The two main challenges in solar cell technology are the cost and the energy conversion efficiency of solar cells. Different materials and structures have been tested for several decades to address these challenges. As a result, the technology has evolved from the first solar cell generation, starting with crystalline silicon based p-n junctions, to the third generation, which includes organic photovoltaics (OPVs), dye sensitized solar cells (DSSCs), and perovskite (PVSK) solar cells. While the choices of the photoactive material in different devices (organic semiconductors in OPVs, dyes in DSSCs, and perovskites in PVSKs) are mainly based up on which materials provide strong light absorption and efficient charge generation, the device structures must be designed to collect the charges efficiently from the photoactive materials and transfer the charges to the device electrodes. The approach for selective collection of electrons from photoactive layers in OPVs, DSSCs, and PVSKs is to use a layer of a material, referred to as an electron transport layer (ETL), having an energy structure that can block holes but is transparent to electrons so as to enable electron transport.
The energy levels in the ETL and the energy barrier between ETL and the photoactive layer are critical to achieve high energy conversion efficiency in a device. Therefore, many different materials have been tested for use in forming ETLs in OPVs, DSSCs, and PVSKs. These materials include metal oxides, such as titanium oxide (TiO2) and zinc oxide (ZnO), and organic materials. Although, in theory, some materials should be more effective in improving device characteristics, in practice, significant improvement has not been achieved when ETL materials having matched energy levels have been used. This is mainly due to the other requirements for ETLs, such as optical transparency and high mobility of carriers. The combination of all the requirements of an ETL has limited the choice of material for ETL formation to only a few materials. For instance, TiO2 has been the dominant ETL in DSSCs for more than two decades.
From the above discussion, it can be appreciated that it would be desirable to have alternative ETLs that provide improved energy conversion efficiency.
The present disclosure may be better understood with reference to the following figures. Matching reference numerals designate corresponding parts throughout the figures, which are not necessarily drawn to scale.
As described above, it would be desirable to have alternative electron transfer layers (ETLs) that provide improved energy conversion efficiency in solar cells. Disclosed herein are ETLs that undergo mechanical deformation during use of the solar cell that generates a voltage or charge that modifies the energy barrier between the ETL and the photoactive layer of the solar cell so as to increase the energy conversion efficiency of the cell. The ETLs are made of a piezoelectric material and the mechanical deformation of the ETL can be achieved in various ways. In some embodiments, the ETL is deformed during use of the device by applying an external force to the cell, and this deformation results in the voltage/charge generation. In other embodiments, the ETL is formed (e.g., deposited or grown) on a substrate while it is in a deformed state. Once the ETL is completed, the substrate can be enabled to relax and return to its natural state and this creates internal stress within the ETL that results in the voltage/charge generation. The deformation of the substrate during ETL formation can be achieved in various ways. For example, an external force can be applied to the substrate to cause it to deform. Alternatively, the substrate can be heated during the ETL formation process so as to cause thermal expansion that subsides once the temperature is reduced.
In the following disclosure, various specific embodiments are described. It is to be understood that those embodiments are example implementations of the disclosed inventions and that alternative embodiments are possible. All such embodiments are intended to fall within the scope of this disclosure.
Piezoelectricity is an effect in certain materials i.e., piezoelectric materials, through which electric charges are generated on the surface of the materials in response to mechanical deformations.
S=s·T+d·E (1)
D=d·T+ε·E (2)
where S, T, D, and E are mechanical strain and stress, electric displacement, and electric field, respectively, and s, d, and ε are elasticity coefficient, piezoelectric charge coefficient, and permittivity, respectively. Considering that S, T, D, and E are vectors, s, d, and ε are generally in the form of matrices. Therefore, Equation 2 suggests that any stress to a piezoelectric material (even shear stress, see
Zinc oxide (ZnO) is one of the emerging piezoelectric materials with possible applications in various electro-mechanical devices. ZnO can be deposited as a film with conventional methods, such as sputtering. In addition, ZnO nanowires can be vertically grown on a substrate using a simple hydrothermal growth process. Furthermore, grown nanowires can be shaved and laid on a flexible substrate for making piezoelectric sensors. Experiments have shown that a voltage difference appears along the nanowires when they are bent. Other experiments have shown that piezoelectric voltage is generated by vertically grown ZnO nanowires when shear stresses are applied by an atomic force microscope tip.
