WO2018232358A1 - Visibly transparent, near-infrared-absorbing and ultraviolet-absorbing photovoltaic devices - Google Patents

Visibly transparent, near-infrared-absorbing and ultraviolet-absorbing photovoltaic devices Download PDF

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Publication number
WO2018232358A1
WO2018232358A1 PCT/US2018/037923 US2018037923W WO2018232358A1 WO 2018232358 A1 WO2018232358 A1 WO 2018232358A1 US 2018037923 W US2018037923 W US 2018037923W WO 2018232358 A1 WO2018232358 A1 WO 2018232358A1
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Prior art keywords
visibly transparent
group
substituted
photovoltaic device
unsubstituted
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PCT/US2018/037923
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English (en)
French (fr)
Inventor
Miles BARR
Richa Pandey
Matthew JUROW
Bo He
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Ubiquitous Energy, Inc.
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Priority to CN201880049706.3A priority Critical patent/CN110944986A/zh
Priority to KR1020217017129A priority patent/KR102427886B1/ko
Priority to CA3066092A priority patent/CA3066092A1/en
Priority to JP2019569755A priority patent/JP2020524404A/ja
Priority to KR1020207000947A priority patent/KR102263356B1/ko
Priority to EP18818288.5A priority patent/EP3638656A4/en
Priority to AU2018283407A priority patent/AU2018283407B2/en
Priority to KR1020227026207A priority patent/KR102655233B1/ko
Publication of WO2018232358A1 publication Critical patent/WO2018232358A1/en
Priority to AU2021203483A priority patent/AU2021203483B2/en
Priority to JP2023061212A priority patent/JP2023113595A/ja

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    • 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
    • H10K30/80—Constructional details
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    • 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
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/324—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising aluminium, e.g. Alq3
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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    • 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
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    • H10K30/80—Constructional details
    • H10K30/81—Electrodes
    • H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
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    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/84—Layers having high charge carrier mobility
    • H10K30/85—Layers having high electron mobility, e.g. electron-transporting layers or hole-blocking layers
    • H—ELECTRICITY
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    • H10K85/30—Coordination compounds
    • H10K85/311—Phthalocyanine
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/321—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3]
    • H10K85/322—Metal complexes comprising a group IIIA element, e.g. Tris (8-hydroxyquinoline) gallium [Gaq3] comprising boron
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    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/621—Aromatic anhydride or imide compounds, e.g. perylene tetra-carboxylic dianhydride or perylene tetracarboxylic di-imide
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • 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

  • This application relates generally to the field of optically active materials and devices, and, more particularly, to visibly transparent photovoltaic devices and materials for visibly transparent photovoltaic devices.
  • window glass utilized in automobiles and architecture are typically 70-80% and 55-90% transmissive, respectively, to the visible spectrum, e.g., light with wavelengths from about 450 to 650 nanometers (nm).
  • OLED organic photovoltaic
  • Described herein are materials, methods, and systems related to visibly transparent photovoltaic devices. More particularly, the present description provides boron- dipyrromethene-based compounds, near-infrared absorbing photoactive compounds, near- infrared donor acceptor (near-IR DA) molecules, metal dithiolate compounds, ultraviolet electron acceptor molecules (UV acceptor), visibly transparent tetracyano quinoidal thiophene compounds, visibly transparent tetracyano indacene compounds, visibly transparent carbazole thiaporphyrin compounds, visibly transparent dithiophene squarine compounds, phthalocyanine compounds, phthalocyanine derivative compounds, and structurally related compounds and methods and systems incorporating the materials, molecules, and compounds as a photoactive material of a visibly transparent photovoltaic device.
  • Embodiments of the present invention provide transparent photoactive materials, including organic semiconductor materials, useful in visibly transparent photovoltaic devices. The invention is applicable to a variety of applications in photovolta
  • Materials, methods, and system for transparent photovoltaic devices are disclosed, such as those that are transparent to visible light but absorb near-infrared light and/or ultraviolet light.
  • the photovoltaic devices make use of transparent electrodes and visibly transparent boron-dipyrromethene (BODIPY)-based compounds, near-infrared donor acceptor (near-IR DA) molecules, metal dithiolate compounds, ultraviolet electron acceptor molecules (UV acceptor), visibly transparent tetracyano quinoidal thiophene compounds, visibly transparent tetracyano indacene compounds, visibly transparent carbazole
  • BODIPY visibly transparent boron-dipyrromethene
  • near-IR DA near-infrared donor acceptor
  • metal dithiolate compounds metal dithiolate compounds
  • UV acceptor ultraviolet electron acceptor molecules
  • visibly transparent tetracyano quinoidal thiophene compounds visibly transparent tetracyano indacene compounds
  • phthalocyanine compounds phthalocyanine compounds, phthalocyanine derivative compounds, or structurally related compounds, which may be useful as photoactive materials, buffer materials, and/or optical layers, for example.
  • the disclosed visibly transparent photoactive compounds exhibit a maximum near-infrared absorption strength and a maximum visible absorption strength, wherein the maximum near-infrared absorption strength is greater than the maximum visible absorption strength.
  • embodiments of the present invention provide methods and systems for absorbing near-infrared and/or ultraviolet radiation for photovoltaic power generation while being transparent to visible light.
  • these optical characteristics provide for the ability to generate electricity from incident solar radiation in a photovoltaic device, while still allowing useful visible light to be passed through, permitting a viewer to see through the photovoltaic device.
  • the photoactive compounds described herein provide suitable electron donor and/or electron acceptors for generation and separation of electron-hole pairs via absorption of light in order to provide a DC voltage or current to an external circuit.
  • the disclosed photoactive compounds include those that are transparent to visible light or absorb only relatively small amounts of light in the visible band, such as between about 450 and about 650 nm, while exhibiting a greater absorption strength in the near-infrared (NIR) band, such as between about 650 nm and about 1400 nm.
  • the disclosed photoactive compounds exhibit a peak absorption in the NIR band.
  • the disclosed photoactive compounds exhibit an absorption in the visible band having a strength less than that in the NIR band.
  • the disclosed photoactive compounds exhibit a peak absorption in the UV band.
  • the disclosed photoactive compounds exhibit an absorption in the visible band having a strength less than that in the UV band.
  • the disclosed photoactive compounds exhibit materials properties providing advantages for manufacturing and performance of visibly transparent photovoltaic devices as well.
  • devices including photoactive compounds described herein may be manufactured using techniques in which the photoactive compound is applied to a substrate using vacuum deposition techniques rather than a solution-based application technique.
  • Use of vacuum deposition techniques may advantageously allow high purity photoactive layers to be generated, improving device efficiency and performance and reducing manufacturing complexity.
  • transparent photovoltaic devices may incorporate the disclosed photoactive compounds into active material layers by way of vacuum thermal evaporation techniques, eliminating use of solution based photoactive material application steps and associated waste product handling and disposal.
  • the disclosed photoactive compounds may be purified by an evaporation and/or sublimation technique. Purification by evaporation and/or sublimation may be useful for generating high purity photoactive materials and compounds, which may, in turn, allow improved transparent photovoltaic device production and performance.
  • a visibly transparent photovoltaic device may comprise a visibly transparent substrate; a first visibly transparent electrode coupled to the visibly transparent substrate; a second visibly transparent electrode above the first visibly transparent electrode; a first visibly transparent active layer between the first visibly transparent electrode and the second visibly transparent electrode, wherein the first visibly transparent photoactive layer comprises a visibly transparent photoactive compound, such as any visibly transparent photoactive compound described herein, including a visibly transparent photoactive compound that exhibits a first maximum near-infrared or ultraviolet absorption strength and a first maximum visible absorption strength, such as a first maximum near-infrared or ultraviolet absorption strength that is greater than the first maximum visible absorption strength; and a second visibly transparent photoactive layer between the first visibly transparent electrode and the second visibly transparent electrode and exhibiting a second maximum absorption strength in the near-infrared or ultraviolet and a second maximum visible absorption strength, such as a second maximum absorption strength that is greater than the second maximum visible absorption strength.
  • visibly transparent photovoltaic devices may further comprise a first buffer layer disposed between the first visibly transparent electrode and the first visibly transparent active layer.
  • visibly transparent photovoltaic devices may further comprise a second buffer layer disposed between the second visibly transparent active layer and the second visibly transparent electrode.
  • the first visibly transparent photoactive layer is coupled to the first visibly transparent electrode.
  • the first visibly transparent photoactive layer is coupled to the second visibly transparent electrode.
  • the second visibly transparent photoactive layer is coupled to the first visibly transparent electrode.
  • the second visibly transparent photoactive layer is coupled to the second visibly transparent electrode.
  • two objects or layers being coupled refers to the condition where the two objects or layers are directly coupled (i.e., in physical contact) or indirectly coupled, such as with one or more additional objects or layers between them. Coupling of objects or layers may indicate that the objects or layers are part of a single overall structure or device.
  • the photoactive compound functions as an electron acceptor material.
  • the second visibly transparent photoactive layer may include an electron donor material.
  • the photoactive compound functions as an electron donor material.
  • the photoactive compound functions as an electron donor material, the second visibly transparent photoactive layer may include an electron acceptor material.
  • the first visibly transparent photoactive layer and the second visibly transparent photoactive layer may each independently have thicknesses of 1 nm to 300 nm, such as about 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 65 nm, 70 nm, 75 nm, 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 105 nm, 110 nm, 115 nm, 120 nm, 125 nm, 130 nm, 135 nm, 140 nm, 145 nm, 150 nm, 155 nm, 160 nm, 165 nm, 170 nm, 175 nm, 180 nm, 185 nm, 190 nm, 195 nm, 200 nm, 205
  • Example photoactive compounds described herein and useful for a photoactive layer in a visibly transparent photovoltaic device include boron-dipyrromethene-based photoactive compounds, such as those incorporating boron difluoride moieties, such as fluoro boron dipyrromethene moieties, fluoro boron azadipyrromethene moieties, and fluoro diazaborolo and related cores structures.
  • boron-dipyrromethene-based photoactive compounds described herein include those incorporating boron dioxide moieties, which may generally correspond to compounds including oxygen substituted boron difluoride moieties.
  • a photoactive compound provided herein has the formula
  • each A2 is independently a fused or unfused aromatic or heteroaromatic group including one or more R group substituents.
  • each X is independently S, N, or C— R.
  • each L group is independently a single bond or a bivalent linking group selected from a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted
  • heteroaromatic group a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • R— L. I- may further be characterized by the formula:
  • Example photoactive compounds described herein and useful for a photoactive layer in a visibly transparent photovoltaic device include an acceptor material comprising a near- infrared absorbing photoactive compound, such as a near-infrared absorbing donor-acceptor (near-IR DA) molecule.
  • a near-infrared absorbing photoactive compound such as a near-infrared absorbing donor-acceptor (near-IR DA) molecule.
  • the near-infrared absorbing photoactive compound may exhibit a first maximum near-infrared absorption strength and a first maximum visible absorption strength, such as a first maximum near-infrared absorption strength is greater than the first maximum visible absorption strength.
  • Example photoactive compounds described herein include, but are not limited to, visibly transparent near-IR DA molecules, such as dicyano-indandiones, benzo-fos-thiadiazoles, diketopyrrolopyrrole diphenylthienylamines, and derivatives thereof.
  • visibly transparent near-IR DA molecules such as dicyano-indandiones, benzo-fos-thiadiazoles, diketopyrrolopyrrole diphenylthienylamines, and derivatives thereof.
  • the second visibly transparent photoactive layer absorbs in the near- infrared such that the second visibly transparent photoactive layer exhibits a second maximum absorption strength in the near-infrared and a second maximum visible absorption strength, such as a second maximum absorption strength that is greater than the second maximum visible absorption strength.
  • maximum near-infrared absorption by the acceptor material is redshifted relative to maximum near-infrared absorption by the donor material.
  • maximum near-infrared absorption by the acceptor material is blueshifted relative to maximum near-infrared absorption by the donor material. For example, a peak near-infrared absorption by the acceptor molecule may be blueshifted or redshifted relative to a peak near-infrared absorption by the donor molecule.
  • a near infrared absorbing photoactive compound has a molecular weight between 200 amu and 1000 amu, between 300 amu and 800 amu, or between 400 amu and 600 amu.
  • the near infrared absorbing photoactive compound may have a molecular weight of between 200 amu and 220 amu, between 220 amu and 240 amu, between 240 amu and 260 amu, between 260 amu and 280 amu, between 280 amu and 300 amu, between 300 amu and 320 amu, between 320 amu and 340 amu, between 340 amu and 360 amu, between 360 amu and 380 amu, between 380 amu and 400 amu, between 400 amu and 420 amu, between 420 amu and 440 amu, between 440 amu and 460 amu, between 460 amu and 480 amu, between 480 amu and 500 amu, between 500 amu and 520 amu, between 520 amu and 540 amu,
  • a near-infrared absorbing photoactive compound such as a near-IR DA molecule
  • a visibly transparent photoactive compound useful in a photoactive layer of a visibly transparent photovoltaic cell.
  • useful visibly transparent photoactive compounds include those selected from a dicyano-indandione, a dicyano-indandione derivative, a benzo-fos-thiadiazole, a benzo-fos-thiadiazole derivative, a benzothiadiazole, a benzothiadiazole derivative, a diketopyrrolopyrrole diphenylthienylamine, or a
  • n is an integer 0-5.
  • X is C(CN) 2 , O, S, C(O), or S0 2 .
  • Ar is aryl, such as phenyl, thienyl, thiazolyl, and the like.
  • t is 1 or 2.
  • X is.
  • each Z is independently H or a radical having the formula:
  • pi systems include, some of which may also be fused pi systems, anthra[l,9-£c:5, 10-£'c dithiophene diradicals (e.g., anthra[l,9-£c:5, 10-£'c dithiophen-l,6- diyl); 4,9-dihydro-s-indaceno[l, 2-0:5, e- ⁇ 'Jdithiophene diradicals (e.g., 4,9-dihydro-s- indaceno[l,2-£:5,6-£ dithiophen-2,7-diyl); unsubstituted and 5-substituted 5H-dithieno[3,2- b:2',3'-h]carbazole diradicals (e.g., 5-methyl-5H-dithieno[3,2-b:2',3'-h]carbazol-2,8-diyl); unsubstituted and
  • the pi system has the formula:
  • the fused pi system has the formula: where R may optionally be hydrogen or alkyl.
  • the fused pi system has the formula: where R may optionally be hydrogen or alkyl.
  • Examples of pi systems may also include unfused moieties such as amine radicals including triphenylamine diradicals (e.g., N-phenyl-di(phen-4, l- diyl)amine), thiophenylamine diradicals (e.g., N-methyl-di(thiophen-2,5-diyl)amine and N- phenyl-(phen-4, l-diyl)-(thiophen-2,5-diyl)-amine); biphenyl diradicals (e.g., l, l'-biphen-4,4'- diyl), thiophene diradicals (e.g., thiophen-2,5-diyl), phenylene diradicals (e.g., phen-l,
  • a benzo-fos-thiadiazole has the formula
  • each of Ri, R 2 Ri, R 2 ,
  • R 3 , and R 4 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl.
  • Ai and A 2 are independently selected from the group consisting of alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclylene.
  • X is selected from the group consisting of O, S, Se, and Te.
  • Ri, and R 4 are independently selected from:
  • Ai and A 2 are independently selected from arylene and heteroarylene.
  • Ai and A 2 are thiophene diradicals (e.g., thiophene-2,5-diyl).
  • each of Ri, R 2 , R 3 , R 4 are aryl (e.g., phenyl).
  • a benzothiadiazole has the formula .
  • each of Ri, R 2 , and R 3 has the formula .
  • R 3 , and R 4 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl.
  • Ai and A 2 are independently selected from the group consisting of alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclylene.
  • X is selected from the group consisting of O, S, Se, and Te.
  • Ri, and R 4 are independently selected from:
  • Ai and A 2 are independently selected from arylene and heteroarylene.
  • Ai and A 2 are thiophene diradicals (e.g., thiophene-2,5-diyl).
  • each of Ri, R 2 , R 3 , R 4 are aryl (e.g., phenyl).
  • the structures may be readily modified by selecting linker (A groups) and their substitution (R groups) with aliphatic or aromatic groups. Additionally the X groups can be chosen from O, N, S, Se or a combination thereof.
  • a diketopyrrolopyrrole diphenylthienylamine has the formula
  • Ri and R 2 are
  • Ai and A 2 are independently selected from alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclylene.
  • Example photoactive compounds described herein and useful for a photoactive layer in a visibly transparent photovoltaic device include those incorporating metal dithiolate complexes, also referred to as metal dithiolate compounds or metal dithiolene compounds, such as nickel dithiolate compounds, cobalt dithiolate compounds, iron dithiolate compounds, zinc dithiolate compounds, molybdenum dithiolate compounds, palladium dithiolate compounds, platinum dithiolate compounds, etc.
  • metal dithiolate complexes also referred to as metal dithiolate compounds or metal dithiolene compounds, such as nickel dithiolate compounds, cobalt dithiolate compounds, iron dithiolate compounds, zinc dithiolate compounds, molybdenum dithiolate compounds, palladium dithiolate compounds, platinum dithiolate compounds, etc.
  • a photoactive compound such as nickel dithiolate compounds, cobalt dithiolate compounds, iron dithiolate compounds, zinc dithiolate compounds, molybdenum di
  • each M is independently a metal, such as Fe, Co, Ni, Cu, Zn, Mo, Pd, or Pt.
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, or a substituted or unsubstituted alkoxy group.
  • each A is independently a fused polycyclic ring group having one or more R group substituents.
  • one or more R groups are each independently a methoxy group, a dimethyl amino group, a cyano group a thiazolyl group, a phenyl group, a maleimide group, a naphthyl group, or a phenanthrene group.
  • a visibly transparent photoactive compound having the formula: may be further characterized by the formula:
  • a visibly transparent photoactive compound having the formula: may be further characterized by the formula , where each A is independently a fused polycyclic ring group having one or more R group substituents.
  • the visibly transparent photoactive compound may have the formula
  • Example photoactive compounds described herein, useful as photoactive materials in a visibly transparent photovoltaic device include near-infrared absorbing donor-acceptor (near- IR DA) molecules, naphthalenetetracarboxylic diimides, bisimide coronenes, fluoranthenes, corannulenes, and derivatives thereof.
  • the UV acceptor-molecule is selected from the group consisting of a naphthalenetetracarboxylic diimide, a
  • the visibly transparent photoactive compound exhibits little or no visible absorption.
  • the visibly transparent photoactive compound may exhibit a first maximum visible absorption strength that is between 0.1% and 10% of a first maximum ultraviolet absorption strength of the acceptor material, such as about 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10%.
  • a first maximum visible absorption strength of the acceptor material such as about 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10%.
  • a naphthalenetetracarboxylic diimide has the formula
  • each X is independently F, CI, Br, alkyl, alkoxy, or aryl.
  • each subscript n is independently 0, 1, 2, 3, 4, or 5.
  • each Y is independently H, alkyl, unsubstituted aryl, or substituted aryl.
  • each ring marked "Ar" is an independently selected aryl group.
  • a bisimide coronene has the formula
  • each R is independently H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, or an electron-withdrawing group (e.g., CN, halogen, and the like).
  • an electron-withdrawing group e.g., CN, halogen, and the like.
  • a fluoranthene has the formula
  • the corannulene has a structure according to Formula VII as described herein.
  • R is H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, or heterocyclyl.
  • X and Y are independently H or an electron- withdrawing group (e.g., CN, halogen, and the like).
  • Zi and Z 2 are independently H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, or heterocyclyl.
  • naphthalenetetracarboxylic diimides, bisimide coronenes, fluoranthenes, and corannulenes described herein are generally employed as electron acceptor materials.
  • Example photoactive compounds described herein and useful for a photoactive layer in a visibly transparent photovoltaic device include those incorporating quinoidal structures, tetracyano quinoidal thiophene structures, tetracyano indacene structures, carbazole thiaporphyrin structures, and dithiophene squarine structures.
  • a photoactive compound provided herein has a formula
  • each n is 0, 1, 2, 3, 4, 5, 6, or 7.
  • each X is independently O, N-R, S, or Se.
  • each A is independently a fused or unfused aromatic or heteroaromatic group including one or more R group substituents.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • one or more R is a donor moiety.
  • one or more R is an acceptor moiety.
  • a visibly transparent photoactive compound such as a quinoidal compound has a quinoidal backbone structure.
  • Example quinoidal compounds or compounds including a quinoidal backbone include those having the formula: .
