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WO2011068950A1 - Assemblage hiérarchique d'hétérojonctions organiques nano-structurées pour dispositifs photovoltaïques - Google Patents

Assemblage hiérarchique d'hétérojonctions organiques nano-structurées pour dispositifs photovoltaïques Download PDF

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WO2011068950A1
WO2011068950A1 PCT/US2010/058698 US2010058698W WO2011068950A1 WO 2011068950 A1 WO2011068950 A1 WO 2011068950A1 US 2010058698 W US2010058698 W US 2010058698W WO 2011068950 A1 WO2011068950 A1 WO 2011068950A1
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molecules
hbc
substrate
ito
contorted
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WO2011068950A9 (fr
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Colin Nuckolls
Alon Gorodetsky
Noah Tremblay
Ioannis Kymissis
Chien-Yang Chiu
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Columbia University in the City of New York
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/624—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing six or more rings
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • H10K2102/103—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO] comprising indium oxides, e.g. ITO
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/20—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising organic-organic junctions, e.g. donor-acceptor junctions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • H10K30/35—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains comprising inorganic nanostructures, e.g. CdSe nanoparticles
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/50—Photovoltaic [PV] devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/211—Fullerenes, e.g. C60
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • BHJ active layer architectures can be employed in efficient organic photovoltaics (OPVs).
  • OOVs organic photovoltaics
  • This type of structure can include an interpenetrating network of p-type semiconducting molecules as the electron donors and n-type semiconducting molecules as the electron acceptors.
  • the resulting device can exhibit an extensive interface for separation of photogenerated excitons, thereby yielding higher efficiencies.
  • one challenge is controlling the formation and size of the donor and acceptor domains within the BHJ. Addressing these challenges can lead to further improvements in device performance.
  • an apparatus for converting light energy to electrical energy includes one or more organic photovoltaic devices.
  • Photovoltaic devices can include a cathode in electrical contact with the apparatus and an anode in electrical contact with the apparatus.
  • Photovoltaic devices can further include an acceptor layer having molecules forming a supramolecular network on a substrate and a donor layer having fullerene molecules bonded onto the supramolecular network.
  • an organic photovoltaic device includes a cathode, an anode, an acceptor layer having molecules forming a supramolecular network on a substrate, and a donor layer having fullerene molecules bonded onto the supramolecular network.
  • a method for generating an organic photovoltaic device is also provided. In one embodiment, the method includes forming an anode layer of molecules arranged as a supramolecular network on a substrate, thermally evaporating a donor layer of fullerene molecules on the anode layer, and electrically connecting an anode and cathode to the assembly of the anode and donor layers.
  • Some embodiments include a class of molecules, dibenzotetrathienocoronenes (DBTTCs), shown below. These molecules can be used for hierarchical self-assembly at the molecular level and stack into columnar superstructures that in turn form a supramolecular network of cables on indium tin oxide (ITO) and ITO/poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS). This network can function as a scaffold for the molecular recognition and directed assembly of buckminsterfullerene (C 6 o). The templated growth of the C 6 o film creates a nanostructured p-n heteroj unction, which can enable more efficient conversion of sunlight into electricity.
  • DBTTCs dibenzotetrathienocoronenes
  • the molecules are members of a class of polycyclic aromatic molecules known as contorted hexabenzocoronones (HBCs). These molecules can include three fused interpenetrating pentacene subunits that form a doubly concave shape due to steric interactions at the periphery of the molecule. These molecules form columnar nano structures in self-assembled monolayers, cables, and liquid crystalline phases, with concomitant field effect mobilities of up to 1 cm 2 /V*s.
  • the embodiments also include a class of contorted structures that have four of their benzo rings exchanged for fused thienyl rings.
  • the unsubstituted DBTTC 1A and the hexyl-substituted DBTTC IB can be prepared, for example, through the high yield (> 90%) procedure outlined in Scheme 1 (shown below), which proceeds in three steps and, in certain embodiments, utilizes only commercially available reagents.
  • the 1,1,8,8-tetrabromobisolefin can be coupled with the appropriate thienyl boronic esters under Suzuki-Miyaura reaction conditions to yield the bis- tetrasubsituted olefins 2A and 2B (Scheme 1).
  • the synthesis can be completed with a Katz-modified Mallory photocyclization. BRIEF DESCRIPTION OF THE DRAWINGS
  • Figure 1 illustrates (A) a depiction of ball-and-socket interfaces in bilayer and bulk heteroj unction devices; (B) a chemical model of the contorted-HBC; and (C) the correlation between depiction (top) and molecular structure from the co- crystal of HBC and C 6 o (bottom).
  • Figure 2 illustrates the organization of HBC and C 6 o in co-crystals of C60 and HBC (A) from solution as complex 1 (left) and (B) from the gas phase as complex 2 (right).
  • Figure 3 (A) is a labeled photograph of a single-crystal device of complex 1 and (B) is a graph showing the inverse temperature vs. sheet resistance of the device.
