WO2016130761A1

WO2016130761A1 - Solar cell employing phosphorescent materials

Info

Publication number: WO2016130761A1
Application number: PCT/US2016/017482
Authority: WO
Inventors: Vidhya CHAKRAPANI
Original assignee: Rensselaer Polytechnic Institute
Current assignee: Rensselaer Polytechnic Institute
Priority date: 2015-02-13
Filing date: 2016-02-11
Publication date: 2016-08-18
Anticipated expiration: 2017-08-13
Also published as: US20230335662A1; US20180025849A1; US12389712B2

Abstract

A solar cell device having a solid state light absorber region that incorporates a donor- acceptor particle structure. The particle structure includes acceptor particles that generate a flow of electrons in the solid state light absorber region in response to absorbed photons; and donor particles comprising a phosphorescent material, wherein each donor particle is coupled to a group of acceptor particles, and wherein the phosphorescent material absorbs high energy photons and emits lower energy photons that are absorbed by the acceptor particles.

Description

SOLAR CELL EMPLOYING PHOSPHORESCENT MATERIALS

PRIORITY^" CLAIM

This application claims priority to co-pending US provisional patent application "Solar Cell Employing Phosphorescent Materials, serial number 62/1 15,667 filed on February 13, 2015, the content of which is hereby incorporated, by reference.

TECHNICAL FIELD

[0001] The subject matter of this inventi on relates to solar cells employing phosphorescent materials, and more particularly to solar cells having a solid state absorber region that integrates phosphor particles with light acceptor particles.

BACKGROUND

[0002] Con verting solar energy to electricity is the one of t he cleanest methods of producing useable energy. Among the various renewable energy technologies available, solar cells hold significant promise. One major drawback of this technology is the lack of flexibility, e.g.. solar cells only have the ability to generate power during daylight hours and thus cannot provide an uninterrupted power supply without, incorporating additional components.

Another drawback is the relatively low efficiency of known devices. Hence, a solar cell with improved efficiency that, can generate power during non-daylight hours and/or that enables efficient storage of energy generated during daylight hours is desirable. SUMMARY

[0003] The disclosed solution describes a solar cell device that has improved efficiency in converting light to electrical energy and the abili ty to output power in the dark after a period of excitation in light. The device incorporates a phosphorescent material w ithin cont rolled proximity of the light absorber used in solar cells. The phosphorescent material is designed and synthesized -so as to match its emission wavelength with the absorption spectrum of the light absorber.

[0004] The aforementioned phosphorescent material comprises a donor clrromophore (donor particles) that absorbs high energy photons of solar light and emits light of low energy photons over extended time periods. The transfer of energy from the phosphorescent material to the absorber (acceptor particles) results in the generation of additional electron-hole pairs in the solar cell as compared to those produced in the absence of the phosphorescent material, and leads to an improvement in the efficiency of the solar cell. A device comprising the energy transfer system described herein can be adapted for various solar cell technologies.

[0005] A. solid state light absorber region is provided that includes a donor-acceptor particle siructiire having acceptor particles adsorbed on a large surface area of inert nanoparticles that serve as current collectors. Upon excitation, a generation, injection, and flow of electrons in the solid state light absorber region results in response to absorbed photons. Donor particles are pro vided comprising a phosphorescent material that are coupled to groups of acceptor particles such that the phosphorescent material absorbs high energy photons and emits lower energy photons that are absorbed by the acceptor particles,

[0006] In a first aspect, the in vention provides a solar cell device, comprising-, a solid state light absorber region that includes a donor-acceptor particle structure having: acceptor particles adsorbed on an inert nanoparticles current collector, which causes a flow of electrons i the solid state light absorber region i response to absorbed photons; and donor particles composing a phosphorescent material, wherein each donor particle is coupled to a group of acceptor particles, and wherein the phosphorescent material absorbs high energy photons and emits lower energy photons that are absorbed by the acceptor particles.

