Efficient interconnecting layer for tandem solar cells

Abstract

A tandem solar cell comprises a front subcell; a back subcell; and an interconnecting layer of Cr/MoO.sub.3 between the front subcell and the back subcell and connecting the two subcells in series. The back subcell may be an isoindigo-based polymer. The front subcell may comprise a carbazole-thienyl-benzothiadiazole based polymer. The front subcell may comprise an isoindigo-based polymer. The isoindigo-based polymer is a repeating 2-thiophene-terminated polymer. A tandem solar cell comprises a substrate layer; a layer of PCDTBT:PC.sub.71BM applied on the substrate layer; a bilayer of chromium and MoO.sub.3 applied to the PCDTBT:PC.sub.71BM layer; a layer of P(T3-il)-2:PC.sub.71BM applied on the bilayer of chromium and MoO.sub.3; and Ca and Al electrode layer on the top.

Claims

1. A tandem solar cell, comprising: a substrate layer; a layer of PCDTBT:PC.sub.71BM applied directly to the substrate layer; a bilayer of chromium and MoO.sub.3 applied on the PCDTBT:PC.sub.71BM layer; a layer of P(T3-iI)-2:PC.sub.71BM applied on the bilayer of chromium and MoO.sub.3, wherein P(T3-iI)-2 is a 2-thiophene-terminated polymer consisting of the following repeat unit: ##STR00001## directly on the bilayer of chromium and MoO.sub.3; and an electrode layer applied on top of the a layer of P(T3-iI)-2:PC.sub.71BM.

2. The tandem solar cell of claim 1, wherein the substrate is a PEDOT:PSS coated ITO glass substrate.

3. The tandem solar cell of claim 1, wherein the layer of PCDTBT:PC.sub.71BM is about 80-130 nm thick.

4. The tandem solar cell of claim 1, wherein the layer of PCDTBT:PC.sub.71BM is about 80 nm thick.

5. The tandem solar cell of claim 1, wherein the bilayer of chromium and MoO.sub.3 comprises thermally evaporated chromium and MoO.sub.3.

6. The tandem solar cell of claim 1, wherein the bilayer of chromium and MoO.sub.3 comprises a layer of chromium about 1-3 nm thick.

7. The tandem solar cell of claim 1, wherein the bilayer of chromium and MoO.sub.3 comprises a layer of chromium about 2 nm thick.

8. The tandem solar cell of claim 1, wherein the bilayer of chromium and MoO.sub.3 comprises a layer of MoO.sub.3 about 5-15 nm thick.

9. The tandem solar cell of claim 1, wherein the bilayer of chromium and MoO.sub.3 comprises a layer of MoO.sub.3 about 12 nm thick.

10. The tandem solar cell of claim 1, wherein the layer of P(T3-iI)-2:PC.sub.71BM is about 70-130 nm thick.

11. The tandem solar cell of claim 1, wherein the layer of P(T3-iI)-2:PC.sub.71BM is about 100 nm thick.

12. The tandem solar cell of claim 1, further comprising applying a top electrode of Ca/Al over the P(T3-iI)-2:PC.sub.71BM layer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the present invention and, together with a general description of the invention given above, and the detailed description of the embodiments given below, serve to explain the principles of the present invention.

(2) FIGS. 1A-1B illustrate molecular structures the donor organic polymers, P(T3-il)-2 and PCDTBT (FIG. 1A), and acceptor PC.sub.71BM molecules (FIG. 1B) of the disclosed invention;

(3) FIG. 1C depicts UV-visible-near infrared absorption spectra of the donor organic polymers, P(T3-il)-2 and PCDTBT (FIG. 1A), and acceptor PC.sub.71BM molecules of FIG. 1B;

(4) FIGS. 2A-2B illustrate a single-junction device structure and J-V curves of P(T3-il)-2:PC.sub.71BM solar cells having different active layer thicknesses;

(5) FIG. 3A illustrates the UV-Vis NIR absorption spectra of an 80 nm PCDTBT:PC.sub.71BM BHJ composite film, a 100 nm P(T3-il)-2:PC.sub.71BM BHJ composite film, and a bilayer of the two with 2 nm Cr/12 nm MoO.sub.3 in between;

(6) FIG. 3B depicts a tandem device structure, according to the present invention, in which a Cr/MoO.sub.3 interconnecting layer is incorporated;

