Transparent photovoltaic cells
09728735 · 2017-08-08
Assignee
Inventors
Cpc classification
H10K30/82
ELECTRICITY
H10K30/10
ELECTRICITY
H10K30/211
ELECTRICITY
H10K30/30
ELECTRICITY
International classification
Abstract
A transparent photovoltaic cell and method of making are disclosed. The photovoltaic cell may include a transparent substrate and a first active material overlying the substrate. The first active material may have a first absorption peak at a wavelength greater than about 650 nanometers. A second active material is disposed overlying the substrate, the second active material having a second absorption peak at a wavelength outside of the visible light spectrum. The photovoltaic cell may also include a transparent cathode and a transparent anode.
Claims
1. A transparent photovoltaic cell, comprising: a transparent substrate; a first transparent active material overlying the transparent substrate, the first transparent active material having an absorption peak at a wavelength greater than about 650 nanometers, the first transparent active material's absorption peak being greater than the first transparent active material's absorption at any wavelength between about 450 and 650 nanometers; a second transparent active material overlying the transparent substrate, the second transparent active material having an absorption peak at a wavelength between 300 and 450 nanometers or between 650 and 2500 nanometers, the second transparent active material's absorption peak being greater than the second transparent active material's absorption at any wavelength between about 450 and 650 nanometers; a transparent cathode; and a transparent anode; the transparent photovoltaic cell having at least one absorption peak at a wavelength greater than about 650 nanometers that is greater than the transparent photovoltaic cell's absorption at any wavelength between about 450 and 650 nanometers, wherein the transparent photovoltaic cell is operable to transmit visible light with wavelengths between 450 and 650 nanometers.
2. The transparent photovoltaic cell of claim 1 wherein at least one of the transparent cathode and the transparent anode is configured to maximize absorption in the first transparent active material.
3. The transparent photovoltaic cell of claim 1 wherein at least one of the transparent cathode and the transparent anode is configured to maximize absorption in the second transparent active material.
4. The transparent photovoltaic cell of claim 1 wherein the first transparent active material and the second transparent active material are located in separate layers.
5. The transparent photovoltaic cell of claim 1, wherein the first transparent active material has a second absorption peak at a wavelength less than about 450 nanometers.
6. The transparent photovoltaic cell of claim 1, wherein the first transparent active material is a donor and the second transparent active material is an acceptor.
7. The transparent photovoltaic cell of claim 1, further comprising a visibly transparent reflector reflecting at near infra-red wavelengths.
8. The transparent photovoltaic cell of claim 1, wherein the first transparent active material comprises an organic material.
9. The transparent photovoltaic cell of claim 1, wherein the first transparent active material comprises at least one of: a phthalocyanine, a porphyrin, a naphthalocyanine dye or nanotubes.
10. The transparent photovoltaic cell of claim 1, wherein the first transparent active material comprises chloroaluminum phthalocyanine.
11. The transparent photovoltaic cell of claim 1, wherein the first transparent active material comprises tin phthalocyanine.
12. The transparent photovoltaic cell of claim 1, wherein the second transparent active material comprises at least one of carbon 60 (C60) or a nanotube.
13. The transparent photovoltaic cell of claim 1, wherein the first and second transparent active materials are configured for use with flexible encapsulation layers.
14. The transparent photovoltaic cell of claim 1, wherein the transparent photovoltaic cell is incorporated into one of a display screen, a watch crystal, automotive glass or architectural glass.
15. A transparent photovoltaic array comprising a plurality of electrically interconnected transparent photovoltaic cells according to claim 1.
16. The transparent photovoltaic cell of claim 1, wherein the transparent substrate is flexible.
17. A transparent photovoltaic cell, comprising: a transparent substrate; a first transparent active material overlying the transparent substrate, the first transparent active material having an absorption peak at a wavelength between 300 and 450 nanometers or between 650 and 2500 nanometers, the first transparent active material's absorption peak being greater than the first transparent active material's absorption at any wavelength between about 450 and 650 nanometers; a second transparent active material overlying the transparent substrate, the second transparent active material having an absorption peak at a wavelength greater than about 650 nanometers or less than about 450 nanometers, the second transparent active material's absorption peak being greater than the second transparent active material's absorption at any wavelength between about 450 and 650 nanometers; and a transparent cathode and a transparent anode; the transparent photovoltaic cell having at least one absorption peak at a wavelength greater than about 650 nanometers that is greater than the transparent photovoltaic cell's absorption at any wavelength between about 450 and 650 nanometers, wherein the transparent photovoltaic cell is operable to transmit visible light with wavelengths between 450 and 650 nanometers.
