KR20210069130A - Visibly transparent, near-infrared-absorbing and ultraviolet-absorbing photovoltaic devices - Google Patents

Abstract

Visually transparent photovoltaic devices are disclosed, such as visually transparent photovoltaic devices that are transparent to visible light but absorb near infrared and/or ultraviolet light. Photovoltaic devices use transparent electrodes and visually transparent photoactive compounds, optical materials, and/or buffer materials that absorb near infrared or ultraviolet light.

Description

VISIBLY TRANSPARENT, NEAR-INFRARED-ABSORBING AND ULTRAVIOLET-ABSORBING PHOTOVOLTAIC DEVICES

CROSS REFERENCE TO RELATED APPLICATIONS

This application was filed on June 16, 2017 in U.S. Provisional Patent Application No. 62/521,154, filed on June 16, 2017 in U.S. Provisional Patent Application No. 62/521,158, filed on June 16, 2017 U.S. Provisional Patent Application No. 62/521,160, U.S. Provisional Patent Application No. 62/521,211, filed June 16, 2017, U.S. Provisional Patent Application No. 62/521,214, filed June 16, 2017, and 2017 It claims the benefit of U.S. Provisional Patent Application No. 62/521,224, filed on June 16, , each of which is incorporated herein by reference in its entirety.

technical field

BACKGROUND This application relates generally to optically active materials and devices, and more particularly, to visually transparent photovoltaic devices and materials for visually transparent photovoltaic devices.

The surface area necessary to take advantage of solar energy remains an obstacle in offsetting a significant portion of non-renewable energy consumption. For this reason, there is a need for low-cost, transparent, organic photovoltaic (OPV) devices that can be integrated over the window panes of homes, skyscrapers, and automobiles. For example, window glass used in automobiles and buildings is typically 70 to 80% and 55 to 90% transparent, respectively, for light having a wavelength in the visible spectrum, such as about 450 to 650 nanometers (nm). to be. The limited mechanical flexibility, high module cost, and, more importantly, band-like adsorption of inorganic semiconductors limit their potential use for transparent solar cells. do.

In contrast, the optical properties of organic and molecular semiconductors produce highly structured absorption spectra with absorption maxima and minima that are uniquely distinct from the band absorption of their inorganic counterparts.

However, while a variety of organic and molecular semiconductors exist, many of them exhibit strong absorption in the visible spectrum and are therefore not optimal for use in window glass-based photovoltaic cells.

At the headquarters Materials, methods, and systems related to visually transparent photovoltaic devices are described. More particularly, the present specification relates to 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 acceptors), visually transparent tetracyano quinoidal thiophene compounds, visually transparent tetracyano indacene compounds, visually transparent carbazole thiaporphyrin compounds, visually transparent dithiophene squarine compounds, phthalocyanine compounds, phthalocyanine derivative compounds, and structurally related compounds; and methods and systems for incorporating materials, molecules, and compounds as photoactive materials for visually transparent photovoltaic devices. Embodiments of the present invention provide transparent photoactive materials, including organic semiconductor materials, useful in visually transparent photovoltaic devices. The present invention is applicable to various applications in photovoltaic cells and electronics.

Materials, methods, and systems for transparent photovoltaic devices are disclosed, such as materials, methods, and systems that are transparent to visible light but absorb near-infrared light and/or ultraviolet light. Photovoltaic devices include transparent electrodes and visually transparent boron-dipyrromethene (BODIPY)-based compounds, near-infrared donor acceptor (near-IR DA) molecules, metal dithiolate compounds, ultraviolet electron acceptor molecules (UV acceptors), visually transparent A tetracyano quinoidal thiophene compound, a visibly transparent tetracyano indacene compound, a visibly transparent carbazole thiaporphyrin compound, a visibly transparent dithiophene squarine compound, a phthalocyanine compound, a phthalocyanine derivative compound, or a structurally related compound and such compounds may be useful, for example, as photoactive materials, buffer materials, and/or optical layers. In some embodiments, the disclosed visually transparent photoactive compounds exhibit a maximum near infrared absorption intensity and a maximum visible light absorption intensity, wherein the maximum near infrared absorption intensity is greater than the maximum visible light absorption intensity.

A number of advantages over conventional techniques are achieved by the method of the present invention. For example, 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. Advantageously, this optical property provides the ability to generate electricity within the optoelectronic device from incident solar radiation while still allowing useful visible light to pass through, making it observable by an observer through the photovoltaic device.

In addition, the photoactive compounds described herein provide a DC voltage or current to an external circuit by providing suitable electron donors and/or electron acceptors for the generation and dissociation of electron-hole pairs through absorption of light. . Advantageously, the disclosed photoactive compounds exhibit greater absorption intensities in the near infrared (NIR) band, for example from about 650 nm to about 1400 nm, while being transparent to visible light or in the visible band, for example about 450 nm. those that absorb only a relatively small amount of light from to about 650 nm. In some embodiments, the disclosed photoactive compounds exhibit peak absorption within the NIR band. In some embodiments, the disclosed photoactive compounds exhibit absorption in the visible band with an intensity less than the intensity in the NIR band. In some embodiments, the disclosed photoactive compounds exhibit peak absorption within the UV band. In some embodiments, the disclosed photoactive compounds exhibit absorption in the visible band with an intensity less than the intensity in the UV band.

The disclosed photoactive compounds also exhibit material properties that provide advantages for the fabrication and performance of visually transparent photovoltaic devices. For example, a device comprising a photoactive compound described herein may be fabricated using a technique in which the photoactive compound is applied to a substrate using a vacuum deposition technique rather than a solution-based application technique. The use of vacuum deposition techniques advantageously produces high purity photoactive layers, thereby improving device efficiency and performance and reducing fabrication complexity. For example, transparent photovoltaic devices can eliminate the use of solution-based photoactive material application steps and associated waste product handling and disposal by introducing the disclosed photoactive compounds into the active material layer by the method of vacuum thermal evaporation techniques. In addition, in some embodiments, the disclosed photoactive compounds can be purified by evaporation and/or sublimation techniques. Purification by evaporation and/or sublimation can be useful for producing high purity photoactive materials and compounds, which ultimately enables improved transparent photovoltaic device production and performance.

A visually transparent photovoltaic device comprises: a visually transparent substrate; a first visually transparent electrode coupled to the visually transparent substrate; a second visually transparent electrode over the first visually transparent electrode; A first visually transparent active layer between a first visually transparent electrode and a second visually transparent electrode, wherein the first visually transparent photoactive layer is a visually transparent photoactive compound, such as described herein. any visually transparent photoactive compound comprising a first maximum near infrared or ultraviolet absorption intensity and a first maximum visible light absorption intensity, such as a first greater than the first maximum visible light absorption intensity. a first visually transparent active layer comprising a visually transparent photoactive compound exhibiting a maximum near-infrared or ultraviolet absorption intensity; and a second maximum absorption intensity in the near infrared or ultraviolet and a second maximum visible light absorption intensity between the first and second visually transparent electrodes, such as a second maximum visible light. and a second visually transparent photoactive layer exhibiting a second maximum absorption intensity greater than the absorption intensity. Optionally, the visually transparent photovoltaic device can further comprise a first buffer layer disposed between the first visually transparent electrode and the first visually transparent active layer. Optionally, the visually transparent photovoltaic device can further comprise a second buffer layer disposed between the second visually transparent active layer and the second visually transparent electrode.

Optionally, the first visually transparent photoactive layer is coupled to the first visually transparent electrode. Optionally, the first visually transparent photoactive layer is coupled to the second visually transparent electrode. Optionally, a second visually transparent photoactive layer is coupled to the first visually transparent electrode. Optionally, the second visually transparent photoactive layer is coupled to the second visually transparent electrode. As used herein, two objects or layers that are coupled are indirectly, such as two objects or layers are directly coupled (ie, in physical contact) or have one or more additional objects or layers therebetween. It refers to a coupled state. Coupling of an object or layer may indicate that the object or layer is part of a single overall structure or device.

Optionally, the photoactive compound acts as an electron acceptor material. In some embodiments, when the photoactive compound acts as an electron acceptor material, the second visually transparent photoactive layer may comprise an electron donor material. Optionally, the photoactive compound acts as an electron donor material. In an embodiment, where the photoactive compound acts as an electron donor material, the second visually transparent photoactive layer may comprise an electron acceptor material.

Various configurations are contemplated for the photoactive layer. For example, the first visually transparent photoactive layer and the second visually transparent photoactive layer each independently have a thickness 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 nm, 210 nm, 215 nm, 220 nm, 225 nm, 230 nm, 235 nm, 240 nm, 245 nm, 250 nm, 255 nm, 260 nm, 265 nm, 270 nm, 275 nm, 280 nm, 285 nm, 290 nm, 295 nm, or 300 nm. Optionally, the first visually transparent photoactive layer and the second visually transparent photoactive layer correspond to separate, mixed, or partially mixed layers.

A variety of compounds are useful as photoactive compounds in the optically transparent photovoltaic devices described. For example, the photoactive compound may optionally exhibit peak absorption in the near infrared. Optionally, the photoactive compound may exhibit peak absorption in ultraviolet light.

,

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, 또는

를 갖는다. 구현예에서, 각각의 A1은 독립적으로 하나 이상의 R 그룹 치환체를 포함하는 융합되거나 융합되지 않은 방향족 또는 헤테로방향족 그룹이다. 구현예에서, 각각의 A2는 독립적으로 하나 이상의 R 그룹 치환체를 포함하는 융합되거나 융합되지 않은 방향족 또는 헤테로방향족 그룹이다. 구현예에서, 각각의 X는 독립적으로 S, N, 또는 C―R이다. 구현예에서, 각각의 L 그룹은 독립적으로 단일 결합이거나 치환되거나 비치환된 알킬렌 그룹, 치환되거나 비치환된 아릴렌 그룹, 또는 치환되거나 비치환된 헤테로아릴렌 그룹으로부터 선택된 2가 연결 그룹이다. 구현예에서, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다.Examples of exemplary photoactive compounds described herein and useful as photoactive layers in visually transparent photovoltaic devices include boron-dipyrromethene-based photoactive compounds, such as boron difluoride moieties (moieties), such as fluorine fluoro boron dipyrromethene moieties, fluoro boron azadipyrromethene moieties, and fluoro diazaborolo and related core structures. Other examples of boron-dipyrromethene-based photoactive compounds described herein include those comprising a boron dioxide moiety, which may generally correspond to a compound comprising an oxygen substituted boron difluoride moiety. In some instances, the photoactive compounds provided herein are of the formula

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, or

has In an embodiment, each A 1 is independently a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents. In an embodiment, each A2 is independently a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents. In embodiments, each X is independently S, N, or C-R. In embodiments, each L group is independently a single bond or a divalent linking group selected from a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group. In embodiments, each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted a heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.

A visually clear photoactive compound having the formula:

can be further characterized by the formula:

,

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, 또는

. 앞서 언급한 화학식의 화합물은 가시광선에서 최대 흡수 강도보다 근적외선에서 보다 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

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. It will be appreciated that the compound of the above-mentioned formula may exhibit a stronger maximum absorption intensity in the near-infrared light than the maximum absorption intensity in the visible light.

A visually clear photoactive compound having the formula:

can be further characterized by the formula:

또는

.

or

.

A visually clear photoactive compound having the formula:

can be further characterized by the formula:

.

.

Examples of photoactive compounds described herein and useful as photoactive layers in visually transparent photovoltaic devices include near-infrared absorbing photoactive compounds, such as acceptor materials comprising near-infrared absorbing donor-acceptor (near-IR DA) molecules. Advantageously, the near infrared absorbing photoactive compound may exhibit a first maximum near infrared absorption intensity and a first maximum visible light absorption intensity, for example, the first maximum near infrared absorption intensity is the first maximum visible light absorption intensity bigger than Examples of photoactive compounds described herein include visually transparent near-IR DA molecules such as dicyano-indandione, benzo- bis -thiadiazole, diketopyrrolopyrrole diphenylthienylamine, and derivatives thereof. including, but not limited to.

Optionally, the second visually transparent photoactive layer absorbs near infrared so that the second visually transparent photoactive layer has a second maximum absorption intensity in the near infrared and a second maximum visible light absorption intensity, such as a second maximum It represents a second maximum absorption intensity greater than the visible light absorption intensity. Optionally, the maximum near-infrared absorption by the acceptor material is redshifted relative to the maximum near-infrared absorption by the donor material. Optionally, the maximum near-infrared absorption by the acceptor material is blueshifted with respect to the maximum near-infrared absorption by the donor material. For example, the peak near-infrared absorption by the acceptor molecule may be blue-shifted or red-shifted relative to the peak near-infrared absorption by the donor molecule.