(7) FIG. 3C depicts an energy diagram for the various layers in an optimized tandem device (values are in eV) according to the present invention;

(8) FIG. 4 illustrates the transmission spectra of ITO on a glass substrate and 2 nm Cr/12 nm MoO.sub.3 film deposited on glass;

(9) FIGS. 5A-5B illustrate J-V curves of tandem PSCs with various thicknesses of rear P(T3-il)-2:PC.sub.71BM cells (FIG. 5A); and the J-V curves of the sub-cells and the optimal tandem polymer cell (FIG. 5B);

(10) FIGS. 6A-6C depict AFM (height) images (5 μm×5 μm) of thin film surface topographies at different stages during progression of tandem cell fabrication on glass/ITO/PEDOT:PSS. (FIG. 6A) 80 nm PCDTBT:PC.sub.71BM; (FIG. 6B) 80 nm PCDTBT:PC.sub.71BM/2 nm Cr/12 nm MoO.sub.3 and (FIG. 6C) 80 nm PCDTBT:PC.sub.71BM/2 nm Cr/12 nm MoO.sub.3/100 nm P(T3-il)-2:PC.sub.71BM.

(11) It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various features illustrative of the basic principles of the invention. The specific design features of the sequence of operations as disclosed herein, including, for example, specific dimensions, orientations, locations, and shapes of various illustrated components, will be determined in part by the particular intended application and use environment. Certain features of the illustrated embodiments have been enlarged or distorted relative to others to facilitate visualization and clear understanding. In particular, thin features may be thickened, for example, for clarity or illustration.

DETAILED DESCRIPTION OF THE INVENTION

(12) In this work, we have developed a new, chemically robust tandem cell IL comprised of a thermally evaporated Cr and MoO.sub.3 bilayer, and we show the utility of this layer through the fabrication of monolithic tandem solar cells from an easily accessible, isoindigo-based low band-gap polymer. A tandem device structure consisting of Glass/ITO/PEDOT:PSS/PCDTBT:PC.sub.71BM/Cr/MoO.sub.3/P(T3-il)-2:PC.sub.71BM/Ca/Al is fabricated and demonstrates successful series connection of subcells with cumulative V.sub.oc. The PCEs of these isoindigo-based polymer tandem devices reached up to 6%, suggesting great promise towards low-cost polymer PV. Cr/MoO.sub.3 is disclosed herein as a new composite interlayer for tandem PSCs composed of a low band-gap polymer which can be synthesized in kilogram quantities. Further efficiency gains may be achieved through optimization of polymer layer thicknesses to match the current densities of each photoactive layer and thereby minimize losses due to electron-hole recombination.

(13) FIG. 1A illustrates the chemical structure of an isoindigo-based low band-gap (E.sub.g=1.6 eV) polymer, P(T3-iI)-2 which may be synthesized in kilogram quantities, greatly improving efficiencies in manufacturing. Its broad absorption spectra, up to 800 nm, high extinction coefficient (˜1.2×10.sup.5 cm.sup.−1 in 550-700 nm region), favorable energy levels, and high solubility in organic solvents are advantageous for construction of BHJ PV devices. Optimized single junction solar cells may be made from a 1:2 weight ratio of [P(T3-il)-2:PC.sub.71BM] (illustrated in FIGS. 1A-1B) active layer deposited from chloroform with 2 to 3 vol. % of 1,8-diiodooctane (DIO). More specifically, the P(T3-il)-2:PC71BM (1:2 weight ratio) blend was dissolved in chloroform at 70° C. for 12 hours with 6-10 mg/mL concentration and 2 volume % of DIO was added to it. Then the blend was deposited on a substrate using a three step spin-coating at 300 rpm for 1 s, then at 500 rpm for 1 s and finally at 800 rpm for 60 s. Thereafter, all samples were dried in a glove box evacuation ante-chamber for about 2 hours.

(14) Solid lines in FIG. 1C represent thin film samples, while dotted lines are from samples in CHCl.sub.3 (chloroform) solution. A small red shift in the absorption spectra, moving from solution to film, may be related to polymer aggregation.

