Patent Application
20130247993
Generally, the preset invention relates to polymer solar cells. In particular, the present invention relates to polymer solar cells using aligned magnetic nanochains. More particularly, the present invention relates to polymer solar cells using aligned Fe3O4 nanochains that are induced by the self-assembly of Fe3O4 nanoparticles in the presence of an applied magnetostatic field to increase the photoelectric conversion efficiency of the solar cell.
Polymer solar cells (PSCs) hold the promise for a cost-effective, lightweight solar energy conversion platform, which offers significant benefits over inorganic silicon solar cells. New material combinations and solar cell designs have been developed to realize bulk heterojunction (BHJ) solar cells with increased energy conversion efficiency. Specifically, such efforts are focused on the improvement of three operating parameters that determine the conversion efficiency of the polymer solar cell, including: the open-circuit voltage (Voc), the short-circuit current density (Jsc), and the fill factor (FF), which represents the curvature of the current density-voltage characteristic. To date, polymer solar cells (PSC) have achieved energy conversion efficiencies of approximately 7-8% by reducing both the optical band gap and the highest occupied molecular orbital (HOMO) of the semiconducting polymers forming the solar cell, and by optimizing the morphology of the polymer/fullerene blended film of the active layer of the polymer solar cell with thermal and solvent annealing. While the open-circuit voltage (Voc) and the fill factor (FF) parameters of polymer solar cells have almost reached a level equal to that of inorganic silicon solar cells, the performance of polymer solar cells is still lower, as compared to inorganic solar cells, due to the performance gap in short circuit current density (Jsc) that exists between inorganic and polymer solar cells (PSCs). Moreover, because charge carriers in a polymer solar cell (PSC) are subject to interfacial recombination along the entire internal collection pathway, charge transport through an organic polymer solar cell is typically several orders of magnitude slower than in an inorganic solar cell. This interfacial recombination is caused by the formation of a mobile excited state or excitons that are produced by organic materials when they absorb light, which is in contrast to free electron-hole (e-h) pairs, which are produced in inorganic solar cells.
Thus, the fundamental physical processes exhibited by organic and inorganic solar cells are completely different. For example, the fundamental physical processes in an organic BHJ solar cell device are as follows: photons from sunlight are absorbed inside a solar cell and excite a donor, leading to the creation of excitons in the conjugated polymer active layer of the solar cell. The created excitons begin to diffuse within the donor phase, and if they encounter the interface with an acceptor, a fast dissociation takes place, which leads to a charge separation. The resulting metastable electron-hole pairs formed across the donor/acceptor (D/A) interface are coulombically bound, and an electric field is needed to separate them into free charges. Therefore, under typical operating conditions, the photon-to-free-electron conversion efficiency of polymer solar cells is not maximized. Subsequently, the separated free electrons (holes) are transported, with the aid of the internal electric field formed by the use of electrodes with different work functions, towards the cathode (anode) where they are collected by the electrodes and driven into the external circuit. However, the excitons can decay, resulting in luminescence, if they are generated too far from the donor/acceptance (D/A) interface. Thus, the excitons should be formed within the diffusion length of the interface as an upper limit for the size of the conjugated polymer phase in the organic BHJ solar cell.
As such, there are several primary causes of limited energy conversion efficiency in organic photovoltaic (OPV) devices, such as polymer BHJ-based solar cells, including: energy level misalignment; insufficient light trapping and absorption; low exciton diffusion lengths; non-radiative recombination of charges or charge-transfer excitons (CTEs), which include electrons at the acceptor and holes at the donor that are bound by Coulomb attraction; and low carrier mobilities. In the most efficient polymer-fullerene organic photovoltaic devices, 50% or more of the energy loss is caused by the recombination of charge-transfer excitons.
Therefore, there is a need for an organic polymer solar cell that achieves greater short-circuit current density (Jsc) by utilizing aligned magnetic nanochains, such as Fe3O4 nanochains (NC), that are induced by the self-assembly of magnetic nanoparticles, such as Fe3O4 nanoparticles (NP), in the presence of an applied vertically magnetostatic field. In addition, there is a need for an organic polymer solar cell that has increased photoelectric converted efficiency (PCE).