  • Figure 4 illustrates (A) an exemplary schematic of the OPV device architecture; (B) J-V characteristics of contorted-HBC OPVs; (C) absorbance spectrum of a thin film of contorted-HBC overlaid with the emission of the UV LED light source and the solar spectrum; and (D) J-V characteristics of contorted-HBC OPVs in the dark and illuminated with UV LED light source at 422 nm and an intensity of 1.5 mW/cm 2 .
  • Figure 5 illustrates exemplary GIXD measurements according to exemplary embodiments of the described subject matter.
  • Figure 6 illustrates external Quantum Efficiency (EQE) spectrum of a contorted-HBC/C60 device and EQE of a C 60 device without the HBC layer.
  • EQE Quantum Efficiency
  • Figure 7 illustrates overlaid thin-film absorption spectra of contorted- HBC and flat-HBC along with the emission spectrum of the UV LED light source.
  • Figure 8 depicts exemplary graphs according to exemplary embodiments of the described subject matter.
  • Figure 9 depicts exemplary graphs (A) and (B) according to exemplary embodiments of the described subject matter.
  • Figure 10 depicts exemplary chemical structures of contorted-HBC and flat-HBC.
  • Figure 11 illustrates an exemplary contorted-HBC/C 6 o device and illustrates I-V characteristics compared to those of a flat-HBC/C60 device when illuminated under a UV LED.
  • Figure 12 illustrates an exemplary schematic of the HPVT.
  • Figure 13 is an exemplary graph of data according to exemplary embodiments of the described subject matter.
  • Figure 14 is an exemplary picture from CrystalMakerTM ⁇ - ⁇ distance measurements on complex 2.
  • Figure 15 (A) illustrates an exemplary chemical structure of 1A and IB.
  • (B) illustrates a schematic representation of an exemplary nanostructured OPV.
  • Figure 16 illustrates crystal structure of the hexyl-substituted DBTTC IB. Hydrogen atoms and hexyl side chains are not shown for clarity.
  • A A columnar stacking arrangement is observed along the [100] plane in the crystal.
  • B Armchair conformation of IB observed in the crystal.
  • C Butterfly-shaped conformation of IB observed in the crystal. The lines on the bottom in (B) and (C) indicate the contortion of the central pentacene moiety.
  • Figure 17 illustrates physical characterization of thermally annealed (150 °C) films of IB on bare ITO.
  • a typical tapping mode AFM image is shown in (A)
  • the angle-dependent Cls NEXAFS spectrum is shown in (B).
  • a 2-D CCD image from a representative GIXD measurement is illustrated in (C).
  • the corresponding integrated intensity along Q z and Q r , as well as the simulated powder diffraction pattern, is illustrated in (D).
  • Figure 18 illustrates tapping mode AFM images of films from IB that were (A) unannealed, (B) annealed at 100 0 C, and (C) annealed at 150 °C.
  • Figure 19 is an exemplary schematic illustration of the nanostructured OPV architecture.
  • B illustrates the corresponding energy levels, reported with respect to vacuum, for the donor and acceptor materials.
  • C illustrates exemplary J-V curves for a DBTTC device, both with and without illumination, at 100 mW/cm 2 .
  • Figure 20 illustrates an exemplary synthesis scheme for DBTTC according to exemplary embodiments of the described subject matter.
  • the disclosed subject matter pertains to systems and methods for hierarchical assembly of nanostructured organic heteroj unctions for photovoltaic devices.
  • One aspect of the disclosed subject matter relates to methods and systems for assembling photovoltaic universal joints, including, for example, ball-and-socket interfaces in molecular photovoltaic cells.
  • the disclosed subject matter illustrates methods for epitaxially growing one crystalline organic semiconductor on another and thereby provides a method to tune the electronic nature of the p-n junction in organic photovoltaics (OPVs). While OPVs are attractive as materials for conversion of sunlight into electrical energy, higher conversion efficiencies can enhance the viability of OP Vs.
  • the interface between the hole and electron transporting films is the locus for exciton formation and dissociation, h inorganic materials
  • the interface between two semiconductors is useful in determining and controlling the electrical properties of these materials and is controlled by a heteroepitaxial growth of one crystalline material on another.
  • P-type and n-type organic semiconductors can be designed to have nested shapes that create an epitaxial growth that achieves higher conversion efficiencies and open circuit voltage in these devices, (e.g., within 10% of the theoretical limit).
  • the class of molecules known as contorted hexabenzocoronenes can be used because they are p- type semiconductors and are also photoconductive.
  • This HBC has an unusual shape in that it is contorted and doubly-concave.
  • the size and shape of this molecule are complementary to buckminsterfullerene (C 6 o) > which is one n-type semiconductor (see, e.g., Figure 1C). It is this shape and electronic complementarity between these two molecular structures that makes them useful in heteroepitaxial growth.
  • One embodiment illustrates that HBC and C 60 form co-crystalline, supramolecular assemblies.