Recently, the inventors developed a simple method for inducing piezoelectric charges along vertically grown ZnO nanowires without any need for shaving them or individually bending them. In that method, nanowires were grown on a flexible substrate while the growth solution was stirred, which produced misaligned grown nanowires instead parallel nanowires. Due to the physical contact between nanowires, stress was applied to the nanowires when the substrate was bent. This produced a voltage of approximately 350 mV, which was measured using a devised method in an electrochemical cell. Such a voltage is sufficient to modify the energy structure of a junction in a photovoltaic device.
Early organic photovoltaics (OPVs) were made by forming layers of electron donor (D) and electron acceptor (A) materials between two different electrodes, one being transparent. In an OPV, upon illumination, excited states are generated by promoting electrons from the highest occupied molecular orbitals (HOMO) to the lowest unoccupied molecular orbitals (LUMO), creating excitons (electro-hole pairs). The excitons can diffuse to the interface between the donor and acceptor, where electrons and holes get separated (electrons at the LUMO of A, holes at HOMO level of D). Common organic electron donor and acceptor materials used in OPVs include poly 3-hexylthiophene (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM), respectively.
While early devices showed some photovoltaic effect, it was soon discovered that some modification to the structure was needed for increasing the efficiency. Today, the highest efficiency in a single cell is obtained by a structure called inverted bulk heterojunction (9.2%). The structure and the molecular energy diagram of such a device are shown in
The schematic drawing of
When the electrode is illuminated, the photons pass through the semiconductor and are absorbed by the dye molecules. The absorbed photons promote electrons from the ground state (D+/D) to the excited state (D*) in the dye. Due to the lower energy level in the semiconductor (conduction band energy, Ec) than the excited energy level in the dye, the electrons are transferred to the semiconductor, which acts as the ETL. The positive charges on the dye molecules, on the other hand, receive electrons from the counter electrode (typically made of platinum (Pt)) via the mediators in the electrolyte. This process takes place through oxidation of the mediators at the dye interface and mediator reduction at the counter electrode. The key factor in achieving high energy conversion efficiency is to use materials with appropriate energy levels to rectify the charge transfer at the semiconductor-dye-mediator interfaces. Furthermore, a wide absorption spectrum of the dyes and low charge recombination rate at the semiconductor-electrolyte interface are important. In this regard, the energy difference between Ec in the ETL and D* in the dye is crucial for efficient charge collection.
Energy diagrams similar to those shown in
As mentioned above, the existence of the energy barrier is ignored in the conventional energy diagrams for OPVs, DSSCs, and PVSKs. The energy bending (ΔE1) and depth of the depleted region (W) depends on the structure of the ZnO, surface defects, the growth/deposition method, and the doping level in the semiconductor. It should be noted that the detail of the energy structure on the photoactive layer is also important. However, since both in OPVs and DSSCs, the photoactive layers are made of individual molecules, still the energy structure on the photoactive materials can be presented with HOMO and LUMO levels. As shown in
It has been suggested by others to apply an acoustic wave to induce the piezoelectric voltage inside an OPV to reduce the energy barrier. However, the inventors believe that the approach disclosed in the following paragraphs can address this issue in a simpler way that will lead to a practical solution on how to engineer the barrier without any need for an external vibration source.
Whether the solar cell is an OPV, DSSC, and PVSK solar cell, the cell comprises a substrate, which acts as a first (bottom) transparent electrode of the cell, and an ETL formed on the substrate.
With reference next to
Formed on top of the photoactive layer 22 is an EBL 24 that blocks electrons but is transparent to holes. In some embodiments, the EBL 24 is made of PEDOT:PSS. Finally, formed on the EBL 24 is a second (top) electrode 26 that can be made of a suitable conductive material, such as silver, aluminum, carbon, or ITO.
With reference next to
The use of the OPV/PVSK solar cell 20 and the DSSC 30 is illustrated in
With reference to
As shown in
Once the ETL 42 has been formed, the remainder of the solar cell can be formed. In some embodiments, the substrate 40 can be left in the deformed state while the other layers of the solar cells are formed. In other embodiments, the substrate 40 can be permitted to relax before the other layers are formed. Illustrated in
Formed on top of the photoactive layer 52 is an EBL 54 that blocks electrons but is transparent to holes. In some embodiments, the EBL 54 is made of PEDOT:PSS. Finally, formed on the EBL 54 is a second (top) electrode 56 that can be made of a suitable conductive material, such as silver, aluminum, carbon, or ITO.
With reference next to
Once the solar cell 50, 60 has been fabricated, it can be used in its relaxed state. Because the ETL 42 was formed while the substrate 40 was deformed, however, the internal stress is created within the ETL that generates a piezoelectric voltage or charge that modifies the energy barrier between the ETL and the cell's photoactive layer.
The inventors' preliminary experimental results described below support the feasibility of changing the piezoelectric voltage/charge at the surface of an ETL by simply bending the samples. Also, a drift in the knee voltage of an organic diode has been observed upon mechanical deformation, again supporting the feasibility of employing the piezoelectric effect for energy modification in a device.
The inventors previously grew ZnO nanowires on flexible ITO electrodes using the hydrothermal method. It was discovered that by constantly stirring the growth solution the nanowires would be twisted as they grow. Samples with various lengths of nanowires were fabricated by controlling the growth time. The twisting structure was the key part for obtaining the piezoelectric effect from the nanowires when the electrode is bent. Upon bending, the stress between nanowires increased resulting the generation of the piezoelectric charge/voltage. The piezoelectric effect was characterized at various curvatures of the electrode using a devised electrochemical approach.
In the novel devices/methods disclosed herein, the electrochemical reaction of ferrocene was used as a reference and the cyclic voltammetry (CV) technique was used to find the electrochemical potential of ferrocene when the electrode was relaxed (straight position 0 in
The feasibility of employing the piezoelectric effect in a solid-state device was also tested by fabricating an organic diode. The device was made by coating the surface of an ITO/twisted ZnO nanowire electrode with a layer of P3HT and brushing silver paint on the top of the stack to make the second electrode.
This application claims priority to U.S. Provisional Application Ser. No. 62/206,480, filed Aug. 18, 2015, which is hereby incorporated by reference herein in its entirety.
Number | Name | Date | Kind |
---|---|---|---|
7705523 | Wang et al. | Apr 2010 | B2 |
20100258160 | Wang | Oct 2010 | A1 |
20110041895 | Carroll | Feb 2011 | A1 |
20130276869 | No et al. | Oct 2013 | A1 |
Number | Date | Country |
---|---|---|
10317781 | Jun 2013 | CN |
103199748 | Jul 2013 | CN |
Entry |
---|
Kumar, et al., “Energy harvesting based on semiconducting piezoelectric ZnO nanostructures”, Nano Energy, 2012. |
Kumar, et al., “Piezo-phototronics effect on nano/microwire solar cell”, Energy and Environmental Science, 2012. |
Yang, et al., “Flexible Hybrid energy cell for simultaneously harvesting thermal, mechanical, and solar energies”, ACS Nano, vol. 7, No. 1, 2013. |
Shoaee, et al., “Acoustic enhancement of polymer/ZnO nanorod photovaltaic device performance”, Advanced materials, 26 (2), 2014. |
Number | Date | Country | |
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62206480 | Aug 2015 | US |