In light of the foregoing, it is a first aspect of the present invention to provide a solar cell comprising an at least partially light transparent electrode; an active layer disposed upon the at least partially light transparent electrode, the active layer formed of a composite of at least one conjugated polymer as an electron donor, at least one fullerene as an electron acceptor, and Fe3O4 nanochains formed of Fe3O4 nanoparticles aligned along their magnetic dipole moments; and a second electrode disposed upon the active layer.
It is another aspect of the present invention to provide a method of forming a solar cell comprising providing an at least partially transparent electrode; providing a mixture of at least one polymer as an electron donor, at least one fullerene as an electron acceptor, and Fe3O4 nanoparticles; disposing said mixture upon the at least partially transparent electrode to form an active layer; exposing the mixture to a magnetic field, such that Fe3O4 nanochains are formed from the Fe3O4 nanoparticles, and are aligned along their magnetic dipole moments; and disposing a second electrode upon the active layer.
In another aspect of the present invention a solar cell includes an at least partially light transparent electrode; an active layer disposed upon said at least partially transparent electrode, said active layer formed of a composite of at least one electron donor, at least one electron acceptor, and magnetic nanoparticles aligned along their magnetic dipole moments; and a second electrode disposed upon said active layer.
In yet another aspect of the present invention, a method of forming a solar cell includes providing an at least partially light transparent electrode; providing a mixture of at least one polymer, at least one fullerene, and magnetic nanoparticles; disposing said mixture upon said at least partially light transparent substrate to form an active layer; exposing said mixture to a magnetic field, such that said magnetic nanoparticles are aligned along their magnetic dipole moments; and disposing a second electrode upon said active layer.
These and other features and advantages of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings wherein:
A polymer solar cell in accordance with the concepts of the present invention is generally referred to by numeral 10, as shown in
The polymer solar cell is fabricated, such that the ITO layer 20 is formed as a glass coated substrate that was cleaned with detergent, then ultrasonicated in deionized water, acetone, and isopropanol, and then subsequently dried in an oven overnight. The ITO glass 20 is then treated with oxygen plasma for 40 minutes to reform the surface of the ITO layer 20. Poly(ethylenedioxythiophene), or PEDOT, was doped with poly(styrenesulfonate), or PSS, to form PEDOT:PSS (Baytron P) and was spin-cast, so as to form the buffer layer 30 that is disposed upon the ITO layer 20 at a thickness of approximately 40 nm. The ITO layer 20 and the PEDOT:PSS buffer layer 30 disposed thereon was then preheated on a digitally controlled hotplate at 150 degrees C. for 10 minutes.
The active layer 40 of the solar cell 10 is formed as a composite of a combination of at least one conjugated polymer or p-type organic molecules, at least one fullerene (or fullerene derivative) or n-type organic molecules, and magnetic nanochains or nanoparticles of metal or metal oxide, such as CoO, NiO, Co, Ni, and Fe3O4 for example. However, the following discussion relates to the use of Fe3O4 in forming the active layer 40 of the solar cell 10, however, it is contemplated that any suitable metal or metal oxide may be used. It should be appreciated that the at least one conjugated polymer of the solar cell 10 serves as an electron donor, and the at least one fullerene serves as an electron acceptor. For example, the polymer/fullerene combination may comprise either of: P3HT:PC61BM or PTB7-F20:PC71BM, as shown in
It should be further appreciated that the active layer may be formed of a bulk heterojunction that is a composite of an electron donor and an electron acceptor, with the bulk heterojunction composite including the electron donor, electron acceptor, and functionalized inorganic nanoparticles and/or quantum dots, such as those functionalized by a magnetic field as discussed herein. In one aspect, the functionalized inorganic nanoparticles and/or quantum dots may comprise electronic conductive nanoparticles and magnetic nanoparticles that are functionalized by an external magnetic or electric field.