18. A method of generating electricity, the method comprising: providing a transparent photovoltaic cell comprising: a transparent substrate; a first transparent active material overlying the transparent substrate, the first transparent active material having an absorption peak at a wavelength greater than about 650 nanometers, the first transparent active material's absorption peak being greater than the first transparent active material's absorption at any wavelength between about 450 and 650 nanometers; a second transparent active material overlying the transparent substrate, the second transparent active material having an absorption peak at a wavelength between 300 and 450 nanometers or between 650 and 2500 nanometers, the second transparent active material's absorption peak being greater than the second transparent active material's absorption at any wavelength between about 450 and 650 nanometers; and a transparent cathode and a transparent anode; the transparent photovoltaic cell having at least one absorption peak at a wavelength greater than about 650 nanometers that is greater than the transparent photovoltaic cell's absorption at any wavelength between about 450 and 650 nanometers, wherein the transparent photovoltaic cell is operable to transmit visible light with wavelengths between 450 and 650 nanometers; and exposing the transparent photovoltaic cell to a light source.
19. The method of claim 18, further comprising providing a multi-layer reflector for reflecting near-infrared light.
20. The transparent photovoltaic cell of claim 7, wherein the visibly transparent reflector is a multi-layer distributed Bragg reflector (DBR).
21. The transparent photovoltaic cell of claim 1 wherein the transparent anode comprises a transparent conducting oxide.
22. The transparent photovoltaic cell of claim 1 wherein the transparent cathode comprises a transparent conducting oxide.
23. The method of claim 19 wherein the multi-layer reflector comprises a multi-layer distributed Bragg reflector (DBR).
24. The method of claim 18 wherein the first transparent active material and the second transparent active material are located in separate layers.
25. The method of claim 18 wherein the first transparent active material has a second absorption peak at a wavelength less than about 450 nanometers.
26. The method of claim 18 wherein the first transparent active material is a donor and the second transparent active material is an acceptor.
27. The method of claim 18 wherein the first transparent active material comprises an organic material.
28. The method of claim 18 wherein the first transparent active material comprises at least one of: a phthalocyanine, a porphyrin, a naphthalocyanine dye or nanotubes.
29. The method of claim 18 wherein the first transparent active material comprises chloroaluminum phthalocyanine.
30. The method of claim 18 wherein the first transparent active material comprises tin phthalocyanine.
31. The method of claim 18 wherein the second transparent active material comprises at least one of carbon 60 (C60) or a nanotube.
32. The method of claim 18 wherein the transparent substrate is flexible.
Description
BRIEF DESCRIPTION OF THE FIGURES
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DETAILED DESCRIPTION OF THE INVENTION
(27) Described herein are improved transparent solar cell designs, e.g., transparent organic photovoltaic devices (TOPV). The term transparent as used herein encompasses an average visible transparency of a straight through beam of 45% or more. The term semi-transparent as used herein encompasses an average visible transparency of a straight through beam of approximately 10%-45%. In general, the designs include molecular active layers with strong absorption features outside of the visible light spectrum, e.g., in the ultra-violet (UV) and/or near-infrared (NIR) solar spectrum. The devices may include selective high-reflectivity NIR and broadband anti-reflection contact coatings. Devices may be formed as heterojunction solar cells with an organic active layer, such as chloroaluminum phthalocyanine (ClAlPc) or SnPc as a donor and a molecular active layer such as C.sub.60 acting as an acceptor and having peak-absorption in the UV and NIR solar spectrum. Other suitable materials for the active layers include any suitable phthalocyanine, porphyrin, naphthalocynanine dye, carbon nanotubes or molecular excitonic materials with absorption peaks outside the visible spectrum. Such devices may be formed in a tandem structure with one or more subcells joined via a recombination zone. Such devices may be used in a variety of applications including rigid and flexible computer display screens used in a desktop monitor, laptop or notebook computer, tablet computer, mobile phone, e-readers and the like. Other applications include watch crystals, automotive and architectural glass including sunroofs and privacy glass. The photovoltaic devices may be used for active power generation, e.g., for completely self-powered applications, and battery charging (or battery life extension).
(28) Near-infrared (NIR) as recited herein is defined as light having wavelengths in the range from about 650 to about 850 nanometers (nm). Ultraviolet (UV) as recited herein is defined as light having wavelengths less than about 450 nm. The use of an active layer having absorption in the NIR and the UV allows for the use of selective high-reflectivity near-infrared mirror coatings to optimize device performance while also permitting high transmission of visible light through the entire device. Visible light as recited herein is defined as light having wavelengths to which the human eye has a significant response, from about 450 to about 650 nm.