(15) A single-layer device structure (FIG. 2A) of glass/ITO/PEDOT:PSS (40 nm)/Active layer/Ca (2 nm)/Al (100 nm) may be used to make single active layer control devices, and the device performance shows a strong dependence on the active layer thicknesses. A thin poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) layer (≈40 nm) may be used as a hole conductor, and calcium (Ca) may be used as an electron-buffer layer. The addition of 2 vol. % DIO processing solvent additive in the blend significantly improved the morphology of the active layer and consistently enhanced the PV device performance.

(16) The average PCE of the optimized P(T3-il)-2:PC.sub.71BM solar cell device reaches about 6.1% with a short-circuit current density (J.sub.sc) of 14.0±0.4 mAcm.sup.−2, a V.sub.oc of 0.72±0.02 V, and a fill factor (μF) of 61±4%, when the thickness of the active layer is about 100 nm (see Table 1 below). Increasing the thickness of the active layer further to 130 nm results in a drop in FF and an improvement in J.sub.sc, while V.sub.oc remains almost similar. On the other hand, for a slightly thinner active layer, about 70 nm, J.sub.sc decreases and FF slightly increases due to reduced light absorption and low charge recombination. In this case, the decreased J.sub.sc significantly outweighs the slight increase in FF and a concomitant loss in average PCE to 5.4% is observed. FIG. 2B illustrates the current density-voltage (J-V) characteristics of the highest efficiency single junction P(T3-il)-2:PC.sub.71BM solar cells with various thicknesses (i.e., from 70 to 130 nm). The ultraviolet-visible (UV-Vis) spectrum of the 100 nm thick P(T3-il)-2:PC.sub.71BM film (see FIG. 3A) depicts non-uniform spectral response across its absorption range. Further enhancement in the light absorption, therefore, is highly desirable.

(17) It was determined that the integration of such a low band-gap polymer with a wider band-gap polymeric material into a tandem structure may provide a way to improve the photo response of the solar cell. However, an efficient, transparent recombination layer had to be developed to facilitate integration. Poly [N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) (FIG. 1A), which is an efficient and stable wide band-gap conjugated polymer, was chosen as a visible absorber (FIG. 1C) to enhance the solar absorption of the P(T3-il)-2:PC.sub.71BM PV device. Optimized single junction solar cells, made from a 1:2 weight ratio of in-house synthesized PCDTBT with PC.sub.71BM in chloroform, have a thickness of 80 nm, with the best device efficiency reaching 5.2% under Air Mass 1.5 Global (AM1.5G) illumination (100 mW/cm.sup.2) from a calibrated solar simulator. The UV-Vis absorption spectrum of the 80 nm thick film of PCDTBT:PC.sub.71BM (FIG. 3A) shows slightly higher absorption in the 500-600 nm spectral range than that of a 100 nm thick optimized P(T3-il)-2:PC.sub.71BM film. The absorption spectrum of a bilayer film of 100 nm P(T3-il)-2:PC.sub.71BM and 80 nm PCDTBT:PC.sub.71BM also shows a simple superposition of those of the two individual composites. Thus, the construction of tandem cells with these two BHJ material combinations may be advantageous, depending in the interconnecting layer (IL).

(18) TABLE-US-00001 TABLE 1 Average.sup.a device characteristics of the P(T3-il)-2:PC.sub.71BM based single-junction solar cells with different active layer thicknesses. Thickness V.sub.oc J.sub.sc J.sub.sc EQE.sup.b FF PCE (nm) (V) (mA/cm.sup.2) (mA/cm.sup.2) (%) (%) 70 0.72 ± 0.01 11.9 ± 0.4 (10.9) 63 ± 3 5.4 ± 0.5 (0.73) (12.3) (66) (5.9) 100 0.72 ± 0.02 14.0 ± 0.4 (12.8) 61 ± 4 6.1 ± 0.4 (0.74) (13.6) (65) (6.5) 130 0.71 ± 0.01 14.4 ± 0.6 (13.6) 56 ± 3 5.7 ± 0.7 (0.72) (15.0) (59) (6.4) .sup.aAverages taken for at least 20 devices. .sup.bJsc measured on each of the best performing devices by integrating EQE data; values in parenthesis are for the best performing devices.