Continuing, with regard to the fabrication of the solar cell 10 having a P3HT:PC61BM based polymer/fullerene active layer 40, a donor/acceptor blend ratio of 1:0.8 and a solution concentration of 1 wt %, 100 uL were used and dissolved in ortho-dichlorobenzene (ODCB) by stirring the mixture at room temperature in a glove box, while Fe3O4 nanoparticles (NPs) (5 mg/mL, 1 uL) were added into the mixture at a weight ratio of 0.5 wt %. It should be appreciated that the Fe3O4 nanoparticles have a size of approximately 5 nm, and are capped by surfactant oleic acid (OA) (Sigma Aldrich). Next, the P3HT/PC61BM/Fe3O4 mixture was subjected to ultrasonic processing and stirring for six hours to disperse the Fe3O4 nanoparticles into the polymer/fullerene solution mixture. Next, the P3HT:PC61BM+Fe3O4 mixture was dispersed on the ITO (including PEDOT:PSS layer 30) substrate 20 and alignment treated by a magnetic field produced by square magnets (Amazing Magnets Co. C750, Licensed NdFeB) for about two minutes. The direction of the magnetic field produced by the magnets was perpendicular and substantially vertical to the ITO layer 20 and P3HT:PC61BM+Fe3O4 carried thereon, such that one magnet had its magnetic north (N) pole positioned proximate to the top of the active layer 40, while the other magnet had its magnetic south (S) pole positioned proximate to the bottom of the ITO layer 20. Furthermore, the distances between the two magnets and the ITO layer 20 therebetween were maintained at approximately 5 cm. After the magnetic alignment treatment, the ITO was spin-cast at 800 RPM (revolutions per minute) for 20 seconds, whereupon the magnetic field was again introduced to the active layer 40 with the same distance and direction as previously discussed. The application of this magnetic field was continued until the P3HT:PC61BM/Fe3O4 layer 40 was dried, after approximately three minutes. Finally, after the active layer 40 was dried, solar cell 10 was then transferred to a vacuum chamber (4×10−6 mbar), whereupon the electrode layer 50, formed of calcium (Ca) of approximately 5 nm and aluminum (Al) of approximately 100 nm, was disposed upon the active layer 40. The solar cell 10 was not thermally annealed.
Alternatively, the PTB7-F20:PC71BM based active layer 40 was fabricated using a blend ratio of 1:1.5, 1 wt %, 100 uL that was dissolved in a mixed solvent of ortho-dichlorobenzene (ODCB) 1,8-diiodooctane (DIO) (97%:3% by volume) by stirring at room temperature in a glove box. It should be appreciated that adding about 3% DIO (1,8-diiodooctane (DIO)/ODCB, v/v) to the combination allows better photovoltaic results to be achieved for the solar cell 10 using the PTB7-F20:PC71BM active layer 40. Fe3O4 nanoparticles (5 mg/mL, 1 uL) were added to the blended mixture at a weight ratio of 0.5 wt %, followed by ultrasonic processing and stirring for six hours, so as to disperse the Fe3O4 nanoparticles into the mixture of the PTB7-F20:PC71BM polymer/fullerene. Next, the P3HT:PC61BM+Fe3O4 mixture was dispersed on the ITO substrate 20 (including PEDOT:PSS layer 30) and alignment treated by a magnetic field produced by square magnets (Amazing Magnets Co. C750, Licensed NdFeB) for about two minutes. The direction of the magnetic field produced by the magnets was perpendicular and substantially vertical to the ITO layer 20 and P3HT:PC61BM+Fe3O4 layer 40 carried thereon, such that one magnet had its magnetic north (N) pole positioned proximate to the top of the active layer 40, while the other magnet had its magnetic south (S) pole positioned proximate to the bottom of the ITO layer 20. Furthermore, the distances between the two magnets and the ITO layer 20 therebetween were maintained at approximately 10 cm. After the magnetic alignment treatment, the ITO was spin-cast at 1000 RPM (revolutions per minute) for 15 seconds, whereupon the magnetic field was again introduced to the active layer 40 with the same distance and direction as previously discussed. The application of this magnetic field was continued until the PTB7-F20:PC71BM/Fe3O4 active layer 40 was dried, after approximately three minutes. Thus, after the active layer 40 was dried, the solar cell 10 was then transferred to a vacuum chamber (4×10−6 mbar), whereupon the electrode layer 50, formed of calcium (Ca) of approximately 5 nm and aluminum (Al) of approximately 100 nm, was disposed upon the active layer 40. The solar cell 10 was not thermally annealed.