  • Two examples, one from solution ( Figure 2 A) and one from the gas phase ( Figure 2B) show that the materials form co-crystals. Large purple-gray crystals were produced from a saturated solution of C 6 o and HBC in chlorobenzene.
  • the molecular structure determined from the solution-grown crystals reveals that HBC and C 6 o spontaneously formed an interdigitated supramolecular complex (complex 1).
  • the three-dimensional structure of HBC includes two opposing concave aromatic faces, wherein a C 6 o had nestled into each face ( Figure 2A).
  • a number of organic molecules have been designed to form complementary interactions with C 60 and have yielded co-crystals.
  • the crystal of 1 includes C 60 , HBC, and chlorobenzene (2:1 :1), in which HBC and C 60 organize into a repeating pattern of ABAABA as shown in Figure 2A.
  • HBC has two C 6 o nearest neighbors, and each C 60 has one HBC nearest neighbor and one C 6 o nearest neighbor.
  • the C 60 is centered over one of the six- membered rings on the edge of the coronene core of HBC; in this instance, the vertical ⁇ - ⁇ distance is about 3.00 A.
  • the molecules were co-crystallized without solvent using horizontal physical vapor transport.
  • HBC and C 60 powders were placed in the hot zone (550°C) of a horizontal, gradient-temperature furnace. Crystals (complex 2) formed in the cold zone of the furnace (330°C).
  • the composition of 2 was 1 :1 HBC:C 60 ( Figure 2B).
  • Figure 2b demonstrates that the assembly of HBC and C 60 are different in 2 than in 1.
  • the HBC and C 60 organize in an ABAB repeating pattern in 2 ( Figure 2B), according to one non-limiting embodiment.
  • This structure there are two crystallographically-inequivalent HBC sites. Every HBC has two C 60 nearest neighbors with the C 60 having two non-identical HBC neighbors.
  • Each C 60 is centered directly in the middle of the core six-membered ring in one type of HBC at a ⁇ - ⁇ distance of 2.93 A.
  • Each C 6 o is also centered over another HBC just outside one of the bonds of the core six-membered ring at a ⁇ - ⁇ distance of 3.07 A.
  • the HBC molecules in 2 are organized in sheets (Figure 2B). Even though there are two inequivalent HBC sites, they are assembled into a rectangular array with a center-to- center distance of 11.36 A. Every HBC molecule has a 3.63 A close carbon-to-carbon contact with four neighboring
  • the C 6 o molecules in 2 form columns ( Figure 2B).
  • the center- to- center distance between columns is about 9.88 A, a very short Ceo-Ceo distance.
  • the fullerenes assemble in a zigzag pattern with a 111 ° bend (center-to-center) at each Ceo-
  • the columns are spaced about 15.87 A apart from one another.
  • a spacing of 9.88 A is within the range of previously reported values for C 6 o-C 6 o spacings in the pure crystal, but 15.87 A is significantly larger than those values; thus C 6 o forms columns in 2.
  • the solution-grown crystals are large enough to allow direct measurement of the resistance of single crystals using evaporated silver electrodes (see, e.g., Figure 3). These crystals are insulating, as both HBC and C 6 o individually are semiconductors. The resistance was significantly reduced after the same species was kept in vacuum at room temperature for 12 days. Without being bound by a particular theory, it is believed that this is due, at least in part, to the slow evaporation of chlorobenzene. Illumination of the devices causes a 1,000-fold decrease in resistance.
  • This decrease in resistance implies an increase in the carrier density. This can be due to charge transfer between the n- and p-type molecules, e.g., exciton splitting.
  • OPV devices were constructed to illustrate this concept.
  • An OPV bilayer architecture (see, Figure 4A) was selected over a BHJ architecture since it is easier to optimize OPV bilayers.
  • FIG. 4B A short-circuit current density (J S c) of 3.32 mA/cm 2 , open-circuit voltage (Voc) of 0.88 V, and a fill factor of 0.27 yield an efficiency of 0.77%.
  • Figure 3B illustrates the inverse temperature vs. sheet resistance relationship of the device measured before annealing (triangles), after annealing (circles), with illumination (red), and without illumination (blue).
  • the efficiency of a photovoltaic device is proportional to the magnitude of the V 0 c-
  • the theoretical maximum Voc for devices is the energy difference between the highest occupied molecular orbital (HOMO) of HBC at -5.5 eV and the lowest unoccupied molecular orbital (LUMO) of C 6 o at -4.5 eV.
  • the V 0 c's approach this difference of 1.0 V.
  • the efficiency of a photovoltaic device is also directly proportional to the Jsc- Upon illumination, the current density of the HBC/C 60 devices increases, regardless of the applied bias. This is consistent with the observed photoconductivity in HBC films and HBC/C 60 co-crystals (see, e.g., Figure 3).
  • GIXD data was collected from HBC-coated silicon substrates after stepwise depositions of C 6 o onto the HBC (25 nm).
  • the thickness (x nm) of the C 60 layer was increased from 0 nm to the optimal device thickness of 40 nm ( Figure 5).