  • Example quinoidal compounds or compounds including a quindoidal backbone include tetracyano quinoidal thiophene compound having the formula:
  • photoactive compounds include those having the formula:
  • these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible. In some embodiments, these compounds may exhibit stronger maximum absorption strengths in the ultraviolet than maximum absorption strengths in the visible.
  • a visibly transparent photoactive compound such as a tetracyano indacene compound having the formula:
  • It w e apprec ate t at t ese compoun s may ex t stronger maximum absorption strengths in the ultraviolet than maximum absorption strengths in the visible. In some embodiments, these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • Example photoactive compounds described herein, useful in a photoactive layer of a visibly transparent photovoltaic cell include phthalocyanines and naphthalocyanines such as aluminum (Al)-containing phthalocyanines and naphthalocyanines, cobalt (Co)-containing phthalocyanines and naphthalocyanines, copper (Cu)-containing phthalocyanines and naphthalocyanines, iron (Fe)-containing phthalocyanines and naphthalocyanines, lead (Pb)- containing phthalocyanines and naphthalocyanines, magnesium (Mg)-containing phthalocyanines and naphthalocyanines.
  • phthalocyanines and naphthalocyanines such as aluminum (Al)-containing phthalocyanines and naphthalocyanines, cobalt (Co)-containing phthalocyanines and naphthalocyanines, copper (Cu)-containing phthalocyanines and naphthalocyanines, iron (Fe)
  • phthalocyanines and naphthalocyanines manganese (Mn)-containing phthalocyanines and naphthalocyanines, nickel (Ni)-containing phthalocyanines and naphthalocyanines, palladium (Pd)-containing phthalocyanines and naphthalocyanines, platinum (Pt)-containing
  • phthalocyanines and naphthalocyanines silicon (Si)-containing phthalocyanines and naphthalocyanines, tin (Sn)-containing phthalocyanines and naphthalocyanines, vanadium (V)-containing phthalocyanines and naphthalocyanines, zinc (Zn)-containing phthalocyanines and naphthalocyanines, and derivatives thereof.
  • a phthalocyanine compound has the formula
  • a naphthalocyanine has the formula
  • phthalocyanine has the formula , where M is a metal, and Ai, A 2 , A 3 , and
  • a 4 are each substituted or unsubstituted fused aromatic ring groups.
  • at least one of Ai A 2 , A3, or A 4 is of a different number of fused rings than at least one other of Ai, A 2 , A3, or A 4 .
  • Ai optionally includes a different number of fused rings from at least one of A 2 , A3, or A4.
  • phthalocyanines may exhibit non-symmetric structures, which may be useful for preventing the compounds from absorbing in the visible regtion, for example.
  • M is selected from Sn, SnCb, SnO, Pb, Mg, Mn, AlCl, AIOH, GaCl, MnCl, SiCb, Si(OH) 2 , PbCb, VO, Co, Fe, FeCl, Ni, TiO, and TiCh.
  • each M independently comprises a metal, such as Cu, Co, Ni, Zn, Mg, C1A1, SnCb, Pb, Pt, or Pd.
  • each Ri to R 2 4 is independently H, F, CI, phenyl, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl, or an electron withdrawing group (e.g., an electronegative organic ligand or other electronegative substituent).
  • subscripts m, n, o, and p are independently integers 1 to 5.
  • each X and each Y is
  • each X is independently selected from the group consisting of O, S, Se, and Te.
  • electron withdrawing groups include, but are not limited to, sulfonyl groups (e.g., tosyl, triflyl, mesyl, and the like), haloalkyl groups (e.g., trifluorom ethyl,
  • visibly transparent photoactive compounds are provided, which may be useful, for example, as photoactive materials in a photoactive layer of a visibly transparent photovoltaic device.
  • a photoactive compound of this aspect may have the formula: , where each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group, and each X is independently S, N, or C— R.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • one or more R groups are independently H, CH 3 , F, CI, CN, OCH 3 , C(CH 3 ) 3 , or Ar— R, where Ar is an aromatic or heteroaromatic group, and where Ar— R corresponds to the aromatic or heteroaromatic group having one or more R group substituents.
  • one or more R groups are independently a thiazolyl group, a phenyl group, a pyridinyl group, an imidazolyl group, a pyrrolyl group, a thiophenyl group, a naphthyl group, a pyrenyl group, an indolyl group, a benzothiophenyl group, a benzimidazolyl group, or a benzothiazolyl group.
  • two or more R groups form an unfused aromatic or heteroaromatic group or two or more R groups form a fused aromatic or heteroaromatic group. It will be appreciated that these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • a photoactive compound of this aspect may have the formula:
  • a photoactive compound may have the formula:
  • Specific visibly transparent photoactive compounds include those having the formula:
  • these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • a photoactive compound of this aspect may alternatively have the formula:
  • each L group is independently a single bond or a bivalent linking group selected from a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group
  • each X is independently S, N, or C— R.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • one or more R groups are independently H, CH 3 , F, CI, CN, OCH 3 , C(CH 3 ) 3 , or Ar— R, where Ar is an aromatic or heteroaromatic group, and where Ar— R corresponds to the aromatic or heteroaromatic group having one or more R group substituents.
  • one or more R groups are
  • two or more R groups form an unfused aromatic or heteroaromatic group or wherein two or more R groups form a fused aromatic or heteroaromatic group. It will be appreciated that these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • a photoactive compound of this aspect may have the formula:
  • each Ar is independently an aromatic or heteroaromatic group having one or more R group substituents.
  • a photoactive compound has the formula: Again, it will be appreciated that these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • a photoactive compound of this aspect may alternatively have the formula:
  • each A2 is independently a fused or unfused aromatic or heteroaromatic group including one or more R group substituents
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group, or wherein two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • Al comprises a 5-membered or 6-membered aromatic or heteroaromatic ring including one or more R group substituents.
  • Al comprises an unsubstituted or R substituted ring group including one or more of a thiazole ring, a benzene ring, a pyridine ring, a imidazole ring, a pyrrole ring, a thiophene ring, a naphthalene, a pyrene, an indole, a benzothiophene, a benzimidazole, a benzothiazole, or a triazine ring.
  • each A2 comprises a 5-membered or 6-membered aromatic or heteroaromatic ring including one or more R group substituents.
  • each A2 comprises an unsubstituted or R substituted ring group including one or more of a thiazole ring, a benzene ring, a pyridine ring, a imidazole ring, a pyrrole ring, a thiophene ring, a naphthalene, a pyrene, an indole, a benzothiophene, a benzimidazole, a benzothiazole, or a triazine ring.
  • one or more R groups are independently H, CH 3 , F, CI, CN, OCH 3 , C(CH 3 ) 3 , or Ar— R, where Ar is an aromatic or heteroaromatic group, and where Ar— R corresponds to the aromatic or heteroaromatic group having one or more R group substituents.
  • one or more R groups are independently a thiazolyl group, a phenyl group, a pyridinyl group, an imidazolyl group, a pyrrolyl group, a thiophenyl group, a naphthyl group, a pyrenyl group, an indolyl group, a benzothiophenyl group, a benzimidazolyl group, or a benzothiazolyl group.
  • two or more R groups form an unfused aromatic or heteroaromatic group or wherein two or more R groups form a fused aromatic or heteroaromatic group. It will be appreciated that these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • a photoactive compound of this aspect may have the formula:
  • photoactive compounds include those having the formula:
  • a photoactive compound of this aspect may alternatively have the formula:
  • each A2 is independently a fused or unfused aromatic or heteroaromatic group including one or more R group substituents
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • Al comprises a 5-membered or 6-membered aromatic or heteroaromatic ring including one or more R group substituents.
  • Al comprises fused 5- membered or 6-membered aromatic or heteroaromatic rings including one or more R group substituents.
  • each A2 comprises a 5-membered or 6-membered aromatic or heteroaromatic ring including one or more R group substituents.
  • each A2 comprises an unsubstituted or R substituted ring group including one or more of a thiazole ring, a benzene ring, a pyridine ring, a imidazole ring, a pyrrole ring, a thiophene ring, a naphthalene, a pyrene, an indole, a benzothiophene, a benzimidazole, or a benzothiazole.
  • a thiazole ring including one or more of a thiazole ring, a benzene ring, a pyridine ring, a imidazole ring, a pyrrole ring, a thiophene ring, a naphthalene, a pyrene, an indole, a benzothiophene, a benzimidazole, or a benzothiazole.
  • one or more R groups are independently H, CH 3 , F, CI, CN, OCH 3 , C(CH 3 ) 3 , or Ar— R, where Ar is an aromatic or heteroaromatic group, and where Ar— R corresponds to the aromatic or heteroaromatic group having one or more R group substituents.
  • one or more R groups are independently a thiazolyl group, a phenyl group, a pyridinyl group, an imidazolyl group, a pyrrolyl group, a thiophenyl group, a naphthyl group, a pyrenyl group, an indolyl group, a benzothiophenyl group, a benzimidazolyl group, or a benzothiazolyl group.
  • two or more R groups form an unfused aromatic or heteroaromatic group or wherein two or more R groups form a fused aromatic or heteroaromatic group. It will be appreciated that these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • a photoactive compound of this aspect may have the formula: , where each A3 is independently an aromatic or heteroaromatic group including one or more R group substituents.
  • Photoactive compounds of this aspect may further be characterized by the formula:
  • photoactive compounds include those, having the formula:
  • these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • Another photoactive compound of this aspect may have the formula: , where M is a metal, each A is independently a fused polycyclic ring group having one or more R group substituents, and each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, or a substituted or unsubstituted alkoxy group.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • M is Fe, Co, Ni, Cu, Zn, Mo, Pd, or Pt.
  • one or more R groups are each independently a methoxy group, a phenyl group, a dimethyl amino group, a cyano group a thiazolyl group, or a phenyl group.
  • A includes a thiazolyl group, a phenyl group, a maleimide group, a naphthyl group, an acenaphthalene group, or a phenanthrene group. It will be appreciated that these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • a photoactive compound of this aspect may have the formula:
  • a compound of this aspect has the formula:
  • photoactive compounds include those having the formula:
  • a photoactive compound of this aspect may alternatively have the formula:
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, or a substituted or unsubstituted alkoxy group, or wherein two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • one or more R groups are independently a methoxy group, a phenyl group, a dimethyl amino group, a cyano group a thiazolyl group, or a phenyl group. It will be appreciated that these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • a photoactive compound of this aspect may have the formula:
  • a photoactive compound has the formula
  • photoactive compounds include those having the formula:
  • these compounds may exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • visibly transparent photoactive compounds are provided, which may be useful, for example, as photoactive materials in a photoactive layer of a visibly transparent photovoltaic device.
  • a photoactive compound of this aspect may have the formula:
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group
  • n is 0, 1, 2, 3, 4, 5, 6, or 7, and each X is independently O, N-R, S, or Se.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • one or more R groups are independently H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heteroaromatic group. It will be appreciated that these compounds may exhibit a maximum near-infrared or ultraviolet absorption strength and a maximum visible absorption strength, such as a maximum near- infrared or ultraviolet absorption strength that is greater than the maximum visible absorption strength.
  • a photoactive compound of this aspect may have the formula:
  • a photoactive compound of this aspect has the formula:
  • e compounds include those having the formula
  • these compounds may be visibly transparent and exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • a photoactive compound of this aspect may alternatively have the formula:
  • each A is independently a fused or unfused aromatic or heteroaromatic group including one or more R group substituents
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • A is independently a benzene ring or a thiophene ring.
  • one or more R groups are independently H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heteroaromatic group. It will be appreciated that these compounds may exhibit a maximum near-infrared or ultraviolet absorption strength and a maximum visible absorption strength, such as a maximum near-infrared or ultraviolet absorption strength that is greater than the maximum visible absorption strength.
  • a photoactive compound of this aspect may have the formula:
  • these compounds may be visibly transparent and exhibit stronger maximum absorption strengths in the near-infrared than maximum absorption strengths in the visible.
  • a photoactive compound of this aspect may alternatively have the formula:
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • one or more R groups are H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heteroaromatic group.
  • one or more R groups are a tertiary butyl group. It will be appreciated that these compounds may exhibit a maximum near-infrared or ultraviolet absorption strength and a maximum visible absorption strength, such as a maximum near- infrared or ultraviolet absorption strength that is greater than the maximum visible absorption strength.
  • a compound of this aspect may have the formula:
  • a specific example photoactive compound includes the compound having the formula:
  • R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • one or more R groups are H, a substituted or unsubstituted C1-C6 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted aromatic group, or a substituted or unsubstituted heteroaromatic group.
  • these compounds may exhibit a maximum near-infrared or ultraviolet absorption strength and a maximum visible absorption strength, such as a maximum near-infrared or ultraviolet absorption strength that is greater than the maximum visible absorption strength.
  • a photoactive compound of this aspect may have the formula:
  • the disclosed photoactive compounds exhibit greater maximum or peak near-infrared or ultraviolet absorption strength than the maximum or peak visible absorption strength.
  • the disclosed photoactive compounds exhibit an integrated near-infrared or ultraviolet absorption coefficient that is great than an integrated visible absorption coefficient.
  • some embodiments of the disclosed photoactive compounds exhibit peak absorption outside a visible wavelength band (450 nm to 650 nm), such as in the near-infrared wavelength band (650 nm to 1400 nm) or in the ultraviolet wavelength band (200 nm to 450 nm).
  • the disclosed photoactive compounds may exhibit visible transparency and advantageously be useful for incorporation in visibly transparent photovoltaic devices.
  • a visible transmittance of 30% or absorption of 70% may be desirable for some applications.
  • a visible transmittance of 100% or absorption of 0% may be desirable for some applications.
  • a visibly transparent photovoltaic cell may absorb some visible light as well as near-infrared and/or ultraviolet light for purposes of photovoltaic generation (or incidental absorption), and still meet a target visible transparency level.
  • visible transparency refers to a character of a material that exhibits an overall absorption, average absorption, or maximum absorption in the visible band of 0%-70%, such as less than or about 70%, less than or about 65%, less than or about 60%, less than or about 55%, less than or about 50%, less than or about 45%, less than or about 40%, less than or about 35%, less than or about 30%), less than or about 25%, or less than or about 20%.
  • visibly transparent materials may transmit 30%-100% of incident visible light, such as greater than or about 80% of incident visible light, greater than or about 75% of incident visible light, greater than or about 70% of incident visible light, greater than or about 65% of incident visible light, greater than or about 60% of incident visible light, greater than or about 55% of incident visible light, greater than or about 50% of incident visible light, greater than or about 45%) of incident visible light, greater than or about 40% of incident visible light, greater than or about 35% of incident visible light, or greater than or about 30% of incident visible light. Visibly transparent materials are generally considered at least partially see-through (i.e., not completely opaque) when viewed by a human.
  • visibly transparent materials may be colorless (i.e., not exhibit strong visible absorption features that would provide an appearance of a particular color) when viewed by a human.
  • R-group substitutions are generally contemplated herein.
  • one or more R groups are independently H, CH 3 , F, CI, CN, OCH 3 , C(CH 3 ) 3 , or Ar— R, wherein Ar is an aromatic or heteroaromatic group, and wherein Ar— R corresponds to the aromatic or heteroaromatic group having one or more R group substituents.
  • one or more R groups are independently a thiazolyl group, a phenyl group, a pyridinyl group, an imidazolyl group, a pyrrolyl group, a thiophenyl group, a naphthyl group, a pyrenyl group, an indolyl group, a benzothiophenyl group, a
  • the disclosed photoactive compounds and materials are useful in visibly transparent photovoltaic devices, such as a visibly transparent photovoltaic device that comprises a visibly transparent substrate; a first visibly transparent electrode coupled to the visibly transparent substrate; a first visibly transparent active layer coupled to the first visibly transparent electrode, such as a first visibly transparent photoactive layer that comprises a photoactive compound described herein exhibiting a greater maximum near-infrared absorption strength than maximum visible absorption strength; a second visibly transparent photoactive layer coupled to the first visibly transparent photoactive layer and exhibiting greater maximum ultraviolet absorption strength or maximum near-infrared absorption strength than maximum visible absorption strength; and a second visibly transparent electrode coupled to the second visibly transparent photoactive layer.
  • a visibly transparent photovoltaic device that comprises a visibly transparent substrate; a first visibly transparent electrode coupled to the visibly transparent substrate; a first visibly transparent active layer coupled to the first visibly transparent electrode, such as a first visibly transparent photoactive layer that comprises a photoactive compound described herein
  • the photoactive compounds described herein may be useful as electron donor materials or electron acceptor materials.
  • the second visibly transparent photoactive layer may include a second photoactive compound which may be useful as the opposite material, such as an electron acceptor material when the photoactive material of the first visibly transparent photoactive layer is an electron donor material or as an electron donor material when the photoactive material of the first visibly transparent photoactive layer is an electron acceptor material.
  • the photoactive compounds used in a photoactive layer may have any suitable concentration.
  • a photoactive compound is present as a layer of substantially pure form.
  • photoactive layers may be present as mixed forms, such as where multiple photoactive compounds are present, such as an electron acceptor material and an electron donor material.
  • Different photoactive materials may have any suitable concentration or concentration ratios to achieve photovoltaic generation in the devices described herein.
  • the first and second visibly transparent photoactive layers independently have thicknesses of about 1 nm to about 300 nm.
  • the first visibly transparent photoactive layer and the second visibly transparent photoactive layer correspond to separate, mixed, or partially mixed layers.
  • the other layers used in the visibly transparent photovoltaic devices may exhibit suitable compositions and properties for operation of the transparent photovoltaic device.
  • various visibly transparent substrates may be suitable, such as those composing transparent glasses, transparent polymers, etc.
  • the visibly transparent substrate may be transparent to near-infrared light (i.e., light with a wavelength greater than 650 nm) and/or ultraviolet light (i.e., light with a wavelength less than 450 nm). In this way, the visibly transparent substrate may not absorb near-infrared and/or ultraviolet light that would be suitable for photovoltaic energy generation by the visibly transparent photovoltaic devices. In some embodiments, however, the visibly transparent substrate may absorb infrared and/or ultraviolet light, which may be useful, for example, for configurations where the visibly transparent substrate serves to block excess infrared or ultraviolet radiation incident radiation after passing through the photoactive layer(s) to prevent or reduce overall ultraviolet and/or infrared transmission.
  • near-infrared light i.e., light with a wavelength greater than 650 nm
  • ultraviolet light i.e., light with a wavelength less than 450 nm
  • the visibly transparent substrate may absorb infrared and/or ultraviolet light, which may be
  • Useful visibly transparent substrates include, but are not limited to, those having thicknesses of about 50 nm to about 30 mm.
  • Example visibly transparent electrodes include those comprising indium tin oxide or thin transparent films of conductive elements, such as copper, gold, silver, aluminum, etc. In cases where the visibly transparent electrodes comprise conductive elements, the thickness may be such that even though the conductive element may be opaque in the bulk, when used as a thin film the conductive element may still allow for transmission of visible light.
  • Useful visibly transparent electrodes include, but are not limited to, those having thicknesses of about 1 nm to about 500 nm.
  • a visibly transparent photovoltaic device may optionally comprise one or more buffer layers, such as a first a first buffer layer disposed between the first visibly transparent electrode and the first visibly transparent photoactive layer and/or a second buffer layer disposed between the second visibly transparent photoactive layer and the second visibly transparent electrode.
  • Useful buffer layers may serve a variety of purposes and include various compositions.
  • a buffer layer may comprise a photoactive material or compound described herein.
  • useful buffer layers have thicknesses of about 1 nm to about 500 nm.
  • a method of this aspect comprises providing a transparent substrate; optionally forming one or more optical layers on the transparent substrate; forming a first transparent electrode; optionally forming a first buffer layer on the first transparent electrode; forming one or more photoactive layers, such as including a photoactive compound described herein; optionally forming a second buffer layer; forming a second transparent electrode; and optionally forming one or more optical layers on the second transparent electrode.
  • one or more buffer layers include a photoactive compound described herein.
  • forming one or more layers may include making a photoactive compound and depositing the photoactive compound. Examples of making various photoactive compounds provided herein are described below.
  • the photoactive layers may be provided as separate or mixed layers including electron acceptor and electron donor materials.
  • Different optical layers may be used, for example, such as index matching layers, antireflection layers, etc.
  • Various techniques may be useful for forming one or more layers, including vacuum deposition techniques and solution deposition techniques. In one embodiment, thermal evaporation is used for depositing a photoactive compound as part of a photoactive layer. It will be appreciated that various patterning techniques may be useful in methods of making a visibly transparent photovoltaic device.