To understand how the operation of the fabricated solar cells 10 operate to achieve an increase in short-circuit current density (Jsc), it is necessary to identify not only which factors affect the short-circuit current (Isc), but also how the Fe3O4-aligned nanochains affect the transport of charge carriers when blended into the polymer/fullerene composite of the active layer 40. In particular, limiting the loss of photogenerated charge carriers during their transport can improve the performance of bulk heterojunction (BHJ) solar cells, such as the solar cell 10. Short-circuit current Isc is determined by the product of the photoinduced charge carried density, if loss-free contacts are used, with the charge carrier mobility within the organic semiconductors, where Isc=neμE (1) where n is the density of charge carriers; e is the elementary charge, u is the charge mobility, and E is the electric field. Assuming 100% efficiency of the photoinduced charge generation in a BHJ solar cell device, n is the number of absorbed photons per unit volume.
Traditionally, magnetostatic fields have often been used to direct the assembly of nanoparticles (NPs), generally resulting in the formation of wire or chain-like structures. Under a magnetic field, the Fe3O4 nanoparticles, or other suitable magnetic nanoparticles, align their magnetic dipole moments along the direction of the externally applied magnetic field (H), forming linear chains, or nanochains 210, in a colloidal solution, as shown in
where V is the volume of the particle, Δχ is the difference in the magnetic susceptibilities of the particle, μo is the vacuum permeability, and B is the magnetic field strength, and Δ is the field gradient. Specifically, the external magnetic field exerts a torque on the magnetic dipole moments of the Fe3O4 particles, forcing them to align with the magnetic field. The interparticle magnetic dipole-dipole couplings and the external coupling of the magnetic dipoles to the magnetic field of the Fe3O4 favor linear chain growth along the magnetic-field flux lines. If a magnetic body of infinite size is magnetized, free magnetic dipoles are induced on both its ends. This gives rise to a magnetic field in the opposite direction to the magnetization, which is called the demagnetizing field, Hd. It is given by:
where μo, M, and N are the permeability of a vacuum, the magnetization, and the demagnetization factor (dimensionless quantity), respectively. The demagnetizing factor, N, depends on the shape of the sample, for example, for spheres, N is equal to ⅓. This mechanism of magnetic dipolar interaction, or dipolar coupling, refers to the direct interaction between two magnetic dipoles. The strength of dipolar interactions is relative to the individual particle anisotropy energy Ea arising either from bulk crystalline anisotropy ˜KV, where K is anisotropy constant, and V, which is the particle volume or particle's shape and surface anisotropy. The Fe3O4 nanoparticles formed head-to-tail structures to minimize the systematic energy. Based on the above derivation, dipoles of concentration n create the average electric field,
where ε is the dielectric permittivity of a matrix, the dipole moment p=σlA=σΩ, such that A, l, and Ω are, respectively, the particle face area, particle length, and particle volume. It should be appreciated that f is the dimensionless volume fraction occupied by the dipole particles, and Emax is the electric field strength for a hypothetical uniform polarization with f=1. The energy of a single field-aligned dipole is
The desired strong polarization takes place when |w|>>kT (6) where k is the Boltzmann constant and T is the temperature. Such a strong inequality |w|>>kT shows that there exists a broad range of parameters for which the system is polarized. The strong interdipole interaction
makes the system capable of spontaneous polarization. Based on the foregoing, it can be inferred that the superparamagnetism of aligned Fe3O4 nanochains produce an internal electrical field through dipolar-dipolar interaction and spin-polarization, which both increase the charge separation efficiency in the solar cell 10 and ensure high mobility charge carrier transport with reduced bimolecular recombination in the solar cell 10 by applying a strong electric field to draw the electrons and holes apart.