(29) In one embodiment, devices were fabricated on 150 nm of patterned Indium Tin Oxide (ITO) (15 Ω/sq.) pre-coated onto glass substrates. The ITO is one component of an electrode. The ITO was solvent-cleaned and subsequently treated in oxygen plasma for 30 seconds immediately prior to loading into a high vacuum chamber (<1×10.sup.−6 Torr). ClAlPc and C.sub.60 were purified once by vacuum train sublimation prior to loading. Bathocuproine (BCP) and molybdenum trioxide (MoO.sub.3) were used as purchased. MoO.sub.3 is another component of an electrode. The MoO.sub.3 (20 nm), ClAlPc (15 nm), C.sub.60 (30 nm), BCP (7.5 nm), and a 100 nm thick Ag cathode were sequentially deposited via thermal evaporation at a rate of 0.1 nm/s. The top ITO cathode for the transparent devices was rf-sputtered directly onto the organic layers at low power (7-25 W) with 10 sccm Ar flow (6 mTorr) and 0.005-0.03 nm/second. Cathodes were evaporated through a shadow mask, defining a 1 millimeter (mm)×1.2 mm active device area. A near-infrared distributed Bragg reflector (DBR) utilized as the transparent NIR mirror was grown separately on quartz via sputtering of 7 alternating layers of TiO.sub.2 and SiO.sub.2 at about 0.1 nm/second with thicknesses centered around a wavelength of 800 nm (200 nm stop band). Broad-band antireflection (BBAR) coatings precoated on quartz substrates (1-side) were attached to the DBRs via index matching fluid to reduce additional glass/air interface reflections. Transmission data of the assembled devices were obtained at normal incidence with a Cary Eclipse 5000 dual-beam spectrophotometer without reference samples. Current density versus voltage (J-V) characteristics were measured in the dark and under simulated AM1.5G solar illumination without solar mismatch correction (for reference, the mismatch factor was estimated to be ˜1.05) and external quantum efficiency (EQE) measurements were collected utilizing an NREL calibrated Si detector. Optical interference modeling was carried out according to the method of L. A. A. Pettersson, L. S. Roman, and O. Inganas, Journal of Applied Physics 86, 487 (1999), the contents of which are herein incorporated by reference. The exciton diffusion lengths of ClAlPc and C.sub.60 were estimated from fitting the magnitudes of the photocurrent and EQE to be 5±3 nm and 10±5 nm, respectively.
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(32) TABLE-US-00001 TABLE 1 Cathode Thickness Cathode Jsc Voc FF η.sub.P AVT (nm) Composition (mA/cm.sup.2) (V) — (%) (%) 100 Ag 4.7 0.77 0.55 2.4 0 20 ITO 1.5 0.69 0.39 0.5 67 120 ITO 3.2 0.71 0.46 1.3 65 20 ITO/NIR mir. 2.2 0.73 0.32 0.6 53 40 ITO/NIR mir. 2.5 0.71 0.49 1.1 55 80 ITO/NIR mir. 2.9 0.71 0.46 1.2 56 120 ITO/NIR mir. 4.4 0.71 0.44 1.7 56 170 ITO/NIR mir. 3.2 0.69 0.48 1.3 66
(33) Table 1 generally includes data showing the performance of control OPVs with an Ag cathode, transparent OPVs with ITO cathode, and OPVs with ITO cathode and NIR mirror, at 0.8 sun illumination corrected for solar spectrum mismatch. Short circuit current, JSC, open circuit voltage, VOC, fill factor, FF, power conversion efficiency, η.sub.P, and the average visible transmission, AVT, are indicated. The control device with a thick Ag cathode exhibits a power conversion efficiency (η.sub.p) of 1.9±0.2%, open circuit voltage (Voc)=0.80±0.02V, short-circuit current density (Jsc)=4.7±0.3 mA/cm.sup.2, and fill-factor (FF)=0.55±0.03, which is comparable to previous reports.
(34) When the Ag cathode of the control cell is replaced with ITO, the short-circuit current Jsc drops significantly to 1.5±0.1 mA/cm.sup.2, the FF drops to 0.35±0.02, and the open-circuit voltage Voc decreases slightly to 0.7±0.02V leading to η.sub.p=0.4±0.1%. The FF decreases due to an increase in series resistance from the thin ITO that is observable in the J-V curve under forward bias in
(35) The Jsc decreases as the cathode is switched from Ag to ITO due to reduced cathode reflections that reduce the total absorption across the spectrum in the active layers.