(19) In order to build efficient polymer tandem solar cells based on P(T3-il)-2 materials, proper choice of the IL is important. The combination of ZnO nanoparticles as the electron transport layer and pH-neutral PEDOT:PSS as the hole transport layer did not work well likely due to the complexity of ink formulation and aqueous nature of commercial PEDOT:PSS which potentially damaged the underlayers. However, it was discovered that by depositing a thin bilayer of thermally evaporated chromium (Cr) (˜2 nm) and ˜12 nm MoO.sub.3 yields a robust IL that gives consistently better device performance. Cr, being a relatively chemically inert element, effectively protects the underlayers from subsequent device processing. In addition to its chemical stability, this newly-developed thermally deposited Cr(˜2 nm)/MoO.sub.3(˜12 nm) IL is highly transparent (over 80%) in the range of 400-1000 nm (see FIG. 4), ensuring minimum optical losses when light passes from one subcell to another.

(20) Tandem solar cells may be built from a PCDTBT:PC.sub.71BM front cell and a P(T3-il)-2:PC.sub.71BM back cell using this Cr/MoO.sub.3 recombination (interconnection) layer. FIGS. 3B-3C illustrate the structure of a multilayer tandem cell, according to the present invention, together with the energy band diagram of the different layers. The work functions of Cr and MoO.sub.3 are well aligned with the respective conduction band of PC.sub.71BM and the valence band of P(T3-il)-2. Therefore electrons from the front PCDTBT subcell combine with holes from the back P(T3-il)-2 subcell at the Cr/MoO.sub.3 interface. Since the total photocurrent from a series connected tandem cell is limited by the subcell with the lowest photocurrent, the PCDTBT wide band-gap front cell is the limiting cell in this case. An 80 nm thick PCDTBT front subcell with a high J.sub.sc and FF maintains sufficient transmission to the back subcell in order to achieve high performance in the disclosed tandem cell architectures. Low band-gap P(T3-il)-2 rear cells with three different thickness, ranging from 70 to 130 nm, were studied and the details of the tandem cell device performances are summarized in Table 2.

(21) TABLE-US-00002 TABLE 2 Summary of average.sup.a PV parameters of the optimized solar cells. d V.sub.oc J.sub.sc FF PCE Sample.sup.b (nm).sup.c (V) (mA .Math. cm.sup.−2) (%) (%) PCDT8T 80 0.88 (0.86) 9.9 (10.2) 57 (58) 5.0 (5.2) P(T3-il)-2 100 0.72 (0.74) 14.0 (13.6) 61 (65) 6.1 (6.5) Tandem 80/70  1.48 (1.50) 7.2 (7.5) 47 (50) 5.0 (5.6) Tandem 80/100 1.51 (1.53) 8.3 (8.6) 44 (46) 5.5 (6.0) Tandem 80/130 1.42 (1.45) 7.6 (8.0) 36 (40) 3.9 (4.6) .sup.avalues in parenthesis are for the best performing devices, .sup.bBlend with PC.sub.71BM, .sup.cThickness of the active layer

(22) FIG. 5A illustrates the corresponding J-V curves of the tandem cells measured under simulated 100 mW/cm.sup.2 solar illuminations. The tandem cell with an 80 nm front cell and a 100 nm back cell exhibited the highest performance with the best cell reaching 6.0% PCE. Atomic force microscopy (AFM) images of the thin-film surface topography at different stages of progression during the tandem cell fabrication process showed very small surface roughness values, all within 15 nm (see FIGS. 6A-6C). The J-V characteristics of the best-performing tandem cells are illustrated in FIG. 5B and compared with those of the best-performing single junction subcells of similar thicknesses. These results clearly show that the V.sub.oc of ≈1.53 V of the tandem device with J.sub.sc of 8.6 mA/cm.sup.2 and FF of 46%, is approximately equal to the sum of V.sub.oc's of the front (0.88 V) and back (0.74 V) single junction cells, which confirms an effective series connection by the Cr/MoO.sub.3 IL. With thinner (70 nm) rear cells, the J.sub.sc of tandem devices decrease to an average value of 7.2 mA/cm.sup.2 due to low photon absorption, and increasing rear cell thickness to 130 nm reduced the FF of tandem devices due to increased charge recombination losses (see Table 2 above). In each of the tandem devices tested, very close to additive voltages are obtained which suggests a great opportunity for isoindigo-based low band-gap conjugated polymers for integration in tandem architectures.