The solar cell 10 of the present invention incorporates external magnetic field aligned Fe3O4 nanochains into the polymer/fullerene based BHJ photovoltaic active layer 40 to increase the efficiency of the solar cell 10 that is enhanced by the induced polarization provided by the electric field of the Fe3O4 nanostructures. Thus, it should be appreciated that under the influence of an external magnetic field, Fe3O4 nanoparticles 200 of the active layer 40 align their magnetic dipole moments along the direction of the external magnetic field (H), forming linear nanochains 210 in the polymer/fullerene composites, as shown in
In order to determine the influence of magnetic field aligned Fe3O4 nanoparticles in the polymer solar cell 10 of the present invention, solar cells 10 formed from pristine polymer/fullerene (P3HT:PC61BM and PTB7-F20:PC71BM) and polymer/fullerene+Fe3O4 nanoparticles (P3HT:PC61BM+Fe3O4 and PTB7-F20:PC71BM+Fe3O4) without the magnetic field treatment were fabricated as a control group. Furthermore, all devices were not heat annealed using pervious-annealing or post-annealing. The photovoltaic results of these two types (P3HT:PC61BM and PTB7-F20:PC71BM) of solar cells 10 are listed in Table 1 below. Specifically, Table 1 shows the photovoltaic performances of pristine polymer/fullerene (P3HT:PC61BM and PTB7-F20:PC71BM), and Fe3O4 nanoparticles blended polymer/fullerene (P3HT:PC61BM and PTB7-F20:PC71BM), with and without magnetic field (H) alignment.
aSeries resistance deduced from the inverse slope near Jsc and Voc in the J-V curve under illumination.
In addition, the corresponding J-V curves of a pristine PTB7-F20:PC71BM based solar cell 10, a PTB7-F20:PC71BM based solar cell 10 without magnetic field (H) treatment, and a PTB7-F20:PC71BM based solar cell 10 with magnetic field (H) treatment under illuminated conditions, is shown in
In the first control experiment, a solar cell with an active layer formed of pristine P3HT:PC61BM and PTB7-F20:PC71BM attained a performance level that reached a normal level. For example, the open-circuit voltage (Voc), short-circuit density (Jsc), and fill factor (FF) of the P3HT:PC61BM based solar cell are respectively, 0.6V, 7.81 mA/cm2, and 0.64, while the power conversion efficiency (PCE) reached 2.98%.
The second control groups of solar cells having an active layer formed by polymer/fullerene+Fe3O4 nanoparticles without the external magnetic field aligned treatment, led to a small increase in Jsc, as compared with the pristine polymer/fullerene based control devices. The likely reason for this is that the magnetic field originated from the superparamagnetism of Fe3O4 nanoparticles, resulting in the increase of the population of triplet excitons. Furthermore, considering that efficient energy transduction requires separation of photogenerated electron-hole pairs into long-lived dissociated charges with a high quantum yield and minimal loss of free energy. A potential concern of this charge-separation process is that the electron and hole must overcome their mutual Coulomb attraction,
where e is the charge of an electron, εr is the dielectric constant of the surrounding medium, εo is the permittivity of a vacuum, and r is the electron hole separation distance. Considering the increasing of εr after blending Fe3O4 nanoparticles into the polymer/fullerene system, Coulomb attraction of the electron and hole will be decreased, thus increasing the efficiency of photogenerated electron-hole pairs into long-lived dissociated charges.