  • visibly transparent electrodes may be optionally patterned
  • visibly active photoactive layers may be optionally patterned
  • buffer layers may be optionally patterned
  • optical layers may be patterned
  • Suitable patterning techniques may include, are not limited to, patterning techniques involving lithography, masking, lift-off, etching, etc.
  • FIG. 1 A is a simplified schematic diagram illustrating a visibly transparent photovoltaic device according to an embodiment of the present invention.
  • FIG. IB provides an overview of various configurations of photoactive layer(s) in visibly transparent photovoltaic devices according to embodiments of the present invention.
  • FIG. 2 is simplified plot illustrating the solar spectrum, human eye sensitivity, and exemplary transparent photovoltaic device absorption as a function of wavelength.
  • FIG. 3 is a simplified energy level diagram for a visibly transparent photovoltaic device according to an embodiment of the present invention.
  • FIG. 4A, FIG. 4B, FIG. 4C, and FIG. 4D provide plots showing example absorption profiles for different electron acceptor and donor configurations, which can comprise the photoactive layers.
  • FIG. 5 provides an overview of a method of making visibly transparent photovoltaic devices according to embodiments of the present invention.
  • FIG. 6 provides a plot showing general absorption characteristics
  • FIG. 7 A provides an overview of an example synthetic route for formation of visibly transparent photoactive compounds.
  • FIG. 7B provides an overview of an example synthetic route for formation of visibly transparent photoactive compounds.
  • FIG. 8 provides data showing normalized absorbance spectra of different visibly transparent photoactive compounds in solution.
  • FIG. 9 provides data showing example current density as a function of voltage for an example photovoltaic cell.
  • FIG. 10 provides an overview of an example synthetic route for formation of visibly transparent photoactive compounds.
  • FIG. 11 provides an overview of an example synthetic route for formation of visibly transparent photoactive compounds.
  • FIG. 12 provides data showing normalized absorbance spectra of different visibly transparent photoactive compounds in solution.
  • FIG. 13 provides an overview of example synthetic routes for formation of visibly transparent photoactive compounds.
  • FIG. 14 provides data showing normalized absorbance spectra of different visibly transparent photoactive compounds in solution.
  • FIG. 15 provides data showing example current density as a function of voltage for an example photovoltaic cell.
  • FIG. 16 provides an overview of example synthetic routes for formation of visibly transparent photoactive compounds.
  • FIG. 17 provides an overview of example synthetic routes for formation of visibly transparent photoactive compounds.
  • FIG. 18 provides an overview of example synthetic routes for formation of visibly transparent photoactive compounds.
  • FIG. 19 provides an overview of example synthetic routes for formation of visibly transparent photoactive compounds.
  • FIG. 20 provides an overview of example synthetic routes for formation of visibly transparent photoactive compounds.
  • FIG. 21 provides an overview of example synthetic routes for formation of visibly transparent photoactive compounds.
  • FIG. 22 provides data showing normalized absorbance spectra of different visibly transparent photoactive compounds in solution.
  • FIG. 23 shows examples of synthetic routes for formation of symmetric DiCN compounds.
  • FIG. 24 shows examples of synthetic routes for formation of asymmetric DiCN compounds.
  • FIG. 25 shows examples of synthetic routes for formation of DiCN-IDDT compounds.
  • FIG. 26 shows an example of a synthetic route for formation of DiCN-DTCz compounds.
  • FIG. 27 shows an example of a synthetic route for formation of DiCN-BODIPY compounds.
  • FIG. 28 shows an example of a synthetic route for formation of DiCN-SC compounds.
  • FIG. 29 shows the spectral properties of DiCN compounds.
  • FIG. 30 show the spectral properties of DiCN and D1CN-SO2 compounds.
  • FIG. 31 provides data showing example current density as a function of voltage for an example photovoltaic cell containing asymmetric DiCN acceptor A- 16 and a CuPc donor.
  • FIG. 32 shows an example of synthetic route for the preparation of benzo-bis- thiadiazole (BBT) compounds.
  • FIG. 33 shows an example absorbance spectrum for a photoactive compound.
  • FIG. 34A provides an overview of an example synthetic route for formation of visibly transparent photoactive compounds.
  • FIG. 34B provides an overview of an example synthetic route for formation of visibly transparent photoactive compounds.
  • FIG. 35 provides data showing normalized absorbance spectra of different visibly transparent photoactive compounds in solution.
  • FIG. 36 provides data showing example current density as a function of voltage for an example photovoltaic cell.
  • FIG. 37 provides data showing example current density as a function of voltage for an example photovoltaic cell.
  • FIG. 38 shows an example of a synthetic route for formation of naphthalene- tetracarboxylic diimide (NTCDI) compounds.
  • FIG. 39 shows the spectral properties of NTCDI compound E-1.
  • FIG. 40A provides data showing example current density as a function of voltage for an example photovoltaic cell containing NTCDI acceptor E-1 and a ClAlPc donor.
  • FIG. 40B provides data showing example current density as a function of voltage for an example photovoltaic cell having a cathode buffer layer containing NTCDI compound E-1.
  • FIG. 41 shows examples of synthetic routes for formation of bisimide coronene (CBI) compounds.
  • FIG. 42A shows an example of a synthetic route for formation of fluoranthene derivatives.
  • FIG. 42B shows an example of a synthetic route for formation of fluoranthene derivatives.
  • FIG. 43 provides data showing example current density as a function of voltage for an example photovoltaic cell having fluoranthene as an acceptor with SubPc donor.
  • FIG. 44 shows an example of a synthetic route for formation of corranulene derivatives.
  • FIG. 45 provides an overview of an example synthetic route for formation of visibly transparent photoactive compounds.
  • FIG. 46 provides data showing a normalized absorbance spectrum of an example visibly transparent photoactive compound.
  • FIG. 47 provides an overview of example synthetic routes for formation of visibly transparent photoactive compounds.
  • FIG. 48 provides an overview of an example synthetic route for formation of visibly transparent photoactive compounds.
  • FIG. 49 provides data showing an absorbance spectrum of an example visibly transparent photoactive compound.
  • FIG. 50 provides an overview of an example synthetic route for formation of visibly transparent photoactive compounds.
  • FIG. 51 illustrates absorption of UV/NIR by SnPc, SnNcCh, and SnPcCh.
  • FIG. 52 compares the external quantum efficiency of devices using SnNcCb as a NIR absorbing donor material with devices using ClAlPc, an archetypical donor material used in transparent PVs.
  • FIG. 53 compare the current voltage performance of devices using SnNcCb as a NIR absorbing donor material with devices using ClAlPc, an archetypical donor material used in transparent PVs.
  • FIG. 54 compares the energy levels of materials used in devices using SnNcCb as a NIR absorbing donor material with devices using ClAlPc, an archetypical donor material used in transparent PVs.
  • FIG. 55 shows the performance for exemplary devices using SnPcCb as a NIR acceptor.
  • FIG. 56 illustrates the current-voltage performance of transparent PVs using SnNcCb and SnPcCb as the donor and acceptor materials, respectively.
  • FIG. 57 illustrates the external quantum efficiency performance of transparent PVs using SnNcCb and SnPcCb as the donor and acceptor materials, respectively.
  • FIG. 58 shows examples of synthetic routes for preparation of phthalocyanine compounds.
  • FIG. 59 shows examples of synthetic routes for preparation of phthalocyanine compounds.
  • FIG. 60A shows the spectral properties of phthalocyanine J-14.
  • FIG. 60B shows the spectral properties of phthalocyanine J-3.
  • FIG. 61 shows a comparison of the spectral properties of phthalocyanine J-l, phthalocyanine J-2, and phthalocyanine J-3.
  • the present disclosure relates to visibly transparent photoactive compounds and visibly transparent photovoltaic devices incorporating visibly transparent photoactive compounds.
  • the visibly transparent photoactive compounds absorb light more strongly in the near-infrared region or the ultraviolet region and less strongly in the visible region, permitting their use in visibly transparent photovoltaic devices.
  • the disclosed visibly transparent photovoltaic devices include visibly transparent electrodes with visibly transparent photoactive materials positioned between the visibly transparent electrodes.
  • the disclosed visibly transparent photoactive compounds include boron
  • dipyrromethene based photoactive compounds such as diamino difluoro boron-based organic dyes, and related diamino dioxygen boron-based organic dyes.
  • Example visibly transparent photoactive compounds include a fluorinated or oxygenated boron core in a ring structure including boron-nitrogen bonds.
  • the disclosed photoactive compounds share a
  • a nitrogen atom may exhibit zero charge or a negative charge.
  • other substructures of the visibly transparent photoactive compounds may be organic or heterorganic in nature.
  • visibly transparent compounds may include aromatic or heteroaromatic species, cyclic or heterocyclic species, each of which may be functionalized in order to achieve suitable optical and/or physical properties.
  • the disclosed visibly transparent photoactive compounds include near-IR DA molecules, such as dicyano-indandiones, benzo-fos-thiadiazoles, diketopyrrolopyrrole diphenylthienylamines, and derivatives thereof, which may be functionalized in order to achieve suitable optical and/or physical properties.
  • the disclosed visibly transparent photoactive compounds include metal dithiolate dyes.
  • Example visibly transparent photoactive compounds include metal dithiolate complexes including organic or heterorganic substituents that may be functionalized to modulate the absorption by the compounds.
  • the disclosed photoactive photoactive compounds include near-IR DA molecules, such as dicyano-indandiones, benzo-fos-thiadiazoles, diketopyrrolopyrrole diphenylthienylamines, and derivatives thereof, which may be functionalized in order to achieve suitable optical and/or physical properties.
  • the disclosed visibly transparent photoactive compounds include metal dithiolate dyes.
  • visibly transparent photoactive compounds share a common structural features of , where the wavy lines represent positions at which the structure is connected to another part of the compound, which may be parts of the same compound (i.e., a ring or fused ring structure) or different substructures.
  • other substructures of the visibly transparent photoactive compounds may be organic or heterorganic in nature.
  • visibly transparent compounds may include aromatic or heteroaromatic species, cyclic or heterocyclic species, each of which may be functionalized in order to achieve suitable optical and/or physical properties.
  • the disclosed visibly transparent photoactive compounds include UV acceptor molecules, such as naphthalenetetetracarboxylic diimides, bisimide coronenes, fluoranthenes, and corannulenes, which may be functionalized in order to achieve suitable optical and/or physical properties.
  • UV acceptor molecules such as naphthalenetetetracarboxylic diimides, bisimide coronenes, fluoranthenes, and corannulenes, which may be functionalized in order to achieve suitable optical and/or physical properties.
  • the disclosed visibly transparent photoactive compounds include tetracyano quinoidal thiophene compounds, tetracyano indacene compounds, carbazole thiaporphyrin compounds, and dithiophene squarine compounds.
  • Example visibly transparent photoactive compounds may be functionalized to modulate absorption by the compounds.
  • the disclosed photoactive compounds include dicyano methylene groups, NC ⁇ CN which may be represented as ? where the wavy line represents a position at which the structure is connected to another part of the compound.
  • the disclosed photoactive compounds may include two dicyano methylene groups and be referred to as a tetracyano compound.
  • the disclosed photoactive compounds may include a conjugated structure or fused aromatic or heteroaromatic rings.
  • other substructures of the visibly transparent photoactive compounds may be organic or heterorganic in nature.
  • visibly transparent compounds may include aromatic or heteroaromatic species, cyclic or heterocyclic species, each of which may be functionalized in order to achieve suitable optical and/or physical properties.
  • the disclosed visibly transparent photoactive compounds include phthalocyanines, such as those containing Al, Co, Cu, Fe, Pb, Mg, Mn, Ni, Pd, Pt, Si, Sn, V, Zn, and the like, which may be functionalized in order to achieve suitable optical and/or physical properties.
  • a very high molecular weight e.g., about 500 amu or higher, about 550 amu or higher, about 600 amu or higher, about 650 amu or higher, about 700 amu or higher, about 750 amu or higher, about 800 amu or higher, or between 500 amu and 2000 amu
  • compounds with very high molecular weights may have limited volatilities, and methods of making and purifying visibly transparent photoactive compounds may employ an evaporation or sublimation-based purification method.
  • the visibly transparent photoactive compounds may be deposited into a visibly transparent photovoltaic device using a thermal evaporation technique and compounds of very high molecular weight may be difficult to deposit using thermal evaporation.
  • the visibly transparent photoactive compounds described herein have a molecular weight of 200 amu to 700 amu, less than or about 700 amu, less than or about 650 amu, less than or about 600 amu, less than or about 550 amu, less than or about 500 amu, less than or about 450 amu, less than or about 400 amu, less than or about 350 amu, less than or about 300 amu, less than or about 250 amu, or less than or about 200 amu.
  • visibly transparent photoactive compounds may exhibit a molecular electronic structure where photons of near-infrared light are absorbed, which results in promotion of an electron to a higher molecular orbital, with an energy difference matching that of the absorbed photon.
  • Compounds exhibiting extended aromaticity or extended conjugation are beneficial, as compounds with extended aromaticity or extended conjugation may exhibit electronic absorption with energies matching that of near-infrared and/or ultraviolet photons. In some cases, however, extended aromaticity or extended conjugation may result in absorption in the visible band (i.e., between about 450 nm and about 650 nm).
  • absorption features may be modulated by inclusion of heteroatoms in the organic structure of the visibly transparent photoactive compounds, such as nitrogen or sulfur atoms. Additionally or alternatively, absorption features may be modulated by the presence and positions of electron donating or electron withdrawing groups, such as halogen atoms, alkyl groups, alkoxy groups, etc.
  • absorption features may optionally be modulated by the presence of electron donor groups or electron acceptor group within a photoactive compound.
  • maximum absorption strength refers to the largest absorption value in a particular spectral region, such as the ultraviolet band (200 nm to 450 nm or 280 nm to 450 nm), the visible band (450 nm to 650 nm), or the near-infrared band (650 nm to 1400 nm).
  • a maximum absorption strength may correspond to an absorption strength of an absorption feature that is a local or absolute maximum, such as an absorption band or peak, and may be referred to as a peak absorption.
  • a maximum absorption strength in a particular band may not correspond to a local or absolute maximum but may instead correspond to the largest absorption value in the particular band.
  • Such a configuration may occur, for example, when an absorption feature spans multiple bands (e.g. visible and near-infrared), and the absorption values from the absorption feature that occur within the visible band are smaller than those occurring within the near-infrared band, such as when the peak of the absorption feature is located within the near-infrared band but a tail of the absorption feature extends to the visible band.
  • a visibly transparent photoactive compound described herein may having an absorption peak at a wavelength greater than about 650 nanometers (i.e., in the near-infrared), and the visibly transparent photoactive material's absorption peak may be greater than the visibly transparent photoactive material's absorption at any wavelength between about 450 and 650 nanometers.
  • compositions or compounds are isolated or purified.
  • an isolated or purified compound is at least partially isolated or purified as would be understood in the art.
  • a disclosed composition or compound has a chemical purity of 90%, optionally for some applications 95%, optionally for some applications 99%, optionally for some applications 99.9%, optionally for some applications 99.99%), and optionally for some applications 99.999%) pure.
  • Compounds disclosed herein optionally contain one or more ionizable groups.
  • Ionizable groups include groups from which a proton can be removed (e.g., -COOH) or added (e.g., amines) and groups which can be quaternized (e.g., amines). All possible ionic forms of such molecules and salts thereof are intended to be included individually in the disclosure herein.
  • salts of the compounds described herein it will be appreciated that a wide variety of available counter-ions may be selected that are appropriate for preparation of salts of this invention for a given application. In specific applications, the selection of a given anion or cation for preparation of a salt can result in increased or decreased solubility of that salt.
  • the disclosed compounds optionally contain one or more chiral centers.
  • this disclosure includes racemic mixtures, diasteromers, enantiomers, tautomers and mixtures enriched in one or more stereoisomer.
  • Disclosed compounds including chiral centers encompass the racemic forms of the compound as well as the individual enantiomers and non-racemic mixtures thereof.
  • group and “moiety” may refer to a functional group of a chemical compound.
  • Groups of the disclosed compounds refer to an atom or a collection of atoms that are a part of the compound.
  • Groups of the disclosed compounds may be attached to other atoms of the compound via one or more covalent bonds.
  • Groups may also be characterized with respect to their valence state.
  • the present disclosure includes groups characterized as monovalent, divalent, trivalent, etc. valence states.
  • substituteduent may be used interchangeably with the terms "group” and "moiety.”
  • alkylene and alkylene group are used synonymously and refer to a divalent group derived from an alkyl group as defined herein.
  • the present disclosure includes compounds having one or more alkylene groups. Alkylene groups in some compounds function as attaching and/or spacer groups. Disclosed compounds optionally include substituted and/or unsubstituted C1-C20 alkylene, C1-C10 alkylene and Ci- C5 alkylene groups.
  • cycloalkylene and cycloalkylene group are used synonymously and refer to a divalent group derived from a cycloalkyl group as defined herein.
  • the present disclosure includes compounds having one or more cycloalkylene groups. Cycloalkyl groups in some compounds function as attaching and/or spacer groups. Disclosed compounds optionally include substituted and/or unsubstituted C3-C20
  • cycloalkylene C3-C10 cycloalkylene and C3-C5 cycloalkylene groups.
  • arylene and “arylene group” are used synonymously and refer to a divalent group derived from an aryl group as defined herein.
  • the present disclosure includes compounds having one or more arylene groups.
  • an arylene is a divalent group derived from an aryl group by removal of hydrogen atoms from two intra-ring carbon atoms of an aromatic ring of the aryl group.
  • Arylene groups in some compounds function as attaching and/or spacer groups.
  • Arylene groups in some compounds function as chromophore, fluorophore, aromatic antenna, dye and/or imaging groups.
  • Disclosed compounds optionally include substituted and/or unsubstituted C3-C30 arylene, C3- C20 arylene, C3-C10 arylene and C1-C5 arylene groups.
  • heteroarylene and “heteroarylene group” are used synonymously and refer to a divalent group derived from a heteroaryl group as defined herein.
  • the present disclosure includes compounds having one or more heteroarylene groups.
  • a heteroarylene is a divalent group derived from a heteroaryl group by removal of hydrogen atoms from two intra-ring carbon atoms or intra-ring nitrogen atoms of a heteroaromatic or aromatic ring of the heteroaryl group.
  • Heteroarylene groups in some compounds function as attaching and/or spacer groups. Heteroarylene groups in some compounds function as chromophore, aromatic antenna, fluorophore, dye and/or imaging groups. Disclosed compounds optionally include substituted and/or unsubstituted C3-C30 heteroarylene, C3-C20 heteroarylene, C1-C10 heteroarylene and C3-C5 heteroarylene groups.
  • alkenylene and “alkenylene group” are used
  • the present disclosure includes compounds having one or more alkenylene groups.
  • Alkenylene groups in some compounds function as attaching and/or spacer groups.
  • Disclosed compounds optionally include substituted and/or unsubstituted C2-C20 alkenylene, C2-C10 alkenylene and C2-C5 alkenylene groups.
  • cylcoalkenylene and “cylcoalkenylene group” are used synonymously and refer to a divalent group derived from a cylcoalkenyl group as defined herein.
  • the present disclosure includes compounds having one or more cylcoalkenylene groups. Cycloalkenylene groups in some compounds function as attaching and/or spacer groups. Disclosed compounds optionally include substituted and/or unsubstituted C3-C20 cylcoalkenylene, C3-C10 cylcoalkenylene and C3-C5 cylcoalkenylene groups.
  • alkynylene and “alkynylene group” are used
  • the present disclosure includes compounds having one or more alkynylene groups.
  • Alkynylene groups in some compounds function as attaching and/or spacer groups.
  • Disclosed compounds optionally include substituted and/or unsubstituted C2-C20 alkynylene, C2-C10 alkynylene and C2-C5 alkynylene groups.
  • halo refers to a halogen group, such as a fluoro (-F), chloro (-C1), bromo (-Br), or iodo (-1).
  • heterocyclic refers to ring structures containing at least one other kind of atom, in addition to carbon, in the ring.
  • examples of such atoms include sulfur, selenium, tellurium, nitrogen, phosphorus, silicon, germanium, boron, aluminum, and a transition metal.
  • heterocyclic rings include, but are not limited to, pyrrolidinyl, piperidyl, imidazolidinyl, tetrahydrofuryl, tetrahydrothienyl, furyl, thienyl, pyridyl, quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridinyl, benzoxadiazolyl, benzothiadiazolyl, triazolyl and tetrazolyl groups.
  • Atoms of heterocyclic rings can be bonded to a wide range of other atoms and functional groups, for example, provided as substituents.
  • the term "carbocyclic” refers to ring structures containing only carbon atoms in the ring. Carbon atoms of carbocyclic rings can be bonded to a wide range of other atoms and functional groups, for example, provided as substituents.
  • alicyclic refers to a ring that is not an aromatic ring. Alicyclic rings include both carbocyclic and heterocyclic rings.
  • aliphatic refers to non-aromatic hydrocarbon compounds and groups. Aliphatic groups generally include carbon atoms covalently bonded to one or more other atoms, such as carbon and hydrogen atoms. Aliphatic groups may, however, include a non- carbon atom, such as an oxygen atom, a nitrogen atom, a sulfur atom, etc., in place of a carbon atom. Non- substituted aliphatic groups include only hydrogen substituents.
  • Substituted aliphatic groups include non-hydrogen substituents, such as halo groups and other substituents described herein.
  • Aliphatic groups can be straight chain, branched, or cyclic.
  • Aliphatic groups can be saturated, meaning only single bonds join adjacent carbon (or other) atoms.
  • Aliphatic groups can be unsaturated, meaning one or more double bonds or triple bonds join adjacent carbon (or other) atoms.
  • Alkyl groups include straight-chain, branched and cyclic alkyl groups. Alkyl groups include those having from 1 to 30 carbon atoms. Alkyl groups include small alkyl groups having 1 to 3 carbon atoms. Alkyl groups include medium length alkyl groups having from 4-10 carbon atoms. Alkyl groups include long alkyl groups having more than 10 carbon atoms, particularly those having 10-30 carbon atoms.
  • the term cycloalkyl specifically refers to an alky group having a ring structure such as ring structure comprising 3-30 carbon atoms, optionally 3-20 carbon atoms and optionally 3-10 carbon atoms, including an alkyl group having one or more rings.
  • Cycloalkyl groups include those having a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-member carbon ring(s) and particularly those having a 3-, 4-, 5-, 6-, or 7-member ring(s).
  • the carbon rings in cycloalkyl groups can also carry alkyl groups.
  • Cycloalkyl groups can include bicyclic and tricycloalkyl groups. Alkyl groups are optionally substituted.
  • Substituted alkyl groups include, among others, those which are substituted with aryl groups, which in turn can be optionally substituted.
  • Specific alkyl groups include methyl, ethyl, n- propyl, iso-propyl, cyclopropyl, n-butyl, s-butyl, t-butyl, cyclobutyl, n-pentyl, branched- pentyl, cyclopentyl, n-hexyl, branched hexyl, and cyclohexyl groups, all of which are optionally substituted.
  • Substituted alkyl groups include fully-halogenated or semi- halogenated alkyl groups, such as alkyl groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms.
  • Substituted alkyl groups include fully-fluorinated or semi-fluorinated alkyl groups, such as alkyl groups having one or more hydrogens replaced with one or more fluorine atoms.
  • alkoxy group is an alkyl group that has been modified by linkage to oxygen and can be represented by the formula R-0 and can also be referred to as an alkyl ether group.
  • alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy and heptoxy.
  • Alkoxy groups include substituted alkoxy groups wherein the alky portion of the groups is substituted as provided herein in connection with the description of alkyl groups. As used herein MeO- refers to CH3O-.
  • Alkenyl groups include straight-chain, branched and cyclic alkenyl groups.
  • Alkenyl groups include those having 1, 2 or more double bonds and those in which two or more of the double bonds are conjugated double bonds. Alkenyl groups include those having from 2 to 20 carbon atoms. Alkenyl groups include small alkenyl groups having 2 to 4 carbon atoms. Alkenyl groups include medium length alkenyl groups having from 5-10 carbon atoms.
  • Alkenyl groups include long alkenyl groups having more than 10 carbon atoms, particularly those having 10-20 carbon atoms.
  • Cycloalkenyl groups include those in which a double bond is in the ring or in an alkenyl group attached to a ring.
  • the term cycloalkenyl specifically refers to an alkenyl group having a ring structure, including an alkenyl group having a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-member carbon ring(s) and particularly those having a 3-, 4-, 5-, 6- or 7-member ring(s).
  • the carbon rings in cycloalkenyl groups can also carry alkyl groups.
  • Cycloalkenyl groups can include bicyclic and tricyclic alkenyl groups. Alkenyl groups are optionally substituted. Substituted alkenyl groups include among others those which are substituted with alkyl or aryl groups, which groups in turn can be optionally substituted.
  • alkenyl groups include ethenyl, prop-l-enyl, prop-2-enyl, cycloprop-l-enyl, but-1- enyl, but-2-enyl, cyclobut-l-enyl, cyclobut-2-enyl, pent-l-enyl, pent-2-enyl, branched pentenyl, cyclopent-l-enyl, hex- 1 -enyl, branched hex enyl, cyclohexenyl, all of which are optionally substituted.
  • Substituted alkenyl groups include fully-halogenated or semi- halogenated alkenyl groups, such as alkenyl groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms.
  • Substituted alkenyl groups include fully-fluorinated or semi-fluorinated alkenyl groups, such as alkenyl groups having one or more hydrogen atoms replaced with one or more fluorine atoms.
  • Aryl groups include groups having one or more 5-, 6- or 7-member aromatic and/or heterocyclic aromatic rings.
  • the term heteroaryl specifically refers to aryl groups having at least one 5-, 6- or 7-member heterocyclic aromatic rings.
  • Aryl groups can contain one or more fused aromatic and heteroaromatic rings or a combination of one or more aromatic or heteroaromatic rings and one or more non-aromatic rings that may be fused or linked via covalent bonds.
  • Heterocyclic aromatic rings can include one or more N, O, or S atoms in the ring, among others. Heterocyclic aromatic rings can include those with one, two or three N atoms, those with one or two O atoms, and those with one or two S atoms, or combinations of one or two or three N, O or S atoms, among others.
  • Aryl groups are optionally substituted. Substituted aryl groups include among others those which are substituted with alkyl or alkenyl groups, which groups in turn can be optionally substituted. Specific aryl groups include phenyl, biphenyl groups, pyrrolidinyl, imidazolidinyl, tetrahydrofuryl,
  • Substituted aryl groups include fully halogenated or semihalogenated aryl groups, such as aryl groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms.
  • Substituted aryl groups include fully fluorinated or semifluorinated aryl groups, such as aryl groups having one or more hydrogens replaced with one or more fluorine atoms.
  • Aryl groups include, but are not limited to, aromatic group- containing or heterocylic aromatic group-containing groups corresponding to any one of the following: benzene, naphthalene, naphthoquinone, diphenylmethane, fluorene, anthracene, anthraquinone, phenanthrene, tetracene, tetracenedione, pyridine, quinoline, isoquinoline, indoles, isoindole, pyrrole, imidazole, oxazole, thiazole, pyrazole, pyrazine, pyrimidine, purine, benzimidazole, furans, benzofuran, dibenzofuran, carbazole, acridine, acridone, phenanthridine, thiophene, benzothiophene, dibenzothiophene, xanthene, xanthone, flavone, coumarin,
  • a group corresponding to the groups listed above expressly includes an aromatic or heterocyclic aromatic group, including monovalent, divalent and polyvalent groups, of the aromatic and heterocyclic aromatic groups listed herein are provided in a covalently bonded configuration in the compounds of the invention at any suitable point of attachment.
  • aryl groups contain between 5 and 30 carbon atoms.
  • aryl groups contain one aromatic or heteroaromatic six-membered ring and one or more additional five- or six-membered aromatic or heteroaromatic ring.
  • aryl groups contain between five and eighteen carbon atoms in the rings.
  • Aryl groups optionally have one or more aromatic rings or heterocyclic aromatic rings having one or more electron donating groups, electron withdrawing groups and/or targeting ligands provided as substituents.
  • Arylalkyl and alkylaryl groups are alkyl groups substituted with one or more aryl groups wherein the alkyl groups optionally carry additional substituents and the aryl groups are optionally substituted.
  • Specific alkylaryl groups are phenyl -substituted alkyl groups, e.g., phenylmethyl groups.
  • Alkylaryl and arylalkyl groups are alternatively described as aryl groups substituted with one or more alkyl groups wherein the alkyl groups optionally carry additional substituents and the aryl groups are optionally substituted.
  • Specific alkylaryl groups are alkyl -substituted phenyl groups such as methylphenyl.
  • Substituted arylalkyl groups include fully-halogenated or semi-halogenated arylalkyl groups, such as arylalkyl groups having one or more alkyl and/or aryl groups having one or more hydrogens replaced with one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms.
  • any of the groups described herein which contain one or more substituents do not contain any substitution or substitution patterns which are sterically impractical and/or synthetically non-feasible.
  • the disclosed compounds include all stereochemical isomers arising from the substitution of these compounds.
  • Optional substitution of alkyl groups includes substitution with one or more alkenyl groups, aryl groups or both, wherein the alkenyl groups or aryl groups are optionally substituted.
  • Optional substitution of alkenyl groups includes substitution with one or more alkyl groups, aryl groups, or both, wherein the alkyl groups or aryl groups are optionally substituted.
  • Optional substitution of aryl groups includes substitution of the aryl ring with one or more alkyl groups, alkenyl groups, or both, wherein the alkyl groups or alkenyl groups are optionally substituted.
  • Optional substituents for any alkyl, alkenyl and aryl group includes substitution with one or more of the following substituents, among others:
  • halogen including fluorine, chlorine, bromine or iodine
  • R is a hydrogen or an alkyl group or an aryl group or, more specifically, where R is a methyl, ethyl, propyl, butyl, or phenyl group, all of which are optionally substituted;
  • -COR where R is a hydrogen or an alkyl group or an aryl group or, more specifically, where R is a methyl, ethyl, propyl, butyl, or phenyl group, all of which are optionally substituted;
  • each R independently of each other R, is a hydrogen or an alkyl group or an aryl group or, more specifically, where R is a methyl, ethyl, propyl, butyl, or phenyl group, all of which are optionally substituted; and where R and R can form a ring which can contain one or more double bonds and can contain one or more additional carbon atoms;
  • each R independently of each other R, is a hydrogen or an alkyl group or an aryl group and, more specifically, where R is a methyl, ethyl, propyl, butyl, or phenyl group, all of which are optionally substituted; and where R and R can form a ring which can contain one or more double bonds and can contain one or more additional carbon atoms;
  • each R independently of each other R, is a hydrogen, or an alkyl group, or an acyl group or an aryl group or, more specifically, where R is a methyl, ethyl, propyl, butyl, phenyl or acetyl group, all of which are optionally substituted; and where R and R can form a ring which can contain one or more double bonds and can contain one or more additional carbon atoms;
  • R is hydrogen or an alkyl group or an aryl group or, more specifically, where R is hydrogen, methyl, ethyl, propyl, butyl, or a phenyl group, all of which are optionally substituted;
  • R is an alkyl group or an aryl group or, more specifically, where R is a methyl, ethyl, propyl, butyl, or phenyl group, all of which are optionally substituted; [0182] -OCOOR where R is an alkyl group or an aryl group;
  • each R independently of each other R, is a hydrogen, an alkyl group, or an aryl group, all of which are optionally substituted, and wherein R and R can form a ring which can contain one or more double bonds and can contain one or more additional carbon atoms;
  • R is H, an alkyl group, an aryl group, or an acyl group, all of which are optionally substituted.
  • R can be an acyl, yielding -OCOR" where R" is a hydrogen or an alkyl group or an aryl group and more specifically where R" is methyl, ethyl, propyl, butyl, or phenyl groups, all of which are optionally substituted.
  • Specific substituted alkyl groups include haloalkyl groups, particularly
  • substituted aryl groups include mono-, di-, tri, tetra- and penta-halo-substituted phenyl groups; mono-, di-, tri-, tetra-, penta-, hexa-, and hepta-halo-substituted naphthalene groups; 3- or 4-halo- substituted phenyl groups, 3- or 4-alkyl-substituted phenyl groups, 3- or 4-alkoxy-substituted phenyl groups, 3- or 4-RCO-substituted phenyl, 5- or 6-halo-substituted naphthalene groups.
  • substituted aryl groups include acetylphenyl groups, particularly 4- acetylphenyl groups; fluorophenyl groups, particularly 3 -fluorophenyl and 4-fluorophenyl groups; chlorophenyl groups, particularly 3-chlorophenyl and 4-chlorophenyl groups;
  • FIG. 1 A is a simplified schematic diagram illustrating a visibly transparent photovoltaic device according to an embodiment of the present invention.
  • the visibly transparent photovoltaic device 100 includes a number of layers and elements discussed more fully below.
  • visibly transparent indicates that the photovoltaic device absorbs optical energy at wavelengths outside the visible wavelength band of 450 nm to 650 nm, for example, while substantially transmitting visible light inside the visible wavelength band.
  • FIG. 1 A is a simplified schematic diagram illustrating a visibly transparent photovoltaic device according to an embodiment of the present invention.
  • the visibly transparent photovoltaic device 100 includes a number of layers and elements discussed more fully below.
  • visibly transparent indicates that the photovoltaic device absorbs optical energy at wavelengths outside the visible wavelength band of 450 nm to 650 nm, for example, while substantially transmitting visible light inside the visible wavelength band.
  • Substrate 105 which can be glass or other visibly transparent materials providing sufficient mechanical support to the other layers and structures illustrated, supports optical layers 110 and 112. These optical layers can provide a variety of optical properties, including antireflection (AR) properties, wavelength selective reflection or distributed Bragg reflection properties, index matching properties, encapsulation, or the like. Optical layers may advantageously be visibly transparent.
  • An additional optical layer 114 can be utilized, for example, as an AR coating, an index matching later, a passive infrared or ultraviolet absorption layer, etc.
  • optical layers may be transparent to ultraviolet and/or near- infrared light or transparent to at least a subset of wavelengths in the ultraviolet and/or near- infrared bands.
  • additional optical layer 114 may also be a passive visible absorption layer.
  • Example substrate materials include various glasses and rigid or flexible polymers. Multilayer substrates may also be utilized. Substrates may have any suitable thickness to provide the mechanical support needed for the other layers and structures, such as, for example, thicknesses from 1 mm to 20 mm. In some cases, the substrate may be or comprise an adhesive film to allow application of the visibly transparent photovoltaic device 100 to another structure, such as a window pane, display device, etc.
  • each individual material or layer in a visibly transparent photovoltaic device has a high transparency in the visible range, such as greater than 30%> (i.e., between 30%) and 100%>).
  • transmission or absorption may be expressed as a percentage and may be dependent on the material's absorbance properties, a thickness or path length through an absorbing material, and a concentration of the absorbing material, such that a material with an absorbance in the visible spectral region may still exhibit a low absorption or high transmission if the path length through the absorbing material is short and/or the absorbing material is present in low concentration.
  • photoactive materials in various photoactive layers advantageously exhibit minimal absorption in the visible region (e.g., less than 20%, less than 30%), less than 40%, less than 50%, less than 60%, or less than 70%), and instead exhibit high absorption in the near-infrared and/or ultraviolet regions (e.g., an absorption peak of greater than 50%, greater than 60%, greater than 70%, or greater than 80%).
  • absorption in the visible region may be as large as 70%.
  • Various configurations of other materials, such as the substrate, optical layers, and buffer layers may allow these materials to provide overall visible transparency, even though the materials may exhibit some amount of visible absorption.
  • a thin film of a metal may be included in a transparent electrode, such as a metal that exhibits visible absorption, like Ag or Cu; when provided in a thin film configuration, however, the overall transparency of the film may be high.
  • materials included in an optical or buffer layer may exhibit absorption in the visible range, but may be provided at a concentration or thickness where the overall amount of visible light absorption is low, providing visible transparency.
  • the visibly transparent photovoltaic device 100 also includes a set of transparent electrodes 120 and 122 with a photoactive layer 140 positioned between electrodes 120 and 122.
  • These electrodes which can be fabricated using ITO, thin metal films, or other suitable visibly transparent materials, provide electrical connection to one or more of the various layers illustrated.
  • thin films of copper, silver, or other metals may be suitable for use as a visibly transparent electrode, even though these metals may absorb light in the visible band.
  • a film having a thickness of 1 nm to 200 nm e.g., about 5 nm, about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 30 nm, about 35 nm, about 40 nm, about 45 nm, about 50 nm, about 55 nm, about 60 nm, about 65 nm, about 70 nm, about 75 nm, about 80 nm, about 85 nm, about 90 nm, about 95 nm, about 100 nm, about 105 nm, about 110 nm, about 115 nm, about 120 nm, about 125 nm, about 130 nm, about 135 nm, about 140 nm, about 145 nm, about 150 nm, about 155 nm, about 160 nm, about 165 nm, about 170 nm, about 175 nm, about
  • thin metal films when used as transparent electrodes, may exhibit lower absorption in the ultraviolet band than other semiconducting materials that may be useful as a transparent electrode, such as ITO, as some semiconducting transparent conducting oxides exhibit a band gap that occurs in the ultraviolet band and thus are highly absorbing or opaque to ultraviolet light.
  • an ultraviolet absorbing transparent electrode may be used, such as to screen at least a portion of the ultraviolet light from underlying components, as ultraviolet light may degrade certain materials.
  • a variety of deposition techniques may be used to generate a transparent electrode, including vacuum deposition techniques, such as atomic layer deposition, chemical vapor deposition, physical vapor deposition, thermal evaporation, sputter deposition, epitaxy, etc. Solution based deposition techniques, such as spin-coating, may also be used in some cases.
  • transparent electrodes may be patterned using techniques known in the art of microfabrication, including lithography, lift off, etching, etc.
  • Buffer layers 130 and 132 and photoactive layer 140 are utilized to implement the electrical and optical properties of the photovoltaic device. These layers can be layers of a single material or can include multiple sub-layers as appropriate to the particular application.
  • buffer layer 130 is not intended to denote a single layer of a single material, but can include multiple sub-layers of the same or different materials.
  • buffer layer 130, photoactive layer(s) 140 and buffer layer 132 are repeated in a stacked
  • tandem device configuration to provide tandem device configurations, such as including multiple
  • the photoactive layer(s) include electron donor materials and electron acceptor materials, also referred to as donors and acceptors. These donors and acceptors are visibly transparent, but absorb outside the visible wavelength band to provide the photoactive properties of the device.
  • Useful buffer layers include those that function as electron transport layers, electron blocking layers, hole transport layers, hole blocking layers, exciton blocking layers, optical spacers, physical buffer layers, charge recombination layers, or charge generation layers. Buffer layers may exhibit any suitable thickness to provide the buffering effect desired and may optionally be present or absent. Useful buffer layers, when present, may have thicknesses from 1 nm to 1 ⁇ .
  • buffer layers including fullerene materials, carbon nanotube materials, graphene materials, metal oxides, such as molybdenum oxide, titanium oxide, zinc oxide, etc., polymers, such as poly(3,4- ethylenedioxythiophene), polystyrene sulfonic acid, polyaniline, etc., copolymers, polymer mixtures, and small molecules, such as bathocuproine.
  • Buffer layers may be applied using a deposition process (e.g., thermal evaporation) or a solution processing method (e.g., spin coating).
  • FIG. IB depicts an overview of various example single junction configurations for photoactive layer 140.
  • Photoactive layer 140 may optionally correspond to mixed
  • photoactive layer 140 may comprise a planar heteroj unction including separate donor and acceptor layers.
  • Photoactive layer 140 may alternatively comprise a planar-mixed heteroj unction structure including separate acceptor and donor layers and a mixed donor- acceptor layer. Photoactive layer 140 may alternatively comprise a mixed heteroj unction structure including a fully mixed acceptor-donor layer or those including a mixed donor- acceptor layer with various relative concentration gradients.
  • Photoactive layers may have any suitable thickness and may have any suitable concentration or composition of photoactive materials to provide a desired level of transparency and ultraviolet/near-infrared absorption characteristics.
  • Example thicknesses of a photoactive layer may range from about 1 nm to about 1 ⁇ , about 1 nm to about 300 nm, or about 1 nm to about 100 nm.
  • photoactive layers may be made up of individual sub-layers or mixtures of layers to provide suitable photovoltaic power generation characteristics, as illustrated in FIG IB. The various configurations depicted in FIG. IB may be used and dependent on the particular donor and acceptor materials used in order to provide advantageous photovoltaic power generation.