  • Figure 4 illustrates (A) an exemplary schematic of the OPV device architecture: PEDOT:PSS (25nm), HBC (25nm), C60 (40nm), Aluminum (60nm).
  • the surface area of the device is 0.16 cm 2 ;
  • (B) illustrates J-V characteristics of contorted-BBC OPVs in the dark and illuminated with 1.5 AM solar simulated light source;
  • (C) depicts absorbance spectrum of a thin film of contorted-BBC overlaid with the emission of the UV LED light source and the solar spectrum; and
  • (D) depicts J-V characteristics of contorted-BBC OPVs in the dark and illuminated with UV LED light source at 422 nm and an intensity of 1.5 mW/cm .
  • XPS probing the C Is region provides direct evidence for an electronic interaction between C 6 o and HBC in the deposited films.
  • the bilayers have a shift to higher binding energy by 0.2 eV ; a change in peak shape, and a narrowing in peak width.
  • Such features are consistent with charge transfer at the donor-acceptor interface, which affects the ability of the system to screen and stabilize the core-ionized final state, thereby altering the shape, width and energy of the photo emission peak. This supports the presence of an intimate interaction between the donor and acceptor molecules.
  • HBC/C 6 o bilayer in the Auger electron yield (AEY) signal, which probes the -1 -2 nm near- surface region; i.e. the HBC/C 60 interface.
  • AEY Auger electron yield
  • the HBC molecules interacting with C 60 are estimated to be oriented at an average tilt angle of -40° with respect to the surface plane. If the HBC ordering is related to a spontaneous assembly of the molecular partners at the bilayer interface into complex 2, this HBC tilt angle orients the (110) plane of the co-crystal parallel to the surface plane.
  • Devices made with the two HBC molecules behaved differently under simulated solar irradiation.
  • Devices based on contorted-HBC are more efficient than those based on flat-HBC (0.55% versus 0.07%).
  • Devices based on contorted-HBC also have higher Voc's than the latter (0.84 V versus 0.19 V). This supports the notion that shape complementarity contributes to the higher Voc values for contorted- HBC.
  • the emission spectrum of the UV-LED covers the longest-wavelength absorbance shoulder for thin films of both HBCs (see Figure 4C).
  • contorted-HBC devices had Voc's similar to those of flat-HBC devices under solar irradiation, the Voc's of contorted-HBC devices were over ten times greater than ⁇ Zat-HBC (0.80 V versus 0.07 V) under UV light.
  • Shape complementarity can improve the donor/acce tor interface and, consequently, the photovoltaic properties of bilayer OP Vs. It has been shown that contorted-HBC forms intimate complexes with the fullerenes. It has also been shown that differences in complementarity directly translate to differences in OPV performance. Better shape complementary improves the interface between donor and acceptor materials and leads to some of the highest V 0 c's known to date, with a maximum of 0.95 V. Efficiencies of up to 5.7% were observed in ambient atmosphere for narrow width UV irradiation and 1.04% for solar illumination. This data indicates that the OPV cells can be partnered with longer wavelength absorbing layers to achieve higher efficiency solar cells.
  • O s organic photovoltaic devices
  • OPVs Complementarity in shape between the donor (contorted hexabenzocoronene, HBC) and acceptor (buckminsterfullerene, C 6 o) molecules resulted in OPVs that perform surprisingly well.
  • the OPVs exhibit conversion efficiencies ( ⁇ ) of 5.7 % under ambient UV irradiation and over 1% under ambient solar illumination, with open circuit voltages (VOC) of 0.95 V, within 10% of the theoretical maximum of 1.0 V.
  • VOC open circuit voltages
  • Some embodiments of the presently disclosed subject matter provide air stable organic photovoltaics from small molecules acene derivatives.
  • Photovoltaics can play a role in satisfying the long-term global demand for cheap and renewable energy.
  • organic small molecules can be used. Indeed, small molecules can be easy to synthesize and purify, are monodisperse, exhibit high carrier mobilities, and can be processed directly from solution.
  • the described subject matter illustrates the molecular design of organic small molecules for device stability in ambient atmosphere and provides photovoltaics that are not only efficient but are also stable in the presence of oxygen.
  • the molecules include denvatized pentacenes and other extended acene systems as the p- type donor materials in bilayer device architectures.
  • HBC derivatives are suitable as donor materials in bulk heteroj unction device structures.
  • Solar cells manufactured from the materials described herein do not require encapsulation, allowing for facile device fabrication. Consequently, the described materials provide for the manufacture of photo voltaics with improved air- stability.
  • Some embodiments relate to photovoltaic universal joints including ball-and-socket interfaces in molecular photovoltaic cells.
  • Contorted hexabenzocoronene and derivatives (contorted-HBC) and hexa-peri-hexabenzocoronene (flat-HBC) were synthesized according to literature procedures (see, e.g., S. Xiao, Q. Miao, S. Sanaur, K. Pang, M. L. Steigerwald, C. Nuckolls, Angew. Chem. Int. Ed. 2005, 44, 7390-7394 and S. Xiao, J. Tang, T. Beetz, X. Guo, N. Tremblay, T. Siegrist, Y. Zhu, M. L. Steigerwald, C. Nuckolls, J. Am.