Optionally, the near infrared absorbing photoactive compound has a molecular weight of 200 amu to 1000 amu, 300 amu to 800 amu, or 400 amu to 600 amu. For example, the near-infrared absorbing photoactive compound may be 200 amu to 220 amu, 220 amu to 240 amu, 240 amu to 260 amu, 260 amu to 280 amu, 280 amu to 300 amu, 300 amu to 320 amu, 320 amu to 340 amu , 340 amu to 360 amu, 360 amu to 380 amu, 380 amu to 400 amu, 400 amu to 420 amu, 420 amu to 440 amu, 440 amu to 460 amu, 460 amu to 480 amu, 480 amu to 500 amu, 500 amu to 520 amu, 520 amu to 540 amu, 540 amu to 560 amu, 560 amu to 580 amu, 580 amu to 600 amu, 600 amu to 620 amu, 620 amu to 640 amu, 640 amu to 660 amu, 660 amu to 680 amu, 680 amu to 700 amu, 700 amu to 720 amu, 720 amu to 740 amu, 740 amu to 760 amu, 760 amu to 780 amu, 780 amu to 800 amu, 800 amu to 820 amu, 820 amu to 840 amu , 840 amu to 860 amu, 860 amu to 880 amu, 880 amu to 900 amu, 900 amu to 920 amu, 920 amu to 940 amu, 940 amu to 960 amu, 960 amu to 980 amu, or 980 amu to 1000 amu has a molecular weight.

또는

를 갖는다. 임의로, Y는 F, Cl, Br, 알콕시, 알킬, 또는 아릴이다. 임의로, n은 0 내지 5의 정수이다. 임의로, X는 C(CN)₂, O, S, C(O), 또는 SO₂이다. 임의로, Ar은 아릴, 예를 들면, 페닐, 티에틸, 티아졸릴 등이다. 임의로, t는 1 또는 2이다. 임의로, X는 이다. 임의로, 각각의 Z는 독립적으로 H 또는 다음 화학식을 갖는 라디칼이고:In some embodiments, a near-infrared absorbing photoactive compound, eg, a near-IR DA molecule, is a visually transparent photoactive compound useful in the photoactive layer of a visually transparent photoelectric cell. Useful visually transparent photoactive compounds include dicyano-indandione, dicyano-indandione derivatives, benzo- bis -thiadiazole, benzo- bis -thiadiazole derivatives, benzothiadiazole, benzothiadiazole derivatives, diketopy. rolopyrrole diphenylthienylamine, or diketopyrrolopyrrole diphenylthienylamine derivatives. In some embodiments, dicyano-indandione has the formula

or

has Optionally, Y is F, Cl, Br, alkoxy, alkyl, or aryl. Optionally, n is an integer from 0 to 5. Optionally, X is C(CN) ₂ , O, S, C(O), or SO ₂ . Optionally, Ar is aryl, such as phenyl, thiethyl, thiazolyl, and the like. Optionally, t is 1 or 2. Optionally, X is Optionally, each Z is independently H or a radical having the formula:

, 여기서 물결선은 pi 시스템에 대한 부착 점을 나타내고, X, Y, Ar, 및 n은 위에서 정의한 바와 같다.

, where the wavy line represents the point of attachment to the pi system, and X, Y, Ar, and n are as defined above.

Examples of pi systems include, some of which may also be fused pi systems : anthra[1,9-bc :5,10- b'c' ]dithiophene diradicals (eg , anthra [1,9- bc :5,10- b'c' ]dithiophene-1,6-diyl); 4,9-dihydro- s -indaceno[1,2- b :5,6- b' ]dithiophene radical (eg , 4,9-dihydro- s -indaceno[1,2- b : 5,6- b′ ]dithiophene-2,7-diyl); Unsubstituted and substituted 5 H 5-a dithieno [3,2-b: 2 ', 3'-h] carbazole is a radical (e. G., 5-methyl -5 H - in dithieno [3,2 -b:2',3'-h]carbazole-2,8-diyl); unsubstituted and 4-substituted 4H -dithieno[3,2- b :2′,3′- d ]pyrrole radicals (eg , 4-methyl- 4H -dithieno[3,2- b: 2 ', 3'- d] pyrrol-2,6-diyl or 4- (4-methylphenyl) -4 H - rowing dt [3,2- b: 2', 3'- d] pyrrole -2 ,6-diyl); dithieno[3,2- b :2',3'- d ]thiophene radical (eg , dithieno[3,2- b :2',3'- d ]thiophene-2,6- diyl); thieno[3,2- b ]thiophene radicals (eg , thieno[3,2- b ]thiophene-2,6-diyl). Optionally, the fused pi system comprises groups unsubstituted or substituted, for example, with aryl, alkyl, heteroaryl, halo, and the like. In some embodiments, the fused pi system has the formula:

, 또는

, 여기서 R^D는 임의로 수소 또는 알킬일 수 있다. 일부 구현예에서, pi 시스템은 다음 화학식을 가지며:

, or

, wherein R ^D may optionally be hydrogen or alkyl. In some embodiments, the pi system has the formula:

, 또는

, 여기서 R^D는 임의로 수소 또는 알킬일 수 있다. 일부 구현예에서, 융합된 pi 시스템은 다음 화학식을 가지며:

, or

, wherein R ^D may optionally be hydrogen or alkyl. In some embodiments, the fused pi system has the formula:

,

,

,

, 또는

, 여기서 R^D는 임의로 수소 또는 알킬일 수 있다. pi 시스템의 예는 또한 융합되지 않은 모이어티, 예를 들면, 트리페닐아민 이라디칼(예컨대, N-페닐-디(펜-4,1-디일)아민), 티오페닐아민 이라디칼(예컨대, N-메틸-디(티오펜-2,5-디일)아민 및 N-페닐-(펜-4,1-디일)-(티오펜-2,5-디일)-아민); 비페닐 이라디칼(예컨대, 1,1'-비펜-4,4'-디일), 티오펜 이라디칼(예컨대, 티오펜-2,5-디일), 페닐렌 이라디칼(예컨대, 펜-1,4-디일)을 포함하는 아민 라디칼을 포함할 수 있다. 임의로, 상기 융합되지 않은 pi 시스템은 비치환되거나 예를 들면, 아릴, 알킬, 헤테로아릴, 할로 등으로 치환된 그룹을 포함한다.

,

,

,

, or

, wherein R ^D may optionally be hydrogen or alkyl. Examples of pi systems also include unfused moieties such as triphenylamine radicals (eg N-phenyl-di(phen-4,1-diyl)amine), thiophenylamine radicals (eg N -methyl-di(thiophen-2,5-diyl)amine and N-phenyl-(phen-4,1-diyl)-(thiophen-2,5-diyl)-amine); Biphenyl radicals (eg 1,1'-biphen-4,4'-diyl), thiophene radicals (eg thiophene-2,5-diyl), phenylene radicals (eg phen-1, 4-diyl). Optionally, the unfused pi system comprises groups unsubstituted or substituted with, for example, aryl, alkyl, heteroaryl, halo, and the like.

In some embodiments, benzo- bis -thiadiazole has the formula:

,

, 또는

. 임의로, 각각의 R₁, R₂, R₃, 및 R₄는 알킬, 알케닐, 알키닐, 아릴, 헤테로아릴, 사이클로알킬, 및 헤테로사이클릴로 이루어진 그룹으로부터 독립적으로 선택된다. 임의로, A₁ 및 A₂는 알킬렌, 아릴렌, 헤테로아릴렌, 사이클로알킬렌, 및 헤테로사이클릴렌으로 이루어진 그룹으로부터 독립적으로 선택된다. 임의로, X는 O, S, Se, 및 Te로 이루어진 그룹으로부터 선택된다. 일부 구현예에서, R₁, R₂, R₃, 및 R₄는 다음으로부터 독립적으로 선택된다:

,

, or

. Optionally, each of R ₁ , R ₂ , R ₃ , and R ₄ is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl. Optionally, A ₁ and A ₂ are independently selected from the group consisting of alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclylene. Optionally, X is selected from the group consisting of O, S, Se, and Te. In some embodiments, R ₁ , R ₂ , R ₃ , and R ₄ are independently selected from:

,

, 및

. 일부 구현예에서, A₁ 및 A₂는 아릴렌 및 헤테로아릴렌으로부터 독립적으로 선택된다. 일부 구현예에서, A₁ 및 A₂는 티오펜 이라디칼(예컨대, 티오펜-2,5-디일)이다. 일부 이러한 구현예에서, 각각의 R₁, R₂, R₃, R₄는 아릴(예컨대, 페닐)이다.

,

, and

. In some embodiments, A ₁ and A ₂ are independently selected from arylene and heteroarylene. In some embodiments, A ₁ and A ₂ are thiophene radicals (eg , thiophene-2,5-diyl). In some such embodiments, each of R ₁ , R ₂ , R ₃ , R ₄ is aryl (eg , phenyl).

In some embodiments, benzothiadiazole has the formula:

,

, 또는

. 임의로, 각각의 R₁, R₂, R₃, 및 R₄는 알킬, 알케닐, 알키닐, 아릴, 헤테로아릴, 사이클로알킬, 및 헤테로사이클릴로 이루어진 그룹으로부터 독립적으로 선택된다. 임의로, A₁ 및 A₂는 알킬렌, 아릴렌, 헤테로아릴렌, 사이클로알킬렌, 및 헤테로사이클릴렌으로 이루어진 그룹으로부터 독립적으로 선택된다. 임의로, X는 O, S, Se, 및 Te로 이루어진 그룹으로부터 선택된다. 일부 구현예에서, R₁, R₂, R₃, 및 R₄는 다음으로부터 독립적으로 선택된다:

,

, or

. Optionally, each of R ₁ , R ₂ , R ₃ , and R ₄ is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl. Optionally, A ₁ and A ₂ are independently selected from the group consisting of alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclylene. Optionally, X is selected from the group consisting of O, S, Se, and Te. In some embodiments, R ₁ , R ₂ , R ₃ , and R ₄ are independently selected from:

,

, 및

. 일부 구현예에서, A₁ 및 A_2는 아릴렌 및 헤테로아릴렌으로부터 독립적으로 선택된다. 일부 구현예에서, A₁ 및 A₂는 티오펜 이라디칼(예컨대, 티오펜-2,5-디일)이다. 일부 이러한 구현예에서, 각각의 R₁, R₂, R₃, R₄는 아릴(예컨대, 페닐)이다. 구조는 링커(A 그룹)를 선택하고 이들을 지방족 또는 방향족 그룹으로 치환(R 그룹)시켜 용이하게 개질시킬 수 있다. 또한, X 그룹은 O, N, S, Se 또는 이들의 조합으로부터 선택될 수 있다.

,

, and

. In some embodiments, A ₁ and A _{2 are} independently selected from arylene and heteroarylene. In some embodiments, A ₁ and A ₂ are thiophene radicals (eg , thiophene-2,5-diyl). In some such embodiments, each of R ₁ , R ₂ , R ₃ , R ₄ is aryl (eg , phenyl). The structure can be readily modified by selecting linkers (group A) and substituting them with aliphatic or aromatic groups (group R). In addition, the X group may be selected from O, N, S, Se, or combinations thereof.

을 갖는다. 임의로, R₁ 및 R₂는 알킬 및 사이클로알킬로부터 독립적으로 선택된다. 임의로, A₁ 및 A₂는 알킬렌, 아릴렌, 헤테로아릴렌, 사이클로알킬렌, 및 헤테로사이클릴렌으로부터 독립적으로 선택된다.In some embodiments, diketopyrrolopyrrole diphenylthienylamine has the formula

has Optionally, R ₁ and R ₂ are independently selected from alkyl and cycloalkyl. Optionally, A ₁ and A ₂ are independently selected from alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclylene.

,

,

,

,

,

,

,

,

,

, 또는

. 구현예에서, 각각의 M은 독립적으로 금속, 예를 들면, Fe, Co, Ni, Cu, Zn, Mo, Pd, 또는 Pt이다. 구현예에서, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 알케닐 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 구현예에서, 각각의 A는 독립적으로 하나 이상의 R 그룹 치환체를 갖는 융합된 폴리사이클릭 환 그룹이다. 임의로, 하나 이상의 R 그룹은 각각 독립적으로 메톡시 그룹, 디메틸 아미노 그룹, 시아노 그룹, 티아졸릴 그룹, 페닐 그룹, 말레이미드 그룹, 나프틸 그룹, 또는 페난트렌 그룹이다.Exemplary photoactive compounds described herein and useful as photoactive layers in visually transparent photovoltaic devices are metal dithiolate complexes, such as nickel dithiolate compounds, also referred to as metal dithiolate compounds or metal dithiolene compounds. , cobalt dithiolate compounds, iron dithiolate compounds, zinc dithiolate compounds, molybdenum dithiolate compounds, palladium dithiolate compounds, platinum dithiolate compounds, and the like. In some examples, the photoactive compounds provided herein have the formula:

,

,

,

,

,

,

,

,

,

, or

. In embodiments, each M is independently a metal, eg, Fe, Co, Ni, Cu, Zn, Mo, Pd, or Pt. In embodiments, each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fusion an aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, or a substituted or unsubstituted alkoxy group. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. In an embodiment, each A is independently a fused polycyclic ring group having one or more R group substituents. Optionally, 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.

Formula:

을 갖는 가시적으로 투명한 광활성 화합물은 다음 화학식에 의해 추가로 특징화될 수 있다:

Visually transparent photoactive compounds having a can be further characterized by the formula:

,

,

,

,

,

, 또는

. 다음 화학식:

,

,

,

,

,

, or

. Formula:

을 갖는 가시적으로 투명한 광활성 화합물은 다음 화학식에 의해 추가로 특징화될 수 있으며:

, 여기서 각각의 A는 독립적으로 하나 이상의 R 그룹 치환체를 갖는 융합된 폴리사이클릭 환 그룹이다. 예를 들면, 가시적으로 투명한 광활성 화합물은 화학식

,

,

,

, 또는

를 가질 수 있다. 구체적인 광활성 화합물은 다음을 포함하나, 이에 한정되지 않는다:

Visually transparent photoactive compounds having a can be further characterized by the formula:

, wherein each A is independently a fused polycyclic ring group having one or more R group substituents. For example, a visually transparent photoactive compound has the formula

,

,

,

, or

can have Specific photoactive compounds include, but are not limited to:

,

,

,

,

,

,

,

,

,

,

,

, 및

.

