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WO2012162794A1 - Copolymères conjugués utiles en électronique - Google Patents

Copolymères conjugués utiles en électronique Download PDF

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WO2012162794A1
WO2012162794A1 PCT/CA2012/000498 CA2012000498W WO2012162794A1 WO 2012162794 A1 WO2012162794 A1 WO 2012162794A1 CA 2012000498 W CA2012000498 W CA 2012000498W WO 2012162794 A1 WO2012162794 A1 WO 2012162794A1
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block copolymer
phase
nanocrystals
composite material
substituted
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Dwight S. Seferos
Jon HOLLINGER
Lianshan Li
Dong GAO
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University of Toronto
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University of Toronto
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    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
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    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
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    • H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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    • Y02E10/549—Organic PV cells

Definitions

  • Copolymers having a conjugated backbone are disclosed.
  • the copolymers are useful as e.g., semiconductors.
  • a specific copolymer is a selenophene-thiophene block copolymer, which can be incorporated as part of a composite material in combination with an electron acceptor such as a fullerene, quantum dot, etc.
  • Composite materials can be used as the active semiconducting material in a solar cell.
  • Fully conjugated polymers are useful because they are generally electrically conductive, and can be used in the making of a variety of electronic devices.
  • Conjugated/nonconjugated block copolymers can be prepared, however, they require the incorporation of insulating segments into the polymer system. 4 Fully conjugated block polythiophenes have been synthesized where each block contains a unique alkyl side chain. 5 Side chains mainly control intermolecular interactions, which influence properties; however, this is primarily an indirect and unpredictable way to control optical properties.
  • phase separable block copolymers comprising at least two distinct fully conjugated homopolymers, wherein each distinct homopolymer comprises a distinct repeated monomer, and wherein each distinct monomer of each distinct homopolymer comprises a distinct heterocycle. Because of the use of the distinct heterocycles, these copolymers are fully conjugated (and therefore favorable for use in electronic devices). The presence of the distinct heterocycles also leads to a surprising self-assembly of the copolymer into distinct domains upon phase separation. This self-assembly is surprising because thiophene and selenophene are quite similar in structure. Therefore, the optical and morphological properties of these block copolymers can be controlled.
  • copolymers were synthesized as the first proof-of-principle of this new class of block copolymers.
  • Ns nanocrystals
  • PL Photoluminescence quenching studies show efficient excitation energy transfer between NCs and polymer nanofibers.
  • Both the block copolymer and the nanocrystal-copolymer composite have useful applications applicable to a wide range of electronics applications.
  • Organic solar cell (OSC) technology is considered a next-generation solar energy technology due to the potential for lightweight, low-cost and flexible devices. Central to to to the development of the technology are efforts to produce new
  • compositions that can (1 ) be synthesized and processed more cheaply; and (2) improve the performance characteristics of solar devices.
  • OSCs Because of the anticipated commercial value as well as the interesting physical processes that govern the operation of such devices, OSCs have received increasing attention and have been developed rapidly during the past two decades 1"6 .
  • Schilinsky et al. and coworkers disclosed a device with 2.8% power conversion efficiency (PCE) in 2002 which was composed of a thiophene polymer 7 . Since then, device efficiency of this composition has been improved to 5% 8 .
  • PCE power conversion efficiency
  • typical solar efficiencies for orgnanic photovoltaics (OPV) lie in the range of 1-5% 9"11 .
  • Viable commercial devices have been achieved at -2% module efficiency according to recent reports 12"16 .
  • To further boost device performance more efficient polymer material is a key factor.
  • Such efforts include selenophene polymer, which was disclosed by Ballantyne et al. in 2007 with device efficiency of 2.
  • a method for making a photovoltaic device includes (i) providing a solution of a block copolymer of the invention; and (ii) applying the solution to a substrate.
  • One or the other or both of the solution and substrate is controlled to be at least 40°C, as for example by heating, during the step of applying the solution to the substrate.
  • the temperature of the solution and/or substrate is preferably between 50°C and 100°C, or 50° and 90°C, or 60°C and 90°C, or 70°C and 90°C.
  • a suitable temperature in a particular embodiment described below was found to be around 80°C, and both the substrate and solution were heated to be about this temperature when applying the solution to the substrate.
  • both the copolymer solution and the substrate are heated during the application step.
  • the copolymer is usually applied to form a film on the substrate to which it directly adheres.
  • conditions are controlled such that the film is made up of fibers of the block copolymer, the fibers having a thickness of from 5 to 500 nm, more preferably between 5 and 50 nm, and they can be between 5 and 40 nm or between 5 and 30 nm or 5 and 20 nm or between 10 and 20 nm. Fibers spacing of 10 to 20 nm was obtained.
  • the temperature of the solution and/or the substrate can be controlled during the application process to form a film having an average roughness (Ra) of less than 8, 7, 6, 5 4 or 3 nm, and is typically greater than 0.1 or 0.3 or 0.5 nm. It is thought an Ra close to about 1 nm e.g., about 0.7 nm can provide an OSC having a suitable power conversion efficiency.
  • Ra can be in the range of 0.1 to 8, or 0.3 to 7, or 0.3 to 6 or 0.5 to 6, or 0.5 to 5, or 0.5 to 4 or 0.5 to 3 or 0.7 to 4 nm.
  • the film is dried shortly or immediately after application of the copolymer solution.
  • the temperature can be equal to or greater than the temperature of the solution that was applied, and/or the temperature of the substrate during the application step.
  • the film is maintained at a temperature greater than or equal to the temperature of step (i) throughout step (ii) and the step of drying the film.
  • An electrode can be installed in contact with the film in the manufacture of a solar cell.
  • a substrate typically comprises a conductor layer such as indium tin oxide coated with PEDOT:PSS.
  • a copolymer solution is applied directly to the conductor layer.
  • the polymer solution includes admixed therewith an electron acceptor.
  • An electron acceptor can be one or more of a fullerene, a fullerene derivative, a nanoparticle, nanocrystal, quantum dot, etc.
  • Exemplary quantum dots include one or more of e.g., CdSe, CdTe, CdS, PbS, PbSe, CulnS 2 , CulnSe 2 , Cd 3 As 2 , Cd 3 P2-
  • a preferred photovoltaic device is a solar cell having a power conversion efficiency of at least 2.7% when exposed to simulated sunlight of an intensity of 1 Sun under AM1.5 G conditions.
  • the film is formed in accordance with a method described above, and thus includes a copolymer film having a suitable Ra obtainable by the method.
  • the film can comprise fibers of copolymer having a suitable or optimized average thickness obtainable by the method.
  • the film would also include an electron acceptor incorporated into and throughout the film formed on the substrate.
  • Figure 1 is a scheme showing the polymer structure and depicting the self- assembly of selenophene-thiophene block copolymers with and without CdSe NCs.
  • Figure 2 is a scheme depicting the synthesis of selenophene monomers.
  • Figure 3 is a scheme depicting the synthesis of the block copolymer.
  • Figure 4 shows the 1 H NMR spectra of the statistical polymer, P3HT (poly-3- hexylthiophene), P3HS (poly-3-hexylselenophene), selenophene.thiophene copolymer, and selenophene:thiophene short-chain polymer ("oligomer”), from top to bottom in the figure.
  • Figure 5 shows a) absorbance, b) emission spectra of block and statistical copolymers in solution, as well as absorbance of c) block and d) statistical copolymers as thin films after annealing. Corresponding homopolymers are included for reference.
  • Figure 6 shows atomic force microscopy (AFM) height and phase (inset) images of a) block b) statistical copolymers and c) blended homopolymers.
  • Figure 7 shows scanning transmission electron microscopy (STEM) elemental mapping image of block copolymer.
  • Figure 8 shows the H NMR spectra of the 77:23 selenophene-thiophene block copolymer.
  • Figure 9 shows a) dark-field STEM images of polymer nanofibers self- assembled with (a-e) and without (f, g) CdSe NCs.
  • Figure 10 shows dark-field STEM image and elemental linescan of a poly(selenophene)-/ poly(thiophene) film showing selenium, sulfur, and titanium content as a function of position.
  • Figure 11 shows dark-field STEM image and elemental linescan of a poly(selenophene)-/ poly(thiophene)/CdSe film showing selenium, cadmium, and titanium content as a function of position.
  • Figure 12 shows (a) the wide-angle X-ray scattering (WAXS) spectra of selenophene-thiophene block copolymers with (lower curve) and without (upper curve) CdSe NCs; and (b) photoluminescence spectra of selenophene-thiophene block copolymer (1.2% (w/w)) with CdSe NCs (lower curve) and CdSe NCs (upper curve), taken at 475nm excitation.
  • WAXS wide-angle X-ray scattering
  • Figure 13 shows the absorbance spectra (a) of a neat CdSe film (black) and a 1.2% (w/w) CdSe/poly(selenophene)-fo-poly(thiophene) blend (grey).
  • the dashed lines show the excitation lines that were used in photoluminescence experiments.
  • Figure 14 shows the photoluminescence (PL) spectra of (from top to bottom in the figure) neat CdSe NCs, and polyselenophene-, poly(selenophene)-/
  • Figure 15 is a schematic of a typical OSC device incorporating a composite material of the invention.
  • Figure 16 shows typical l-V characteristics of P3HS-6-P3HT:PCBM devices prepared at different annealing times and temperatures.
  • Figure 17 is a typical EQE spectrum of a P3HS- ?-P3HT:PCBM device annealed at 100°C for 10 minutes.
  • Figure 18 shows power conversion efficiencies of P3HS-/ P3HT:PCBM devices annealed at 100°C as a function of annealing time.
  • Figure 19 shows AFM height (a, b, c) and phase (d, e, f) images of P3HS-i - P3HT:PCBM films without annealing (a, d), annealed at 80 °C (b, e), and annealed at 130 °C (c,f) for 30 min.
  • Figure 20 shows normalized PCE as a function of post-annealing
  • FIG. 21 shows PCE as a function of post-annealing time of P3HS-j - P3HT:PCBM (squares), P3HS:P3HT:PCBM (circles), and P3HT:PCBM (triangles) devices.
  • the annealing temperature is 80 °C.
  • Figure 22 shows l-V characteristics of P3HS-b-P3HT:PCBM (upper plot) and P3HT:PCBM (lower plot) devices after post-annealing at 80°C for 0, 5, 10, 20 and 30 minutes, the plots for the listed times appearing in the direction of the arrow.
  • Figure 23 shows typical l-V characteristics of P3HS-£>-P3HT:CdSe devices prepared under different conditions.
  • Figure 24 is a typical EQE spectrum of a P3HS-/ P3HT:CdSe devices.
  • the terms, “comprises” and “comprising” are to be construed as being inclusive and open ended, and not exclusive. Specifically, when used in this specification including claims, the terms, “comprises” and “comprising” and variations thereof mean the specified features, steps or components are included. These terms are not to be interpreted to exclude the presence of other features, steps or components.
  • exemplary means “serving as an example, instance, or illustration,” and should not be construed as preferred or advantageous over other configurations disclosed herein.
  • homopolymer means a polymer comprising only a single type of repeated monomers.
  • block copolymer means a polymer formed by covalently bonding together of two or more distinct homopolymers ("blocks").
  • a diblock copolymer is one that is formed by two distinct homopolymers.
  • a triblock copolymer is formed by three distinct homopolymers. Block copolymers containing more than three distinct homopolymers are also possible.
  • Alkyl includes hydrocarbon structures having 1 to 100 carbon atoms, more preferably, 1 to 50, or 1 to 30 carbon atoms, preferably 1 to 25 carbon atoms, but may contain 1 to 20, 1 to 15, 1 to 10, more preferably 1 to 8 carbon atoms or 1 to 6 carbon atoms.
  • An alkyl group or radical may be "linear alkyl” or “branched alkyl”. For any use of the term “alkyl”, unless clearly indicated otherwise, it is intended to embrace all variations of alkyl groups disclosed herein, as measured by the number of carbon atoms, the same as if each and every alkyl group were explicitly and individually listed for each usage of the term.
  • alkyl residue having a specific number of carbons When an alkyl residue having a specific number of carbons is named, all geometric isomers having that number of carbons are included, so, for example, "butyl” is includes n-butyl, sec-butyl, iso-butyl and t- butyl.
  • Suitable alkyl substituents for heterocyles of polymers described herein e.g., thiophene and selenophene include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl and octyl.
  • heteroalkyl group or radical indicates an alkyl radical in which one or more hydrogen atoms is replaced by a corresponding one or more halogen atoms, or one or more carbon atoms, CH groups or CH 2 groups is replaced by a corresponding one or more heteroatoms, respectively, the group being replaced having a valence corresponding to that of the heteroatom.
  • the heteroalkyl group -CF 3 is a methyl group in which three hydrogen atoms have each been replaced by fluorine
  • the heteroalkyl group -CH 2 -0-CH 2 - is an alkyl group in which a CH 2 group has been replaced by an oxygen atom
  • the heteroalkyl group -CH 2 -NH-CH 3 is an alkyl group in which a CH radical has been replaced by a nitrogen atom
  • the heteroalkyl group -Si(CH 3 )3 is an alkyl group in which a carbon atom has been replaced by a silicon atom.
  • the number of replacements is from 1 to 6 and each "heteroatom" is, independently of the other heteroatoms, O, S, N, Se, P, B, CI, F, I, Br, Si, Ge or Sn.
  • the number of replacements can be up to 20 hydrogens in the alkyl group.
  • heterocycle means a cyclic compound
  • heterocycles containing at least two different elements on its ring.
  • a particular subclass of heterocycles includes carbon-based rings wherein one or more of the nodal carbons is replaced with a non-carbon atom.
  • heterocylic rings are aromatic and the terms heterocycle and heteroaryl are used interchangeably.
  • An alkyl group, a heteroalkyl group, or a heteroaryl group can be substituted with one or more of nitro, carboxyl, formyl, alkylcarbonyl (-C(O)-R) and
  • heteroalkylcarbonyl The alkyl group of an alkylcarbonyl or heteroalkyl of a
  • heteroalkylcarbonyl group can also be substituted with a nitro or carboxyl group.
  • Copolymers of the invention that can exist as a salt are intended to be covered by the structural representations of the copolymers provided herein.
  • a copolymer in which a substituent R-group of a heteroaryl ring that contains a carboxyl group can exist as a salt depending upon conditions used for isolation of the copolymer.
  • the invention may also be said broadly to be composed of the parts, elements and features referred to or indicated herein, individually or collectively, in their various possible combinations. It is to be understood that those combinations and/or subcombinations and e.g., subranges are described as though each is explicitly described herein. So, for example, in one aspect, the invention includes a block copolymer having a first heterocycle that is thiophene, optionally substituted in one or both of the 3-position and the 4-position, and a second heterocycle that is selenophene, optionally substituted in one or both of the 3-position and the 4- position, wherein an optional substituent is an alkyl group.
  • n is larger than 1 and less than 10,000, values for n include 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, and 24. a range of n from 3 to 24 is thus described as though explicitly described in the foregoing description.
  • statistical copolymers means a polymer composed of two or more chemically distinct monomers which are distributed randomly throughout the polymer chain.
  • phase separation refers to any process by which a substance, initially in a single, substantially homogenous phase, separates into two or more distinct phases.
  • phase means a region of material that has substantially similar composition and structure throughout.
  • association with means linked together by means of the electromagnetic force.
  • good electrical communication means having an energy bandgap between a conduction state and a bound state of an electron that corresponds to the energy of a photon in any one of the infrared, visible, and ultraviolet ranges.
  • conjugated means a compound having alternating single and multiple bonds.
  • a copolymer is fully conjugated when the backbone of the polymer is substantially fully conjugated from end to end of the backbone.
  • the polymer represented by formula (1 ) can have any level of regioregularity. That is to say, it can be composed of a plurality of any combination of the four distinct triads shown in formulae (2)-(5). Due to the possibly asymmetrical nature of the monomer shown by formula (1 ) (the monomer is asymmetrical when R and R 2 are chemically distinct), the polymer comprising repeated such monomers can comprise a plurality of any combination of these four distinct triads. 11
  • Examples include a novel selenophene-thiophene block copolymer. Also disclosed is a class of composite materials comprising the above mentioned phase-separable fully conjugated block copolymers and nanocrystals, as well as methods for the assembly of the nanocrystals through the phase separation of the polymers. These materials and methods have applications in a variety of electronic devices, particularly optoelectronic devices, even more particularly devices such as diodes, light-emitting diodes, transistors, solar cells, photodiodes and light-emitting transistors as conductive, semi-conductive or light absorbing materials.
  • Polythiophene is well-studied and known to organize into ordered domains. Polyselenophene is a new conjugated polymer with a narrower gap between the HOMO (highest occupied molecular orbital) level and the LUMO (lowest unoccupied molecular orbital) level than in polythiophene. Both polymers can be synthesized under quasi-living conditions, which allows for the synthesis of distinct block copolymers.
  • polymers can be designed to undergo phase separation by synthesizing copolymers that contain regions with distinct functional groups, and when combined with nanoparticles, block copolymer self- assembly offers a means to control the organization of nanoparticles within a film. 6
  • This strategy has been demonstrated for several coil-coil-type block copolymers including poly(styrene)-b-poly(ethylene propylene), poly(styrene)-b- poly(methylmethacrylate), and poly(styrene)-b-poly(vinyl pyridine). 6
  • this approach has not been tested for rod-rod type copolymers, which includes all classes of conjugated diblock copolymers.
  • Selenophene-thiophene block copolymers can be used to drive the self- assembly of spherical nanocrystals (NCs) within a conjugated polymer film ( Figure 1).
  • the resultant composite materials consist of nanofibers of phase-separated conjugated polymer with NCs that are aligned into continuous networks, and preferentially associated with one polymer phase. Photoluminescence quenching experiments demonstrate that this approach leads to films with good electronic communication between the organic and inorganic semiconducting materials.
  • Self-assembled fibers of selenophene-thiophene block copolymers can be used to align spherical NCs into periodic linear networks. Interestingly, the NCs appear to have a selective affinity for the thiophene phase of the phase-separated block copolymer.
  • Prior art teaches the production of polymer-nanoparticle
  • the invention includes a phase-separable block copolymer comprising a first fully conjugated homopolymer and a second fully conjugated homopolymer,
  • said first fully conjugated homopolymer comprises a first monomer, wherein said first monomer comprises a first heterocycle,
  • said second fully conjugated homopolymer comprises a second
  • the first heterocycle can be thiophene, optionally substituted in one or both of the 3-position and the 4-position, the substitutions being independent of each other.
  • the second heterocycle can be selenophene, optionally substituted in one or both of the 3-position and the 4-position, these substitutions also being independent of each other.
  • the optional substituents can be selected from the group consisting of nitro, carboxyl, formyl, and alkylcarbonyl, and alkyl optionally substituted with one or more of nitro, carboxyl, formyl, alkylcarbonyl and heteroalkylcarbonyl, or heteroalkyl optionally substituted with one or more of nitro, carboxyl, formyl, and alkylcarbonyl.
  • the first monomer can be selected from the group consisting of unsubstituted thiophene, thiophene that is substituted in the 3-position, thiophene that is
  • the second monomer can be selected from the group consisting of
  • selenophene unsubstituted selenophene, selenophene that is substituted in the 3-position, selenophene that is substituted in the 4-position, and selenophene that is substituted in both the 3-position and the 4-position.
  • the first fu opolymer is shown by formula (1-S)
  • each R is independently selected from the group consisting of H, N0 2 , NH 2 , COOH, CHO, F, CI, Br, I, BH 2 , OH, SH, SeH, OR 1 , SR 2 , SeR 3 , COR 4 , a functional group, and a hydrocarbon chain that is 1 to 100 carbon atoms in length that may or may not have hydrocarbon and heteroatomic substituents;
  • R , R 2 , R 3 , and R 4 are each independently hydrocarbons that contain 1 to 100 carbon atoms;
  • m is from 2 to 10,000.
  • the second fully conjugated homopolymer is shown by formula
  • each R is independently selected from the group consisting of H, N0 2 , NH 2 , COOH, CHO, F, CI, Br, I, BH 2 , OH, SH, SeH, OR 1 , SR 2 , SeR 3 , COR 4 , a functional group, and a hydrocarbon chain that is 1 to 100 carbon atoms in length that may or may not have hydrocarbon and heteroatomic substituents;
  • R 1 , R 2 , R 3 , and R 4 are each independently hydrocarbons that contain
  • n is from 2 to 10,000.
  • the first fully conjugated homopolymer is poly(3-hexyl- thiophene) and/or the second fully conjugated homopolymer is poly(3-hexylseleno- phene).
  • the molar ratio of 3-hexylthiophene to 3-hexylselenophene can be greater than 1 :2000 and less than 2000:1.
  • the molar ratio of 3-hexylthiophene to 3-hexylselenophene is greater than 1 :1000 and less than 1000:1 , or is greater than 1 :500 and less than 500:1 , or is greater than 1 :200 and less than 200:1 , or is greater than 1 :100 and less than 100:1 , or is greater than 1 :50 and less than 50:1 , or is greater than 1 :10 and less than 10:1 , or is greater than 1 :5 and less than 5:1 , or is between 1 :2 and 2:1.
  • the molar ratio of 3-hexylthiophene to 3- hexylselenophene is about 1 :1 in a phase-separable block copolymer.
  • the invention includes an optoelectronic device containing a copolymer of the invention.
  • a device can be a diode, a light-emitting diode, a transistor, a solar cell, a photodiode, or a light-emitting transistor.
  • a copolymer-nanocrystal composite of the invention can be the phase- separable block copolymer and a plurality of nanocrystals.
  • a copolymer-nanocrystal composite includes a phase-separable block copolymer of the invention that is phase-separated.
  • a copolymer-nanocrystal composite of the invention is a phase-separable block copolymer arranged in nanofibers, and preferably, the plurality of nanocrystals is substantially associated with a phase of said phase- separable block copolymer.
  • the plurality of nanocrystals can be arranged in a substantially periodic linear fashion.
  • the mass ratio of a phase-separable block copolymer to the plurality of nanocrystals is about 1 :1.
  • a copolymer-nanocrystal composite of the invention preferably has the phase- separable block copolymer in good electrical communication with the plurality of nanocrystals.
  • Such a plurality of nanocrystals of a copolymer-nanocrystal composite can be nanocrystals with a conduction band below a LUMO level of the phase-separable block copolymer and a valence band below a HOMO level of the phase-separable block copolymer.
  • the invention includes a method of arranging a plurality of nanocrystals comprising the steps of
  • phase separating said phase-separable block copolymer
  • the invention also includes a method of adjusting a set of properties of a phase-separable block copolymer wherein
  • phase-separable block copolymer comprises a first fully conjugated homopolymer and a second fully conjugated homopolymer
  • said first fully conjugated homopolymer comprises a first monomer
  • said first monomer comprises a first heterocycle
  • said second fully conjugated homopolymer comprises a second monomer, said second monomer comprises a second heterocycle chemically distinct from said first heterocycle, and
  • said method comprises the steps of
  • phase separating said phase-separable block copolymer
  • the invention includes a semiconductor composite material containing a block copolymer of the invention in combination with an electron acceptor material.
  • the invention is an optoelectronic device having a power conversion efficiency between 0.1 and 15%, or between 2.7 and 15%, or 2.7 and 13%, or 2.7 and 11%, or 2.7 and 9%, or 2.7 and 7%, or 2.7 and 5%, or at least 2.7%, or at least 3.0%, or at least 4.0%.
  • a preferred optoelectronic device includes a semiconductor composite material of the invention formed as a film on a conductive substrate in which the film has an Ra of less than 3 nm and the film is formed directly onto the substrate in direct electrical connection therewith.
  • the invention includes use of a semiconductor composite material in the formation of a semiconducting film.
  • Thickness of a film on the substrate can be between 1 nm and 10,000 nm, or between 5 nm and 8,000 nm, or between 5 nm and 5,000 nm, or between 5 nm and 2,000 nm, or between 5 nm and 1 ,000 nm, or between 10 nm and 800 nm or between 10 nm and 500 nm, or between 10 nm and 300 nm, or between 20 nm and 300 nm, or between 40 and 200 nm, or between 20 and 300 nm, or it can be about 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, or 150 nm.
  • the invention thus also includes a method of manufacturing a semiconductor, the method including steps of:
  • a method can be of manufacturing a solar cell, that includes:
  • the invention includes solar cell comprising (i) a cathode and an anode, (ii) an active layer having a first surface and a second surface disposed between the cathode and the anode, and (iii) a titanium dioxide layer formed to be in electrical contact with one of the first surface and the second surface of the active layer, wherein the active layer comprises a semiconductor composite material of the invention.
  • Such a solar cell can have power conversion efficiency between 0.1 and 15%, preferably greater than about 2.7%.
  • Described below are examples demonstrating the feasibility of using a block copolymer of the invention in conjunction with an electron acceptor to form a semiconductor composite material.
  • the material can be used, for example, as part of a photovoltaic device. Examples demonstrate the usefulness of inorganic
  • PCBM fullerene derivative
  • an "electron acceptor” is defined as any molecule, fullerene, nanoparticle, nanocrystal, quantum dot, or composition that can accept an excited-state electron from the block copolymer.
  • the terms nanoparticles, nanocrystal and quantum dots are used interchangeably.
  • fullerenes and CdSe nanoparticles were used in studies described herein, but other materials, such as CdS, CdTe, PbS, PbSe, CulnS 2 , CulnSe2, Cd 3 As 2 , and/or CdaP 2 can be used. Other shapes, such as spheres, stars, tetrapods can be used also.
  • the fullerene derivative [6,6]-phenyl Cei butyric acid methyl ester was used in the studies described herein, but other fullerenes and/or their derivatives can be used.
  • Fullerene derivatives of the invention are capable of acting as an electron acceptor and include alkyl ester derivatives, particularly PCBM.
  • Fullerenes of the invention include Cm, C 70 , Cs4, and derivatives such as ester derivatives e.g., the [6,6]-phenyl C 7 i butyric acid.
  • Materials that can also be incorporated into e.g., an organic solar cell of the invention include carbon nanotubes and graphene.
  • One of the most likely to be used electron acceptors is the fullerene derivative [6,6]-phenyl C6i butyric acid methyl ester used in Examples 3 and 4.
  • the inventors have surprisingly found that the power conversion efficiency of a prototype solar cell comprising a block copolymer of the invention does not markedly change with thermal annealing of the polymer as is observed for cells that include P3HT as an electron donor. Even more surprising was the finding that cell performance could be improved by spin-coating a solution of the block copolymer onto the substrate when casting is carried out using a heated solution. It is known that use of such a "fast-dry" process in making a solar cell with P3HT:PCBM leads to lower performance (Li, G.; Shrotriya, V.; Huang, J.
  • One embodiment of the present disclosure is exemplified using as an example chemical compounds termed selenophene-thiophene block copolymers.
  • Thiophene and selenophene monomers with identical side chains were prepared.
  • the thiophene monomers (2,5-dibromo-3-hexylthiophene) were synthesized according to previously reported procedures.
  • the selenophene monomers (2,5-dibromo-3-hexylselenophene) were synthesized by an initial alkylation of 3-iodoselenophene with n-hexylmagnesium bromide under Kumada- type coupling conditions followed by isolation and dibromination using N- bromosuccinimide ( Figure 2).
  • the selenophene monomers were activated with n-butylmagnesium chloride and treated with [1 ,3- bis(diphenylphosphino)propane]nickel(ll)chloride [Ni(dppp)CI] to initiate
  • n and m denote the number of selenophenes and thiophenes, respectively.
  • n is larger than 1 and less than 10,000
  • m is larger than 1 and less than 10,000.
  • R, R', R", and R'" are independently variable substitutents. Common values for n and m, which are independent of each other, are 3, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 18, 20, 22, and 24.
  • selenophene:thiophene ratios are found to be 57:43 and 45:55 for the block and statistical copolymers, respectively ( Figure 4).
  • the aromatic resonances of thiophene and selenophene appear at different chemical shifts when the alternate heterocycle is present at the 5-position.
  • the spectrum of the statistical copolymer was therefore particularly useful for quantifying each combination of units along the backbone.
  • the thiophene-thiophene.thiophene- selenophene: selenophene-selenophene distribution is 29:50:21 , confirming the statistical distribution of monomers in the chain.
  • copolymer contains intact polythiophene and polyselenophene chromophores.
  • the solution fluorescence spectra are also indicative of structure.
  • P3HT and P3HS emit at 578 and 623 nm, respectively ( Figure 5b).
  • the block copolymer emission spectrum is dominated by emission from the thiophene block because of this block's greater fluorescence intensity.
  • the statistical copolymer emits weakly at 598 nm, a frequency positioned between the P3HT and P3HS emissions.
  • copolymer possesses shoulders (marked by arrows in Figure 5c) that coincide with the 77-stacking bands of both P3HT and P3HS. These features indicate association and organization of blocks with corresponding blocks in adjacent chains. This observation stands in contrast to that for the statistical copolymer, which has a nearly featureless absorption profile.
  • the film morphology of the block copolymer was also investigated using atomic force microscopy (AFM). Distinct domains are present in the film ( Figure 6). This morphology is striking when compared with the statistical copolymer film, which has much smaller domains with a smoother morphology, or when compared with blends of the two pure polymers, which appear unstructured at the nanoscale ( Figure 6). Taken together, the absorption and AFM data
  • n-butylmagnesium chloride (0.14 mL, 2.0 M in THF, 0.28 mmol) was added to 2,5-dibromo-3- hexylthiophene (87 mg, 0.27 mmol) in dry THF (1.5 mL) and the solution was refluxed for 1 hour (Solution B).
  • Solution A was refluxed for 10 hours at which time Solution B was added drop-wise.
  • the combined mixture was refluxed for an additional 10 hours, then quenched with dilute hydrochloric acid and precipitated into methanol.
  • the precipitated solid was purified by Soxhlet extraction using hexanes, methanol, and chloroform.
  • Block copolymer-NC blends (1 :1 ; w/w) were prepared in chlorobenzene (10 mg/mL) and investigated their morphology after drop casting.
  • a surprising co- self-assembly of NCs with polymer fibers is observed.
  • Numerous new, aligned features can be seen on the nanofibers ( Figure 9a).
  • a magnified image shows that the new features are NCs that arrange in a linear order onto the polymer fibers
  • copolymer-NC blends were investigated by wide-angle X-ray scattering (WAXS).
  • WAXS wide-angle X-ray scattering
  • the block copolymer film is clearly crystalline, showing two strong diffraction peaks at 2 ⁇ angles of 5.64° and 7.30°, corresponding values of 15.49 and 12.14 A, respectively ( Figure 12a).
  • the 15.49 A spacing is likely due to the interlayer stacking (d100) of the hexylthiophene phase (dP3HT). This value is very close to the reported lamellar structure of poly-3-hexylthiophene (P3HT) which has an interlayer spacing of 16.0 ⁇ 0.2 A.