  • Anhydrous chlorobenzene (Catalog No: 284513; CAS:108-90-7) was obtained from Sigma- Aldrich.
  • PEDOT:PSS was obtained under the name Baytron P (Catalog No: 01016141; CAS: 7732-18-5) from H.C. Stark.
  • the thicknesses of all thin films were calibrated via atomic force microscopy of either a masked off edge and/or a stretched film. All thermal depositions were performed under a pressure of -1*10 "6 torr at an average rate of -1.0 A/sec. Patterned indium-tin oxide glass substrates were cleaned thoroughly by sonication in acetone and isopropyl alcohol, dried under a stream of nitrogen, and UV-ozone etched for five minutes. PEDOT:PSS was spun at 5000 rpm for 60 seconds and the film was subsequently baked at 200 °C for 30-45 minutes. The unmodified contorted- BC or flat-HBC were thermally evaporated to a thickness of 25 nm.
  • Solution processable HBC derivatives were spincoated from a 2-4 mg/mL toluene solution at 1000 rpm. Either C 60 or C 0 was then thermally evaporated to a thickness of ⁇ 40 nm. The substrates were taken out of ultra-high vacuum (UHV) and moved to a nitrogen atmosphere where they were masked and placed under UHV again. Aluminum was deposited to a thickness of ⁇ 60 nm.
  • UHV ultra-high vacuum
  • Finished devices possessed an area of 0.16 cm 2 . They were moved to ambient atmosphere and measured with Keithley 2602/2400 sourcemeters under both dark conditions and under illumination with a solar simulated light source. Ultraviolet light emitting diodes (LEDs) were obtained from NEBOTM. All illumination sources were calibrated using a silicon photodiode.
  • LEDs Ultraviolet light emitting diodes
  • the optical power of the UV source was measured with a silicon photodiode. Light was incident on the detector, and the current induced was recorded. The area of the photodetector was 1 cm 2 yielding units of A cm 2 .
  • the spectrum of the light source was then taken using a spectrometer and this spectrum was normalized (to set the integral to unity) and point-wise multiplied by the responsivity curve of the photodetector to compensate for nonlinearities in the current response.
  • the resulting integration is the power conversion factor for the light source, in Watts/Amp. This value directly converts the previous photovoltaic response to the optical power of the light source.
  • FIG. 14 An example of a ⁇ - ⁇ distance calculation is shown in Figure 14.
  • a plane was generated through the three carbons on HBC closest to C 6 o (in this case it was three from the center six-membered ring on HBC). All carbons of the C 60 were selected and a centroid was calculated. A distance of 6.439 A was found from that centroid to the plane, centered directly on the six-membered ring.
  • a mean nuclear radius of that C 6 o was generated as part of the centroid calculation output (3.5139 A).
  • Samples were prepared by cutting silicon wafers (with native oxide) to a size of approximately l l cm. Silicon substrates were cleaned by sonication in acetone and isopropyl alcohol followed by drying in a stream of nitrogen gas. HBC was thermally evaporated to a thickness of 25 nm using the same deposition conditions as for the photovoltaic devices. Subsequently, C 60 layers of various thicknesses were evaporated onto the silicon substrates. All samples were made in duplicate to ensure consistency. Samples were packaged within two sealed mylar bags under a nitrogen atmosphere and then shipped to the Stanford Synchrotron Radiation Lightsource (SSRL), where the measurements were performed.
  • SSRL Stanford Synchrotron Radiation Lightsource
  • Grazing Incidence X-ray Diffraction (GIXD) measurements were performed at the Stanford Synchrotron Radiation Lightsource on beam line 11-3 at a photon energy of 12.7 keV.
  • the incident x-ray beam, kj n has a grazing incidence angle with the sample surface.
  • a 2D MAR345 image plate detector (pixel size 0.15 mm), positioned a distance L from the sample, records the scattered beam, ko Ut . This is converted into an image of the reciprocal space (Q-space) with the scattering expressed as a function of the scattering vector
  • Q-space reciprocal space
  • the sample-to- detector distance L calibrated with a LaB polycrystalline standard, was 398.6 mm.
  • the incidence angle was chosen as 0.1°, slightly above the critical angle for total external reflection from the organic film surface. This reduces any background scattering from the substrate and gives a large diffracting volume.
  • the samples were kept under a helium atmosphere during measurement to minimize damage to the films from the intense x-ray beam and eliminate X-ray scattering from air.
  • a linear background defined by regions before and after the diffraction peaks, was subtracted from the reciprocal space map.
  • a dark (blank) image scan was also subtracted from the measurements to help isolate weaker signals from the samples.