  • Donor materials and acceptor materials may be provided in any ratio or concentration to provide suitable photovoltaic power generation characteristics.
  • the relative concentration of donors to acceptors is optionally between about 20 to 1 and about 1 to 20.
  • the relative concentration of donors to acceptors is optionally between about 5 to 1 and about 1 to 5.
  • donors and acceptors are present in a 1 to 1 ratio.
  • visibly transparent photovoltaic device 100 comprises transparent electrode 120, photoactive layer 140 and transparent electrode 122, and that any one or more of substrate 105, optical layers 110, 112, and 114, and buffer layers 130 and 132 may be optionally included or excluded.
  • diamino difluoro boron-based organic dyes and related diamino dioxygen boron-based organic dyes for one or more of the buffer layers, optical layers, and/or the photoactive layers.
  • These compounds can include suitably functionalized versions for modification of the electrical and/or optical properties of the core structure.
  • the disclosed compounds can include functional groups that decrease the absorption properties in the visible wavelength band between 450 nm to 650 nm and increase the absorption properties in the NIR band at wavelengths greater than 650 nm.
  • the disclosed visibly transparent photoactive compounds are useful as an electron donor photoactive material, in some embodiments, and may be paired with suitable electron acceptor photoactive materials in order to provide a useful photoactive layer in the photovoltaic device.
  • the disclosed visibly transparent photoactive compounds are useful as an electron acceptor photoactive material, and may be paired with suitable electron donor photoactive materials in order to provide a useful photoactive layer in the photovoltaic device.
  • Example donor and acceptor materials are described in U.S.
  • the chemical structure of the disclosed photoactive compounds can be functionalized with one or more directing groups, such as electron donating groups, electron withdrawing groups, or substitutions about or to a core metal atom, in order to provide desirable electrical characteristics to the material.
  • one or more directing groups such as electron donating groups, electron withdrawing groups, or substitutions about or to a core metal atom, in order to provide desirable electrical characteristics to the material.
  • the photoactive compounds are functionalized with amine groups, phenol groups, alkyl groups, phenyl groups, or other electron donating groups to improve the ability of the material to function as an electron donor in a photovoltaic device.
  • the photoactive compounds are functionalized with cyano groups, halogens, sulfonyl groups, or other electron withdrawing groups to improve the ability of the material to function as an electron acceptor in a photovoltaic device.
  • the photoactive compounds are functionalized to provide desirable optical characteristics.
  • the photoactive compounds may be functionalized with an extended conjugation to redshift the absorption profile of the material.
  • conjugation may refer to a derealization of pi electrons in a molecule and may be characterized by alternating single and multiple bonds in a molecular structure.
  • functionalizations that extend the electron conjugation may include fusing one or more aromatic groups to the molecular structure of the material.
  • Other functionalizations that may provide extended conjugation include alkene
  • the molecular framework of the photoactive materials can be tailored to control the morphology of the materials.
  • the introduction of functional groups as described herein can have large impacts to the morphology of the material in the solid state, regardless of whether such modifications impact the energetics or electronic properties of the material.
  • Such morphological variations can be observed in pure materials and when a particular material is blended with a corresponding donor or acceptor.
  • morphology include, but are not limited to, addition of alkyl chains, conjugated linkers, fluorinated alkanes, bulky groups (e.g., tert-butyl, phenyl, naphthyl or cylcolhexyl), as well as more complex coupling procedures designed to force parts of the structure out of the plane of the molecule to inhibit excessive crystallization.
  • the photoactive compounds may exhibit portions of the molecule that may be characterized as electron donating while other portions of the molecule may be characterized as electron accepting.
  • molecules including alternating electron donating and electron accepting portions may result in redshifting the absorption characteristics of the molecule as compared to similar molecules lacking alternating electron donating and electron accepting portions.
  • alternating electron donating and electron accepting portions may decrease or otherwise result in a lower energy gap between a highest occupied molecular orbital and a lowest unoccupied molecular orbital.
  • Organic donor and/or acceptor groups may be useful as R-group substituents, such as on any aryl, aromatic, heteroaryl, heteroaromatic, alkyl, or alkenyl group, in the visibly transparent photoactive compounds described herein. [0203] , which may be considered strong acceptor groups.
  • Example organic acceptor groups include
  • Example organic acceptor groups include:
  • R A may optionally be hydrogen or alkyl, for example.
  • the wavy lines represent positions at which the illustrated structure is connected to another substructure.
  • Example organic donor groups include:
  • Example organic donor groups include:
  • Example organic donor groups include:
  • the photoactive compounds may exhibit symmetric structures, such as structures having two or more points of symmetry. Symmetric structures may include those where a core group is functionalized on opposite sides by the same groups, or where two of the same core groups are fused or otherwise bonded to one another. In other embodiments, the photoactive compounds may exhibit asymmetric structures, such as structures having fewer than two points of symmetry. Asymmetric structures may include those where a core group is functionalized on opposite sides by different groups or where two different core groups are fused or otherwise bonded to one another.
  • the layer thicknesses can be controlled to vary device output, absorbance, or transmittance. For example, increasing the donor or acceptor layer thickness can increase the light absorption in that layer. In some cases, increasing a concentration of donor/acceptor materials in a donor or acceptor layer may similarly increase the light absorption in that layer. However, in some embodiments, a concentration of donor/acceptor materials may not be adjustable, such as when active material layers comprise pure or substantially pure layers of donor/acceptor materials or pure or substantially pure mixtures of donor/acceptor materials.
  • donor/acceptor materials may be provided in a solvent or suspended in a carrier, such as a buffer layer material, in which case the concentration of donor/acceptor materials may be adjusted.
  • the donor layer concentration is selected where the current produced is maximized.
  • the acceptor layer concentration is selected where the current produced is maximized.
  • the charge collection efficiency can decrease with increasing donor or acceptor thickness due to the increased "travel distance" for the charge carriers. Therefore, there may be a trade-off between increased absorption and decreasing charge collection efficiency with increasing layer thickness. It can thus be advantageous to select materials as described herein that have a high absorption coefficient and/or concentration to allow for increased light absorption per thickness.
  • the donor layer thickness is selected where the current produced is maximized.
  • the acceptor layer thickness is selected where the current produced is maximized.
  • the thickness and composition of the other layers in the transparent photovoltaic device can also be selected to enhance absorption within the photoactive layers.
  • the other layers are typically selected based on their optical properties (index of refraction and extinction coefficient) in the context of the thin film device stack and resulting optical cavity.
  • a near-infrared absorbing photoactive layer can be positioned in the peak of the optical field for the near-infrared wavelengths where it absorbs to maximize absorption and resulting current produced by the device. This can be accomplished by spacing the photoactive layer at an appropriate distance from the electrode using a second photoactive layer and/or optical layers as spacer.
  • a similar scheme can be used for ultraviolet absorbing photoactive layers.
  • the peaks of the longer wavelength optical fields will be positioned further from the more reflective of the two transparent electrodes compared to the peaks of the shorter wavelength optical fields.
  • the donor and acceptor can be selected to position the more red absorbing (longer wavelength) material further from the more reflective electrode and the more blue absorbing (shorter wavelength) closer to the more reflective electrode.
  • optical layers may be included to increase the intensity of the optical field at wavelengths where the donor absorbs in the donor layer to increase light absorption and hence, increase the current produced by the donor layer.
  • optical layers may be included to increase the intensity of the optical field at wavelengths where the acceptor absorbs in the acceptor layer to increase light absorption and hence, increase the current produced by the acceptor layer.
  • optical layers may be used to improve the transparency of the stack by either decreasing visible absorption or visible reflection.
  • the electrode material and thickness may be selected to enhance absorption outside the visible range within the photoactive layers, while preferentially transmitting light within the visible range.
  • enhancing spectral coverage of a visibly transparent photovoltaic device is achieved by the use of a multi-cell series stack of visibly transparent photovoltaic devices, referred to as tandem cells, which may be included as multiple stacked instances of buffer layer 130, photoactive layer 140, and buffer layer 132, as described with reference to FIG. 1 A.
  • This architecture includes more than one photoactive layer, which are typically separated by a combination of buffer layer(s) and/or thin metal layers, for example.
  • the currents generated in each subcell flow in series to the opposing electrodes and therefore, the net current in the cell is limited by the smallest current generated by a particular subcell, for example.
  • the open circuit voltage is equal to the sum of the VOCs of the subcells.
  • FIG. 2 is simplified plot illustrating the solar spectrum, human eye sensitivity, and exemplary visibly transparent photovoltaic device absorption as a function of wavelength.
  • embodiments of the present invention utilize photovoltaic structures that have low absorption in the visible wavelength band between about 450 nm and about 650 nm, but absorb in the UV and NIR bands, i.e., outside the visible wavelength band, enabling visibly transparent photovoltaic operation.
  • the ultraviolet band or ultraviolet region may be described, in embodiments, as wavelengths of light of between about 200 nm and 450 nm. It will be appreciated that useful solar radiation at ground level may have limited amounts of ultraviolet less than about 280 nm and, thus, the ultraviolet band or ultraviolet region may be described as wavelengths of light of between about 280 nm and 450 nm, in some
  • FIG. 3 provides a schematic energy level diagram overview for operation of an example organic photovoltaic device, such as visibly transparent photovoltaic device 100.
  • various photoactive materials may exhibit electron donor or electron acceptor characteristics, depending on their molecular properties and the types of materials that are used for buffer layers, electrodes, etc. As depicted in FIG.
  • each of the donor and acceptor materials have a highest occupied molecular orbital (HOMO) and a lowest unoccupied molecular orbital (LUMO).
  • a transition of an electron from the HOMO to the LUMO may be imparted by absorption of photons.
  • the energy between the HOMO and the LUMO (the HOMO-LUMO gap) of a material represents approximately the energy of the optical band gap of the material.
  • the HOMO-LUMO gap for the electron donor and electron acceptor materials preferably falls outside the energy of photons in the visible range.
  • the HOMO-LUMO gap may be in the ultraviolet region or the near-infrared region, depending on the photoactive materials. It will be appreciated that the HOMO is comparable to the valence band in conventional conductors or semiconductors, while the LUMO is comparable to the conduction band in conventional conductors or semiconductors.
  • the narrow absorption spectrum of many organic molecules, such as organic semiconductors, can make it difficult to absorb the entire absorption spectra using a single molecular species. Therefore, electron donor and acceptor molecules are generally paired to afford a complementary absorption spectrum and increase spectral coverage of light absorption. Additionally, the donor and acceptor molecules are selected such that their energy levels (HOMO and LUMO) lie favorably with respect to one another.
  • the difference in the LUMO level of donor and acceptor provides a driving force for dissociation of electron-hole pairs (excitons) created on the donor whereas the difference in the HOMO levels of donor and acceptors provides driving force for dissociation of electron-hole pairs (excitons) created on the acceptor.
  • VOC open circuit voltage
  • Such donor-acceptor pairings within the photoactive layer may be accomplished by appropriately pairing one of the materials described herein with a complementary material, which could be a different visibly transparent photoactive compound described herein or a completely separate material system, as described below with reference to FIG. 6.
  • the buffer layer adjacent to the donor is selected such that HOMO level or valence band (in the case of inorganic materials) of the buffer layer is aligned in the energy landscape with the HOMO level of the donor to transport holes from the donor to the anode (transparent electrode).
  • HOMO level or valence band in the case of inorganic materials
  • the buffer layer adjacent to the acceptor is selected such that LUMO level or conduction band (in the case of inorganic materials) of the buffer layer is aligned in the energy landscape with the LUMO level of the acceptor to transport electrons from the acceptor to the cathode (transparent electrode).
  • LUMO level or conduction band in the case of inorganic materials
  • FIG. 4A, FIG. 4B, FIG. 4C, and FIG. 4D provide plots showing example absorption bands for different electron donor and electron acceptor configurations useful with visibly transparent photovoltaic devices.
  • the donor material exhibits absorption in the NIR, while the acceptor material exhibits absorption in the UV.
  • FIG. 4B depicts the opposite configuration, where the donor material exhibits absorption in the UV, while the acceptor material exhibits absorption in the NIR.
  • FIG. 4C depicts an additional configuration, where both the donor and acceptor materials exhibit absorption in the NIR.
  • the solar spectrum exhibits significant amounts of useful radiation in the NIR with only relatively minor amounts in the ultraviolet, making the configuration depicted in FIG.
  • FIG. 5 provides an overview of a method 500 for making a visibly transparent photovoltaic device in accordance with some embodiments.
  • Method 500 begins at block 505, where a transparent substrate is provided.
  • useful transparent substrates include visibly transparent substrates, such as glass, plastic, quartz, and the like. Flexible and rigid substrates are useful with various embodiments.
  • the transparent substrate is provided with one or more optical layers preformed on top and/or bottom surfaces.
  • one or more optical layers are optionally formed on or over the transparent substrate, such as on top and/or bottom surfaces of the transparent substrate.
  • the one or more optical layers are formed on other materials, such as an intervening layer or material, such as a transparent conductor.
  • the one or more optical layers are positioned adjacent to and/or in contact with the visibly transparent substrate. It will be appreciated that formation of optical layers is optional, and some embodiments may not include optical layers adjacent to and/or in contact with the transparent substrate.
  • Optical layers may be formed using a variety of methods including, but not limited to, one or more chemical deposition methods, such as plating, chemical solution deposition, spin coating, dip coating, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition, or one or more physical deposition methods, such as thermal evaporation, electron beam evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, ion beam deposition, and electrospray deposition.
  • useful optical layers include visibly transparent optical layers.
  • Useful optical layers include those that provide one or more optical properties including, for example, antireflection properties, wavelength selective reflection or distributed Bragg reflection properties, index matching properties, encapsulation, or the like.
  • Useful optical layers may optionally include optical layers that are transparent to ultraviolet and/or near-infrared light. Depending on the configuration, however, some optical layers may optionally provide passive infrared and/or ultraviolet absorption. Optionally, an optical layer may include a visibly transparent photoactive compound described herein.
  • a transparent electrode is formed.
  • the transparent electrode may correspond to an indium tin oxide thin film or other transparent conducting film, such as thin metal films (e.g., Ag, Cu, etc.), multilayer stacks comprising thin metal films (e.g., Ag, Cu, etc.) and dielectric materials, or conductive organic materials (e.g.
  • transparent electrodes include visibly transparent electrodes.
  • Transparent electrodes may be formed using one or more deposition processes, including vacuum deposition techniques, such as atomic layer deposition, chemical vapor deposition, physical vapor deposition, thermal evaporation, sputter deposition, epitaxy, etc. Solution based deposition techniques, such as spin-coating, may also be used in some cases.
  • transparent electrodes may be patterned by way of microfabrication techniques, such as lithography, lift off, etching, etc.
  • buffer layers are optionally formed, such as on the transparent electrode.
  • Buffer layers may be formed using a variety of methods including, but not limited to, one or more chemical deposition methods, such as a plating, chemical solution deposition, spin coating, dip coating, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition, or one or more physical deposition methods, such as thermal evaporation, electron beam evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, ion beam deposition, and electrospray deposition.
  • chemical deposition methods such as a plating, chemical solution deposition, spin coating, dip coating, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition
  • physical deposition methods such as thermal evaporation, electron beam evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, ion beam deposition, and electrospray deposition.
  • useful buffer layers include visibly transparent buffer layers.
  • Useful buffer layers include those that function as electron transport layers, electron blocking layers, hole transport layers, hole blocking layers, optical spacers, physical buffer layers, charge recombination layers, or charge generation layers.
  • the disclosed visibly transparent photoactive compounds may be useful as a buffer layer material.
  • a buffer layer may optionally include a visibly transparent photoactive compound described herein.
  • photoactive layers are formed, such as on a buffer layer or on a transparent electrode.
  • photoactive layers may comprise electron acceptor layers and electron donor layers or co-deposited layers of electron donors and acceptors.
  • Useful photoactive layers include those comprising the visibly transparent photoactive compounds described herein.
  • Photoactive layers may be formed using a variety of methods including, but not limited to, one or more chemical deposition methods, such as a plating, chemical solution deposition, spin coating, dip coating, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition, or one or more physical deposition methods, such as thermal evaporation, electron beam evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, ion beam deposition, and electrospray deposition.
  • chemical deposition methods such as a plating, chemical solution deposition, spin coating, dip coating, chemical vapor deposition, plasma enhanced chemical vapor deposition, and atomic layer deposition
  • physical deposition methods such as thermal evaporation, electron beam evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, ion beam deposition, and electrospray deposition.
  • visibly transparent photoactive compounds useful for photoactive layers may be deposited using a vacuum deposition technique, such as thermal evaporation.
  • Vacuum deposition may take place in a vacuum chamber, such as at pressures of between about 10 "5 Torr and about 10 "8 Torr. In one example, vacuum deposition may take place at a pressure of about 10 "7 Torr.
  • various deposition techniques may be applied.
  • thermal evaporation is used. Thermal evaporation may include heating a source of the material (i.e., the visibly transparent photoactive compound) to be deposited to a temperature of between 200 °C and 500 °C.
  • the temperature of the source of material may be selected so as to achieve a thin film growth rate of between about 0.01 nm/s and about 1 nm/s.
  • a thin film growth rate of 0.1 nm/s may be used. These growth rates are useful to generate thin films having thicknesses of between about 1 nm and 500 nm over the course of minutes to hours.
  • various properties e.g., the molecular weight, volatility, thermal stability
  • a thermal decomposition temperature of the material being deposited may limit the maximum temperature of the source.
  • a material being deposited that is highly volatile may require a lower source temperature to achieve a target deposition rate as compared to a material that is less volatile, where a higher source temperature may be needed to achieve the target deposition rate.
  • the material being deposited may be evaporated from the source, it may be deposited on a surface (e.g., substrate, optical layer, transparent electrode, buffer layer, etc.) at a lower temperature.
  • the surface may have a temperature from about 10 °C to about 100 °C.
  • the temperature of the surface may be actively controlled. In some cases, the temperature of the surface may not be actively controlled.
  • one or more buffer layers are optionally formed, such as on the photoactive layer.
  • the buffer layers formed at block 530 may be formed similar to those formed at block 520. It will be appreciated that blocks 520, 525, and 530 may be repeated one or more times, such as to form a multilayer stack of materials including a photoactive layer and, optionally, various buffer layers.
  • a second transparent electrode is formed, such as on a buffer layer or on a photoactive layer.
  • Second transparent electrode may be formed using techniques applicable to formation of first transparent electrode at block 515.
  • one or more additional optical layers are optionally formed, such as on the second transparent electrode.
  • FIG. 5 provides a particular method of making a visibly transparent photovoltaic device according to various embodiments of the present invention. Other sequences of steps may also be performed according to alternative embodiments. For example, alternative embodiments of the present invention may perform the steps outlined above in a different order. Moreover, the individual steps illustrated in FIG. 5 may include multiple sub-steps that may be performed in various sequences as appropriate to the individual step. Furthermore, additional steps may be added or removed depending on the particular applications. It will be appreciated that many variations, modifications, and alternatives may be used.
  • Method 500 may optionally be extended to correspond to a method for generating electrical energy.
  • a method for generating electrical energy may comprise providing a visibly transparent photovoltaic device, such as by making a visibly transparent photovoltaic device according to method 500.
  • Methods for generating electrical energy may further comprise exposing the visibly transparent photovoltaic device to visible, ultraviolet and/or near-infrared light to drive the formation and separation of electron-hole pairs, as described above with reference to FIG. 3, for example, for generation of electrical energy.
  • the visibly transparent photovoltaic device may include the visibly transparent photoactive compounds described herein as photoactive materials, buffer materials, and/or optical layers.
  • FIG. 6 provides a plot showing general absorption characteristics
  • Useful visibly transparent photoactive layers in visibly transparent photovoltaic devices may include one or more photoactive compounds of the different classes illustrated.
  • photoactive compounds described herein may be incorporated into a visibly transparent photoactive layer as an acceptor compound along with another photoactive compound of the classes depicted in FIG. 6.
  • boron-dipyrromethene (BODIPY)-based compounds described herein may be incorporated into a visibly transparent photoactive layer as a donor or acceptor compound along with another photoactive compound of the classes depicted in FIG. 6.
  • BODIPY boron-dipyrromethene
  • boron-dipyrromethene (BODIPY)-based compound may be paired with an electron donor photoactive material from the classes illustrated in FIG. 6 as a counterpart in order to provide a useful photoactive layer in the photovoltaic device.