[0007] I a second aspect, the invention provides a dye sensitive solar cell (DSSC) device, comprising: counter electrode; an electrolyte region; a transparent back contact; and a transparent electrode disposed between the electrolyte region and transparent back content, wherein the transparen electrode includes a donor-acceptor particle structure having:

acceptor particles adsorbed on an inert nanoparticles current collector, which upon absoxption of photons, results in a flow of free electrons in the acceptor particles, injection of electrons into the inert nanoparticles current collector, and transport of injected electrons by the inert nanoparticles current collector to the transparent back contact; and donor particles comprising a phosphorescent material, wherein each donor particle is coupled to a group of acceptor particles, and wherein the phosphorescent material absorbs high energy photons and emits lower energy photons that are absorbed by the acceptor particles.

[0008] in a third aspect, the invention provides a method of forming a dye sensitive solar cell (DSSC) device, comprising: providing a first and a second transparent back contact; forming a transparent electrode on the first transparent back contact wherein the transparent electrode includes a donor-acceptor particle structure having; acceptor particles adsorbe on a inert nanoparticles current collector; and donor particles comprising a phosphorescent material, wherein each donor particle is coupled to a group of acceptor particles, and wherein the phosphorescent material absorbs high energy photons and emits lower energy photons that are absorbed by the acceptor particles; forming a counter electrode on the second transparent back contact; and forming an electrolyte region between the counter electrode and transparent electrode; wherein the transparent electrode forms a light absorption region, which upon absorption of photons results in a flow of free electrons in the acceptor particles, injection of electrons into the inert nanopartieles current collector and transport of injected electrons by the inert nanopartieles current collector to the first transparent back contact.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] These and other features of this, invention will he more readily understood ftom the following detailed description of the various aspects of the invention taken in conjunction with the accompanying drawings in which:

[0010] Figure 1 depicts a donor-acceptor particle structure according to embodiments.

[001 1] Figure 2 depicts a dye sensitive solar cell according to embodiments.

[0012] Figure 3 depicts a graph showing spectral matching of donor and acceptor particles according to embodiments,

[0013] The drawings are not necessarily to scale. The dra wings are merely schematic representations, not intended to portray specific parameters of the invention. The drawings are intended to depict onl typical embodiments of the invention, and therefore should not be considered as limiting the scope of the invention, m the drawings. like numbering represents like elements.

DETAILED DESCRIPTIO

[0014] A. solar cell device and associated method for forming the device are disclosed having a solid state light absorber region or chromophore that includes coated phosphor "donor ^' particles placed in close proximity to associated "acceptor" particles. While both types of particles act as chromophores (light absorbers), the donor particles include a phosphorescent material that absorbs high energy phoions of solar light and emits light of tow energy phoions over extended time periods. The phosphorescent materia! is selected so as to enable spectra! overlap of its emission wavelen gth with the absorption spectrum of the acceptor particles. The transfer of energy from the phosphorescent material to the acceptor particles results in the generation of additional electron-hole pairs hi the absorber chromophore as compared to those produced in the absence of the phosphorescent material, and leads to the improvement in the efficiency of the solar cell. Irs addition, because the phosphorescent material continues to emit low energy photons even -after the removal o -an excitation fight source (e.g._., the son in the present case), the resulting solar cell device has the ability to output power in the dark after a period of excitation i light.

[0015] In an illustrative embodiment;, the donor-acceptor particie structure is implemented in a solid state form with inorganic phosphor particles having a very high phosphorescence efficiency in which the distance between each donor paiticle and associaied acceptor particles is carefully controlled to optimize energy transfer between the two. The use of inorganic phosphorescent materials allows emission of radiation for many hours in darkened conditions, which can be used to power a solar cell device in the absence of light.