(23) The following examples illustrate particular properties and advantages of some of the embodiments of the present invention. Furthermore, these are examples of reduction to practice of the present invention and confirmation that the principles described in the present invention are therefore valid but should not be construed as in any way limiting the scope of the invention.

Examples

(24) Single Junction Device Fabrication. All solar cell devices were fabricated on patterned ITO glass (Sheet resistance of 15Ω/□). On the day of deposition, the ITO glass substrates were cleaned sequentially by sonicating with detergent, deionized water, acetone, and iso-propanol, followed by drying with high flow of nitrogen and UV-ozone treatment for 20 min. Filtered (0.45 micron PVDF filter) poly-(3,4-ethylenedioxythiophene:poly(styrenesulfonic acid) (PEDOT:PSS; Clevios Al4083 from Heraeus Materials Technology) was spin-coated on clean ITO glass substrates at 3000 rpm for 60 s and then dried on a ceramic hot-plate at 160° C. for 20 min in air. Thereafter, substrates were immediately taken to a nitrogen-filled glove box for active layer deposition. For single junction PCDTBT device of different thickness, PCDTBT:PC.sub.71BM (1:2 weight ratio; 2 volume % of DIO as processing additive) blend in chloroform was spin-coated on top of ˜40 nm PEDOT:PSS at 2000 rpm for 60 s in the concentration range of 5-12 mg/mL. After spin-coating the active layer, the samples were immediately loaded with a shallow-mask into a glove-box integrated thermal evaporation chamber for Ca (˜2 nm)/Al (˜150 nm) deposition at a base pressure of 2×10.sup.−6 torr. For the P(T3-il)-2 active layer, P(T3-il)-2:PC.sub.71BM (1:2 weight ratio) were dissolved in chloroform at 70° C. for 12 hours with 6-10 mg/mL concentration and 2 volume % of DIO was added to it. The blend was deposited using a three step spin-coating at 300 rpm for 1 s, then at 500 rpm for 1 s and finally at 800 rpm for 60 s. Then all samples were dried in a glove box evacuation ante-chamber for about 2 hours before transferring them into a thermal evaporator for Ca/Al electrode deposition. The active area of each device is 0.1 cm.sup.2, measured by the overlap of top Ca/Al electrode and ITO.

(25) Tandem Device Fabrication. Tandem device structure, as depicted in FIG. 3B, was built layer-by-layer on top of PEDOT:PSS coated ITO glass substrate. Active layers were deposited using the same protocol as practiced for single junction device fabrication. The major addition in the process steps is the insertion of a thermally evaporated Cr (˜2 nm)/MoO.sub.3 (˜12 nm) interconnecting layer between two active layers. The chromium layer is thermally evaporated first, followed by the MoO.sub.3 layer, which is also thermally evaporated. In order to avoid the overestimation of photocurrent density by the optical piping effect (any cross talking between two adjacent cells), device active area was defined by careful mechanical scribing by a sharp razor blade together with the use of an optical aperture.

(26) The disclosed process may be utilized to manufacture high performance polymer tandem solar cells from an isoindigo-based low band-gap polymer which may be easily obtainable from renewable and sustainable synthetic sources. The importance of a new, chemically robust Cr/MoO.sub.3 IL is also illustrated for consistent tandem cell device performance. The constructed tandem cells reached promising PCEs (5.5% average, 6.0% for a champion cell) with V.sub.oc of 1.51±0.02 V, approaching 94% of the sum of the single junction subcells.

(27) One skilled in the art could readily realize the possible substitutions in materials, device architectures, fabrication tools, and processing steps that can be made without significantly detracting from the invention. For example, the present interconnecting layer can be applied to fabricate tandem devices comprising a variety of materials and their possible combinations. The substrates, interlayers, growth environments, ink formulation and the method of deposition for each individual layer in the device may be altered too. Alternative fabrication methods for photoactive layers include but not limited to thermal evaporation, ink-jet printing, aerosol-jet printing, spray coating, doctor-blading, transfer printing, etc. The interconnecting layer may be deposited by chemical/physical vapor deposition, reactive magnetron sputtering, atomic layer deposition or any solution-based approach.

(28) While the present invention has been illustrated by a description of one or more embodiments thereof and while these embodiments have been described in considerable detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and method, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept.