepared using Whatman's nanoporous anodized aluminum oxide membrane as substrate. Then, 200 nm ITO is coated on one side of the substrate surface (or the entire surface of the membrane by atomic layer deposition method). Next, 5 nm Pt is sputtered on one side of the substrate (or the entire surface of the membrane is coated with Pt nanoclusters by soaking the membrane in a H2PtCl6 in ethanol solution and sintered at 300 C to reduce H2PtCl6 into Pt). A thin metal wire (26) (such as silver or gold) is attached to the cathode surface using silver paste or a wire bonder for electrical contact. These two kinds of cathodes can be directly placed atop the TiO2 nanoparticle layer. The internal space of the cell is filled with an electrolyte (0.5 M LiI, 50 mM I2, 0.5 M 4-tertbutylpyridine in 3-methoxypropionitrile) by capillary action. The cell is sealed with a polymer sealant (Surlyn, 25 μm thick, Solaronix).
B. A DSSC using Nanoscale Interdigitated Anode and Cathode
As illustrated in FIG. 3, all surfaces of the AAO membrane (Whatman) (30) are first coated with a 20 nm thick TCO (typically, ITO layer) as electron-collecting anode using the atomic layer deposition (ALD) method (32). Next, a 20 nm TiO2 layer (34) is deposited on all surfaces (via the ALD method) as an electron harvesting semiconducting layer. Subsequently, an insulating Al2O3 layer (36) is coated by atomic layer deposition. Then, a TCO (e.g. ITO) is sputtered to one side of the AAO template to close off the holes. Then, Pt nanowires (38) are deposited into the nanotubes using pulse AC electrochemical deposition method (Step 3). To free the TiO2 surface, the previously coated Al2O3 is selectively etched off in 1M NaOH solution. Then, the surface of TiO2 is sensitized with solar absorbing dye molecules (e.g. N719 dye), followed by filling the voids with redox electrolyte solutions (40).
The invention has been described in an illustrative manner, and it is to be understood that the terminology used is intended to be in the nature of words of description rather than of limitation.
Obviously, many modifications and variations of the present invention are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

## Claims

1. A highly efficient dye-sensitized solar cell comprising:
a transparent conducting anode comprising a transparent conducting oxide on a glass,
an array of metallic micropillars in direct contact with said anode,
a layer of semiconducting nanoparticles on said anode, and
a cathode oriented in direct contact with said nanoparticles,
wherein the micropillars are completely buried in the layer of semiconducting nanoparticles.

2. The solar cell of claim 1, wherein the transparent conducting anode is microtextured.

3. The solar cell of claim 2, wherein said transparent conducting anode comprises the transparent conducting oxide coated on a microtextured glass.

4. The solar cell of claim 3, wherein said transparent conducting oxide comprises indium tin oxide.

5. The solar cell of claim 2, wherein the transparent conducting anode is microgrooved.

6. The solar cell of claim 2, wherein the micropillars comprise nickel or zinc.

7. The solar cell of claim 2, wherein the metallic micropillars are in contact with the semiconducting nanoparticles.

8. The solar cell of claim 7, wherein the layer of semiconducting nanoparticles is sintered.

9. The solar cell of claim 8, wherein the metallic micropillars extend away from the anode.

10. The solar cell of claim 2, wherein said semiconducting nanoparticles comprise TiO2.

11. The solar cell of claim 2, wherein said cathode comprises a Pt-coated nanoporous anodized aluminum oxide (AAO).

12. The solar cell of claim 1, wherein said micropillars have hemispherical tips.

13. The solar cell of claim 1, wherein said transparent conducting oxide comprises indium tin oxide.

14. The solar cell of claim 1, wherein said semiconducting nanoparticles comprise TiO2.

15. The solar cell of claim 1, wherein said cathode comprises a Pt-coated nanoporous anodized aluminum oxide (AAO).

16. The solar cell of claim 1, wherein the micropillars comprise nickel or zinc.

17. The solar cell of claim 1, wherein the metallic micropillars are in contact with the semiconducting nanoparticles.

18. The solar cell of claim 1, wherein the layer of semiconducting nanoparticles is sintered.

19. The solar cell of claim 1, wherein the metallic micropillars extend away from the anode.