Experimental results in a dye sensitive solar cell application show approximately a 60% improvement in the solar cell device's efficiency under illumination using simulated sunlight and 300 times improvemeat in the dark. Because the energy transfer is achieved in a solid state, the present approach is not restricted to organic phosphors embedded in liquid electrolytes, such as photoelectrochemical (PEC) solar cells, but ca instead be adapted for a wide variety of known solar cells,

[0016] Referring now to ie drawings. Figure 1 depicts a donor-acceptor particle structure 10 that includes a phosphor (donor) particle 16 having a coating or spacer 14 coupled to a group of acceptor particles 12. The acceptor particles 12 are adsorbed on inert itanoparticJes that serve as current collectors, the structure generally being referred to as an "inert nanoparticles current, collector" 15, When incorporated into a solar cell device, the phosphorescent material that makes up the phosphor particle 16 is excited by high .energy photons of sunlight, which is transferred to the acceptor particles 12 to both enhance efficiency daring lighted conditions and allow for extended periods of use (e.g., several hours) in darkened conditions.

[0017] Figure 2 depicts an illustrative embodiment of a dye sensitized solar cell (DSSC) device 20 that employs the abovementioned donor-acceptor particle structure 10. Device 20 generally includes a first transparent back contact 22. a top electrode 24 (i.e., anode) that incorporates the donor-acceptor particle structure 1.0 and inert nanopart!cies current collector 15 to form a solid state light, absorbing region, an electrolyte 26, a counter electrode 28 (cathode) and a second transparent back contact 30, The illustrative solar cell device 20 is generally implemented using a standard dye sensitized solar cell (DSSC) architectore, with the additional phosphor material incorporated with the acceptor particles in the top electrode 24.

[0018] In the illustrative DSSC embodiment 20, phosphor particles 16 may for example comprise S.r AI2O4 coated with a. thin layer of polycrystallme T1O2 film that forms the spacer 14. Acceptor particles 12 may for example be comprised of an absorber such as dye or quantum dot. material adsorbed on a TiOz nanoparticle current collector. The I^'iOa film (i.e., spacer 14) prevents the direct contact of the phosphor material 16 with the electrolyte 26, thus preveutiag the c enching of phosphorescent signals by the iodide/tri iodide or other redox couples. The spacer 14 also serves as a barrier against direct charge transfer between the phosphor particle 16 and the acceptor particles 1:2, and serves as an electrical conduit for injected electrons from the excited dye to the back contact 30 of the solar cell. TiCb is transparent to the visible light (e.g., ^:::520 nni) emitted by the phosphor particles 16, In one illustrative embodiment, the thickness of the TiOa spacer may be in the range of 8-10 nm.

[0019] DSSC device 20 generally includes a solid dye structure formed within the top electrode 24 for catching photons of incoming light, which convert the energy into excited electrons. The excited electrons are then, injected into a conduction band of the TiCb nanopartieles in the electrode 24, and conducted away (upward in Figure 2) to the first transparent back contact 22 by the layer's ΉΟ2 nanopartieles current collector 15 (Figure I). Electrol vte 26 closes the circuit 32 allowing the electrons to return to the dye within electrode layer 24, The movement of the electrons through the electrical circuit 32 can be used to run electrical devices and thus produce usable work. By incorporating the donor-acceptor particle structure 10 into the top electrode 24, the number of electron hole pairs is increased, thus improving efficiency. Furthermore^ because the phosphorescent material continues to emit energy for many hours after excitation, the device will continue to output electricity m darkened conditions.

[0020] Although described in a DSSC embodiment, the described donor-acceptor partic le structure 10 may likewise be incorporated into other types of devices, such as quantum dot solar cells, polymer solar cells and thin film solar cells.

[0021] In the case of DSSC device, the following illustrati ve fabrication process may be utilized, with reference to Figures 1 and 2. First, a light emitting phosphor 1 is selected,

phosphor having particle diameters of approximately 230 mesh and 300 mesh respectively. Next the phosphor particles 16 are coated with a film (ix., spacer) 1 . This may for example be done by repeatedly spraying a mixture of 0.1 M titanium (TV) isopropoxide and 1.2 M aeetykeetonate in etbano! on the phosphor particles 16 dispersed on a silicon wafer maintained at 40 °C. Afte the deposition, the particles may be annealed at 500 "C for 30 minutes to remove trace o ganics. The thickness of the coa ing may be in range of 8-10 run, which may be accomplished with 40 deposition cycles.