(36) Despite the significant impact on the photocurrent, the average visible transmissivity (AVT) shows little variation with ITO thickness (see e.g.,
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(38) To highlight the transparency of the fully assembled device,
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(40) Optimizing the transparent OPV structure with just the cathode thickness, power conversion efficiency of 1.0±0.1% is obtained, with a simultaneous average transmission of 66±3%. Incorporation of the NIR reflector and BBAR coatings with the optimized ITO thickness (see
(41) Switching from planar to bulk-heterojunctions in these structures, efficiencies of 2-3% may be possible for this material set with nearly identical visible transmission, and is currently under investigation. Tandem stacking of subcells with active layer absorption deeper into the infrared could also enhance these efficiencies; combined with more sophisticated NIR mirrors, efficiencies beyond several percent and average visible transmission >70% are possible.
(42) In another embodiment, SnPc, e.g., SnPc-C.sub.60, may be used to construct transparent solar cells. Solar cell designs based on SnPc may achieve >2% efficient solar cell with >70% transmission of visible light (˜70% average transmission across visible spectrum). The following layers were used in this example: ITO/SnPc(10 nm)/C60(30 nm)/BCP(10 nm)/ITO(10 nm)/DBR. In this example, the ITO was sputtered directly. The distributed Bragg reflectors (DBR) were applied with index matching fluid (IMF).
(43) TABLE-US-00002 TABLE 2 Cathode Jsc Voc FF η (%) Ag 6.15 0.40 0.55 1.3 ITO 1.54 0.33 0.48 0.2 ITO-DBR 2.25 0.34 0.44 0.3
(44) The device may include a NIR mirror (transparent to visible light) composed of either metal/oxide (e.g. TiO.sub.2/Ag/TiO.sub.2) or dielectric stacks (DBRs e.g. consisting of SiO.sub.2/TiO.sub.2). Anti-reflection coatings may be composed of single or multilayer dielectric materials. As noted above, the molecular active layer may also be composed of any suitable phthalocyanine, porphyrin, naphthalocyanine dye, carbon nanotube, or molecular excitonic materials with absorption peaks outside of the visible spectrum.
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(46) TABLE-US-00003 TABLE 3 Donor Thick Jsc Voc FF η (%) SnPc 100 6.15 0.40 0.50 1.2 CIAIPc 200 4.70 0.77 0.55 2.0
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(49) The structure shown in
(50) An optimization process may generally be performed as follows:
(51) i) Optimize for d.sub.Donor, d.sub.Acceptor (total);
(52) ii) Fix d.sub.Donor, d.sub.Acceptor (total);
(53) iii) Vary d.sub.mixed;
(54) iv) d.sub.Donor=d.sub.Donor (total)−(d.sub.mixed/2);
(55) v) d.sub.Acceptor=d.sub.Acceptor (total)−(d.sub.mixed/2); and
(56) vi) Optimize for ratio (d.sub.Donor:d.sub.Acceptor).
(57) For devices having a mixed layer only, optimization may include an adjustment of the thickness of the mixed layer (step iii) and an adjustment of the ratio d.sub.Donor:d.sub.Acceptor (step vi).
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(59) It should be understood that multiple bandgaps may be selected for successive layers stacked in a tandem device in order to yield a device with the desired efficiency. In such devices, overall transparency is improved over devices that are independently fabricated and post integrated or macroscopically combined. This is possible because such a device benefits from a closely matched index of refraction at each interface between successive layers. The stacked structure may be transparent or semi-transparent.
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(62) In conclusion, near-infrared absorbing, transparent planar organic solar cells with a maximum power of 1.4±0.1% and average visible transmission of exceeding 55±2% have been demonstrated. This average visible transmission is sufficiently transparent for incorporation on architectural glass. The excitonic character of organic semiconductors is advantageously exploited to produce unique photovoltaic architectures not easily accessible via inorganic semiconductors. By positioning the active layer absorption selectively in the NIR, it is possible to optimize the architecture using a NIR reflector composed of a DBR mirror centered at 800 nm that results in a transparent solar cell efficiency approaching that of the non-transparent control cell. Ultimately these devices provide a guide for achieving high efficiency and high transparency solar cells that can be utilized in windows to generate power, reduce cooling costs, and scavenge energy in a variety of applications.