Next, solar cells 10 having active layer 40 formed of polymer/fullerene and Fe3O4 nanoparticles (P3HT:PC61BM+Fe3O4 and PTB7-F20:PC71BM+Fe3O4) were treated by an external magnetic field in which the magnetic field direction was vertical to the active layer 10, as previously discussed. The P3HT/PC61BM active layer 40 with aligned Fe3O4 nanochains attained a photo conversion efficiency of (PCE) 5.80% (Voc=0.63 V, Jsc=13.86 mA/cm2, and FF=0.66). The Voc in these two types of polymer/fullerene based systems have not been affected by Fe3O4 nanoparticles without and with the external magnetic field treatment. In actuality, the Voc will be decreased when the concentration of Fe3O4 nanoparticles is too high, and the optimum ratio of 0.5 wt % Fe3O4 nanoparticles in the composite of P3HT/PC61BM provided the best efficiency.
Table 2 below shows the performance of the solar cell 10 when Fe3O4 nanoparticles were mixed with P3HT:PC61BM and blended in ODCB with a different weight ratio with external magnetic field aligned treatment (The optimal condition is 1.0% (v/v) of Fe3O4 nanoparticles in P3HR:PC61BM.).
aThe concentration of Fe3O4 nanoparticles (NPs) is 5 mg/mL on toluene;
bThe concentration of P3HT:PC61BM is 10 mg/mL, P3HT:PC61BM = 1:0.8, (w/w).
For example, Jsc, for an active aligned active layer 40 formed of P3HT:PC61BM+Fe3O4 with magnetically aligned nanochains reached to 8.97 mA/cm2, an increase of about 6.9%, as compared with an active layer 40 of P3HT:PC61BM+Fe3O4 nanoparticles that were not treated by an external magnetic field-based device (Jsc=8.39 mA/cm2). Compared with the pristine P3HT:PC61BM based control solar cells, which achieved a Jsc=7.81 mA/cm2, the Jsc attained an increase of about 14.8%. With the same trends, the Jsc of solar cells using PTB7-F20:PC71BM+Fe3O4 nanochains treated with magnetic field alignment attained an increase of about 6.1%, as compared with solar cells formed of PTB7-F20:PC71BM+Fe3O4 nanoparticles without the magnetic field alignment, and attained an increase of about 15.4%, as compared with solar cells formed of pristine PTB7-F20:PC71BM. Considering that solar cell efficiency is closely related to the BHJ thickness and the performance of the solar cell, it is submitted that the thickness of the three types of active layers considered above (i.e. pristine polymer/fullerene; polymer/fullerene+Fe3O4 nanoparticles; and polymer/fullerene+Fe3O4 with aligned nanochains) were equal, and therefore, the factor of active layer thickness influencing the efficiency can be excluded. Thus, the Fe3O4 nanochains play an important role in the BHJ active layer 40, and provide several operational benefits. Simultaneously, with the enhancement of the short-circuit current density (Jsc), the fill factor (FF) of the PTB7-F20:PC71BM+aligned Fe3O4 nanochain-based solar cell 10 is found to be 66.4%, which is higher than that of the control devices (63.6% and 65.3%). Furthermore, the same trend was also found in P3HT:PC61BM based solar cells, which suggests that the charge transport properties are substantially improved. In addition, it is observed that a series resistance (Rs) reduction enhancement to the solar cell 10 also accompanies the introduction of the aligned Fe3O4 nanochains into the solar cell 10. This means that the introduced Fe3O4 nanochains contribute to increase the conductivity of the active layer 40 formed of the polymer/fullerene composites of P3HT:PC61BM and PTB7-F20:PC71BM. Thus, the significant reduction in series resistance (Rs) values for organic photovoltaic devices (OPV), such as solar cell 10, that are achieved using new materials or fabrication techniques discussed herein, results in increased operational efficiency of the solar cell 10.
The accuracy of the photovoltaic measurements can be confirmed by the external quantum efficiency (EQE) of the solar cells 10. Specifically, the EQE curves of the solar cells 10 fabricated were measured under the same optimized conditions as those used for the J-V measurements. The external quantum efficiency (EQE) values for solar cell 10 having PTB7-F20:PC71BM blended with magnetic field aligned Fe3O4 nanochains is shown in
The external quantum efficiency (EQE) value for the solar cell containing PTB7-F20:PC71BM+Fe3O4 nanochains induced by a magnetic field is higher than those for pristine PTB7-F20:PC71BM and PTB7-F20:PC71BM+Fe3O4 nanoparticles in the absence of a magnetic field in mostly wavelength. For example, the solar cells 10 using PTB7-F20:PC71BM+Fe3O4 aligned nanochains was found to have an EQE maximum of 60.7% at 620 nm, and the EQE of the hybrid photovoltaic device with PTB7-F20:PC71BM+Fe3O4 nanoparticles is 57.9% at the same wavelength. The difference is a consequence of increasing the rate of exciton generation and the probability of exciton dissociation, thereby enhancing Jsc density. The EQE results closely matches the values measured from J-V characteristics, which indicate that the photovoltaic results are reliable.
It should be appreciated that for a given absorption profile of a given material, the bottleneck is the mobility of charge carriers, and it is one of the major concerns in designing organic photovoltaic materials and in fabricating polymer solar cells (PSC). High charge carrier mobility is preferred for efficient transportation and photocurrent collection of the photo-induced charge carriers. In order to make a realistic evaluation on the apparent charge carrier mobility in the active layer, the electron and hole mobilities of Fe3O4 nanoparticle blended polymers (P3HT and PTB7-F20) and fullerenes (PC61BM and PC71BM) based active layers 40 were measured by a space-charge limited current (SCLC) method with the hole-only and electron-only devices. This was done to investigate the effect of the Fe3O4 nanoparticles and nanochains on the electron and hole mobility, respectively, and the results are discussed herein.
Specifically, the thickness of the films was measured with atomic force microscopy (AFM). The current-density-voltage (J-V) curves were measured using a Keithley 2400 source measuring unit. The photocurrent was measured under AM 1.5G illumination at 100 mW/cm−2 under a Newport Thermal Oriel 91192 1000W solar simulator (4 in.×4 in. beam size). The light intensity was determined by a monosilicon detector with a KG-5 visible color filter calibrated by National Renewable Energy Laboratory (NREL) to reduce spectral mismatching. After collecting external quantum efficiency (EQE) data, the AM 1.5G standard spectrum, the Oriel solar simulator (with 1.5G filter) spectrum, and EQE data of both the reference cell and tested polymer solar cells to calculate the spectral mismatch factor in accordance with standard accepted procedures.
The SCLC method was used to test the hole and electron mobility. The dielectric constant εr is assumed to be 3 in the analysis, which is a typical value for conjugated polymers.
Hole mobility was measured using a diode configuration of ITO/PEDOT:PSS/polymer or polymer+Fe3O4/MoO3/Ca/Al by taking current-voltage current in the range of 0-2 V and fitting the results to a space charge limited form. Specifically,
Electron mobility was measured using a diode configuration of ITO/Ca/Al/polymer or polymer+Fe3O4/Ca/Al by taking current-voltage current in the range of 0-2 V.
As shown in Table 3 below, polymer+Fe3O4 nanoparticles with magnetic field aligned treatment-based films obtained higher electron mobility than pristine fullerene and fullerene+Fe3O4 nanoparticles without magnetic field treatment-based films. With the same trend, fullerene+Fe3O4 nanochain based films obtained higher electron mobility than pristine fullerene and fullerene+Fe3O4 nanoparticles based films. These results are good and included higher Jsc value and lower Rs of the polymer solar cell 10 with P3HT:PC61BM and PTB7-F20:PC71BM+Fe3O4 nanochain based devices.
Moreover, for the electron or hole-only solar cells space-charge limited current (SCLC) is described by:
where J is the current density, εr is the dielectric constant of the polymer and fullerene derivatives, respectively, ε0 is the permittivity of a vacuum, L is the thickness of the blended film or active layer 40, V=Vappl−Vbi, Vappl is the applied potential, and Vbi is the built-in potential which results from the difference in the work function of the anode and the cathode (in these device structures, Vbi=0 V).