  • Samples were prepared by cutting indium tin oxide (ITO) to a size of approximately 12 mm x 5 mm. ITO substrates were cleaned by sonication in acetone and isopropyl alcohol followed by drying in a stream of nitrogen gas. Pure films of HBC and C 6 o, respectively, were thermally evaporated to a thickness of 10 nm on the ITO using the same deposition conditions as for the photovoltaic devices. To model the C 6 o-HBC interface, 2nm of C 6 o was deposited on separate 10 nm HBC films, prepared under the same conditions. All samples were made in duplicate to ensure consistency. Samples were packaged within two sealed mylar bags under a nitrogen atmosphere and transported to the Stanford Synchrotron Radiation Lightsource (SSRL), where the measurements were performed.
  • SSRL Stanford Synchrotron Radiation Lightsource
  • Beamline 13-2 has a spherical grating monochromator and an energy range of 250-1100 eV, and the focused beam has a spot size of 0.01 x 0.075 mm 2 . It is equipped with an elliptically polarizing undulator (EPU) that can be used in three different polarization modes: elliptical, horizontal and vertical; circular polarization was accomplished by summing spectra for elliptical polarization with opposite elliptical distortion.
  • the BL13-2 station is designed for surface and solid state demonstrations with ultra-high vacuum compatible samples up to 10 mm in diameter.
  • the main chamber has an electron spectrometer (SES-R3000, VG-Scienta) for photoemission spectroscopy and X-ray absorption spectroscopy.
  • XAS spectra were simultaneously measured in both total (TEY) and Auger electron yield (AEY) modes.
  • the reference absorption intensity (I 0 ) of the incoming x-ray beam was measured simultaneously and used to normalize the spectra to avoid any artifacts due to beam instability.
  • TEY was obtained by the sample drain current (sampling depth > 5nm).
  • AEY mode the electron spectrometer was tuned to a kinetic energy window of 230-240 eV, which was chosen obtaining information restricted to the near-surface ( ⁇ l-2 nm) region. All spectra were recorded in the photon energy range 280-310 eV with energy resolution better than 100 meV.
  • the energy scale was calibrated using photoemission lines of a reliable peak from the second and third order diffracted photon, here the Cls of our C 6 o reference sample.
  • the spectra were normalized by fitting the data points before the absorption edge by a straight line taken as zero, and normalizing the maximum intensity of the s* resonance (at -300 eV) to 1.
  • XPS spectra were measured with energy resolution better than 100 meV.
  • the XPS binding energy scale spectra taken at photon energy 600 eV was shifted 2.3 eV to higher binding energy; using the calibrated shift between the monochromator at 310 eV and actual energy (determined by higher order
  • current vs. voltage graphs show the average device characteristics for 1) contorted-HBC/Ceo dark current and illuminated current. 2) contorted-HBC/Cjo da k current and illuminated current. 3) _/7at-HBC/C 6 o dark current and illuminated current.
  • Figure 9 illustrates (A) C ls region XPS measured at photon energy 600 eV for: C 60 (10nm)/ITO, HBC (10nm)/ITO, and C 6 o(2nm)/HBC(10nm)/ITO; and (B) depicts polarization dependent XAS of HBC(10nm)/ITO, C 60 (10nm) ITO, and C 60 (2nm)/HBC(10nm)/ITO measured in Total Electron Yield (TEY) mode.
  • TEY Total Electron Yield
  • AEY Auger Electron Yield
  • a schematic of the C 6 o-HBC bilayer interface is inset.
  • Figure 13 shows the temperature (in degrees Celsius) of the gradient in the quartz tube plotted as a function of displacement along tube (in inches).
  • Some embodiments include the hierarchical assembly of nanostructured organic heterojunctions for photovoltaic devices.
  • BHJ bulk heterojunction active layer architecture
  • OOVs organic photovoltaics
  • this type of structure includes an interpenetrating network of p-type semiconducting molecules as the electron donors and n-type semiconducting molecules as the electron acceptors.
  • the resulting device possesses an extensive interface for separation of photogenerated excitons, thereby yielding higher efficiencies.
  • controlling the formation and size of the donor and acceptor domains within the BHJ can increase device performance.
  • an exemplary class of DBTTC molecules shown in Figure 15 A, can be used to control the formation and size of the donor and acceptor domains within the BHJ. These molecules have been designed for hierarchical self-assembly at the molecular level and stack into columnar
  • the following description includes an exemplary design, synthesis, and structure of DBTTC exemplary molecules including contorted HBCs, which are members of a class of polycyclic aromatic molecules. They include three fused interpenetrating pentacene subunits that form a doubly concave shape due to steric interactions at the periphery of the molecule. These molecules form columnar nanostructures in self-assembled monolayers, cables, and liquid crystalline phases, with concomitant field effect mobilities of up to ⁇ 1 cm 2 /V-s. Since such structured HBC films have also demonstrated one-dimensional photoconductivity, they can be suitable for organic photovoltaics. Contorted HBCs can form a shape-complementary complex with the n-type acceptors, such as C 6 o and C70, yielding an intimate, self-assembled donor/acceptor interface.