  • the disclosed photoactive compounds may fall within the illustrated acceptor-donor-acceptor structure (A-D-A) and may be useful as a near-infrared absorbing electron acceptor photoactive material and be paired with an electron donor photoactive material from the classes illustrated in FIG. 6 as a counterpart in order to provide a useful photoactive layer in the photovoltaic device.
  • phthalocyanines described herein may be incorporated into a visibly transparent photoactive layer as a donor or acceptor compound along with another photoactive compound of the classes depicted in FIG. 6.
  • a phthalocyanine may be paired with an electron acceptor photoactive material from the classes illustrated in FIG. 6 as a counterpart in order to provide a useful photoactive layer in the photovoltaic device.
  • a phthalocyanine is used as an electron acceptor photoactive material, it may be paired with an electron donor photoactive material from the classes illustrated in FIG. 6 as a counterpart in order to provide a useful photoactive layer in the photovoltaic device.
  • the compounds described herein may be incorporated into a visibly transparent photoactive layer as an acceptor compound along with another donor photoactive compound of the classes depicted in FIG. 6.
  • the compound may be paired with an electron donor photoactive material from the classes illustrated in FIG. 6 as a counterpart in order to provide a useful photoactive layer in the photovoltaic device.
  • the compounds described herein may be incorporated into a visibly transparent photoactive layer as a donor compound along with another acceptor photoactive compound of the classes depicted in FIG. 6.
  • the compound is used as an electron donor photoactive material, it may be paired with an electron acceptor photoactive material from the classes illustrated in FIG. 6 as a counterpart in order to provide a useful photoactive layer in the photovoltaic device.
  • TAPC may be used as a UV absorbing electron donor.
  • fullerenes or fullerene derivatives may optionally be used as a UV absorbing electron acceptor.
  • a cyanine salt may be used as a near-infrared absorbing electron donor.
  • a molecule with a donor-acceptor-donor structure D-A-D may be useful as a near- infrared absorbing electron donor photoactive material or an electron acceptor photoactive material.
  • a molecule with an acceptor-donor-acceptor structure may be useful as a near-infrared absorbing electron acceptor photoactive material.
  • Example acceptor groups and donor groups for D-A-D and A-D-A structures are described above.
  • the different classes illustrated may exhibit overlapping absorption features (i.e., spectral ranges). It may be desirable, however, to select a counterpart photoactive compound with absorption features from a different spectral region or that do not have overlapping absorption features or that have different peak absorption wavelengths.
  • the visibly transparent photoactive compounds useful as photoactive materials, buffer materials, and/or optical layers, include boron-dipyrromethene-based compounds, such as difluoro boron-based organic dyes, and related dioxygen boron-based organic dyes.
  • boron-dipyrromethene-based compounds such as difluoro boron-based organic dyes, and related dioxygen boron-based organic dyes.
  • a photoactive compound exhibits a greater maximum near-infrared absorption strength than maximum visible absorption strength and has a chemical formula
  • each L group is independently a single bond or a bivalent linking group selected from a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group.
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • substitutions may include substituted phenyl rings (e.g., alkyl substituted, halogen
  • 7B may also be made to modify the ring structure fused to the boron-nitrogen ring, such as a benzoindole or a naphthoindole, a thienopyrrole, etc.
  • Table 1 provides example difluoro boron-based organic dyes along with shorthand identifiers (ID).
  • FIG. 8 provides exemplary normalized absorbance spectra for a number of the compounds in Table 1, showing that these compounds exhibit strong absorbance in the near- infrared with some absorbance in the ultraviolet and minimal absorbance in the visible band.
  • Sample photovoltaic devices were constructed using a number of the transparent photoactive compounds in Table 1 and tested for photovoltaic efficiency. Two device configurations were used for testing purposes, generally constructed as depicted in FIG 1 A, with the transparent photoactive compounds used as donor molecules with C 6 o used as an acceptor. In one configuration, two transparent electrodes were used to generate a fully transparent device. In a second configuration, one transparent electrode (indium tin oxide) was used and one opaque electrode was used.
  • a transparent photovoltaic device using the visibly transparent photoactive compound identified as D-10 with an opaque configuration was constructed as follows. An about 8 nm thick anode buffer layer was deposited over a visibly transparent substrate and indium tin oxide (ITO) transparent conductor. An about 20 nm thick layer of D-10 as a donor was deposited over the anode buffer layer. An about 50 nm thick layer including C 6 o as an acceptor was deposited over the donor layer.
  • ITO indium tin oxide
  • FIG. 9 provides example data for the D-10 photovoltaic cell, showing current density as a function of voltage. Table 2.
  • FIG. 10 provides an overview of a synthetic route for forming dioxygen boron-based compounds using reaction involving a difluoride boron-based compounds and catechol. It will be appreciated that any of the difluoride boron-based compounds described herein may be substituted for that shown in FIG. 10. It will further be appreciated that other reactants may be substituted for the catchetol, such as other dixhydroxy aromatic derivatives (e.g., 2,3-dihydroxynaphthalene).
  • FIG. 10 provides an overview of a synthetic route for forming dioxygen boron-based compounds using reaction involving a difluoride boron-based compounds and catechol. It will be appreciated that any of the difluoride boron-based compounds described herein may be substituted for that shown in FIG. 10. It will further be appreciated that other reactants may be substituted for the catchetol, such as other dixhydroxy aromatic derivatives (e.g., 2,3-dihydroxynaphthalene).
  • FIG. 10 provides an overview of
  • FIG. 11 provides an alternative synthetic scheme for forming dioxygen boron-based compounds, by way of a reaction involving a methoxy substituted compound and BCb.
  • Table 3 provides example dioxygen boron-based organic dyes along with shorthand identifiers (ID).
  • FIG. 12 provides comparative data showing absorbance spectra for difluoro boron-based compound D-1 and dioxygen boron -based compound D-3, showing similar absorption profiles, though compound D-3 exhibits slightly less absorption in the visible band than compound D-1.
  • Difluoro boron-based visibly transparent photoactive compounds and dioxygen boron-based visibly transparent photoactive compounds may have a structure in which the ring including the boron and adjacent nitrogen atoms may exhibit fused ring configurations, such as those exhibiting a greater maximum near-infrared absorption strength than maximum
  • each X is independently S, N, or C— R.
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted
  • heteroaromatic group a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • the ring including the boron and adjacent nitrogen atoms may be fused to 5-membered or 6-membered rings, such as a thiazole ring, a benzene ring, a pyridine ring, a imidazole ring, a pyrrole ring, a thiophene ring, a
  • FIG. 13 provides synthetic schema for forming fused visibly transparent photoactive compounds. Absorption spectra for three thiophene fused visibly transparent photoactive compounds (1-33, 1-34, and 1-35) are illustrated in FIG. 14. The spectra for the phenyl substituted (1-33) and tert-butyl -phenyl substituted (1-35) fused compounds show good spectral properties with little absorption in the visible band. The spectrum for the thiophene substituted fused compound, 1-34, shows broader absorption features, but still exhibits considerably less absorption in the visible band.
  • An example photovoltaic device was constructed using the phenyl substituted thiophene fused visibly transparent photoactive compound identified as 1-35 with an opaque configuration was constructed as follows. An about 8 nm thick anode buffer layer was deposited over a visibly transparent substrate and indium tin oxide (ITO) transparent conductor. An about 20 nm thick layer of 1-35 as a donor was deposited over the anode buffer layer. An about 30 nm thick layer including C 6 o as an acceptor was deposited over the donor layer. An about 5 nm thick cathode buffer layer was deposited over the acceptor layer. Finally, an opaque aluminum layer about 80 nm thick was deposited as a top electrode. The cell was illuminated and performance monitored. FIG. 15 provides example data for the 1-35 photovoltaic cell, showing current density as a function of voltage.
  • ITO indium tin oxide
  • a reduction in molecular weight may be advantageous.
  • D-33, D-34, D-35, 1-33, 1-34, and 1-35 exhibit molecular weights in excess of 600 amu. Reduction of the molecular weight may improve use of the visibly transparent photoactive compounds in formation of visibly transparent photovoltaic devices, as lower molecular weight compounds tend to have higher volatilities and be more easily deposited using vacuum deposition techniques.
  • the molecular weights are reduced to less than 600 amu.
  • Lower molecular weights may also be advantageous for synthetic purposes, as some synthesis techniques may use sublimation for purification purposes.
  • FIG. 16 provides an overview of synthetic schema for producing compounds with reduced molecular weight.
  • An additional configuration for the visibly transparent photoactive compounds may incorporate a bis structure in which two boron-nitrogen containing rings are included in the compound.
  • visibly transparent photoactive compounds may exhibit a greater maximum near-infrared absorption strength than maximum visible absorption strength and
  • each A2 is independently a fused or unfused aromatic or heteroaromatic group including one or more R group substituents.
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • each Al optionally independently comprises an unsubstituted or R substituted ring group including one or more of a thiazole ring, a benzene ring, a pyridine ring, a imidazole ring, a pyrrole ring, a thiophene ring, a naphthalene, a pyrene, an indole, a benzothiophene, a benzimidazole, a benzothiazole, or a triazine ring.
  • each A2 independently comprises a 5-membered or 6-membered aromatic or heteroaromatic ring including one or more R group substituents.
  • each A2 independently comprises an unsubstituted or R substituted ring group including one or more of a thiazole ring, a benzene ring, a pyridine ring, a imidazole ring, a pyrrole ring, a thiophene ring, a naphthalene, a pyrene, an indole, a benzothiophene, a benzimidazole, a benzothiazole, or a triazine ring.
  • a thiazole ring including one or more of a thiazole ring, a benzene ring, a pyridine ring, a imidazole ring, a pyrrole ring, a thiophene ring, a naphthalene, a pyrene, an indole, a benzothiophene, a benzimidazole, a benzothiazole, or
  • visibly transparent photoactive compounds may have the
  • each A3 independently an aromatic or heteroaromatic group including one or more R group substituents.
  • Table 4 provides example specific compounds with a bis configuration
  • FIG. 17, FIG. 18, FIG. 19, FIG. 20, and FIG. 21 provides example synthetic schema for forming compounds with a bis configuration. Table 4.
  • D-56 The absorption spectra of the photoactive compound identified as D-56 is shown in FIG. 22 with that of D-1, for comparison. D-56 shows a broader and slightly blueshifted low energy absorption peak in the near-infrared, but still exhibits low absorption in the visible band.
  • BODIPY-based compounds can be used as donor materials and paired with a number of useful acceptor materials.
  • a visibly transparent photovoltaic device may contain a BODIPY-based donor material and an acceptor material containing a fullerene (e.g., C60, C70, or a combination thereof).
  • the donor material includes one or more BODIPY compounds as described herein, and the acceptor material includes a nickel dithiolate (NDT) compound, a dicyano-indandione (DiCN), a benzothiadiazole (BT), a benzo-fos-thiadiazole (BBT), a diketopyrrolopyrrole diphenythienylamine (DPP-DPTA), a
  • NDT nickel dithiolate
  • DICN dicyano-indandione
  • BT benzothiadiazole
  • BBT benzo-fos-thiadiazole
  • DPP-DPTA diketopyrrolopyrrole diphenythienylamine
  • naphthalenetetracarboxylic diimide NTCDI
  • CBI bisimide coronene
  • fluoranthene a corannulene
  • corannulene a phthalocyanine
  • naphthalocyanine a combination thereof.
  • useful NDT compounds include those described herein.
  • useful DiCNs, BTs, BBTs, and DPP-DPTAs but are not limited to, those described herein.
  • useful NTCDIs, CBIs, fluoranthenes, and corannulenes include, but are not limited to, those described herein.
  • useful phthalocyanines and naphthalocyanines include, but are not limited to, those described herein.
  • the acceptor material includes a DiCN, a BT, a BBT, a DPP- DPTA, an NTCDI, a fluoranthene, or a combination thereof.
  • the acceptor material includes an NDT.
  • the acceptor material includes a CBI, a corranulene, a phthalocyanine, a naphthalocyanine, or a combination thereof.
  • the donor material contains a BODIPY compound, and the acceptor material also contains a BODIPY compound. In such instances, the acceptor BODIPY may be functionalized with an electron withdrawing group or an acceptor moiety as described herein.
  • BODIPY compounds functionalized in this manner can also be used as acceptor materials when paired with a donor material such as an NDT, a DiCN, a BT, a BBT, a DPP-DPTA, a phthalocyanine, or a naphthalocyanine.
  • a donor material such as an NDT, a DiCN, a BT, a BBT, a DPP-DPTA, a phthalocyanine, or a naphthalocyanine.
  • the visibly transparent photoactive compounds useful as photoactive materials, buffer materials, and/or optical layers, include near-infrared absorbing donor-acceptor (near- IR DA) molecules.
  • donor-acceptor molecule refers to a compound having different moieties providing different relative electron withdrawing or electron donating character.
  • a donor-acceptor molecule may include a donor moiety providing an electron donating character and an acceptor moiety providing an electron withdrawing character.
  • a donor-acceptor molecule may include a first moiety providing relatively more electron donating character and a second moiety providing an relatively less electron donating character.
  • a donor-acceptor molecule may include a first moiety providing relatively more electron withdrawing character and a second moiety providing an relatively less electron withdrawing character.
  • Donor-acceptor molecules may also be referred to as "push-pull" molecules and may include one or more different electron withdrawing or electron donating moieties on opposite sides of the molecule or within different regions of the molecule.
  • a push-pull molecule may have a donor-acceptor-donor structure or an acceptor-donor-acceptor structure.
  • a push-pull molecule may have a strong or very strong donor moiety one on side of a double bond or conjugated moiety and may have a strong or very strong acceptor moiety on the opposite side of the double bond or conjugated system.
  • the push-pull molecules described herein include those that behave as electron acceptors in a photovoltaic device.
  • the donor-acceptor molecules described herein include those that behave as electron acceptors in a photovoltaic device.
  • a DA molecule may contain both acceptor donor moieties and acceptor moieties, it can be used as the principal acceptor material when paired with a donor material (e.g., a nickel dithiolate, a BODIPY, or other donor material) as described herein.
  • a donor material e.g., a nickel dithiolate, a BODIPY, or other donor material
  • near-IR DA molecules include, but are not limited to, dicyano-indandiones, benzo-fos-thiadiazoles, benzothiadiazoles, diketopyrrolopyrrole diphenylthienylamines, and derivatives thereof.
  • the active layer comprises an acceptor having a structure A-D-A, wherein each "A" moiety is an acceptor moiety and the "D" moiety is a donor moiety.
  • each "A" moiety can be independently selected from
  • R are hydrogen or alkyl, and the wavy lines represent positions at which the illustrated structure is connected to another substructure
  • the active layer comprises an acceptor having a structure D-A-D, wherein each "D" moiety is a donor moiety and the "A" moiety is an acceptor moiety.
  • each "D" moiety can be independently selected from
  • R A are hydrogen or alkyl, and the wavy lines represent positions at which the illustrated structure is connected to another substructure.
  • Dicyano-indandiones can be used as acceptors in the devices described herein.
  • Dicyano-indandiones and derivatives thereof (including, but not limited to, dicyano-indandione indacenodithiophenes, dicyano-indandione dithienocarbazoles, dicyano- indandione, anthradithiophenes, dicyano-indandione boron-dipyrromethenes, dicyano- benzo[£]thiophen-3(2H)-one 1,1 -dioxides) can be used as acceptors in the devices described herein.
  • ITIC ⁇ i.e., 3,9-bis(2-methylene-(3-(l,l-dicyanomethylene)-indanone))- 5,5, 11,1 l-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[l,2-b:5,6- b']dithiophene) has demonstrated good performance as a non-fullerene acceptor in organic photovoltaic devices but has not previous been employed in transparent photovoltaic devices.
  • Dicyano-indandiones typically exhibit absorption maxima in the near-infrared.
  • Example DiCN structures include those according to Formula I:
  • Y is F, CI, Br, alkoxy, alkyl, or aryl in compounds of Formula I.
  • n is an integer 0-5 in compounds of Formula I.
  • X is C(CN) 2 , O, S, C(O), or S0 2 in compounds of Formula I.
  • Ar is aryl, such as phenyl, thienyl, thiazolyl, and the like.
  • fused pi systems include, but are not limited to, anthra[l,9-£c:5, 10- £'c dithiophene diradicals ⁇ e.g., anthra[l,9-£c:5, 10-£'c dithiophen-l,6-diyl); 4,9-dihydro-s- indaceno[l,2-£:5,6-£ dithiophene diradicals ⁇ e.g., 4,9-dihydro-s-indaceno[l,2-£:5,6- £]dithiophen-2,7-diyl); unsubstituted and 5-substituted 5H-dithieno[3,2-b:2',3'-h]carbazole diradicals (e.g., 5-methyl-5H-dithieno[3,2-b:2',3'-h]carbazol-2,8-diyl); unsubstituted and 4- substitute
  • the fused pi system in compounds of Formula I is selected from:
  • R may optionally be hydrogen or alkyl.
  • the fused pi system in compounds of Formula I is selected from:
  • R may optionally be hydrogen or alkyl.
  • the fused pi system in compounds of Formula I is selected from:
  • DiCN compounds also include those having unfused pi systems and asymmetric structures (with fused or unfused pi systems).
  • the DiCN compound has a structure according to Formula II to Formula II:
  • Y is F, CI, Br, alkoxy, alkyl, or aryl in compounds of Formula I.
  • n is an integer 0-5 in compounds of Formula II.
  • t is 1 or 2 in compounds of Formula II.
  • X is C(CN) 2 , O, S, C(O), or S0 2 in compounds of Formula II.
  • Ar is aryl, such as phenyl, thienyl, thiazolyl, and the like in compounds of Formula II.
  • each Z is independently H or a radical having the formula:
  • pi systems present in compounds of Formula II include, but are not limited to, fused pi systems such as anthra[l,9-£c:5,10-£'c dithiophene diradicals (e.g., anthra[ 1 ,9-bc : 5 , 10-b 'c * ] dithiophen- 1 ,6-diyl); 4, 9-dihydro-s-indaceno[ 1 ,2-b : 5 , 6-b * ] dithiophene diradicals (e.g., 4,9-dihydro-5-indaceno[l,2- ⁇ :5,6- ⁇ ']dithiophen-2,7-diyl); unsubstituted and 5-substituted 5H-dithieno[3,2-b:2',3'-h]carbazole diradicals (e.g., 5-methyl-5H-dithieno[3,2- b:2',3
  • Examples of pi systems present in compounds of Formula II also include unfused moieties such as amine radicals including triphenyl amine diradicals (e.g., N-phenyl-di(phen- 4,l-diyl)amine), thiophenylamine diradicals (e.g., N-methyl-di(thiophen-2,5-diyl)amine and N-phenyl-(phen-4, l-diyl)-(thiophen-2,5-diyl)-amine); biphenyl diradicals (e.g., ⁇ , ⁇ -biphen- 4,4'-diyl), thiophene diradicals (e.g., thiophen-2,5-diyl), phenylene diradicals (e.g., phen-1,4- diyl).
  • amine radicals including triphenyl amine diradicals (e.g., N-phenyl-di(phen- 4,
  • the fused and unfused pi systems includes groups that are unsubstituted or substituted, such as with aryl, alkyl, heteroaryl, halo, etc.
  • the pi system in compounds of Formula II is selected from: and
  • R u may optionally be hydrogen or alkyl.
  • the pi system in compounds of Formula II is selected from:
  • R may optionally be hydrogen or alkyl.
  • the pi system in compounds of Formula II is selected from
  • R may optionally be hydrogen or alkyl.
  • FIGs. 23-28 provide example synthetic schema for making symmetric and asymmetric DiCN compounds, including compounds according to Formula I and Formula II.
  • 2-(3-oxo-2,3-dihydro-lH-inden-l-ylidene)malononitrile (CAS No. 1080-74-6) can be condensed with a number of di- and tri-aldehydes, optionally in the presence of reagents such as acetic anhydride, to provide symmetric DiCN compounds.
  • Asymmetric DiCN compounds can be prepared by using mono-functional aldehydes as shown in FIG. 24. Other methods can also be used for DiCN preparation as described, for example, in J. Am. Chem.
  • DiCN compounds are also commercially available including, for example, ITIC (CAS No. 1664293-06-4), ITIC-M isomers (CAS Nos.
  • Tables 5-9 provide non-limiting examples of DiCN compounds along with shorthand identifiers (ID).
  • the DiCN and derivatives thereof described herein may optionally be characterized as "acceptor-donor-acceptor" molecules.