Charge carrier mobility is not a parameter of a material, but a device parameter, and it is sensitive to the nanoscale morphology of the thin film of the photoactive layer. In a van der Waals crystal for example, the final nano-morphology depends on film preparation. Parameters such as solvent type, solvent evaporation (crystallization) time, temperature of the substrate, and/or deposition method can change the nano-morphology. In the present invention, although the processing conditions (e.g. solvent, concentration, spin-coating parameters, etc.) of the magnetic field aligned Fe3O4 nanoparticles blended polymer/fullerene (P3HT:PC61BM and PTB7-F20:PC71BM) devices are similar to those used for the fabrication of the control devices, (i.e. pristine polymer/fullerene device and Fe3O4 nanoparticles blended polymer/fullerene device without the magnetic field alignment treatment), differences were apparent in the nano-morphology and phase separation among the thin films of the pristine polymer/fullerene, the polymer/fullerene+Fe3O4 nanoparticles without and with magnetic field alignment treatment, as confirmed by the transmission electron microscopy (TEM) and atomic force microscopy (AFM) measurements, shown in
Specifically,
The morphology of polymer/fullerene BHJ films influenced by Fe3O4 nanoparticles and an external magnetic field were investigated using atomic force microscopy (AFM).
Thus, the solar cell 10 utilizes the spin polarization effect of magnetic nanostructures, which is implemented by the alignment of Fe3O4 nanoparticles (NPs) to form nanochains (NCs) upon exposure to an external magnetic field through dipolar-dipolar interactions between nanoparticles. The paramagnetism of the aligned Fe3O4 nanochains produce an internal electrical field through spin-polarization, which both increase the charge separation efficiency of the solar cell 10 and ensure high mobility charge carrier transport in the active layer 40 of the BHJ based solar cell 10. Furthermore, the solar cell 10 utilizes two types of polymer/fullerene systems, P3HT:PC61BM and PTB7-F20:PC71BM blended with Fe3O4 nanoparticles, which after being introduced to an external magnetic field, form Fe3O4 nanochains. As a result, the photon conversion efficiency (PCE) achieved by solar cell 10 increased by 14.8% and 15.4%, as compared with their pristine polymer/fullerene based devices, respectively. The enhanced photon conversion efficiency was mainly the result of the increased short-circuit current density (Jsc).
Therefore, one advantage of the present invention is that a polymer solar cell (PSC) is manufactured using simple solution processing, so as to increase its conversion efficiency. Another advantage of the present invention is that a polymer solar cell increases the short circuit current density (Jsc) therein. Still another advantage of the present invention is that a polymer solar cell increases the short circuit current density (Jsc) by adjusting the morphology and phase separation of the polymer/fullerene based active layers. Yet another advantage of the present invention is that an internal electric field induced by spin-polarization of the aligned Fe3O4 nanochains of a solar cell increases the charge separation and charge transport processes of the solar cell, and thus enhances the short circuit current density (Jsc). Still another advantage of the present invention is that a polymer solar cell includes an active layer that is formed of a solution-processed composite material, whereby the solution process includes spin-casting, dip-casting, drop-casting, as well as any printing technology, such as spray-coating, dip-coating, doctor-blade coating, slot coating, dispensing, ink-jet printing, thermal transfer printing, silk-screen printing, offset printing, gravure printing, and flexo printing. Yet another advantage of the present invention is that a polymer solar cell using an active layer with aligned Fe3O4 nanochains has a reduced series resistance (Rs), allowing the solar cell to have increased efficiency.
Thus, it can be seen that the objects of the invention have been satisfied by the structure and its method for use presented above. While in accordance with the Patent Statutes, only the best mode and preferred embodiment has been presented and described in detail, it is to be understood that the invention is not limited thereto or thereby. Accordingly, for an appreciation of the true scope and breadth of the invention, reference should be made to the following claims.
This application claims the benefit of U.S. Provisional Patent Application No. 61/614,741, filed on Mar. 23, 2012, the contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 61614741 | Mar 2012 | US |