[0022] TiC¾ nanopartieles may be prepared as a transparent T1O2 paste with hydrothermal synthesis using titanium (IV) isopropoxide as the precursor. For example, the procedure may utilize the drop wise addition of 3.7 mL of the precursor to a beaker containing a mixture of 1 mL of 2-propanol, 8 ml of acetic acid, and 25 mL distilled water kept over an ice bath.

[0023] The mixture can then be heated at 80 °C for 25 minutes. Tire entire contents can then be transferred to an aiitoclave and beated to a temperature o 250 °C for approximately 13 hours. The resulting particles are repeatedly washed with distilled water, centtiiuged, and finally suspended in ethanol until further -use. Particles obtained by this procedure comprise pure anatase phase of TI G : with an average particles size of -20 nm. Scattering TiOa nanoparticles may he prepared, by dispersing 10 grams of P25 (Degussa) powder in 30 mL of ethanol. The mixture may then be sonicated for 30 minutes.

[0024] The top electrode 24 ma be fabricated as follows. First, a floorine-doped tin oxide coated glass (FTO substrate -~ i.e., first transparent back contact 22) is coated with a transparent blocking layer of Tit¾, such as the provided by SOLARONfX®, and annealed in a furnace at 500°C for 30 minutes, which is then followed with a deposition of thick transparent Ti<¾ nanoparticles. The film is then dried and coated with 150 urn of paste containing scattering TiO nanoparticles and Ti ¾ coated SrAhCXi. The vohirnetric ratio of TtOs to phosphor particles may for example be in the range of approximately 10: 1. The film is then annealed at 500°C for 60 minutes to achieve a total film thickness of approximately 100 microns. Before sensitization with rntheniuro dye (e.g.., ?j 9, SIGMA ALDRiCH®}, the substrate is immersed in 0.02M TiCk solution for 10 minutes, and annealed again at 450*0 for 60 minutes. The resulting substrate is then immersed in a 0.5 wM N7I dye dissolved in 1 : 1 (v/v) ratio of aceionitriie and tert-butyl alcohol at 4°C to form top electrode 24.

[0025] A platinum counter electrode 28 may be prepared by applying a thin coating of chloroplatinic acid on a second FTO substrate (i.e., second transparent back contact 30), followed by annealing at 500°C for 1 hour. [0026] The electrodes 24, 28 may be assembled using a 200 piii-tiiick hot-melt film (Surlyn 1702, SOLAR IX®) as spacer between the transparent electrode 24 and counter electrode 28. An electrolyte 26, e.g., consisting of 0.6 M PMJI, 0.05 M h, 0.05M tertbtityl pyridine (0.04 M) and 0.Ό25Μ guaaid niura fhiocyanate in 4: 1 (v/v) ratio of acetomtrile and valeronitrile, may be injected through a small, predrilled hole in the counter electrode 28, [0027] As noted herein,_, the emission spectra of the donor partic les should be selected to overlap the absorption spectra of the acceptor particle to maximize efficiency of the device. Figure 3, for example, shows the absorption and emission spectra of N719 dye dissolved, in tert-^'bu yl alcohol along with the emission spectra of SrAlsO* (dispersed on a copper foil) recorded at room temperature at an excitation wavelength of 373 nm. The absorption spectrum of N7I9 dye shows an absorption peak at 520 mn and has a good spectral overlap with the emission range of SrAfeO*, which is necessary for efficient excitation energy transfer. SrA O.* has a broad excitatio spectrum from 460-250 am, and thus can be excited by solar radiation. The phosphor exhibits a broad band photo luminescence (PL) with

maximum intensity occurring at 520 nm.

[0028] The foregoing description of various aspects of the inven tion has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention ^'to the precise form disclosed, and obviously, .many modifications .and variations are possible. Such modifications and variations that may be apparent to an individual in the art are included, within the scope of the invention as defined b the accompanying claims,

Claims

1. A solar eel! device, comprising:

a solid state light absorber region that includes a donor-acceptor particle stracture havinsi:

acceptor particles adsorbed on m inert nanoparticles current collector, which results, in a flow of electrons in the solid state light absorber region in response to absorbed photons; and

donor particles comprising a phosphorescent material wherein each donor particle is coupled to a group of acceptor particles, and wherein the phosphorescent material absorbs high energy photons and emits lower energy photons that are absorbed by the acceptor particles.