,

,

,

,

,

,

,

,

,

,

,

, and

.

Examples of photoactive compounds described herein and useful as photoactive materials in visually transparent photovoltaic devices include near-infrared absorbing donor-acceptor (near-IR DA) molecules, naphthalenetetracarboxylic diimides, bisimide coronene, fluoranthene, chola Nullene, and derivatives thereof. In some embodiments, the UV receptor-molecule is naphthalenetetracarboxylic diimide, naphthalenetetracarboxylic diimide derivative, bisimide coronene, bisimide coronene derivative, fluoranthene, fluoranthene derivative, coranulene, coranulene. derivatives, and combinations thereof. Optionally, the visually transparent photoactive compound has little or no visible absorption. For example, the optically clear photoactive compound may contain 0.1% to 10% of the first maximum ultraviolet absorption intensity of the receptor material, such as about 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, a first maximum visible light absorption of 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, or 10% strength can be expressed.

In some embodiments, the naphthalenetetracarboxylic diimide has the formula:

,

,

,

, 또는

. 임의로, X₁, X₂, X₃, X₄는 독립적으로 아릴, 헤테로아릴, 알킬, 알케닐, 알키닐, 사이클로알킬, 또는 헤테로사이클릴이다. 임의로, R₁ 및 R₂는 독립적으로 H, 아릴, 헤테로아릴, 알킬, 알케닐, 알키닐, 사이클로알킬, 또는 헤테로사이클릴이다. 임의로, 각각의 X는 독립적으로 F, Cl, Br, 알킬, 알콕시, 또는 아릴이다. 임의로, 각각의 첨자 n은 독립적으로 0, 1, 2, 3, 4, 또는 5이다. 임의로, 각각의 Y는 독립적으로 H, 알킬, 비치환된 아릴, 또는 치환된 아릴이다. 임의로, "Ar"로 표시된 각각의 환은 독립적으로 선택된 아릴 그룹이다.

,

,

,

, or

. Optionally, X ₁ , X ₂ , X ₃ , X ₄ are independently aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, or heterocyclyl. Optionally, R ₁ and R ₂ are independently H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, or heterocyclyl. Optionally, each X is independently F, Cl, Br, alkyl, alkoxy, or aryl. Optionally, each subscript n is independently 0, 1, 2, 3, 4, or 5. Optionally, each Y is independently H, alkyl, unsubstituted aryl, or substituted aryl. Optionally, each ring designated "Ar" is an independently selected aryl group.

In some embodiments, the bisimide coronene has the formula:

또는

. 임의로, 각각의 R은 독립적으로 H, 아릴, 헤테로아릴, 알킬, 알케닐, 알키닐, 사이클로알킬, 헤테로사이클릴, 또는 전자-구인 그룹(예컨대, CN, 할로겐 등)이다.

or

. Optionally, each R is independently H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, or an electron-withdrawing group (eg , CN, halogen, etc.).

In some embodiments, fluoranthene has the formula:

. 일부 구현예에서, 코라눌렌은 본원에 기술된 바와 같은 화학식 VII에 따른 구조를 갖는다. 임의로, R은 H, 아릴, 헤테로아릴, 알킬, 알케닐, 알키닐, 사이클로알킬, 또는 헤테로사이클릴이다. 임의로, X 및 Y는 독립적으로 H 또는 전자-구인 그룹(예컨대, CN, 할로겐 등)이다. 임의로, Z₁ 및 Z₂는 독립적으로 H, 아릴, 헤테로아릴, 알킬, 알케닐, 알키닐, 사이클로알킬, 또는 헤테로사이클릴이다.

. In some embodiments, coranulene has a structure according to Formula VII as described herein. Optionally, R is H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, or heterocyclyl. Optionally, X and Y are independently H or an electron-withdrawing group (eg, CN, halogen, etc.). Optionally, Z ₁ and Z ₂ are independently H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, or heterocyclyl.

As described in further detail below, the naphthalenetetracarboxylic diimides, bisimide coronenes, fluoranthenes, and coranulenes described herein are commonly used as electron acceptor materials.

,

,

,

,

, 또는

를 갖는다. 구현예에서, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 구현예에서, 각각의 n은 0, 1, 2, 3, 4, 5, 6, 또는 7이다. 구현예에서, 각각의 X는 독립적으로 O, N-R, S, 또는 Se이다. 구현예에서, 각각의 A는 독립적으로 하나 이상의 R 그룹 치환체를 포함하는 융합되거나 융합되지 않은 방향족 또는 헤테로방향족 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 임의로, 하나 이상의 R은 공여체 모이어티이다. 임의로, 하나 이상의 R은 수용체 모이어티이다.Examples of photoactive compounds described herein and useful as photoactive layers in visually transparent photovoltaic devices include quinoidal structures, tetracyano quinoidal thiophene structures, tetracyano indacene structures, carbazole thiaporphyrin structures, and dithiophene squarines. includes those that contain structures. In some instances, the photoactive compounds provided herein are of the formula

,

,

,

,

, or

has In embodiments, each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted a heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group. In embodiments, each n is 0, 1, 2, 3, 4, 5, 6, or 7. In embodiments, each X is independently O, NR, S, or Se. In embodiments, each A is independently a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. Optionally, one or more R is a donor moiety. Optionally, one or more R is an acceptor moiety.

In an embodiment, a visually transparent photoactive compound, eg, a quinoidal compound, has a quinoidal backbone structure. Examples of quinoidal compounds or compounds comprising a quinoidal skeleton include those having the following formula:

. 퀴노이달 화합물 또는 퀴노이달 골격을 포함하는 화합물의 예는 다음 화학식을 갖는 테트라시아노 퀴노이달 티오펜 화합물을 포함하고:

. Examples of a quinoidal compound or a compound containing a quinoidal skeleton include a tetracyano quinoidal thiophene compound having the following formula:

, 다음 화학식으로 추가로 특징화될 수 있으며:

, can be further characterized by the formula:

, 여기서 m은 0, 1, 2, 3, 4, 또는 5이고, 예를 들면, 다음 화학식을 갖는 화합물로 추가로 특징화될 수 있다:

, wherein m is 0, 1, 2, 3, 4, or 5, and can be further characterized, for example, as a compound having the formula:

,

,

,

,

,

,

,

,

,

, 또는

. 구체적인 광활성 화합물은 화학식:

를 갖는 것들을 포함한다. 이러한 화합물은 가시광선에서 최대 흡수 강도보다 근적외선에서 보다 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다. 일부 구현예에서, 이러한 화합물은 가시광선에서 최대 흡수 강도보다 자외선에서 보다 강력한 최대 흡수 강도를 나타낼 수 있다.

,

,

,

,

,

,

,

,

,

, or

. Specific photoactive compounds have the formula:

include those with It can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in visible light. In some embodiments, such compounds may exhibit a stronger maximum absorption intensity in ultraviolet light than the maximum absorption intensity in visible light.

A visually transparent photoactive compound, for example a tetracyano indacene compound having the formula:

또는

은 다음의 화학식으로 추가로 특징화될 수 있다:

or

can be further characterized by the formula:

,

,

, 또는

. 이러한 화합물이 가시광선에서 최대 흡수 강도보다 자외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다. 일부 구현예에서, 이러한 화합물은 가시광선에서 최대 흡수 강도보다 근적외선에서 보다 강력한 최대 흡수 강도를 나타낼 수 있다.

,

,

, or

. It can be seen that these compounds can exhibit a stronger maximum absorption intensity in ultraviolet light than the maximum absorption intensity in visible light. In some embodiments, such compounds may exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in visible light.

Examples of photoactive compounds described herein, useful for photoactive layers of visually transparent photovoltaic cells, include phthalocyanines and naphthalocyanines such as aluminum (Al)-containing phthalocyanines and naphthalocyanines, cobalt (Co)-containing phthalocyanines and naphthalocyanines. , copper (Cu)-containing phthalocyanine and naphthalocyanine, iron (Fe)-containing phthalocyanine and naphthalocyanine, lead (Pb)-containing phthalocyanine and naphthalocyanine, magnesium (Mg)-containing phthalocyanine and naphthalocyanine, manganese (Mn)- phthalocyanine and naphthalocyanine containing nickel (Ni)-containing phthalocyanine and naphthalocyanine, palladium (Pd)-containing phthalocyanine and naphthalocyanine, platinum (Pt)-containing phthalocyanine and naphthalocyanine, silicon (Si)-containing phthalocyanine and naphthalocyanine tin (Sn)-containing phthalocyanines and naphthalocyanines, vanadium (V)-containing phthalocyanines and naphthalocyanines, zinc (Zn)-containing phthalocyanines and naphthalocyanines, and derivatives thereof.

In some embodiments, the phthalocyanine compound has the formula:

,

,

,

,

,

, 또는

. 일부 구현예에서, 나프탈로시아닌은 다음 화학식을 갖는다:

,

,

,

,

,

, or

. In some embodiments, the naphthalocyanine has the formula:

또는

. 임의로, 프탈로시아닌은 다음 화학식을 가지며:

, 여기서, M은 금속이고, A₁, A₂, A₃, 및 A₄는 각각의 치환되거나 비치환된 융합된 방향족 환 그룹이다. 임의로, A₁ A₂, A₃, 또는 A₄ 중 적어도 하나는 A₁, A₂, A₃, 또는 A₄ 외에 적어도 하나보다 상이한 수의 융합된 환이다. 예를 들면, A₁은 임의로 A₂, A₃, 또는 A₄ 중 적어도 하나로부터 상이한 수의 융합된 환을 포함한다. 이러한 방식으로, 프탈로시아닌은 비-대칭 구조를 나타낼 수 있으며, 이는 예를 들면, 화합물이 가시광선 영역에서 흡수하는 것을 방지하는데 유용할 수 있다.

or

. Optionally, the phthalocyanine has the formula:

, wherein M is a metal, and A ₁ , A ₂ , A ₃ , and A ₄ are each a substituted or unsubstituted fused aromatic ring group. _{Optionally, A 1 A 2, A 3} , or A ₄ at least one of A _1, A _2, A is a fused ring of _3, or a different number than the at least one in addition to A _4. For example, A ₁ optionally includes a different number of fused rings from at least one of _{A 2} , A ₃ , or A _{4 .} In this way, phthalocyanines can exhibit asymmetric structures, which can be useful, for example, to prevent compounds from absorbing in the visible region.

Optionally, M is Sn, SnCl ₂ , SnO, Pb, Mg, Mn, AlCl, AlOH, GaCl, MnCl, SiCl ₂ , Si(OH) ₂ , PbCl ₂ , VO, Co, Fe, FeCl, Ni, TiO, and TiCl ₂ . Optionally, each M independently comprises a metal, such as Cu, Co, Ni, Zn, Mg, ClAl, SnCl ₂ , Pb, Pt, or Pd. Optionally, each R ₁ -R ₂₄ is independently H, F, Cl, phenyl, alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl, or an electron withdrawing group (such as , electronegative organic ligands or other electronegative substituents). Optionally, the subscripts m, n, o, and p are independently integers 1-5. Optionally, each X and each Y is independently H, F, Cl, Br, alkoxy, alkyl, or aryl. Optionally, Z is Cl, =O, and -OH. Optionally, each X is independently selected from the group consisting of O, S, Se, and Te. Examples of electron withdrawing groups include sulfonyl groups (eg , tosyl, trifyl, mesyl, etc.), haloalkyl groups (eg , trifluoromethyl, trichloromethyl, etc.), cyano, sulfonates, nitro, and carboxylates. including, but not limited to.

In another aspect, a visually transparent photoactive compound is provided, which may be useful, for example, as a photoactive material in a photoactive layer of a visually transparent photovoltaic device. The photoactive compound of this embodiment may have the formula:

, 여기서 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이고, 각각의 X는 독립적으로 S, N, 또는 C―R이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 임의로, 하나 이상의 R 그룹은 독립적으로 H, CH₃, F, Cl, CN, OCH₃, C(CH₃)₃, 또는 Ar―R이고, 여기서 Ar은 방향족 또는 헤테로방향족 그룹이며, 여기서 Ar―R은 하나 이상의 R 그룹 치환체를 가진 방향족 또는 헤테로방향족 그룹에 상응한다. 임의로, 하나 이상의 R 그룹은 독립적으로 티아졸릴 그룹, 페닐 그룹, 피리디닐 그룹, 이미다졸릴 그룹, 피롤릴 그룹, 티오페닐 그룹, 나프틸 그룹, 피레닐 그룹, 인돌릴 그룹, 벤조티오페닐 그룹, 벤즈이미다졸릴 그룹, 또는 벤조티아졸릴 그룹이다. 임의로, 2개 이상의 R 그룹은 융합되지 않은 방향족 또는 헤테로방향족 그룹을 형성하거나 2개 이상의 R 그룹은 융합된 방향족 또는 헤테로방향족 그룹을 형성한다. 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

, wherein each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted heteroaromatic group a group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group, wherein each X is independently S, N, or C-R. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. Optionally, one or more R groups are independently H, CH ₃ , F, Cl, CN, OCH ₃ , C(CH ₃ ) ₃ , or Ar—R, where Ar is an aromatic or heteroaromatic group, wherein Ar—R corresponds to an aromatic or heteroaromatic group having one or more R group substituents. Optionally, 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. Optionally, 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 can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

For example, the photoactive compound of this embodiment may have the formula:

,

,

,

,

,

,

,

,

, 또는

, 여기서 각각의 Ar은 독립적으로 하나 이상의 R 그룹 치환체를 가진 방향족 또는 헤테로방향족 그룹이다. 다른 예로서, 광활성 화합물은 다음 화학식을 가질 수 있다:

,

,

,

,

,

,

,

,

, or

, wherein each Ar is independently an aromatic or heteroaromatic group having one or more R group substituents. As another example, the photoactive compound may have the formula:

또는

. 구체적인 가시적으로 투명한 광활성 화합물은 다음 화학식을 갖는 것들을 포함한다:

or

. Specific visually transparent photoactive compounds include those having the formula:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, 또는

. 다시, 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 보다 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

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,

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,

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,

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,

,

,

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,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, or

. Again, it can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

The photoactive compounds of this embodiment may alternatively have the formula:

, 여기서, 각각의 L 그룹은 독립적으로 단일 결합이거나, 치환되거나 비치환된 알킬렌 그룹, 치환되거나 비치환된 아릴렌 그룹, 또는 치환되거나 비치환된 헤테로아릴렌 그룹으로부터 선택된 2가의 연결 그룹이고, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이며, 각각의 X는 독립적으로 S, N, 또는 C―R이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 임의로, 하나 이상의 R 그룹은 독립적으로 H, CH₃, F, Cl, CN, OCH₃, C(CH₃)₃, 또는 Ar―R이고, 여기서 Ar은 방향족 또는 헤테로방향족 그룹이며, 여기서 Ar―R은 하나 이상의 R 그룹 치환체를 가진 방향족 또는 헤테로방향족 그룹에 상응한다. 임의로, 하나 이상의 R 그룹은 독립적으로 티아졸릴 그룹, 페닐 그룹, 피리디닐 그룹, 이미다졸릴 그룹, 피롤릴 그룹, 티오페닐 그룹, 나프틸 그룹, 피레닐 그룹, 인돌릴 그룹, 벤조티오페닐 그룹, 벤즈이미다졸릴 그룹, 또는 벤조티아졸릴 그룹이다. 임의로, 2개 이상의 R 그룹은 융합되지 않은 방향족 또는 헤테로방향족 그룹을 형성하거나 여기서 2개 이상의 R 그룹은 융합된 방향족 또는 헤테로방향족 그룹을 형성한다. 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 보다 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

, wherein each L group is independently a single bond, a divalent 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 hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, 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, wherein each X is independently S, N, or C-R. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. Optionally, one or more R groups are independently H, CH ₃ , F, Cl, CN, OCH ₃ , C(CH ₃ ) ₃ , or Ar—R, where Ar is an aromatic or heteroaromatic group, wherein Ar—R corresponds to an aromatic or heteroaromatic group having one or more R group substituents. Optionally, 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. Optionally, 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 can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

For example, the photoactive compound of this embodiment may have the formula:

,

,

,

,

,

,

,

,

,

, 또는

, 여기서 각각의 Ar은 독립적으로 하나 이상의 R 그룹 치환체를 갖는 방향족 또는 헤테로방향족 그룹이다. 임의로, 광활성 화합물은 다음 화학식을 갖는다:

,

,

,

,

,

,

,

,

,

, or

, wherein each Ar is independently an aromatic or heteroaromatic group having one or more R group substituents. Optionally, the photoactive compound has the formula:

또는

. 구체적인 광활성 화합물은 다음 화학식을 갖는 것들을 포함한다:

or

. Specific photoactive compounds include those having the formula:

,

,

,

,

,

, 또는

. 다시, 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

,

,

,

,

,

, or

. Again, it can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

The photoactive compounds of this embodiment may alternatively have the formula:

, 여기서 A1은 하나 이상의 R 그룹 치환체를 포함하는 융합되거나 융합되지 않은 방향족 또는 헤테로방향족 그룹이고, 각각의 A2는 독립적으로 하나 이상의 R 그룹 치환체를 포함하는 융합되거나 융합되지 않은 방향족 또는 헤테로방향족 그룹이며, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이거나, 여기서 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 임의로, A1은 하나 이상의 R 그룹 치환체를 포함하는 5-원 또는 6-원 방향족 또는 헤테로방향족 환을 포함한다. 임의로, A1은 하나 이상의 티아졸 환, 벤젠 환, 피리딘 환, 이미다졸 환, 피롤 환, 티오펜 환, 나프탈렌, 피렌, 인돌, 벤조티오펜, 벤즈이미다졸, 벤조티아졸, 또는 트리아진 환을 포함하는 비치환되거나 R 치환된 환 그룹을 포함한다. 임의로, 각각의 A2는 하나 이상의 R 그룹 치환체를 포함하는 5-원 또는 6-원 방향족 또는 헤테로방향족 환을 포함한다. 임의로, 각각의 A2는 하나 이상의 티아졸 환, 벤젠 환, 피리딘 환, 이미다졸 환, 피롤 환, 티오펜 환, 나프탈렌, 피렌, 인돌, 벤조티오펜, 벤즈이미다졸, 벤조티아졸, 또는 트리아진 환을 포함하는 비치환되거나 R 치환된 환 그룹을 포함한다. 임의로, 하나 이상의 R 그룹은 독립적으로 H, CH₃, F, Cl, CN, OCH₃, C(CH₃)₃, 또는 Ar―R이고, 여기서 Ar은 방향족 또는 헤테로방향족 그룹이며, 여기서 Ar―R은 하나 이상의 R 그룹 치환체를 가진 방향족 또는 헤테로방향족 그룹에 상응한다. 임의로, 하나 이상의 R 그룹은 독립적으로 티아졸릴 그룹, 페닐 그룹, 피리디닐 그룹, 이미다졸릴 그룹, 피롤릴 그룹, 티오페닐 그룹, 나프틸 그룹, 피레닐 그룹, 인돌릴 그룹, 벤조티오페닐 그룹, 벤즈이미다졸릴 그룹, 또는 벤조티아졸릴 그룹이다. 임의로, 2개 이상의 R 그룹은 융합되지 않은 방향족 또는 헤테로방향족 그룹을 형성하거나 여기서 2개 이상의 R 그룹은 융합된 방향족 또는 헤테로방향족 그룹을 형성한다. 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

, wherein A1 is a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents, and each A2 is independently a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents, Each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, 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, wherein at least two R groups are either a substituted or unsubstituted ring group or a substituted or unsubstituted fused group. to form a ring group. Optionally, A1 comprises a 5- or 6-membered aromatic or heteroaromatic ring comprising one or more R group substituents. Optionally, A1 is one or more thiazole ring, benzene ring, pyridine ring, imidazole ring, pyrrole ring, thiophene ring, naphthalene, pyrene, indole, benzothiophene, benzimidazole, benzothiazole, or triazine ring including unsubstituted or R substituted ring groups. Optionally, each A2 comprises a 5- or 6-membered aromatic or heteroaromatic ring comprising one or more R group substituents. Optionally, each A2 is one or more thiazole ring, benzene ring, pyridine ring, imidazole ring, pyrrole ring, thiophene ring, naphthalene, pyrene, indole, benzothiophene, benzimidazole, benzothiazole, or triazine Including unsubstituted or R substituted ring groups including rings. Optionally, one or more R groups are independently H, CH ₃ , F, Cl, CN, OCH ₃ , C(CH ₃ ) ₃ , or Ar—R, where Ar is an aromatic or heteroaromatic group, wherein Ar—R corresponds to an aromatic or heteroaromatic group having one or more R group substituents. Optionally, 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. Optionally, 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 can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

For example, the photoactive compound of this embodiment may have the formula:

,

,

,

, 또는

, 여기서 각각의 X는 독립적으로 S, N, 또는 C―R이다. 구체적인 광활성 화합물은 다음 화학식을 갖는 것들을 포함한다:

,

,

,

, or

, wherein each X is independently S, N, or C-R. Specific photoactive compounds include those having the formula:

,

,

,

,

,

,

,

, 또는

. 다시, 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

,

,

,

,

,

,

,

, or

. Again, it can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

The photoactive compounds of this embodiment may alternatively have the formula:

, 여기서 A1은 하나 이상의 R 그룹 치환체를 포함하는 융합되거나 융합되지 않은 방향족 또는 헤테로방향족 그룹이고, 각각의 A2는 독립적으로 하나 이상의 R 그룹 치환체를 포함하는 융합되거나 융합되지 않은 방향족 또는 헤테로방향족 그룹이며, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 임의로, A1은 하나 이상의 R 그룹 치환체를 포함하는 5-원 또는 6-원 방향족 또는 헤테로방향족 환을 포함한다. 임의로, A1은 하나 이상의 R 그룹 치환체를 포함하는 융합된 5-원 또는 6-원 방향족 또는 헤테로방향족 환을 포함한다. 임의로, 각각의 A2는 하나 이상의 R 그룹 치환체를 포함하는 5-원 또는 6-원 방향족 또는 헤테로방향족 환을 포함한다. 임의로, 각각의 A2는 하나 이상의 티아졸 환, 벤젠 환, 피리딘 환, 이미다졸 환, 피롤 환, 티오펜 환, 나프탈렌, 피렌, 인돌, 벤조티오펜, 벤즈이미다졸, 또는 벤조티아졸을 포함하는 비치환되거나 R 치환된 환 그룹을 포함한다. 임의로, 하나 이상의 R 그룹은 독립적으로 H, CH₃, F, Cl, CN, OCH₃, C(CH₃)₃, 또는 Ar―R이고, 여기서 Ar은 방향족 또는 헤테로방향족 그룹이며, 여기서 Ar―R은 하나 이상의 R 그룹 치환체를 가진 방향족 또는 헤테로방향족 그룹에 상응한다. 임의로, 하나 이상의 R 그룹은 독립적으로 티아졸릴 그룹, 페닐 그룹, 피리디닐 그룹, 이미다졸릴 그룹, 피롤릴 그룹, 티오페닐 그룹, 나프틸 그룹, 피레닐 그룹, 인돌릴 그룹, 벤조티오페닐 그룹, 벤즈이미다졸릴 그룹, 또는 벤조티아졸릴 그룹이다. 임의로, 2개 이상의 R 그룹은 융합되지 않은 방향족 또는 헤테로방향족 그룹을 형성하거나 여기서 2개 이상의 R 그룹은 융합된 방향족 또는 헤테로방향족 그룹을 형성한다. 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

, wherein A1 is a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents, and each A2 is independently a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents, Each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, 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. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. Optionally, A1 comprises a 5- or 6-membered aromatic or heteroaromatic ring comprising one or more R group substituents. Optionally, A1 comprises a fused 5-membered or 6-membered aromatic or heteroaromatic ring comprising one or more R group substituents. Optionally, each A2 comprises a 5- or 6-membered aromatic or heteroaromatic ring comprising one or more R group substituents. Optionally, each A2 comprises one or more thiazole ring, benzene ring, pyridine ring, imidazole ring, pyrrole ring, thiophene ring, naphthalene, pyrene, indole, benzothiophene, benzimidazole, or benzothiazole unsubstituted or R substituted ring groups. Optionally, one or more R groups are independently H, CH ₃ , F, Cl, CN, OCH ₃ , C(CH ₃ ) ₃ , or Ar—R, where Ar is an aromatic or heteroaromatic group, wherein Ar—R corresponds to an aromatic or heteroaromatic group having one or more R group substituents. Optionally, 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. Optionally, 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 can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

For example, the photoactive compound of this embodiment may have the formula:

, 여기서 각각의 A3는 독립적으로 하나 이상의 R 그룹 치환체를 포함하는 방향족 또는 헤테로방향족 그룹이다. 본 양태의 광활성 화합물은 다음 화학식에 의해 추가로 특징화될 수 있다:

, wherein each A3 is independently an aromatic or heteroaromatic group comprising one or more R group substituents. The photoactive compounds of this aspect may be further characterized by the formula:

,

,

, 또는

, 여기서 각각의 X는 독립적으로 S, N, 또는 C―R이다. 구체적인 광활성 화합물은 다음 화학식을 갖는 것들을 포함한다:

,

,

, or

, wherein each X is independently S, N, or C-R. Specific photoactive compounds include those having the formula:

,

,

,

, 또는

. 다시, 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

,

,

,

, or

. Again, it can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

Other photoactive compounds of this embodiment may have the formula:

, 여기서 M은 금속이고, 각각의 A는 독립적으로 하나 이상의 R 그룹 치환체를 갖는 융합된 폴리사이클릭 환 그룹이며, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 알케닐 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 임의로, M은 Fe, Co, Ni, Cu, Zn, Mo, Pd, 또는 Pt이다. 임의로, 하나 이상의 R 그룹은 각각 독립적으로 메톡시 그룹, 페닐 그룹, 디메틸 아미노 그룹, 시아노 그룹, 티아졸릴 그룹, 또는 페닐 그룹이다. 임의로, A는 티아졸릴 그룹, 페닐 그룹, 말레이미드 그룹, 나프틸 그룹, 아세나프탈렌 그룹, 또는 페난트렌 그룹을 포함한다. 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

, wherein 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 hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted heteroaromatic group, substituted or unsubstituted fused heteroaromatic group, or It is a substituted or unsubstituted alkoxy group. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. Optionally, M is Fe, Co, Ni, Cu, Zn, Mo, Pd, or Pt. Optionally, 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. Optionally, A includes a thiazolyl group, a phenyl group, a maleimide group, a naphthyl group, an acenaphthalene group, or a phenanthrene group. It can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

,

,

,

, 또는

. 임의로, 본 양태의 화합물은 다음 화학식을 갖는다:For example, The photoactive compound of this embodiment may have the formula:

,

,

,

, or

. Optionally, the compound of this embodiment has the formula:

,

,

,

, 또는

. 구체적인 가시적으로 투명한 광활성 화합물은 다음 화학식을 갖는 것들을 포함한다:

,

,

,

, or

. Specific visually transparent photoactive compounds include those having the formula:

,

,

,

, 또는

. 다시, 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

,

,

,

, or

. Again, it can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

The photoactive compounds of this embodiment may alternatively have the formula:

, 여기서 M은 금속, 예를 들면, Fe, Co, Ni, Cu, Zn, Mo, Pd, 또는 Pt이고, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 알케닐 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 또는 치환되거나 비치환된 알콕시 그룹이거나, 여기서 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 임의로, 하나 이상의 R 그룹은 독립적으로 메톡시 그룹, 페닐 그룹, 디메틸 아미노 그룹, 시아노 그룹, 티아졸릴 그룹, 또는 페닐 그룹이다. 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

, wherein M is a metal, for example Fe, Co, Ni, Cu, Zn, Mo, Pd, or Pt, and each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group , substituted or unsubstituted alkenyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted heteroaromatic group, substituted or unsubstituted fused heteroaromatic group, or substituted or an unsubstituted alkoxy group, wherein two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. Optionally, 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 can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

For example, The photoactive compound of this embodiment may have the formula:

. 임의로, 광활성 화합물은 다음 화학식을 갖는다:

. Optionally, the photoactive compound has the formula:

또는

. 구체적인 광활성 화합물은 다음 화학식을 갖는 것들을 포함한다:

or

. Specific photoactive compounds include those having the formula:

또는

. 다시, 이러한 화합물이 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

or

. Again, it can be seen that these compounds can exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in the visible light.

In another aspect, a visually transparent photoactive compound is provided, which may be useful, for example, as a photoactive material in a photoactive layer of a visually transparent photovoltaic device. The photoactive compound of this embodiment may have the formula:

, 여기서 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이고, n은 0, 1, 2, 3, 4, 5, 6, 또는 7이며, 각각의 X는 독립적으로 O, N-R, S, 또는 Se이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 임의로, 하나 이상의 R 그룹은 독립적으로 H, 치환되거나 비치환된 C1-C6 알킬 그룹, 치환되거나 비치환된 C2-C6 알케닐 그룹, 치환되거나 비치환된 방향족 그룹, 또는 치환되거나 비치환된 헤테로방향족 그룹이다. 이러한 화합물은 최대 근적외선 또는 자외선 흡수 강도 및 최대 가시광선 흡수 강도, 예를 들면, 최대 가시광선 흡수 강도보다 더 큰 최대 근적외선 또는 자외선 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

, wherein each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted heteroaromatic group a 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; , each X is independently O, NR, S, or Se. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. Optionally, 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 is a group It will be appreciated that such compounds may exhibit a maximum near infrared or ultraviolet absorption intensity and a maximum visible light absorption intensity, eg, a maximum near infrared or ultraviolet absorption intensity greater than the maximum visible light absorption intensity.

For example, in this aspect The photoactive compound may have the formula:

, 여기서 m은 0, 1, 2, 3, 4, 또는 5이다. 임의로, 본 양태의 광활성 화합물은 다음 화학식을 갖는다:

, where m is 0, 1, 2, 3, 4, or 5. Optionally, the photoactive compound of this embodiment has the formula:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, 또는

. 구체적인 가시적으로 투명한 광활성 화합물은 다음 화학식을 갖는 것들을 포함한다:

,

, or

. Specific visually transparent photoactive compounds include those having the formula:

,

,

,

,

, 또는

. 다시, 이러한 화합물은 가시적으로 투명할 수 있으며 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

,

,

,

,

, or

. Again, it will be appreciated that these compounds can be visually transparent and exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in visible light.

The photoactive compounds of this embodiment may alternatively have the formula:

또는

, 여기서 각각의 A는 독립적으로 하나 이상의 R 그룹 치환체를 포함하는 융합되거나 융합되지 않은 방향족 또는 헤테로방향족 그룹이고, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 임의로, A는 독립적으로 벤젠 환 또는 티오펜 환이다. 임의로, 하나 이상의 R 그룹은 독립적으로 H, 치환되거나 비치환된 C1-C6 알킬 그룹, 치환되거나 비치환된 C2-C6 알케닐 그룹, 치환되거나 비치환된 방향족 그룹, 또는 치환되거나 비치환된 헤테로방향족 그룹이다. 이러한 화합물은 최대 근적외선 또는 자외선 흡수 강도 및 최대 가시광선 흡수 강도, 예를 들면, 최대 가시광선 흡수 강도보다 더 큰 최대 근적외선 또는 자외선 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

or

, wherein each A is independently a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents, and each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group , substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted heteroaromatic group, substituted or unsubstituted fused heteroaromatic group, substituted or unsubstituted amine group, or substituted or It is an unsubstituted alkoxy group. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. Optionally, A is independently a benzene ring or a thiophene ring. Optionally, 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 is a group It will be appreciated that such compounds may exhibit a maximum near infrared or ultraviolet absorption intensity and a maximum visible light absorption intensity, eg, a maximum near infrared or ultraviolet absorption intensity greater than the maximum visible light absorption intensity.

For example, in this aspect The photoactive compound may have the formula:

,

,

, 또는

. 광활성 화합물의 구체적인 예는 다음 화학식을 갖는 것들을 포함한다:

,

,

, or

. Specific examples of photoactive compounds include those having the formula:

,

,

, 또는

. 다시, 이러한 화합물은 가시적으로 투명할 수 있으며 가시광선에서 최대 흡수 강도보다 근적외선에서 더 강력한 최대 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

,

,

, or

. Again, it will be appreciated that these compounds can be visually transparent and exhibit a stronger maximum absorption intensity in the near infrared than the maximum absorption intensity in visible light.

The photoactive compounds of this embodiment may alternatively have the formula:

, 여기서 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 임의로, 하나 이상의 R 그룹은 H, 치환되거나 비치환된 C1-C6 알킬 그룹, 치환되거나 비치환된 C2-C6 알케닐 그룹, 치환되거나 비치환된 방향족 그룹, 또는 치환되거나 비치환된 헤테로방향족 그룹이다. 임의로, 하나 이상의 R 그룹은 3급 부틸 그룹이다. 이러한 화합물은 최대 근적외선 또는 자외선 흡수 강도 및 최대 가시광선 흡수 강도, 예를 들면, 최대 가시광선 흡수 강도보다 더 큰 최대 근적외선 또는 자외선 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

, wherein each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted heteroaromatic group group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. Optionally, 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 . Optionally, at least one R group is a tertiary butyl group. It will be appreciated that such compounds may exhibit a maximum near infrared or ultraviolet absorption intensity and a maximum visible light absorption intensity, eg, a maximum near infrared or ultraviolet absorption intensity greater than the maximum visible light absorption intensity.

For example, in this aspect The compound may have the formula:

. 광활성 화합물의 구체적인 예는 다음 화학식을 갖는 화합물을 포함한다:

. Specific examples of photoactive compounds include compounds having the formula:

.

.

The photoactive compounds of this embodiment may alternatively have the formula:

, 여기서 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 임의로, 하나 이상의 R 그룹은 H, 치환되거나 비치환된 C1-C6 알킬 그룹, 치환되거나 비치환된 C2-C6 알케닐 그룹, 치환되거나 비치환된 방향족 그룹, 또는 치환되거나 비치환된 헤테로방향족 그룹이다. 이러한 화합물은 최대 근적외선 또는 자외선 흡수 강도 및 최대 가시광선 흡수 강도, 예를 들면, 최대 가시광선 흡수 강도보다 더 큰 최대 근적외선 또는 자외선 흡수 강도를 나타낼 수 있음을 알 수 있을 것이다.

, wherein each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted heteroaromatic group group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. Optionally, 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 . It will be appreciated that such compounds may exhibit a maximum near infrared or ultraviolet absorption intensity and a maximum visible light absorption intensity, eg, a maximum near infrared or ultraviolet absorption intensity greater than the maximum visible light absorption intensity.

For example, in this aspect The photoactive compound may have the formula:

또는

. 구체적인 예의 광활성 화합물은 다음 화학식을 갖는 화합물이다:

or

. A specific example of a photoactive compound is a compound having the formula:

.

.

Advantageously, the disclosed photoactive compounds exhibit a maximum or peak near infrared or ultraviolet absorption intensity greater than the maximum or peak visible light absorption intensity. In some embodiments, the disclosed photoactive compounds exhibit an integrated near-infrared or ultraviolet absorption coefficient that is greater than the integrated visible absorption coefficient. For example, some embodiments of the disclosed photoactive compounds are outside the visible wavelength band (450 nm to 650 nm), such as within the near infrared wavelength band (650 nm to 1400 nm) or the ultraviolet wavelength band (200 nm to 450 nm). peak absorption. Preferably by absorbing near infrared or ultraviolet radiation, the disclosed photoactive compounds exhibit visible transparency and may be useful for inclusion in advantageously visually transparent photovoltaic devices. It will be appreciated that in various embodiments, different maximum visible absorption or minimum visible transmittance may be selected for a particular target application. For example, in some embodiments, a visible transmittance of 30% or an absorption of 70% may be desirable for some applications. In other embodiments, a visible transmittance of 100% or an absorption of 0% may be desirable for some applications. In this way, a visually transparent photovoltaic cell can absorb some visible light as well as near infrared and/or ultraviolet light for the purpose of photovoltaic generation (or incidental absorption) and still meet the target visible transmittance level.

As used herein, the terms visible transmittance, visually transparent, etc., refer to 0% to 70%, such as about 70% or less, about 65% or less, about 60% or less, about 55% or less, about 50% or less. , about 45% or less, about 40% or less, about 35% or less, about 30% or less, about 25% or less, or about 20% or less of a material that exhibits total absorption, average absorption, or maximum absorption within the visible light band refers to In other words, a visually transparent material may comprise from 30% to 100% incident visible light, e.g., at least about 80% incident visible light, at least about 75% incident visible light, at least about 70% incident visible light, at least about 65% incident visible light, about At least 60% incident visible light, at least about 55% incident visible light, at least about 50% incident visible light, at least about 45% incident visible light, at least about 40% incident visible light, at least about 35% incident visible light, or transmits at least about 30% incident visible light can do it A material that is visually transparent is generally considered to be at least partially see-through (ie, not completely opaque) to human observation. Optionally, the visibly transparent material can be colorless (ie, not exhibiting strong visible absorption characteristics that can give the appearance of a special color) to human observation.

A variety of different R-group substitutions are generally contemplated herein. For example, in some embodiments, one or more R groups are independently H, CH ₃ , F, Cl, CN, OCH ₃ , C(CH ₃ ) ₃ , or Ar—R, where Ar is aromatic or heteroaromatic. group, wherein Ar-R corresponds to an aromatic or heteroaromatic group having one or more R group substituents. Optionally, 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. In some embodiments, 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.

The disclosed photoactive compounds and materials can be applied to visually transparent photovoltaic devices, such as visually transparent substrates; a first visually transparent electrode coupled to the visually transparent substrate; A first visually transparent active layer coupled to a first visually transparent electrode, for example, a first photoactive compound as described herein that exhibits a maximum near infrared absorption intensity greater than the maximum visible light absorption intensity. a visually transparent photoactive layer; a second visually transparent photoactive layer coupled to the first visually transparent photoactive layer and exhibiting a maximum ultraviolet absorption intensity or a maximum near infrared absorption intensity greater than the maximum visible light absorption intensity; and a second visually transparent electrode coupled to the second visually transparent photoactive layer.

As described in further detail below, the photoactive compounds described herein may be useful as electron donor materials or electron acceptor materials. In an embodiment, the second visually transparent photoactive layer is an opposite material, e.g., an electron acceptor material when the photoactive material of the first visually transparent photoactive layer is an electron donor material or as the first When the photoactive material of the visually transparent photoactive layer is an electron acceptor material, it may comprise a second photoactive compound which may be useful as an electron donor material. The photoactive compound used in the photoactive layer may have any suitable concentration. In some embodiments, the photoactive compound is present as a layer in substantially pure form. However, in some embodiments, the photoactive layer may exist in a mixed form, for example when multiple photoactive compounds are present, eg, an electron acceptor material and an electron donor material. The different photoactive materials may optionally have suitable concentrations or concentration ratios to achieve photovoltaic cell production in the devices described herein. Optionally, the first and second visually transparent photoactive layers are independently about 1 nm to about 300 nm thick. Optionally, the first visually transparent photoactive layer and the second visually transparent photoactive layer correspond to separate, mixed, or partially mixed layers.

Other layers used in visually transparent photovoltaic devices may exhibit compositions and properties suitable for operation of transparent photovoltaic devices. For example, it may be suitable to construct a variety of visually transparent substrates, such as transparent glass, transparent polymers, and the like. In some embodiments, a visually transparent substrate can be transparent to near-infrared light (ie, light having a wavelength greater than 650 nm) and/or ultraviolet light (ie, light having a wavelength less than 450 nm). In this way, the visually transparent substrate may not absorb near infrared and/or ultraviolet light that may be suitable for photovoltaic energy generation by a visually transparent photovoltaic device. However, in some embodiments, the visually transparent substrate is capable of absorbing infrared and/or ultraviolet light, which may result in excessive infrared or ultraviolet incident radiation, for example after the visually transparent substrate has passed through the photoactive layer(s). Blocking may be useful in configurations that prevent or reduce overall ultraviolet and/or infrared transmission by blocking. Useful visually transparent substrates include, but are not limited to, those with a thickness of from about 50 nm to about 30 mm.

Examples of visually transparent electrodes include those comprising a transparent thin film of indium tin oxide or a conductive element such as copper, gold, silver, aluminum, or the like. When the visually transparent electrode includes a conductive element, the thickness may allow the conductive element to be mostly opaque, but when used as a thin film, the conductive element may still allow transmission of visible light. Useful visually transparent electrodes include, but are not limited to, those with a thickness of from about 1 nm to about 500 nm.

Other layers may be present in the visually transparent photovoltaic devices described herein. For example, a visually transparent photovoltaic device may optionally include one or more buffer layers, such as a first buffer layer disposed between the first visually transparent electrode and the first visually transparent photoactive layer and/or or a second buffer layer disposed between the second visually transparent photoactive layer and the second visually transparent electrode. Useful buffer layers can serve a variety of purposes and can include a variety of compositions. For example, in some cases, the buffer layer may include a photoactive material or compound described herein. Optionally, useful buffer layers are from about 1 nm to about 500 nm thick.

In another aspect, methods, such as methods of making a visually transparent photoactive material and a method of making a visually transparent photovoltaic device, are provided. In one embodiment, the method of this aspect comprises providing a transparent substrate; optionally, forming one or more optical layers over 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 comprising, for example, a photoactive compound described herein; optionally, forming a second buffer layer; forming a second transparent electrode; and optionally forming one or more optical layers over the second transparent electrode. Optionally, at least one buffer layer comprises a photoactive compound described herein. Optionally, forming the one or more layers comprises preparing the photoactive compound and depositing the photoactive compound. Examples of steps for preparing the various photoactive compounds provided herein are described below.

Variations on these different steps will occur in light of the present disclosure. For example, the photoactive layer may be provided as a separate or mixed layer comprising electron acceptor and electron donor materials. For example, different optical layers may be used, such as an index matching layer, an antireflection layer, and the like.

A variety of techniques may be useful in forming one or more layers, including various techniques, for example, vacuum deposition techniques and solution deposition techniques. In one embodiment, thermal evaporation is used to deposit the photoactive compound as part of the photoactive layer. It will be appreciated that a variety of patterning techniques may be useful in methods of manufacturing visually transparent photovoltaic devices. For example, a visually transparent electrode may optionally be patterned, a visually active photoactive layer may optionally be patterned, a buffer layer may optionally be patterned, an optical layer or the like may be patterned. can Suitable patterning techniques include, but are not limited to, patterning techniques including lithography, masking, lift-off, etching, and the like.

These and other embodiments and aspects of the present invention, along with many advantages and features thereof, are described in greater detail in the following text and in conjunction with the accompanying drawings.

1A is a simplified schematic diagram illustrating a visually transparent photovoltaic device according to an embodiment of the present invention.
1B provides an overview of various configurations of photoactive layer(s) in a visually transparent photovoltaic device in accordance with embodiments of the present invention.
2 is a simplified plot showing the solar spectrum, human eye sensitivity, and exemplary transparent optoelectronic device absorption as a function of wavelength.
3 is a simplified energy level schematic for a visually transparent photovoltaic device in accordance with an embodiment of the present invention.
4A, 4B, 4C, and 4D provide plots showing examples of absorption profiles for different electron acceptor and donor configurations, which may include a photoactive layer.
5 provides an overview of a method of manufacturing a visually transparent photovoltaic device according to an embodiment of the present invention.
6 provides plots showing general absorption characteristics and donor/acceptor behavior for different classes of organic molecules.
7A provides an overview of an example of a synthetic route for the formation of a visually transparent photoactive compound.
7B provides a schematic diagram of an example of a synthetic route for the formation of a visually transparent photoactive compound.
8 provides data showing normalized absorbance spectra of different visually clear photoactive compounds in solution.
9 provides data representing an example of current density as a function of voltage for an example of a photovoltaic cell.
10 provides an overview of an example of a synthetic route for the formation of a visually transparent photoactive compound.
11 provides an overview of an example of a synthetic route for the formation of a visually transparent photoactive compound.
12 provides data representing normalized absorption spectra of different visually transparent photoactive compounds in solution.
13 provides an overview of an example of a synthetic route for the formation of a visually transparent photoactive compound.
14 provides data showing normalized absorption spectra of different visually clear photoactive compounds in solution.
15 provides data representing an example of current density as a function of voltage for an example of a photovoltaic cell.
16 provides an overview of examples of synthetic routes for the formation of visually transparent photoactive compounds.
17 provides an overview of examples of synthetic routes for the formation of visually transparent photoactive compounds.
18 provides an overview of examples of synthetic routes for the formation of visually transparent photoactive compounds.
19 provides an overview of examples of synthetic routes for the formation of visually transparent photoactive compounds.
20 provides an overview of examples of synthetic routes for the formation of visually transparent photoactive compounds.
21 provides an overview of examples of synthetic routes for the formation of visually transparent photoactive compounds.
22 provides data showing normalized absorption spectra of different visually clear photoactive compounds in solution.
23 shows an example of a synthetic route for the formation of symmetric DiCN compounds.
24 shows an example of a synthetic route for the formation of asymmetric DiCN compounds.
25 shows an example of a synthetic route for the formation of DiCN-IDDT compounds.
26 shows an example of a synthetic route for the formation of DiCN-DTCz compounds.
27 shows an example of a synthetic route for the formation of DiCN-BODIPY compounds.
28 shows an example of a synthetic route for the formation of a DiCN-SO _{2 compound.}
29 shows the spectral characteristics of the DiCN compound.
30 shows the spectral characteristics of DiCN and DiCN-SO _{2 compounds.}
31 provides data showing examples of current density as a function of voltage for an example of a photovoltaic cell containing an asymmetric DiCN acceptor A-16 and a CuPc donor.
32 shows an example of a synthetic route for the preparation of a benzo- bis-thiadiazole (BBT) compound.
33 shows an example of an absorption spectrum for a photoactive compound.
34A provides an overview of an example of a synthetic route for the formation of a visually transparent photoactive compound.
34B provides an overview of an example of a synthetic route for the formation of a visually transparent photoactive compound.
35 provides data showing normalized absorption spectra of different visually clear photoactive compounds in solution.
36 provides data representing an example of current density as a function of voltage for an example of a photovoltaic cell.
37 provides data representing an example of current density as a function of voltage for an example of a photovoltaic cell.
38 shows an example of a synthetic route for the formation of a naphthalene-tetracarboxylic diimide (NTCDI) compound.
39 shows the spectral characteristics of NTCDI compound E-1.
40A provides data showing an example of current density as a function of voltage for an example of a photovoltaic cell containing an NTCDI acceptor E-1 and a ClAlPc donor.
40B provides data showing examples of current density as a function of voltage for an example of a photovoltaic cell having a cathode buffer layer containing NTCDI compound E-1.
41 shows an example of a synthetic route for the formation of a bisimide coronene (CBI) compound.
42A shows an example of a synthetic route for the formation of a fluoranthene derivative.
42B shows an example of a synthetic route for the formation of a fluoranthene derivative.
43 provides data showing examples of current density as a function of voltage for an example of a photovoltaic cell with fluoranthene as an acceptor with a SubPc donor.
44 shows an example of a synthetic route for the formation of a coranulene derivative.
45 provides an overview of an example of a synthetic route for the formation of a visually transparent photoactive compound.
46 provides data showing normalized absorption spectra of examples of visually clear photoactive compounds.
47 provides an overview of examples of synthetic routes for the formation of visually transparent photoactive compounds.
48 provides an overview of an example of a synthetic route for the formation of a visually transparent photoactive compound.
49 provides data showing absorption spectra of examples of visually transparent photoactive compounds.
50 provides an overview of examples of synthetic routes for the formation of visually transparent photoactive compounds.
51 shows absorption of UV/NIR by SnPc, SnNcCl ₂ , and SnPcCl _{2 .
FIG. 52 compares the external quantum efficiency of a device using SnNcCl 2} as the NIR absorbing donor material to a device using ClAlPc, a typical donor material used for transparent PV.
_{53 compares the current voltage performance of a device using SnNcCl 2} as the NIR absorbing donor material to a device using ClAlPc, a typical donor material used for transparent PV.
_{FIG. 54 compares the energy levels of materials used in devices using SnNcCl 2} as the NIR absorbing donor material to devices using ClAlPc, a typical donor material used for transparent PV.
55 shows performance for an exemplary device using _{SnPcCl 2} as the NIR acceptor.
56 shows the current-voltage performance of transparent PVs using _{SnNcCl 2} and SnPcCl ₂ as donor and acceptor materials, respectively.
57 shows the external quantum efficiency performance of transparent PVs using _{SnNcCl 2} and SnPcCl ₂ as donor and acceptor materials, respectively.
58 shows an example of a synthetic route for the preparation of a phthalocyanine compound.
59 shows an example of a synthetic route for the preparation of a phthalocyanine compound.
Figure 60a shows the spectral characteristics of phthalocyanine J-14.
Figure 60b shows the spectral characteristics of phthalocyanine J-3.
Fig. 61 shows comparison of spectral characteristics of phthalocyanine J-1, phthalocyanine J-2, and phthalocyanine J-3.

The present disclosure relates to a visually transparent photoactive compound and a visually transparent photovoltaic device comprising a visually transparent photoactive compound. Visibly transparent photoactive compounds absorb light more strongly in the near-infrared region or ultraviolet region and little strongly in the visible region, allowing their use in visually transparent photovoltaic devices. The disclosed visually transparent photovoltaic device includes a visually transparent electrode having a visually transparent photoactive material disposed between the visually transparent electrodes.

또는

의 일반적인 구조적 특징을 공유하며, 여기서 물결선 결합은 화합물의 다른 부위에 대한 연결을 나타내고, 이러한 화합물은 동일한 화합물의 부분들 또는 상이한 서브구조일 수 있다. 이러한 일반적인 구조적 특징은 나타낸 바와 같이 본원에 나타낼 수 있지만, 이의 상이한 성분은 전기적으로 하전되어 화합물에 대한 원자가 요건을 만족시킬 수 있음을 알 수 있을 것이다. 이러한 전하는 나타낼 수 없지만, 당해 분야의 기술자는 이해할 수 있을 것이다. 예를 들면, 붕소 원자는 음성 전하를 나타낼 수 있다. 다른 예로서, 질소 원자는 양성 전하를 나타낼 수 있다. 임의로, 질소 원자는 0 전하 또는 음성 전하를 나타낼 수 있다. 디아미노 디플루오로 또는 이산소 붕소 성분 외에, 가시적으로 투명한 광활성 화합물의 다른 서브 구조는 본질적으로 유기 또는 헤테로유기일 수 있다. 예를 들면, 가시적으로 투명한 화합물은 방향족 또는 헤테로방향족 종, 사이클릭 또는 헤테로사이클릭 종을 포함할 수 있으며, 이들 각각은 작용화되어 적합한 광학적 및/또는 물리적 특성을 달성할 수 있다.The disclosed visually clear photoactive compounds absorb boron dipyrromethene-based photoactive compounds, such as diamino difluoro boron-based organic dyes, and related diamino boron dioxyboron-based organic dyes. Examples of visually transparent photoactive compounds include a fluorinated or oxygenated boron core in a ring structure comprising boron-nitrogen bonds. For example, the disclosed photoactive compounds may be

or

, where wavy bonds indicate links to other sites of the compound, and such compounds may be parts of the same compound or different substructures. While these general structural features may be represented herein as shown, it will be appreciated that the different components thereof may be electrically charged to satisfy the valence requirements for the compound. Such charges cannot be shown, but will be understood by those skilled in the art. For example, a boron atom may exhibit a negative charge. As another example, the nitrogen atom may exhibit a positive charge. Optionally, the nitrogen atom may exhibit a zero charge or a negative charge. Besides the diamino difluoro or boron dioxygen component, other substructures of the visually transparent photoactive compounds may be organic or heteroorganic in nature. For example, a visually clear compound may include aromatic or heteroaromatic species, cyclic or heterocyclic species, each of which may be functionalized to achieve suitable optical and/or physical properties.

Disclosed visually clear photoactive compounds include near-IR DA molecules such as dicyano-indandione, benzo- bis -thiadiazole, diketopyrrolopyrrole diphenylthienylamine, and derivatives thereof, which act may be formulated to achieve suitable optical and/or physical properties.