  • the DiCN and derivatives thereof may behave as acceptors in a transparent photovoltaic. These molecules have may absorb NIR and may be characterized as non-fullerene acceptors when used in some in high efficiency organic photovoltaic devices.
  • these materials may be useful in semitransparent PV devices with very high efficiency, such as when a DiCN type acceptor is paired with one or more donors that absorb at a blue shifted position to the DiCN. Such a blue shifted absorption may be partially in the visible spectrum. However, this severely limits the transparency.
  • a highly transparent device advantageously may be achieved by pairing a DiCN material with a UV-selective donor molecule (similar to FIG. 4B), or an NIR-selective donor that is red shifted relative to DiCN (similar to FIG. 4D).
  • DiCN compounds can be used as acceptor materials and be paired with a number of useful donor materials.
  • the acceptor material contains a DiCN compound or a DiCN derivative and the donor material comprises a boron-dipyrromethene (BODIPY) compound, a phthalocyanine, a naphthalocyanine, a nickel dithiolate (NDT) compound, or a combination thereof.
  • BODIPY boron-dipyrromethene
  • phthalocyanine a phthalocyanine
  • NDT nickel dithiolate
  • the donor material contains a BODIPY, a phthalocyanine, a naphthalocyanine, or a combination thereof.
  • DiCN and derivatives thereof may be formed in a photoactive material layer by a solution processing technique.
  • DiCN and derivatives thereof may, in embodiments, be constructed as a "acceptor-donor-acceptor" molecule.
  • the central donor core may correspond to a large fused aromatic ring with pendant alkyl chains, to provide solubility for solution phase processing.
  • aspects of the DiCN and derivatives thereof may not include pendant alkyl chains of this nature or other thermally unstable side chains or solubilizing functional groups, which may result in lower molecular weight structures, with relatively improved
  • these and other "donor-acceptor-donor" molecules may be processed using gas phase deposition techniques, such as thermal evaporation.
  • FIG. 29 and FIG. 30 provides exemplary normalized absorbance spectra for DiCN compounds.
  • a sample photovoltaic device was constructed using DiCN compound A- 16 and tested for photovoltaic efficiency.
  • A- 16 was used as the acceptor and copper phthalocyanine (CuPc) was used as the donor.
  • An about 8 nm thick anode buffer layer was deposited over a visibly transparent substrate and indium tin oxide (ITO) transparent conductor.
  • An about 10 nm thick layer of CuPc as a donor was deposited over the anode buffer layer.
  • An about 10 nm thick layer including DiCN A- 16 as an acceptor was deposited over the donor layer.
  • An about 5 nm thick cathode buffer layer was deposited over the acceptor layer.
  • an opaque aluminum layer about 80 nm thick was deposited as a top electrode. The cell was illuminated and performance monitored.
  • FIG. 15 provides example data for the A- 16 photovoltaic cell, showing current density as a function
  • BBTs Benzo-fos-thiadiazole compounds
  • BBTs can be used in the devices described herein.
  • BBTs are typically used as acceptors in the devices described herein.
  • BBTs can be used as donors.
  • BBTs typically exhibit absorption maxima in the near-infrared.
  • BBT is a strong electron withdrawing group such that when it is covalently bonded to a strong electron donating group such as an amine, the resulting charge transfer state absorption is in the infra-red portion of the spectrum. This allows for the fabrication of optoelectronic devices which do not absorb light in the visible portion of the spectrum. BBTs are also readily sublimed under vacuum, and can provide better visible transmittance and more neutral color in transparent photovoltaic devices than other acceptors.
  • the BBT compound has a structure according to Formula Ilia, Illb, or lllc:
  • each of Ri, R 2 , R 3 , and R 4 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl in compounds of Formula Ilia, Formula Illb, and Formula IIIc.
  • Ai and A 2 are independently selected from the group consisting of alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclyl ene in compounds of Formula Ilia, Formula Illb, and Formula IIIc.
  • X is selected from the group consisting of O, S, Se, and Te in compounds of Formula Ilia, Formula Illb, and Formula IIIc.
  • Ri, R 2 , R 3 , and R 4 in compounds of Formula Ilia, Formula Illb, and/or Formula IIIc are independently selected from:
  • Ai and A 2 in compounds of Formula Illb or IIIc are independently selected from arylene and heteroarylene.
  • Ai and A 2 in compounds of Formula Illb or IIIc are thiophene diradicals (e.g., thiophene-2,5-diyl).
  • each of Ri, R 2 , R 3 , R4 are aryl (e.g., phenyl).
  • the benzothiadiazole compound has a structure according to Formula IVa, Formula IVb, or Formula IVc:
  • each of Ri, R 2 , R 3 , and R 4 is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl in compounds of Formula IVa, Formula IVb, and Formula IVc.
  • Ai and A 2 are independently selected from the group consisting of alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclyl ene in compounds of Formula IVa, Formula IVb, and Formula IVc.
  • X is selected from the group consisting of O, S, Se, and Te in compounds of Formula IVa, Formula IVb, and Formula IVc.
  • Ri, R 2 , R 3 , and R 4 in compounds of Formula IVa, Formula IVb, and/or Formula IVc are independently selected from:
  • Ai and A 2 in compounds of Formula IVb or IVc are independently selected from arylene and heteroarylene.
  • Ai and A 2 in compounds of Formula Illb or IIIc are thiophene diradicals (e.g., thiophene-2,5-diyl).
  • each of Ri, R 2 , R 3 , R 4 are aryl (e.g., phenyl).
  • the structures be readily modified by selecting linker (A groups) and their substitution (R groups) with aliphatic or aromatic groups. Additionally the X groups can be chosen from O, N, S, Se or a combination thereof.
  • the BBT may be used as an acceptor (in the mixed layers or neat layers) or a transport layer in the device architectures below.
  • FIG. 32 provides example synthetic schema for making BT compounds and BBT compounds, including compounds according to Formula Ilia, Formula Illb, Formula IIIc, Formula IVa, Formula IVb, and Formula IVc.
  • 4,7-dibromobenzo[c]- 1,2,5- thiadiazole (CAS No. 15155-41-6) can be reacted with stannyl thiophenes in a Stille-type coupling reaction to provide thiophene- substituted BT and BBT compounds.
  • Other methods can also be used for BT and BBT preparation as described, for example, in Chem. Mater. 2011, 23, 5484-5490.
  • Table 10 provides non-limiting examples of BT and BBT compounds along with shorthand identifiers.
  • BT compounds and BBT compounds can be used as acceptor molecules and be paired with a number of useful donor materials.
  • the acceptor material contains a BT, a BBT, or a derivative thereof, and the donor material comprises a boron- dipyrromethene (BODIPY) compound, a phthalocyanine, a naphthalocyanine, a nickel dithiolate (NDT) compound, or a combination thereof.
  • BODIPY compounds include, but are not limited to, those described herein.
  • useful phthalocyanines and naphthalocyanines include, but are not limited to, those described herein.
  • Examples of useful NDT compounds include, but are not limited to, those described herein.
  • the donor material contains a BODIPY, a phthalocyanine, a naphthalocyanine, or a combination thereof.
  • DPP-DPTAs Diketopyrrolopyrrole diphenylthienylamines
  • DPP-DPTAs Diketopyrrolopyrrole diphenylthienylamines
  • DPP-DPTAs Diketopyrrolopyrrole diphenylthienylamines
  • DPP-DPTAs Diketopyrrolopyrrole diphenylthienylamines
  • derivatives thereof can be used as acceptors in the devices described herein.
  • DPP-DPTAs are characterized by a donor-acceptor-donor structure, and can exhibit absorption maxima in the near-infrared and visible regions depending on the particular DPP-DPTA.
  • the diketopyrrolopyrrole diphenylthienylamine is a compound according to Formula V:
  • Ri and R 2 in compounds of Formula V are independently selected from the group consisting of alkyl, cycloalkyl.
  • Ai and A 2 are independently selected from the group consisting of alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclylene.
  • DPP-DPTA compounds and DPP-DPTA derivatives are set forth in Table 11.
  • the DPP-DPTA derivative is an isoindigo such as compound C-1.
  • FIG. 33 shows an example absorbance spectrum for a photoactive compound, though this compound absorbs in the visible region more than may be desirable for some visibly transparent photovoltaic device embodiments.
  • the visibly transparent photoactive compounds useful as photoactive materials, buffer materials, and/or optical layers, include metal dithiolene complexes.
  • a photoactive compound exhibits a greater maximum near-infrared absorption strength than maximum visible absorption strength and has a chemical formula
  • each M is independently a metal, such as Fe, Co, Ni, Cu, Zn, Mo, Pd, or Pt.
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, or a substituted or unsubstituted alkoxy group.
  • each A is independently a fused polycyclic ring group having one or more R group substituents.
  • FIG. 34A and FIG. 34B provide example synthetic schema for making visibly transparent photoactive compounds. With reference to FIG. 34A, it will be appreciated that
  • substitutions may be made for the reactant , such as to allow substitution of the phenyl ring pendant to the dithione with another structure structures, such as phenyl rings with more or substituents in different positions, or substitution of both phenyl
  • substitutions may include phenyl rings (e.g., alkyl substituted, halogen substituted, alkoxy substituted, etc.), fused ring structures.
  • Other pendant ring structures may be similarly added, such as naphthyl groups, phenanthryl groups, acenaphthyl groups, etc.
  • Table 12 provides example metal dithione complexes along with shorthand identifiers (ID). Table 12.
  • FIG. 35 provides exemplary normalized absorbance spectra for a number of the compounds in Table 12, showing that these compounds exhibit strong absorbance in the near- infrared with some absorbance in the ultraviolet and minimal absorbance in the visible band.
  • Sample photovoltaic devices were constructed using a number of the transparent photoactive compounds in Table 12 and tested for photovoltaic efficiency. Two device configurations were used for testing purposes, generally constructed as depicted in FIG 1 A, with the transparent photoactive compounds used as a photoactive layer or a buffer layer. In one configuration, two transparent electrodes were used to generate a fully transparent device. In a second configuration, one transparent electrode (indium tin oxide) was used and one opaque electrode was used.
  • a transparent photovoltaic device using the visibly transparent photoactive compound identified as N-l with an opaque configuration was constructed as follows. An about 8 nm thick cathode buffer layer was deposited over a visibly transparent substrate and indium tin oxide (ITO) transparent conductor. An about 15 nm thick layer of a subphthalocyanine (SubPc) dye as a donor was deposited over the anode buffer layer. An about 30 nm thick layer of compound N-l as an acceptor was deposited over the donor layer.
  • ITO indium tin oxide
  • SubPc subphthalocyanine
  • FIG. 36 provides example data for the N-10 photovoltaic cell, showing current density as a function of voltage.
  • FIG. 37 provides example data for the photovoltaic cell, showing current density as a function of voltage.
  • Metal dithiolates can be used as acceptor materials and paired with a number of useful donor materials.
  • the acceptor material includes one or more metal dithiolates
  • the donor material includes a boron-dipyrromethene (BODIPY) compound, a phthalocyanine, a naphthalocyanine, a dicyano-indandione (DiCN), a benzothiadiazole (BT), a benzo-fos-thiadiazole (BBT), a diketopyrrolopyrrole
  • the donor material includes a BODIPY compound, a phthalocyanine, a naphthalocyanine, or a combination thereof.
  • the donor material includes a DiCN, a BT, a BBT, or a DPP-DPTA.
  • the acceptor material contains a metal dithiolate
  • the donor material also contains a metal dithiolate.
  • the donor metal dithiolate may be functionalized with one or more donor groups such as the strong, moderate, and weaker donating groups described above.
  • Metal dithiolates functionalized in this manner can also be used as donor materials when paired with an acceptor material such as a BODIPY, a phthalocyanine, a naphthalocyanine, a DiCN, a BT, a BBT, or DPP-DPTA, a
  • NTCDI naphthalenetetracarboxylic diimide
  • CBI bisimide coronene
  • fluoranthene a corannulene
  • fullerene e.g., C60 or C70
  • useful NTCDIs, CBIs, fluoranthenes, and corannulenes include, but are not limited to, those described herein.
  • the visibly transparent photoactive compounds useful as photoactive materials, buffer materials, and/or optical layers, include UV acceptor molecules including, but not limited to, naphthalenetetracarboxylic diimides, bisimide coronenes, fluoranthenes, corannulenes, and derivatives thereof.
  • UV acceptor molecules including, but not limited to, naphthalenetetracarboxylic diimides, bisimide coronenes, fluoranthenes, corannulenes, and derivatives thereof.
  • Naphthalenetetracarboxylic diimide (NTCDIs) and derivatives thereof including, but not limited to, 4,5,9, 10-tetramino-naphthalenetetracarboxylic diimides and imidazo naphthalenetetracarboxylic diimide) are typically used as acceptors in the devices described herein.
  • NTCDIs and/or derivatives thereof can be used as donors in the.
  • NTCDIs are characterized by good transparency, absorption maxima in the ultraviolet, and synthetic tractability.
  • NTCDIs are useful in certain organic photovoltaic devices in addition to visibly transparent photovoltaic devices.
  • Dimers of naphthalenedicarboximides can be linked through a group which bridges two nitrogens (i.e., one nitrogen in each NTCDI monomer).
  • the structures of the two components can be readily modified at the nitrogen position with various groups such as aliphatic or aromatic groups.
  • the structures can also be modified at the bay positions with various groups such as halides, aliphatic, or aromatic groups.
  • Linkages between NTCDI monomers include, but are not limited to, direct N-N linkages and 1,4 phenyl ene diamine linkages.
  • the NTCDI may be used as an acceptor (in the mixed layers or neat layers) or a transport layer in the devices described herein.
  • Naphthalenedicarboximides absorb in the ultraviolet portion of the electromagnetic spectrum, making them an attractive material class for visibly transparent photovoltaics.
  • Film morphology is extremely important within a photoactive layer. It has been proposed that the three dimensional shape of fullerenes enables their high performance within devices. Thus it is desirable to synthesize molecules with higher dimensionality in order to mimic this property. Dimer structures utilizing planar chromophores are one way to achieve the desired dimensionality.
  • Example NTCDI compounds include those according to Formula VI:
  • Xi, X 2 , X 3 , X 4 are independently selected from the group consisting of aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl in compounds of Formula VI.
  • Ri and R 2 are independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl in compounds of Formula VI.
  • Example NTCDI compounds further include those according to Formula VII:
  • each X is independently selected from the group consisting of F, CI, Br, alkyl, alkoxy, and aryl in compounds of Formula VII.
  • each subscript n is independently 0, 1, 2, 3, 4, or 5 in compounds of Formula VII.
  • each Y is independently selected from the group consisting of H, alkyl, unsubstituted aryl, or substituted aryl in compounds of Formula VII.
  • each ring marked “Ar” is an independently selected aryl group in compounds of Formula VII.
  • each X and each Y is independently selected from the group consisting of F, CI, Br, alkyl, alkoxy, and aryl in compounds of Formula VIII.
  • subscript n is independently 0, 1, 2, 3, 4, or 5 in compounds of Formula VIII.
  • each subscript m is independently 0, 1, or 2 in compounds of Formula VIII.
  • each ring marked “Ar” is an independently selected aryl group in compounds of Formula VIII.
  • Example NTCDI compounds further include those according to Formula IXa:
  • bridging groups (B) can be a direct covalent bond, an arylene linker, a heteroarylene linker, an alkylene linker, or a heteroalkylene linker in compounds of Formula IXa and Formula IXb,
  • each of Xi, X 2 , X 3 , X 4 , X 5 , and X 6 is independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, and halogen in compounds of Formula IXa and Formula IXb.
  • each of Ri, R 2 , R 3 , and R 4 is independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl in compounds of Formula IXa and Formula IXb.
  • the acceptor material contains an NTCDI compound or an NTCDI derivative and the donor material comprises a boron-dipyrromethene (BODIPY) compound, a phthalocyanine, a naphthalocyanine, a nickel dithiolate (NDT) compound, a dicyano-indandione (DiCN), a benzothiadiazole (BT), a benzo-fos-thiadiazole (BBT), a diketopyrrolopyrrole diphenythienylamine (DPP-DPTA), or a combination thereof.
  • BODIPY boron-dipyrromethene
  • a phthalocyanine a naphthalocyanine
  • NTT nickel dithiolate
  • DICN dicyano-indandione
  • BT benzothiadiazole
  • BBT benzo-fos-thiadiazole
  • DPP-DPTA diketopyrrolopyrrole dipheny
  • Examples of useful BODIPY compounds include, but are not limited to, those described herein.
  • Examples of useful phthalocyanines and naphthalocyanines include, but are not limited to, those described herein.
  • Examples of useful NDT compounds include those described herein.
  • Examples of useful DiCNs, BTs, BBTs, and DPP-DPTAs are not limited to, those described herein.
  • FIG. 38 provides an example synthetic scheme for making NTCDI compounds, including compounds according to Formula VI, Formula VII, Formula VIII, Formula IXa, and Formula IXb.
  • 1,4,5,8-naphthalenetetracarboxylic dianhydride (CAS No. 81-30-1) can be reacted with a number of aromatic and aliphatic amines, optionally in the presence of a base such as pyridine, diisopropylethylamine, or the like, to provide a variety of NTCDI compounds.
  • a base such as pyridine, diisopropylethylamine, or the like
  • Other methods can also be used for NTCDI preparation as described, for example, in J. Org. Chem. 2007, 72 (21), 8070-8075.
  • NTCDI compounds including NDI-20D-Br polymer (CAS No. 1100243-35-3) and NDI-2HD-2Br (CAS No. 1459168-68-3), are commercially available and can be used in the devices provided herein.
  • Tables 13-14 provide non-limiting examples of NTCDI compounds along with shorthand identifiers (ID).
  • FIG. 39 provides exemplary normalized absorbance spectra for NTCDI E-1, showing that the compound absorbs strongly in the ultraviolet with limited absorption in the visible and near-infrared.
  • Sample photovoltaic devices were constructed using NTCDI compound E-1 as an acceptor or as a cathode buffer and tested for photovoltaic efficiency. In a first example, E-1 was used as the acceptor and aluminum phthalocyanine chloride
  • ClAlPc ClAlPc
  • ITO indium tin oxide
  • An about 15 nm thick layer of ClAlPc as a donor was deposited over the anode buffer layer.
  • An about 10 nm thick layer including NTCDI E-1 as an acceptor was deposited over the donor layer.
  • An about 5 nm thick cathode buffer layer was deposited over the acceptor layer.
  • a transparent layer of indium tin oxide about 50 nm thick was deposited as a top electrode. The cell was illuminated and performance monitored.
  • FIG. 40A provides example data for the E- 1 photovoltaic cell, showing current density as a function of voltage.
  • E-1 was used in a cathode buffer layer in a cell containing fuller donor. An about 5 nm thick cathode buffer layer containing NTCDI E-1 was deposited over a substrate. An about 60 nm thick layer of C60 (25%:75%) as a donor was deposited over the cathode buffer layer. An about 20 nm thick anode buffer layer was deposited over the donor layer. Finally, an anode of indium tin oxide about 50 nm thick was prepared on top of the anode buffer layer. The cell was illuminated and performance monitored.
  • FIG. 40B provides example data for the E-1 photovoltaic cell, showing current density as a function of voltage.
  • CBIs Bisimide coronenes
  • NTCDIs NTCDIs
  • Example CBI compounds include those according to Formula Xa:
  • each R is independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, and an electron-withdrawing group (e.g., CN, halogen, and the like) in compounds according to Formula Xa and Formula Xb.
  • an electron-withdrawing group e.g., CN, halogen, and the like
  • the acceptor material contains a CBI compound or a CBI derivative and the donor material comprises a boron-dipyrromethene (BODIPY) compound, a phthalocyanine, a naphthalocyanine, a nickel dithiolate (NDT) compound, a dicyano- indandione (DiCN), a benzothiadiazole (BT), a benzo-fos-thiadiazole (BBT), a
  • DPP-DPTA diketopyrrolopyrrole diphenythienylamine
  • BODIPY compounds include, but are not limited to, those described herein.
  • Examples of useful phthalocyanines and naphthalocyanines include, but are not limited to, those described herein.
  • Examples of useful NDT compounds include, but are not limited to, those described herein.
  • Examples of useful DiCNs, BTs, BBTs, and DPP-DPTAs include, but are not limited to, those described herein.
  • FIG. 41 provides example synthetic schema for making CBI compounds, including compounds according to Formula Xa and Formula Xb.