  • P3HT poly-3-hexylthiophene
  • the 12.14 A spacing is ascribed to the interlayer stacking of the hexylselenophene phase (dP3HS).
  • Conjugated block copolymer/NC composites have potential use as light harvesting materials. This is because both the conjugated polymer and NCs are strong light absorbers and the LUMO level of the polymer is positioned above the conduction band of CdSe while the HOMO level of the polymer is positioned above the valence band of CdSe. 7 From an energy transfer perspective, photoinduced charge separation would be expected based on the energy level alignment and physical contact of these two materials.
  • poly-(3-hexylselenophene-b/oc/c-3-hexylthiophene)s are an important new class of copolymer because they have broad optical absorption properties with an onset that is red-shifted by 80 nm compared to P3HT, and the ability to phase separate in the solid-state.
  • phase separation in conjugated polymers has been effected with nonconjugated blocks or pendant groups.
  • phase separation as well as optical properties can be controlled by the heterocycle in the polymer chain. This represents a distinct type of phase separation that is driven by elemental composition, which simultaneously offers a direct means to control optical properties.
  • poly-(3-hexylselenophene-b/oc/c-3-hexylthiophene)s should find utility for fundamental study, such as testing the limits of phase separation, as well as in optoelectronic applications.
  • the polymer poly(3-hexylselenophene)-b/oc/c-poly(3-hexylthiophene) was synthesized as follows: 2,5-dibromo-3-hexylselenophene monomer (657 mg, 1 .76 mmol) was reacted with / ' -propylmagnesium chloride (2.0M, 0.88ml_) in dry THF for one hour at room temperature, then transferred to a separate flask containing [1 ,3- Bis(diphenylphosphino)propane]dichloronickel (Ni(dppp)CI 2 ) (19 mg, 0.035 mmol) and the resulting dark purple mixture was heated to 40 °C for 60 minutes.
  • a typical solar cell device is fabricated and tested as follows. Devices were fabricated on commercial indium tin oxide (ITO) substrates (Colorado Concept
  • Coatings that had a sheet resistance of -10 ⁇ /Q . These substrates were cleaned in aqueous detergent, deionized (Dl) water, acetone and methanol, and subsequently treated in an oxygen-plasma cleaner for 5 minutes to remove any residue and improve charge injection.
  • PEDOT SS poly(3,4- ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT SS) (Clevios P VP Al
  • fullerenes can be used in this device, including, but not limited to Ceo, C70, Cs 4 , or [6,6]-phenyl C71 butyric acid methyl ester. Carbon nanotubes or graphene may also be blended with P3HS-ib-P3HT and used in this device. Finally, a 1 nm LiF layer and a 100 nm Al anode was thermally deposited though shadow masks at -10 "6 torr. Typical device area, as defined by the area of circular Al anode, is 7 mm 2 . A schematical of a device structure is given ( Figure 15).
  • I-V characteristics were measured using a Keithley 2400 source meter under simulated AM 1 .5 G conditions with a power intensity of 100 mW/cm 2 .
  • the mismatch of simulator spectrum was calibrated using a Si diode with a KG-5 filter.
  • External quantum efficiency (EQE) spectra were recorded and compared with a Si reference cell that is traceable to the National Institute of Stands and Technology.
  • Typical l-V curves, EQE spectra and device output characteristics are given below ( Figure 16; Figure 17; Table 1 ).
  • the l-V curves show that these devices produce a photocurrent upon irradiation under simulated solar conditions.
  • Several parameters were optimized including annealing time and temperature. The highest repeatable efficiency obtained so far is 2.7%. High efficiency of a polymer can be attained with purification by extraction and column chromatography to remove residual metal catalysts. Devices containing the polymer should be annealed at 100°C for 10 minutes. Further optimization of P3HS-/>P3HT polymer structure including molecular weight and block ratio should improve this efficiency.
  • Table 1 Summary of P3HS-/ P3HT:PCBM device characteristics.
  • I-V characteristics were measured using a Keithley 2400 source meter under simulated AM 1.5 G conditions with a power intensity of 100 mW/cm 2 .
  • the mismatch of simulator spectrum was calibrated using a Si diode with a KG-5 filter.
  • EQE spectra were recorded and compared with a Si reference cell that is traceable to the National Institute of
  • P3HS-/>P3HT the annealed devices only slightly improved from initial performance (from 2.69% without annealing to 2.76% with annealing, Figure 18).
  • AFM measurements show that P3HS-fe-P3HT:PCBM has a nearly identical fiber-like morphology with or without annealing ( Figure 19a, d).
  • the surface features of the P3HS-/ P3HT:PCBM active layer consists of lamella fibers that are 10-20 nm apart, a distance that is roughly equal to the exciton diffusion length. Fiber-like structures have been considered important to improve phase-separation between the donor and acceptor domains, thereby enhancing charge transport and separation.
  • P3HS-b-P3HT:PCBM device thermal stability of the system was investigated. Finished devices were annealed, referred to here as "post- annealing", and power conversion efficiency was determined as a function of both time and temperature. Post-annealing and device testing were conducted in a nitrogen-filled glove box. The P3HS-b-P3HT:PCBM devices were found to be more robust to the high temperature post-annealing process ( Figure 20). After increasing the post-annealing temperature to 100°C, the P3HS-/ P3HT:PCBM devices retained 83 % of their initial efficiencies, while the performance of P3HT:PCBM devices was found to drop by more than 50%.