  • n-type acceptors such as C 6 o and C70
  • Some embodiments include a prepared class of contorted structures that have four of their benzo rings exchanged for fused thienyl rings.
  • unsubstituted DBTTC 1 A and the hexyl-substituted DBTTC IB were prepared through the high yield (> 90%) procedure illustrated in Figure 20, which proceeds in three robust steps and utilizes commercially available reagents.
  • the 1,1,8,8- tetrabromobisolefin were coupled to the appropriate thienyl boronic esters with Suzuki-Miyaura reaction conditions to yield the bis-tetrasubsituted olefins.
  • the synthesis was then completed with a Katz-modified Mallory photocyclization.
  • FIG 16 depicts several of the molecules from this structure.
  • the DBTTC is made up of two anthradithiophene units fused with a central pentacene moiety.
  • the core of the molecule stacks into a columnar arrangement along the [100] axis within the crystal.
  • the DBTTC molecules also have intimate nearest neighbor contacts with intermolecular carbon-to-carbon distances that are as small as -3.4 A and sulfur-to- carbon distances that are as small as -3.6 A. While not being bound by any particular theory, it is believed that the fused thiophene units likely facilitate such intimate ⁇ - ⁇ stacking interactions.
  • the sterically smaller thiophenes on the periphery of DBTTC can reduce the congestion between adjacent aromatic rings as compared to HBC.
  • One consequence of the alleviated congestion around the exterior is the "flattening" of IB relative to the contorted HBC.
  • a second consequence is the existence of two distinct polymorphs of IB within the crystal.
  • Figure 16B the three intersecting subunits of the DBTTC adopt a motif that is similar to the previously reported HBC derivatives.
  • Figure 16C the molecule resembles a butterfly with the pentacene subunit forming the body and the
  • DBTTC The electrochemical and spectroscopic properties of DBTTC can provide insight into its potential as a p-type donor molecule.
  • a solution-phase cyclic voltammogram of IB provides three oxidative waves at potentials of 1.1 V, 1.5 V, and 1.6 V, as well as a single reductive wave at - 1.7 V.
  • the cathodic to anodic peak ratios indicate that all three oxidative waves are quasi-reversible (the reductive wave is irreversible), so IB is electro chemically stable in several oxidation states.
  • the cyclic voltammetry indicates the potential of DBTTC as an electron donor in a photovoltaic device.
  • the solution and thin-film UV- visible absorbance spectra of IB are also provided.
  • a set of weaker absorptions between 400 and 490 nm can be associated with the radialene ⁇ - ⁇ * triplet states.
  • a corresponding thin film absorbance spectrum is broadened and generally red-shifted with a main peak at ⁇ 370 nm but few other apparent features. This type of spectrum is a hallmark of ⁇ - ⁇ stacking and strong intermolecular interactions among the DBTTC chromophores.
  • Some embodiments of the disclosed subject matter relate to DBTTC nanostructure formation on ITO.
  • films of IB were characterized.
  • Solution-processed, annealed films of IB were examined on ITO with Atomic Force Microscopy (AFM) in non-contact mode (Figure 17A). It was found that films from IB were not uniform, but instead included a network of "cables.” These cables are highly anisotropic: the length was on the order of ten microns, the width was on the order of a micron, and the height was on the order of a hundred nanometers. This network covered the entire substrate and appeared three dimensional, with the cables protruding from the surface.
  • the orientation of IB was determined on ITO with Near Edge X-Ray Absorption Fine Structure (NEXAFS). Films from IB display a pronounced angular- dependence of the intensity of the ⁇ * resonance in the NEXAFS spectrum ( Figure 17B). This resonance is strongest near normal incidence, when the electric field is parallel to the substrate. The ⁇ * orbitals of IB are therefore preferentially oriented in the plane of the substrate, with a high degree of edge-on orientation, which is consistent with alignment of the molecular columns along the long axis of the cables. From NEXAFS, the average molecular tilt angle of ⁇ 64° with respect to the substrate for IB.
  • FIG. 17C shows the GIXD data for IB on bare ITO, overlaid with the simulated DBTTC powder diffraction pattern.
  • the 2-D images reveal that the diffraction intensity is confined to the lateral (Q r or in-plane) and vertical (Q z or out-of-plane) reflections, respectively.
  • Some embodiments provide controlled growth of DBTTC nanostructures on ITO PEDOT:PSS.
  • Three-dimensional cable networks can also be formed on PEDOT:PSS coated ITO, which is commonly utilized for OPVs.
  • GIXD, AFM, and NEXAFS measurements all indicated that the cables formed on PEDOT:PSS covered the entire surface and were very similar to those on bare ITO. Therefore, coarse control was gained over the size and density of the fibers on the technologically relevant PEDOT: PSS surface.
  • Figure 18 shows non-contact mode AFM images of films from IB on PEDOT:PSS coated ITO substrates with and without annealing.