2. The solar ceil device of claim f wherein the acceptor particles comprise an absorber adsorbed on an inert TiC nanoparticles current collector.

3. The solar cell device of claim 1 , wherein the donor particles includes a coating that provides a spacer between each donor particle and group of acceptor particles.

4. The solar cell device of claim 3, wherein the spacer comprises Xi(¾.

5. The solar cell device of claim 1, wherein an emission spectrum of the donor particles o verlaps with an absorption spectrum of the acceptor particles.

6. The solar cell device of claim 1, wherein the solid state light absorber region forms an electrode,

7. The solar ceil device of claim 1 that comprises a device selected from a group consisting of: dye sensitive solar cell, a quantum dot solar cell a polymer solar ceil, and a thin film solar cell.

i l

8. A dye sensitive solar cell (DSSC) device, comprising:

a counter electrode;

an electrolyte region;

a transparent back contact; and

a transparent electrode disposed between the electrolyte .region and transparent back content:., wherein the trans arent electrode includes a donor-acceptor particle structure having:

acceptor particles adsorbed on an inert nanoparticles current collector, which upon absorption of photons, results in a How of tree electrons in the acceptor particles, injection of electrons into the inert nanoparticles current collector, and transport of injected electrons by the inert nanoparticles current collector to the transparent back contact; and

donor particles comprising a phosphorescent materia!, wherein each donor particle is coupled to a group of acceptor parti cles, and wherein the phosphorescent material absorbs high energy photons and emits lower energy photons that are absorbed by the acceptor particles.

9. The DSSC device of claim 8, wherein the acceptor particles comprise a dye, quantum dot or other absorber material anchored onTiCfe nanoparticles.

10. The DSSC device of claim 8, wherein the donor particles include a coating that provides a spacer between each donor particle and group of acceptor particles.

11. The DSSC of claim K wherein the spacer comprises TiCb

12. The DSSC of claim 8, wherein an emission: spectrum of the donor particles overlaps with an absorption spectrum of the acceptor particles.

13. The DSSC of claim 8, wherein a voliimeiric ratio of acceptor particles to donor particles is approximately 10: 1 ,

14. The DSSC of claim 9, wherein the do»or-acceptor particle structure and Tii¾

nanoparticles are coated onto a substrate.

15. A method of forming a dye sensitive solar cell (DSSC) device, comprising: providing a first and a second transparent back contact;

forming a transparent electrode on the first transparent back contact, wherein the transparent electrode includes a donor-acceptor particle structure having:

acceptor particles adsorbed, on an inert nanoparticles current collector; and donor particles comprising a phosphorescent material., wherein each donor particle is coupled to a group of acceptor particles, and wherein the phosphorescen t

.material absorbs high energy photons and emits lower energy photons that are absorbed by the acceptor particles;

forming a counter electrode on the second transparent back contact; and

forming an electrolyte region between the counter electrode and transparent electrode; wherein the transparent electrode forms a light absorption region, which upon absorptio of photons results in a fl ow of free electrons i the acceptor particles , inj ection of electrons into the inert nanopailicles current collector and transport of injected electrons by the inert nanoparticles current collector to the first transparent back contact.

16. The method of claim I , wherein the acceptor particles comprise a dye adsorbed on a TiOj, nanoparticles current c llector .

17. The method, of claim 15, wherei the donor particles include a coating that provides a spacer between each donor particle and group of acceptor particles.

13. The method of claim 17, wherein the spacer comprises TiOj.

19. The method of claim 1.5, wherein an emission spectrum of the donor particles overlaps with mi absorption spectrum of the acceptor particles.

20. The method of claim 15, wherein a volumetric ratio of acceptor particles to donor particles is approximately 10:1.