  • P3HT:PCBM devices remained above 90 % of the initial operating efficiency under the same experimental conditions.
  • P3HT, P3HS or P3HS-6-P3HT and PCBM were mixed in 1 ,2-dichlorobenzene (15 mg/mL total polymer:12 mg/mL PCBM) and stirred for 16 hours at 80°C to completely dissolve the solids.
  • Devices were fabricated on commercial indium tin oxide (ITO) substrates (Colorado Concept Coatings) that had a sheet resistance of -10 ⁇ /D. These substrates were cleaned in aqueous detergent, deionized (Dl) water, acetone and menthol, and subsequently treated in an oxygen-plasma cleaner for 5 minutes. Next, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)
  • PEDOT-.PSS (Clevios P VP Al 4083) was coated onto the substrates at 3000 rpm and the PEDOT:PSS-coated substrates were annealed in air at 130°C for 15 minutes. After annealing, the substrates were transferred into a nitrogen-filled glove box, where polymer: PCBM blends were coated at 800 rpm. After spin-coating, P3HT samples were immediately transferred into closed petri-dishes and slow dried at room temperature (a vapor annealing process; the optimized condition).
  • I-V characteristics were measured using a Keithley 2400 source meter under simulated AM 1.5 G conditions with a power intensity of 100 mW/cim 2 .
  • the mismatch of simulator spectrum was calibrated using a Si diode with a KG-5 filter.
  • EQE spectra were recorded and compared with a Si reference cell that is traceable to the National Institute of Standards and Technology.
  • the thickness of active layer is -150 nm for all devices, determined by AFM.
  • Single carrier devices were fabricated in the same manner as photodiode devices except the LiF/AI cathode was replaced by a Au cathode. I-V characteristics of the single carrier devices were measured under dark conditions and mobility was estimated from the Mott-Gurney law.
  • EXAMPLE 5 Selenophene-Thiophene: CdSe nanocrystal devices
  • CdSe nanorods were synthesized by the following procedure which was adapted from the literature. 18 CdO (0.6420 g, 5 mmol) and thiodipropionic acid (TDPA) (2.79 g, 10 mmol) with 2 g of trioctylphosphine oxide (TOPO) were loaded into a reaction flask and then heated under argon flow. The mixture turned optically clear at around 300 °C. After the solution was kept at this temperature for 5-10 min, it was allowed to cool to room temperatures under N 2 flow. A solid product (Cd-TDPA) was obtained and was removed from the reaction flask.
  • TDPA thiodipropionic acid
  • TOPO trioctylphosphine oxide
  • the resultant CdSe nanorods were washed four times with a mixture of toluene and ethanol to remove excess capping ligand, and the remaining phosphonic acid ligands were exchanged with pyridine by heating the particles in pyridine overnight at 107 °C.
  • Pyridine-treated particles were recovered by precipitation with hexane and dissolved in a 9:1 mixture of chloroform and pyridine at a concentration of 30mg/mL. The resulting solution was sonicated for 1 h and filtered through a 0.45 ⁇ PTFE filter.
  • a typical solar cells device is fabricated and tested as follows. Devices were fabricated on commercial indium tin oxide (ITO) substrates (Colorado Concept Coatings) that had a sheet resistance of ⁇ 10 ⁇ / ⁇ . These substrates were cleaned in aqueous detergent, deionized (Dl) water, acetone and menthol, and subsequently treated in an oxygen-plasma cleaner for 5 minutes to remove any residue and improve charge injection. Next, poly(3,4-ethylenedioxythiophene):poly(styrene- sulfonate) (PEDOT:PSS) (Clevios P VP Al 4083) was coated onto the substrates at 3000 rpm and annealed in air at 130 °C for 15 min.
  • ITO indium tin oxide
  • Table 2 Summary of P3HS-b-P3HT:CdSe device characteristics.

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Abstract

L'invention concerne des copolymères de sélénophène-thiophène en tant que classe de copolymères conjugués qui montrent des propriétés d'absorption lumineuse à large spectre. Des domaines de phases séparées de copolymères à blocs sont observés à l'état solide. La microscopie électronique à balayage par transmission et la cartographie topographique élémentaire montrent que les domaines sont riches soit en sélénophène, soit en thiophène, indiquant que les blocs d'hétérocycles distincts s'associent de préférence entre eux à l'état solide. Par mélange de ces copolymères à blocs avec des NC (nanocomposite), un co-auto-assemblage surprenant de NC et de polymère est observé. La microscopie électronique à balayage par transmission (MEBT) et des expériences de balayage linéaire élémentaire montrent que les NC s'associent de manière sélective avec la phase riche en S pour s'agencer en réseaux de structures linéaires. Des expériences d'extinction de photoluminescence (PL) montrent un transfert d'énergie d'excitation efficace entre les NC et les nanofibres de polymères. La fabrication et l'utilisation de matériaux composites semi-conducteurs utilisant ces copolymères sont décrites.
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US9543529B2 (en) 2014-02-11 2017-01-10 Sabic Global Technologies B.V. Compounds containing electron rich and electron deficient regions and their use in organic electronic applications
CN113122259A (zh) * 2019-12-30 2021-07-16 Tcl集团股份有限公司 一种复合材料及其制备方法、偏振片与液晶显示器

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