  • Unannealed films are morphologically flat with an rms roughness of ⁇ 1 nm ( Figure 18 A). Films annealed at 100°C feature some isolated cable-like structures but otherwise also display a flat morphology ( Figure 18B). However, films annealed at 150°C feature a nearly ideal network of anisotropic cables. Notably, the cables in Figure 18 are smaller than those on bare ITO, with widths of hundreds of nanometers and heights of- 10 to ⁇ 30 nm. This observation is further supported by the GIXD measurements, in which the broadening of the peaks on PEDOT:PSS indicates smaller crystalline domain sizes relative to bare ITO. The size and alignment of the cables in Figure 18C is therefore effective for the formation of an ordered
  • Some embodiments of the disclosed subject matter relate to the construction of photovoltaic devices from the DBTTC network.
  • an electron acceptor (Ceo) was thermally evaporated onto the supramolecular, three-dimensional network formed from IB.
  • the DBTTC network templates the growth and self- assembly of the buckminsterfullerene, which completely covers the surface of the fibers.
  • the C 60 also fills in the gaps between the fibers, thereby yielding mixed films that are smooth and homogeneous, relative to the pristine nanostructures of Figure 18C.
  • FIG. 19 A An exemplary structure of a completed photovoltaic device with an aluminum cathode is illustrated in Figure 19 A, with the energy band diagram depicted in Figure 19B.
  • the corresponding typical J-V characteristics exhibit nearly ideal diode behavior (Figure 19C).
  • a short circuit current density J sc of 13.1 mA/cm , open circuit voltage V oc of 0.50 V, and fill factor FF of 0.46 yield a champion power conversion efficiency of 3.0 %.
  • BHJs can be developed from small molecules as the p-type donor material, with reported peak efficiencies of - 4 %.
  • solution-processable small molecules have demonstrated several advantages over their polymeric counterparts. They can often be easily synthesized and purified, thereby sidestepping device reproducibility problems associated with broad polymeric molecular weight distributions, batch to batch polymer variability, and contamination with reaction side products.
  • small molecules typically possess high carrier mobilities due to their propensity for organization into highly ordered, crystalline domains. All of these features make small molecules highly attractive targets.
  • the described subject matter includes the electronic and self-assembly properties of small molecules for OP Vs.
  • DBTTC yields a donor layer that is made up of a supramolecularly assembled three-dimensional network of one-dimensional cables. This network possesses a large effective interfacial surface area, thereby serving as an effective scaffold for the templated self-assembly of C 60 molecules.
  • the resulting active layer can be free of, or at least relatively free of, the bottlenecks and dead-ends that can accompany thermodynamically formed BHJs, for example small regions of donor material embedded in a larger regions of acceptor material, thereby enabling efficient transport of charge to the anode and cathode along both the DBTTC nano structures and the templated C 6 o overlayer.
  • this morphology represents a quality nanostructured BHJ, thereby yielding high power conversion efficiencies of ⁇ 3 %. Indeed, a clear and general path toward even higher power conversion efficiencies can be demonstrated via improved control over the size and topology of the DBTTC nanostructures.

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Abstract

Cette invention concerne des systèmes et procédés d'assemblage hiérarchique d'hétérojonctions organiques nano-structurées. Plus particulièrement, l'invention concerne un appareil permettant de transformer l'énergie lumineuse en énergie électrique. Un appareil comprend un ou plusieurs dispositifs photovoltaïques. Les dispositifs photovoltaïques comprennent une cathode en contact électrique ave l'appareil et une anode en contact électrique avec l'appareil. De plus, les dispositifs comprennent une couche accepteur comportant des molécules qui forment un réseau supramoléculaire et une couche donneur comportant des molécules de fullerène collées sur le réseau supramoléculaire.
PCT/US2010/058698 2009-12-03 2010-12-02 Assemblage hiérarchique d'hétérojonctions organiques nano-structurées pour dispositifs photovoltaïques Ceased WO2011068950A1 (fr)

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WO2013119783A1 (fr) * 2012-02-07 2013-08-15 University Of Florida Research Foundation, Inc. Couche active supramoléculaire modulaire et dispositifs photovoltaïques organiques
EP2978036A4 (fr) * 2013-03-22 2016-04-20 Fujifilm Corp Transistor à couches minces organiques
CN109593095A (zh) * 2018-12-14 2019-04-09 湖南大学 X型杂稠苝芳烃的双螺烯功能分子材料及其制备和应用
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013119783A1 (fr) * 2012-02-07 2013-08-15 University Of Florida Research Foundation, Inc. Couche active supramoléculaire modulaire et dispositifs photovoltaïques organiques
EP2978036A4 (fr) * 2013-03-22 2016-04-20 Fujifilm Corp Transistor à couches minces organiques
JP2022130408A (ja) * 2015-12-18 2022-09-06 ザ トラスティーズ オブ プリンストン ユニバーシティ 高い開路電圧を有する単接合有機光電池デバイスとそのアプリケーション
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CN109593095A (zh) * 2018-12-14 2019-04-09 湖南大学 X型杂稠苝芳烃的双螺烯功能分子材料及其制备和应用
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