  • perylene CAS No. 198-55-0
  • an N-substituted maleimide such as N-methyl maleimide (CAS No. 930-88-1) and chloranil (1 18-75-2) to provide N-substituted CBI compounds.
  • Further functionality can be introduced by using tetracarboxy perylene or perylene-3,4,9, 10-tetracarboxylic dianhydride (CAS No. 128-69-8) and converting the carboxy/anhydride groups to, e.g., the corresponding amides with variously-substituted amines.
  • Other methods can also be used for CBI preparation as described, for example, in Chem Eur J. 2007, 13 (6), 1746-1753.
  • Non-limiting examples of CBI compounds include CBI F-l and CBI F-2 shown below.
  • Fluoranthenes and derivatives thereof are typically used as acceptors in the devices described herein. In certain embodiments, however, fluoranthenes and/or derivatives thereof can be used as donors in the devices. Fluoranthenes are characterized by absorption maxima in the ultraviolet, synthetic tractability, and tunable energy levels. Fluoranthenes have been employed in certain organic photovoltaic devices but have not been previously employed in transparent photovoltaic devices. [0315] Example fluoranthenes include fused imides the structure:
  • the structure can be readily modified at the nitrogen position with various groups such as aryl groups, alkyl groups, and/or cycloalkyl groups.
  • the structure can also be modified at the Ar positions with halo, aryl, alkyl, cycloalkyl, and the like.
  • the structure can also be modified at the X and Y positions with various groups such as halo, aryl, alkyl, cycloalkyl, and the like.
  • the fluoranthene fused imides may be used as an acceptor or donor (in the mixed layers or neat layers) or a transport layer in the device architectures described herein.
  • the fluoranthene is a compound according to Formula XI:
  • R is selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl in compounds according to Formula XI.
  • X and Y are independently selected from the group consisting of H and an electron-withdrawing group (e.g., CN, halogen, and the like) in compounds according to Formula XI.
  • Zi and Z 2 are independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl in compounds according to Formula XI.
  • the acceptor material contains a fluoranthene or a
  • fluoranthene derivative and the donor material comprises a boron-dipyrromethene (BODIPY) compound, a phthalocyanine, a naphthalocyanine, a nickel dithiolate (DT) compound, a dicyano-indandione (DiCN), a benzothiadiazole (BT), a benzo-fos-thiadiazole (BBT), a diketopyrrolopyrrole diphenythienylamine (DPP-DPTA), or a combination thereof.
  • BODIPY boron-dipyrromethene
  • a phthalocyanine a naphthalocyanine
  • DT nickel dithiolate
  • DT nickel dithiolate
  • DICN dicyano-indandione
  • BT benzothiadiazole
  • BBT benzo-fos-thiadiazole
  • DPP-DPTA diketopyrrolopyrrole diphenythienyl
  • Examples of useful phthalocyanines and naphthalocyanines include, but are not limited to, those described herein.
  • Examples of useful NDT compounds include, but are not limited to, those described herein.
  • Examples of useful DiCNs, BTs, BBTs, and DPP-DPTAs but are not limited to, those described herein.
  • FIGS. 42A and 42B provide example synthetic schema for making fluoranthene compounds, including compounds according to Formula XI.
  • l,3-di(thiophen-2- yl)propan-2-one can be reacted with an acenapthenequinone (e.g., l,2-dioxo-l,2- dihydroacenaphthylene-5-carbonitrile) followed by an N-substituted maleimide (e.g., N- methyl maleimide), to provide a variety of N-substituted fused imide fluoranthenes.
  • acenapthenequinone e.g., l,2-dioxo-l,2- dihydroacenaphthylene-5-carbonitrile
  • N-substituted maleimide e.g., N- methyl maleimide
  • fluoranthenes include fluoranthene G-1 and fluoranthene G-2 shown below.
  • a sample photovoltaic device was constructed using fluoranthene G-1 as the acceptor and boron subphthalocyanine (B-SubPc) as the donor.
  • An about 8 nm thick anode buffer layer was deposited over a visibly transparent substrate and indium tin oxide (ITO) transparent conductor.
  • An about 20 nm thick layer of B-SubPc as a donor was deposited over the anode buffer layer.
  • An about 10 nm thick layer including fluoranthene G-1 as an acceptor was deposited over the donor layer.
  • An about 5 nm thick cathode buffer layer was deposited over the acceptor layer.
  • a transparent layer of indium tin oxide about 50 nm thick was deposited as a cathode. The cell was illuminated and performance monitored.
  • FIG. 43 provides example data for the G-1 photovoltaic cell, showing current density as a function of voltage.
  • Corannulenes and derivatives thereof are typically used as acceptors in the devices described herein. In certain embodiments, however, corannulenes and/or derivatives thereof can be used as donors in the devices. Corannulenes are characterized by absorption maxima in the ultraviolet. Corannulenes have been employed in certain organic photovoltaic devices but have not been previously employed in transparent photovoltaic devices.
  • Example corranulenes include those according to Formula Xlla
  • each R is independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, and an electron-withdrawing group (e.g., CN, halogen, and the like) in compounds according to Formula Xlla and Formula Xllb.
  • an electron-withdrawing group e.g., CN, halogen, and the like
  • the acceptor material contains a corannulene or a
  • corannulene derivative and the donor material comprises a boron-dipyrromethene (BODIPY) compound, a phthalocyanine, a naphthalocyanine, a nickel dithiolate (NDT) compound, a dicyano-indandione (DiCN), a benzothiadiazole (BT), a benzo-fos-thiadiazole (BBT), a diketopyrrolopyrrole diphenythienylamine (DPP-DPTA), or a combination thereof.
  • BODIPY boron-dipyrromethene
  • a phthalocyanine a naphthalocyanine
  • NTT nickel dithiolate
  • DICN dicyano-indandione
  • BT benzothiadiazole
  • BBT benzo-fos-thiadiazole
  • DPP-DPTA diketopyrrolopyrrole diphenythienylamine
  • Examples of useful phthalocyanines and naphthalocyanines include, but are not limited to, those described herein.
  • Examples of useful NDT compounds include, but are not limited to, those described herein.
  • Examples of useful DiCNs, BTs, BBTs, and DPP-DPTAs include, but are not limited to, those described herein.
  • FIG. 44 provides an example synthetic scheme for making corannulenes, including corannulenes according to Formula Xlla and Formula Xllb. For example,
  • acenaphthenequinone (CAS No. 82-86-0) can be reacted with l,3-bis(2-chlorophenyl)propan- 2-one followed by norbornadiene to form 7, 10-bis(2-chlorophenyl)fluoranthene, which can then be converted to the corresponding corannulene using a palladium catalyst.
  • a variety of N-substituted maleimides can be used in place of norbornadiene prior to the palladium-catalyzed corannulene formation step.
  • Other methods can also be used for corranulene preparation as described, for example, in ACS Omega, 2017, 2, 8, 4964-4971.
  • Table 16 provides non-limiting examples of corranulenes along with shorthand identifiers. Table 16.
  • the visibly transparent photoactive compounds useful as photoactive materials, buffer materials, and/or optical layers, include transparent tetracyano quinoidal thiophene, tetracyano indacene, carbazole thiaporphyrin, or dithiophene squarine organic molecules.
  • a photoactive compound exhibits a greater maximum ultraviolet absorption strength or maximum near-infrared absorption strength than maximum visible absorption strength and has the formula
  • each R group is independently a hydrogen, a halogen, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic group, a substituted or unsubstituted fused aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group.
  • each n is 0, 1, 2, 3, 4, 5, 6, or 7.
  • each X is independently O, N-R, S, or Se.
  • each A is independently a fused or unfused aromatic or heteroaromatic group including one or more R group substituents.
  • two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.
  • FIG. 45 provides an example synthetic schema for making visibly transparent
  • photoactive compounds such as those having the formula , which may be referred to herein as tetracyano quinoidal thiophene compo It will be appreciated
  • the reactant may be functionalized with one or more R groups, such as at the 3- or 4-positions on the thiophene ring, such that the reactant may take the fo
  • substituted or unsubstituted alkyl groups or substituted or unsubstituted aromatic groups may be used for the R groups, in addition to others.
  • substitud tetracyano quinoidal thiophene compounds may be created by following the reaction scheme in FIG. 45. Table 17 provides example tetracyano quinoidal thiophene compounds along with shorthand identifiers (ID).
  • FIG. 46 provides an exemplary normalized absorbance spectrum for compound 0-1 in Table 17, showing that the compound exhibits strong absorbance in the near-infrared with limited absorbance in the ultraviolet and visible bands.
  • FIG. 47 provides an example synthetic schemes for making visibly transparent
  • photoactive compounds such as those having the formula or
  • reactant may take the form of action or alternatively, the reactant may be functionalized with one or more R groups, such as at the 3- or 4-
  • substituted or unsubstituted alkyl groups or substituted or unsubstituted aromatic groups may be used for the R groups, in addition to others.
  • various different substituted tetracyano indacene compounds may be created by following the reaction schemes in FIG. 47.
  • Table 18 provides example tetracyano indacene compounds along with shorthand identifiers (ID). Table 18.
  • FIG. 48 provides an example synthetic schemes for making visibly transparent
  • photoactive compounds such as those having the formula , which may be referred to herein as carbazole thiaporphyrin compounds. It will be appreciated that
  • butyl groups such as R groups, such that the reactant may take the form of .
  • R groups such as R groups
  • substituted or unsubstituted alkyl groups or substituted or unsubstituted aromatic groups may be used for the R groups, in addition to others.
  • various different substituted carbazole thiaporphyrin compounds may be created by following the reaction scheme in FIG. 48.
  • Table 19 provides an example carbazole thiaporphyrin compounds along with a shorthand identifier (ID).
  • FIG. 49 provides an exemplary normalized absorbance spectrum for compound L-1 in Table 19, showing that the compound exhibits strong absorbance in the near-infrared and ultraviolet band with limited absorbance in the visible band.
  • FIG. 50 provides an example synthetic schemes for making visibly transparent photoactive compounds, such as those having the formula
  • dithiophene squarine compounds which may be referred to herein as dithiophene squarine compounds. It will be appreciated that many different substitutions may be made
  • reactant may take the form of Additionally or
  • the reactant may be functionalized with one or more R groups, such that the reactant takes the form of .
  • R groups For example, substituted or unsubstituted alkyl groups or substituted or unsubstituted aromatic groups may be used for the R groups, in addition to others.
  • various different substituted dithiophene squarine compounds may be created by following the reaction scheme in FIG. 50.
  • Table 20 provides an example dithiophene squarine compound along with a shorthand identifier (ID).
  • the dithiophene squarine may be regarded as having an electron donor / electron acceptor / electron donor structure.
  • the donor material or the acceptor material includes one or more tetracyano quinoidal thiophene, tetracyano indacene, carbazole thiaporphyrin, or dithiophene squarine compounds as described herein, and the counterpart material includes a nickel dithiolate (NDT) compound, a dicyano-indandione (DiCN), a benzothiadiazole (BT), a benzo-fos-thiadiazole (BBT), a diketopyrrolopyrrole diphenythienylamine (DPP-DPTA), a naphthalenetetracarboxylic diimide (NTCDI), a bisimide coronene (CBI), a fluoranthene, a corannulen
  • Examples of useful NDT compounds include, but are not limted to, those described herein.
  • Examples of useful DiCNs, BTs, BBTs, and DPP-DPTAs but are not limited to, those described herein.
  • Examples of useful NTCDIs, CBIs, fluoranthenes, and corannulenes include, but are not limited to, those described herein.
  • Examples of useful BODIPY compounds include, but are not limited to, those described herein.
  • the visibly transparent photoactive compounds include but are not limited to Al-containing phthalocyanines, Co-containing phthalocyanines, Cu-containing phthalocyanines, Fe- containing phthalocyanines, Pb-containing phthalocyanines, Mg-containing phthalocyanines, Mn-containing phthalocyanines, Ni-containing phthalocyanines, Pd-containing
  • phthalocyanines Pt-containing phthalocyanines, Si-containing, Sn-containing
  • phthalocyanines V-containing phthalocyanines, Zn-containing phthalocyanines, and derivatives thereof.
  • the optical and electrical characteristics of the material may be sensitive to the central metal.
  • the central metal may be Cu, Co, Ni, Zn, Mg, C1A1, SnCb, Pb, Pt, Pd, V, etc.
  • Other metals may be useful with the metal phthalocyanine-based materials, and substitution of a different metal for nickel may result in changes to the absorption profile and or donor/acceptor behavior.
  • oxygen and other protecting groups may be bonded to the central metal.
  • Certain metal phthalocyanines and naphthalocyanines have been shown to display "n-type" (high electron mobility) properties. It can be advantageous to offset the HOMO level of such molecules with respect to the donor to allow for exciton dissociation, so that these materials can better act as acceptor in molecular photovoltaic devices.
  • electronegative substituents can be added to the parent molecule to change its HOMO level and hence, create the desired HOMO level offset.
  • These materials can be replacements for fullerenes such as C 6 o, which are commonly used acceptor material in molecular photovoltaic devices.
  • a material suitable for the layers may include one or more phthalocyanines of Formula XIII:
  • M is selected from the group consisting of Sn, SnCb, SnO, Pb, Mg, Mn, AlCl, AIOH, GaCl, MnCl, SiCb, Si(OH) 2 , PbCb, VO, Co, Fe, FeCl, Ni, TiO, and TiCb
  • each of Ri to Ri6 is independently selected from the group consisting of H, F, CI, and an electron withdrawing group (e.g., an electronegative organic ligand or other electronegative substituent).
  • electron withdrawing groups include, but are not limited to, sulfonyl groups (e.g., tosyl, triflyl, mesyl, and the like), haloalkyl groups (e.g.,
  • a material suitable for the layers may include one or more naphthalocyanines of Formula XIV:
  • M is selected from the group consisting of Sn, SnCb, SnO, Pb, Mg, Mn, AlCl, AIOH, GaCl, MnCl, SiCb, Si(OH) 2 , PbCb, VO, Co, Fe, FeCl, Ni, TiO, and TiCb, and each of Ri to R 2 4 is independently selected from the group consisting of H, F, CI, and an electron withdrawing group.
  • the compounds of Formula XIII and Formula XIV are non-limiting examples of metal phthalocyanines and naphthalocyanines that may be included as a material in an active layer herein, and having an absorption peak in the UV/NTR part of the solar spectrum.
  • SnPc and SnNcCb have been used as donor materials in OPVs while SnPcCb has been shown to have high electron mobility. All three materials absorb the UV/NIR part of the solar spectrum. See FIG. 51.
  • These new materials can be used in an electrically inverted (from top to bottom: Top electrode, Buffer Layer (M0O3). Donor, Acceptor, Buffer Layer (ZnO), Bottom electrode) or a conventional (from top to bottom: Top electrode, Buffer Layer (BCP), Acceptor, Donor, Buffer Layer (M0O3), Bottom electrode) device structure.
  • an inverted device structure electrons (holes) are collected at the bottom (top) electrode.
  • electrons (holes) are collected at the top (bottom) electrode in a conventional device structure.
  • the buffer layers mentioned are non-limiting examples. Buffer layers known in the art and other than those listed may be included in alternate embodiments, as would be recognized by the skilled artisan.
  • MPCs Metal phthalocyanines
  • SnPcCb is an appropriate acceptor material for an active layer herein, and for fabricating transparent PVs.
  • the energy level of SnPcCb may be tuned by adding electronegative substituents to adjust its acceptor properties.
  • Materials suitable for layers herein may include UV/NTR absorbing organic semiconductor materials modified by addition of conjugated substituents. These new materials can be synthesized by adding conjugated substituents to donor or acceptor materials, such as phthalocyanines and naphthalocyanines, which are commonly used as organic semiconductors. The addition of conjugation leads to the red-shifting of the absorption spectrum of the original molecule. The additions may be used to tune the absorption spectrum of materials primarily absorbing in the UV/NTR with some absorption in the visible region to make it completely transparent in the visible region. Additional examples of suitable materials in include those of Formulas XVIII and XIX:
  • R 2 , R 3 , and R 4 are also phenyl. Also, combinations of the compound of Formula XVIII and the compound of Formula XIX are possible.
  • a phthalocyanine has optionally a structure according to Formula XXXII: (XXXII), wherein
  • M is a metal
  • Ai, A 2 , A 3 , and A 4 are each substituted or unsubstituted fused aromatic ring groups, wherein Ai includes a different number of fused rings from at least one of A 2 , A3, or A 4 .
  • phthalocyanines may exhibit non-symmetric structures.
  • Examples of nonsymmetric phthalocyanines of Formula XXXII include those of Formulas XXI, XXII, XXIII, XXIV, and XXV.
  • Phthalocyaninato zinc(II) (PcZn) DBU (0.76 g, 5 mmol) was added to a mixture of sublimed phthalonitrile (0.64 g, 5 mmol) and dry zinc(II) acetate (0.23 g, 1.25 mmol) in dry n-pentanol (20 mL). The mixture was heated for 36 h under reflux. Methanol (50 mL) was added. The isolated product was washed with water and methanol, and then treated with methanol in a Soxhlet apparatus overnight. Yield 0.54 g (75%). The dried PcZn was then purified by zone sublimation at 10-7-10-6 mbar and 370 °C.
  • Non-limiting examples of bases used are presented in Formulas XXVI (DBU), XXVII (TBD), XXVIII (DBN), and XXIX (BEMP), below:
  • phthalocycanines In addition, cyanobenzene starting materials can be further substituted (e.g., with thiophenyl groups or other substituents). Table 21 provides additional non- limiting examples of phthalocyanine compounds that can be prepared via such methods.
  • the phthalocyanine is a compound according to Formula XXXII:
  • each X and each Y is independently selected from the group consisting of H, F, CI, Br, alkoxy, alkyl, and aryl in compounds of Formula XXXII.
  • M is a metal in compounds of Formula XX (e.g., Cu, Fe, Co, Mn, Al, or Sn).
  • the phthalocyanine is a compound according to Formula
  • each of Ri-R 8 is independently selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl in compounds of Formula XXXIII, Formula XXXIV, Formula XXXV, and Formula XXXVI.
  • each X is independently selected from the group consisting of O, S, Se, and Te in compounds of Formula XXXIII, Formula XXXIV, Formula XXXV, and Formula XXXVI.
  • M is a metal in compounds of Formula XXXIII, Formula XXXIV, Formula XXXV, and Formula XXXVI (e.g., Cu, Co, Ni, Zn, Mg, C1A1, SnCb, Pb, Pt, or Pd).
  • FIGs. 60A and 60B and FIG. 61 provide exemplary normalized absorbance spectra for phthalocyanines J- 14, J-l, J-2, and J-3. The spectra demonstrate that the compounds exhibit strong absorption in the UV and near-infrared.
  • the donor material includes a phthalocyanine, a
  • the acceptor material includes a boron- dipyrromethene (BODIPY) compound, a nickel dithiolate (NDT) compound, a dicyano- indandione (DiCN), a benzothiadiazole (BT), a benzo-fos-thiadiazole (BBT), a
  • BODIPY boron- dipyrromethene
  • NDT nickel dithiolate
  • DICN dicyano- indandione
  • BT benzothiadiazole
  • BBT benzo-fos-thiadiazole
  • DPP-DPTA diketopyrrolopyrrole diphenythienylamine
  • NCDI naphthalenetetracarboxylic diimide
  • CBI bisimide coronene
  • fluoranthene a corannulene, or a
  • Examples of useful BODIPY compounds include, but are not limited to, those described herein.
  • Examples of useful NDT compounds include, but are not limited to, those described herein.
  • Examples of useful DiCNs, BTs, BBTs, and DPP-DPTAs include, but are not limited to, those described herein.
  • Examples of useful NTCDIs, CBIs, fluoranthenes, and corannulenes include, but are not limited to, those described herein.
  • the acceptor material includes a DiCN, a BT, a BBT, a DPP- DPTA, or a combination thereof.
  • the acceptor material includes an NDT, an NTCDI, a fluoranthene, a fullerene, or a combination thereof.
  • the acceptor material includes a BODIPY, a CBI, a corranulene, or a combination thereof.
  • the donor material contains a phthalocyanine or
  • naphthalocyanine and the acceptor material also contains a phthalocyanine or
  • the acceptor phthalocyanine/napthalocyanine may be functionalized with an electron withdrawing group or an acceptor group as described herein.
  • Phthalocyanines and napthalocyanines functionalized in this manner can also be used as acceptor materials when paired with a donor material such as a BODIPY, an NDT, a DiCN, a BT, a BBT, or a DPP-DPTA.

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