의 일반적인 구조적 특징을 공유하며, 여기서 물결선은 구조가 화합물의 다른 부분에 연결된 위치를 나타내고, 이러한 화합물은 동일한 화합물(즉, 환 또는 융합된 환 주조) 또는 상이한 소구조의 부분일 수 있다. 금속 디티올레이트 구성성분 외에, 가시적으로 투명한 광활성 화합물의 다른 소구조는 본질적으로 유기 또는 헤테로유기일 수 있다. 예를 들면, 가시적으로 투명한 화합물은 방향족 또는 헤테로방향족 종, 사이클릭 또는 헤테로사이클릭 종을 포함할 수 있으며, 이들 각각은 작용화되어 적합한 광학적 및/또는 물리적 특성을 달성할 수 있다.The disclosed visually transparent photoactive compounds include metal dithiolate dyes. Examples of visually transparent photoactive compounds include metal dithiolate complexes comprising organic or heteroorganic substituents that may be functionalized to modulate absorption by the compound. For example, the disclosed photoactive compounds may be

, where the wavy line indicates where the structure is linked to other moieties of the compound, and such compounds may be parts of the same compound (ie , cast rings or fused rings) or different substructures. In addition to the metal dithiolate constituents, other substructures of the visually transparent photoactive compounds may be organic or heteroorganic in nature. For example, a visually clear compound may include aromatic or heteroaromatic species, cyclic or heterocyclic species, each of which may be functionalized to achieve suitable optical and/or physical properties.

The disclosed visually clear photoactive compounds include UV receptor molecules such as naphthalenetetracarboxylic diimide, bisimide coronene, fluoranthene, and coranulene, which are functionalized to impart suitable optical and/or physical properties. can be achieved

로 나타낼 수 있고, 여기서 물결선은 구조가 화합물의 다른 부분에 연결된 위치를 나타낸다. 일부 구현예에서, 개시된 광활성 화합물은 2개의 디시아노 메틸렌 그룹을 포함할 수 있고 테트라시아노 화합물로 지칭될 수 있다. 일부 구현예에서, 개시된 광활성 화합물은 공액된 구조 또는 융합된 방향족 또는 헤테로방향족 환을 포함할 수 있다. 이러한 성분 외에, 가시적으로 투명한 광활성 화합물의 다른 소구조는 본질적으로 유기 또는 헤테로유기일 수 있다. 예를 들면, 가시적으로 투명한 화합물은 방향족 또는 헤테로방향족 종, 사이클릭 또는 헤테로사이클릭 종을 포함할 수 있으며, 이들 각각은 작용화되어 적합한 광학적 및/또는 물리적 특성을 달성할 수 있다.The disclosed visually transparent photoactive compounds include tetracyano quinoidal thiophene compounds, tetracyano indacene compounds, carbazole thiaporphyrin compounds, and dithiophene squarine compounds. Examples of visually transparent photoactive compounds can be functionalized to modulate absorption by the compound. In some embodiments, the disclosed photoactive compounds comprise dicyano methylene groups, which groups are

, where the wavy line indicates the position where the structure is connected to other moieties of the compound. In some embodiments, the disclosed photoactive compounds may comprise two dicyano methylene groups and may be referred to as tetracyano compounds. In some embodiments, the disclosed photoactive compounds may comprise conjugated structures or fused aromatic or heteroaromatic rings. In addition to these components, other substructures of visually transparent photoactive compounds may be organic or heteroorganic in nature. For example, a visually clear compound may include aromatic or heteroaromatic species, cyclic or heterocyclic species, each of which may be functionalized to achieve suitable optical and/or physical properties.

The disclosed visually clear photoactive compounds include those containing phthalocyanines such as Al, Co, Cu, Fe, Pb, Mg, Mn, Ni, Pd, Pt, Si, Sn, V, Zn, etc., which act may be formulated to achieve suitable optical and/or physical properties.

In some embodiments, for purification of the disclosed visually clear photoactive compounds, very high molecular weights, such as about 500 amu or more, about 550 amu or more, about 600 amu or more, because very high molecular weight compounds can limit volatility, About 650 amu or greater, about 700 amu or greater, about 750 amu or greater, about 800 amu or greater, or between 500 amu and 2000 amu may be preferred, and methods for preparing and purifying visually transparent photoactive compounds include evaporation or sublimation-based purification methods. can be used In addition, visually transparent photoactive compounds can be deposited on visually transparent photovoltaic devices using thermal evaporation techniques and very high molecular weight compounds can be difficult to deposit using thermal evaporation. In various embodiments, the visually clear photoactive compounds described herein have a molecular weight of 200 amu to 700 amu, about 700 amu or less, about 650 amu or less, or about 600 amu or less, or about 550 amu or less, or about 500 amu or less. , or about 450 amu or less, or about 400 amu or less, or about 350 amu or less, or about 300 amu or less, or about 250 amu or less, or about 200 amu or less.

To achieve the desired optical properties, visually transparent photoactive compounds exhibit molecular electronic structures in which photons of near-infrared light are absorbed, resulting in the promotion of electrons to higher molecular orbitals with an energy difference consistent with that of the absorbed proton. can Compounds exhibiting extended aromaticity or extended conjugation are advantageous, as compounds with extended aromaticity or extended conjugation may exhibit electron absorption with energies consistent with those of near-infrared and/or ultraviolet photons. However, in some cases, extended directional or extended conjugation can produce absorption in the visible band (ie, about 450 nm to about 650 nm). In addition to conjugation and aromaticity, the absorption characteristics can be controlled by the incorporation of heteroatoms, such as nitrogen or sulfur atoms, in the organic structure of the visually transparent photoactive compound. Additionally or alternatively, the absorption characteristics can be controlled by the presence and position of electron donating or electron withdrawing groups, for example, halogen atoms, alkyl groups, alkoxy groups, etc. bound to the core structure of the optically transparent photoactive compound. have. In addition, the absorption characteristics can optionally be modulated by the presence of electron donor groups or electron acceptor groups in the photoactive compound.

In general, terms and phrases used herein have their art-recognized meanings, which can be found by reference to standard textbooks, academic references, and contexts known to those skilled in the art. The following definitions are provided to clarify their specific use in the context of the present invention.

As used herein, “maximum absorption intensity” refers to a specific 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). nm to 1400 nm). In some examples, the maximum absorption intensity may correspond to an absorption characteristic that is a local or absolute maximum, eg, the absorption intensity of an absorption band or peak, and may be referred to as a peak absorption. In some examples, the maximum absorption intensity within a particular band may not correspond to a local or absolute maximum, but may instead correspond to a maximum absorption value within a particular band. Such a configuration is, for example, that the absorption characteristic spreads into multiple bands (eg, visible and near-infrared), and absorption values from absorption characteristics occurring within the visible band, for example, the peak of the absorption characteristic is within the near-infrared band. However, if the tail of the absorption feature extends into the visible band, it is smaller than those occurring within the near infrared band. In some embodiments, the visually transparent photoactive compounds described herein can have absorption peaks at wavelengths greater than about 650 nanometers (ie, in the near infrared), and the absorption peaks of the visually transparent photoactive materials are between about 450 and 650. It can be greater than the absorption of a photoactive material that is visually transparent at any wavelength between nanometers.

In one embodiment, a disclosed composition or compound is isolated or purified. In one embodiment, the isolated or purified compound is at least partially isolated or purified as would be understood in the art. In one embodiment, the disclosed composition or compound has a chemical purity of 90%, optionally, in some applications, 95%, optionally, in some applications, 99%, optionally, in some applications, 99.9%, optionally, in some applications, 99.99%, and optionally , 99.999% pure in some applications.

The compounds disclosed herein optionally contain one or more ionizable groups. Ionizable groups include groups from which a proton can be removed (eg, -COOH) or added (eg, amines) and groups capable of being quaternized (eg, amines). All possible ionic forms of such molecules and salts thereof are intended to be individually included in the disclosure herein. With respect to the salts of the compounds described herein, it will be appreciated that a wide variety of available counter-ions suitable for the preparation of the salts of the present invention for a given application may be selected. In specific applications, the choice of a given anion or cation for the preparation of a salt may result in increased or decreased solubility of such salt.

Optionally, the disclosed compounds contain one or more chiral centers. Accordingly, the present disclosure includes racemic mixtures, diastereomers, enantiomers, tautomers and mixtures enriched in one or more stereoisomers. Disclosed compounds containing chiral centers include racemic forms of the compounds as well as individual enantiomers and non-racemic mixtures thereof.

As used herein, the terms “group” and “moiety” may refer to a functional group of a chemical compound. A group of disclosed compounds refers to an atom or group of atoms that are 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 can also be characterized in terms of their valence state. The present disclosure includes groups characterized by valence states, such as monovalent, divalent, trivalent, and the like. In embodiments, the term “substituent” may be used interchangeably with the terms “group” and “moiety”.

As is common and well known in the art, hydrogen atoms in the formulas disclosed herein are not always explicitly represented, for example, carbon atoms of aliphatic, aromatic, cycloaliphatic, carbocyclic and/or heterocyclic rings. The hydrogen atom attached to is not always explicitly shown in the recited formulas. Structural formulas provided herein, for example, in the context of descriptions of any specific formulas and structures recited, are intended to convey the chemical composition of the disclosed compounds of the methods and compositions. It will be appreciated that the structures provided do not represent specific positions of atoms and bond angles between atoms of these compounds.

As used herein, the terms “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 act as attachment and/or spacer groups. The disclosed compounds optionally include substituted and/or unsubstituted C ₁ -C ₂₀ alkylene, C ₁ -C ₁₀ alkylene and C ₁ -C ₅ alkylene groups.

As used herein, the terms “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 act as attachment and/or spacer groups. The disclosed compounds optionally include substituted and/or unsubstituted C ₃ -C ₂₀ cycloalkylene, C ₃ -C ₁₀ cycloalkylene and C ₃ -C ₅ cycloalkylene groups.

As used herein, the terms “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. In some embodiments, arylene is a divalent group derived from an aryl group by removing a hydrogen atom from two intra-ring carbon atoms of the aromatic ring of the aryl group. Arylene groups in some compounds act as attachment and/or spacer groups. Arylene groups in some compounds act as chromophores, fluorophores, aromatic antennas, dyes and/or imaging groups. The disclosed compounds optionally include substituted and/or unsubstituted C ₃ -C ₃₀ arylene, C ₃ -C ₂₀ arylene, C ₃ -C ₁₀ arylene and C ₁ -C ₅ arylene groups.

As used herein, the terms “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. In some embodiments, heteroarylene is a divalent group derived from a heteroaryl group by removing a hydrogen atom from two intra-ring carbon atoms or an intra-ring nitrogen atom of the heteroaromatic or aromatic ring of the heteroaryl group. Heteroarylene groups in some compounds act as attachment and/or spacer groups. Heteroarylene groups in some compounds act as chromophores, aromatic antennas, fluorophores, dyes and/or imaging groups. The disclosed compounds optionally contain substituted and/or unsubstituted C ₃ -C ₃₀ heteroarylene, C ₃ -C ₂₀ heteroarylene, C ₁ -C ₁₀ heteroarylene and C ₃ -C ₅ heteroarylene groups. include

As used herein, the terms “alkenylene” and “alkenylene group” are used synonymously and refer to a divalent group derived from an alkenyl group as defined herein. The present disclosure includes compounds having one or more alkenylene groups. Alkenylene groups in some compounds act as attachment and/or spacer groups. The disclosed compounds optionally include substituted and/or unsubstituted C ₂ -C ₂₀ alkenylene, C ₂ -C ₁₀ alkenylene and C ₂ -C ₅ alkenylene groups.

As used herein, the terms “cycloalkenylene” and “cycloalkenylene group” are used synonymously and refer to a divalent group derived from a cycloalkenyl group as defined herein. The present disclosure includes compounds having one or more cycloalkenylene groups. Cycloalkenylene groups in some compounds act as attachment and/or spacer groups. The disclosed compounds optionally include substituted and/or unsubstituted C ₃ -C ₂₀ cycloalkenylene, C ₃ -C ₁₀ cycloalkenylene and C ₃ -C ₅ cycloalkenylene groups.

As used herein, the terms "alkynylene" and "alkynylene group" are used synonymously and refer to a divalent group derived from an alkynyl group as defined herein. The present disclosure includes compounds having one or more alkynylene groups. Alkynylene groups in some compounds act as attachment and/or spacer groups. The disclosed compounds optionally include substituted and/or unsubstituted C ₂ -C ₂₀ alkynylene, C ₂ -C ₁₀ alkynylene and C ₂ -C ₅ alkynylene groups.

As used herein, the term “halo” refers to a halogen group such as fluoro (-F), chloro (-Cl), bromo (-Br), or iodo (-I).

The term "heterocyclic" refers to a ring structure containing, in addition to carbon, at least one other type of atom in the ring. Examples of such atoms include sulfur, selenium, tellurium, nitrogen, phosphorus, silicon, germanium, boron, aluminum, and transition metals. Examples of heterocyclic rings include pyrrolidinyl, piperidyl, imidazolidinyl, tetrahydrofuran, tetrahydrothiethyl, furyl, thiethyl, pyridyl, quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridinyl, benzoxadiazolyl, benzothiadiazolyl, triazolyl and tetrazolyl groups. Atoms of the heterocyclic ring may be attached to a wide variety of other atoms and functional groups, provided, for example, as substituents.

The term “carbocyclic” refers to a ring structure containing only carbon atoms in the ring. The carbon atom of the carbocyclic ring may be attached to a wide variety of other atoms and functional groups, provided, for example, as substituents.

The term “cycloaliphatic” refers to a ring that is not an aromatic ring. Alicyclic rings include both carbocyclic and heterocyclic rings.

The term “aliphatic” refers to non-aromatic hydrocarbon compounds and groups. Aliphatic groups generally include a carbon atom covalently bonded to one or more other atoms, such as carbon and hydrogen atoms. However, instead of a carbon atom, an aliphatic group may contain a non-carbon atom, for example, an oxygen atom, a nitrogen atom, a sulfur atom, and the like. Non-substituted aliphatic groups contain 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 that only one bond is associated with an adjacent carbon (or other) atom. An aliphatic group may be unsaturated, meaning that one or more double or triple bonds are attached to adjacent (or other) atoms.

Alkyl groups include straight-chain, branched and cyclic alkyl groups. Alkyl groups include those having from 1 to 30 carbons. The alkyl group includes a small alkyl group having 1 to 3 carbon atoms. The alkyl group includes a medium length alkyl group having 4 to 10 carbon atoms. The alkyl group includes a long alkyl group having 10 or more carbon atoms, particularly an alkyl group having 10 to 30 carbon atoms. The term cycloalkyl specifically refers to an alkyl group having a ring structure, for example a ring structure having 3 to 30 carbon atoms, optionally 3 to 20 carbon atoms and optionally 3 to 10 carbon atoms, for example an alkyl group having one or more rings. refers to Cycloalkyl groups include those having 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered carbon ring(s) and in particular 3-, 4-, 5-, 6-, or those with 7-membered ring(s). A carbon ring in a cycloalkyl group may also carry an alkyl group. Cycloalkyl groups may include bicyclic and tricycloalkyl groups. Alkyl groups are optionally substituted. Substituted alkyl groups include, among others, those substituted with aryl groups, which may ultimately be optionally substituted. Specific alkyl groups include methyl, ethyl, n-propyl, iso-propyl, cyclopropyl, n-butyl, s-butyl, t-butyl, cyclobutyl, n-pentyl, branched-pennyl, 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, for example, alkyl groups having one or more hydrogens replaced by one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms. A substituted alkyl group refers to a fully-fluorinated or semi-fluorinated alkyl group, eg, an alkyl group in which one or more hydrogens have been replaced by one or more fluorine atoms.

An alkoxy group is an alkyl group modified by a linkage to oxygen and may be represented by the formula RO and may also be referred to as an alkyl ether group. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy and heptoxy. Alkoxy groups include substituted alkoxy groups, wherein the alkyl portion of the group is substituted as provided herein with respect to the description of the alkyl group. MeO-, as used herein, refers to _{CH 3 O-.}

Alkenyl groups include straight chain, branched and cyclic alkenyl groups. Alkenyl groups include those having one, two or more double bonds and those in which two or more of the double bonds are conjugated double bonds. Alkenyl groups include those having 2 to 20 carbon atoms. The alkenyl group includes a small alkenyl group having 2 to 4 carbon atoms. The alkenyl group includes a medium length alkenyl group having 5 to 10 carbon atoms. The alkenyl group refers to a long alkenyl group having 10 or more carbon atoms, particularly an alkenyl group having 10 to 20 carbon atoms. Cycloalkenyl groups include those in which the double bond is in the ring or in the alkenyl group attached to the ring. The term cycloalkenyl specifically refers to an alkenyl group having a ring structure, for example a 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered carbon ring(s). alkenyl groups having 3-, 4-, 5-, 6- or 7-membered ring(s). A carbon ring in a cycloalkenyl group may also carry an alkyl group. Cycloalkenyl groups can include bicyclic and tricyclic alkenyl groups. An alkenyl group is optionally substituted. Substituted alkenyl groups include, among others, those substituted with alkyl or aryl groups, which groups may ultimately be optionally substituted. Specific alkenyl groups include ethenyl, prop-1-ethyl, prop-2-enyl, cycloprop-1-enyl, but-1-enyl, but-2-enyl, cyclobut-1-enyl, cyclo but-2-enyl, pent-1-enyl, pent-2-enyl, branched pentenyl, cyclopent-1-enyl, hex-1-enyl, branched hexenyl, cyclohexenyl, all of which is optionally substituted. Substituted alkenyl groups include fully-halogenated or semi-halogenated alkenyl groups, for example, alkenyl groups having one or more hydrogens replaced by one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms. . Substituted alkenyl groups include fully fluorinated or semi-fluorinated alkenyl groups, eg, 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-membered aromatic and/or heterocyclic aromatic rings. The term heteroaryl specifically refers to an aryl group having at least one 5-, 6- or 7-membered heterocyclic aromatic ring. An aryl group may 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 which may be fused or linked via a covalent bond. A heterocyclic aromatic ring may contain, among other things, one or more N, O, or S atoms in the ring. Heterocyclic aromatic rings are, among other things, those with 1, 2 or 3 N atoms, those with 1 or 2 O atoms, and those with 1 or 2 S atoms, or those with 1 or 2 or 3 N atoms , O or a combination of S atoms. An aryl group is optionally substituted. Substituted aryl groups include, among other things, those substituted with alkyl or alkenyl groups, which groups may ultimately be optionally substituted. Specific aryl groups include phenyl, biphenyl group, pyrrolidinyl, imidazolidinyl, tetrahydrofuryl, tetrahydrothiethyl, furyl, thiethyl, pyridyl, quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridinyl, benzoxadiazolyl, benzothiadiazolyl, and naphthyl groups, all of which are optionally substituted. Substituted aryl groups include fully halogenated or semi-halogenated aryl groups, for example, aryl groups having one or more hydrogens replaced by one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms. Substituted aryl groups include fully fluorinated or semifluorinated aryl groups, eg, 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 heterocyclic aromatic group-containing groups corresponding to any one of the following: benzene, naphthalene, naphthoquinone, diphenylmethane, fluorene, anthracene, Anthraquinone, phenanthrene, tetracene, tetracenedione, pyridine, quinoline, isoquinoline, indole, isoindole, pyrrole, imidazole, oxazole, thiazole, pyrazole, pyrazine, pyrimidine, purine, benzimidazole , furan, benzofuram, dibenzofuran, carbazole, acridine, acridone, phenanthridine, thiophene, benzothiophene, dibenzothiophene, xanthene, xanthone, flavone, coumarin, azulene or anthracyclines. As used herein, groups corresponding to the groups listed above explicitly include aromatic or heterocyclic aromatic groups, for example, monovalent, divalent and polyvalent groups of aromatic and heterocyclic aromatic groups are provided in the form covalently attached within the compounds of the present invention at any suitable point of attachment. In an embodiment, the aryl group contains 5 to 30 carbon atoms. In embodiments, an aryl group comprises one aromatic or heteroaromatic 6-membered ring and at least one additional 5- or 6-membered aromatic or heteroaromatic ring. In embodiments, the aryl group contains 5 to 18 carbon atoms in the ring. The aryl group optionally has one or more aromatic rings or heterocyclic aromatic rings with 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 group is optionally accompanied by further substituents and the aryl group is optionally substituted. A specific alkylaryl group is a phenyl-substituted alkyl group, such as a phenylmethyl group. Alkylaryl and arylalkyl groups are alternatively described as aryl groups substituted with one or more alkyl groups, wherein the alkyl group optionally carries additional substituents and the aryl group is optionally substituted. A specific alkylaryl group is an alkyl-substituted phenyl group such as methylphenyl. A substituted arylalkyl group is a fully halogenated or semi-halogenated arylalkyl group, for example an arylalkyl group having one or more alkyl and/or one replaced by one or more fluorine atoms, chlorine atoms, bromine atoms and/or iodine atoms. and aryl groups having more than one hydrogen.

As any group described herein that contains one or more substituents, it is understood that such group does not contain any substituents or patterns of substituents that are sterically impractical and/or synthetically impractical. In addition, the disclosed compounds include all stereochemically isomers resulting from the substitution of such compounds. Optional substitution of an alkyl group includes substitution with one or more alkenyl groups, aryl groups, or both, wherein the alkenyl group or aryl group is optionally substituted. Optional substitution of an alkenyl group includes substitution with one or more alkyl groups, aryl groups, or both, wherein the alkyl group or aryl group is optionally substituted. Optional substitution of an aryl group includes substitution of an aryl ring bearing one or more alkyl groups, alkenyl groups, or both, wherein the alkyl group or alkenyl group is optionally substituted.

Optional substitutions for any of the alkyl, alkenyl and aryl groups include substitutions with one or more of the following substituents, among others:

halogens including fluorine, chlorine, bromine or iodine;

pseudohalides comprising -CN;

-COOR, wherein R is 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, wherein R is hydrogen or an alkyl group or an aryl group, or more specifically, wherein R is a methyl, ethyl, propyl, butyl, or phenyl group, all of which are optionally substituted;

-CON(R) ₂ wherein each R independently of each other R is hydrogen or an alkyl group or an aryl group, or more specifically, wherein R is a methyl, ethyl, propyl, butyl, or phenyl group , all of which are optionally substituted; wherein R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms);

-OCON(R) ₂ wherein each R, independently of each other R, is hydrogen or an alkyl group or an aryl group, more specifically, R is a methyl, ethyl, propyl, butyl, or phenyl group , all of which are optionally substituted; wherein R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms);

—N(R) ₂ , wherein each R independently of each other R is hydrogen, or an alkyl group, or an acyl group or an aryl group, or more specifically, wherein R is methyl, ethyl, propyl, butyl , phenyl or acetyl groups, all of which are optionally substituted; wherein R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms);

-SR, wherein R is hydrogen or an alkyl group or an aryl group, or more specifically, wherein R is a hydrogen, methyl, ethyl, propyl, butyl, or phenyl group, all of which are optionally substituted;

—SO ₂ R, or —SOR, wherein R is an alkyl group or an aryl group, or more specifically, wherein R is a methyl, ethyl, propyl, butyl, or phenyl group, all of which are optionally substituted;

-OCOOR, wherein R is an alkyl group or an aryl group;

—SO ₂ N(R) ₂ , wherein each R, independently of each other R, is hydrogen, an alkyl group, or an aryl group, all of which are optionally substituted, wherein R and R are one or more may contain double bonds and may form rings which may contain one or more additional carbon atoms);

-OR, wherein R is H, an alkyl group, an aryl group, or an acyl group, all of which are optionally substituted. In certain instances, R can be acyl, resulting in -OCOR", where R" is hydrogen or an alkyl group or aryl group, more specifically wherein R" is a methyl, ethyl, propyl, butyl, or phenyl group , all of which are optionally substituted.

Specific substituted alkyl groups include haloalkyl groups, especially trihalomethyl groups, and specifically trifluoromethyl groups. Specific 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 group, 3- or 4-alkyl-substituted phenyl group, 3- or 4-alkoxy-substituted phenyl group, 3- or 4-RCO-substituted phenyl, 5- or 6-halo-substituted naphthalene groups. More specifically, the substituted aryl group is an acetylphenyl group, particularly a 4-acetylphenyl group; fluorophenyl groups, especially 3-fluorophenyl and 4-fluorophenyl groups; chlorophenyl groups, especially 3-chlorophenyl and 4-chlorophenyl groups; methylphenyl group, especially 4-methylphenyl group; and a methoxyphenyl group, particularly a 4-methoxyphenyl group.

1A is a simplified schematic diagram illustrating a visually transparent photovoltaic device according to an embodiment of the present invention. As shown in FIG. 1A , a visually transparent photovoltaic device 100 includes multiple layers and elements more fully described below. 2, the visually transparent silver photovoltaic device absorbs light energy at wavelengths outside the visible wavelength band of, for example, 450 nm to 650 nm, while substantially transmitting visible light within the visible wavelength band. indicates. As shown in Figure 1a, UV and/or NIR light is absorbed within the layers and elements of the photovoltaic device while visible light is transmitted through the device. Accordingly, the description of transparency provided herein is to be understood as visible transparency.

Substrate 105 supports optical layers 110 and 112 , which may be glass or other visually transparent material that provides sufficient mechanical support for the other layers and structures shown. Such optical layers may provide a variety of optical properties including antireflection (AR) properties, wavelength selective reflection or distributed Bragg reflection properties, index matching properties, encapsulation, and the like. can The optical layer may advantageously be visually transparent. Additional optical layers 114 may be used, for example as AR coatings, index matching later, passive infrared or ultraviolet absorbing layers, and the like. Optionally, the optical layer may be transparent to ultraviolet and/or near-infrared light or may be transparent to at least a subset of wavelengths in the ultraviolet and/or near-infrared band. Depending on the configuration, the additional optical layer 114 may also be a passive, visible absorbing layer. Examples of substrate materials include various glasses and rigid and flexible polymers. Multilayer substrates may also be used. The substrate may have any suitable thickness, for example between 1 mm and 20 mm, to provide the necessary mechanical support for other layers and structures. In some cases, the substrate may be or include an adhesive film to allow application of the visibly transparent photovoltaic device 100 to other structures, such as window panes, display devices, and the like.

Although the device as a whole may exhibit a visible transmittance, for example, a transmittance of at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, or at most 100%, in the range of 450 to 650 nm, transmittance that is individually It will be appreciated that certain materials, taken as , may exhibit absorption in the portion of the visible spectrum. Optionally, each individual material or layer in the visually transparent photovoltaic device has a high transmittance within the visible range, eg, greater than 30% (ie, 30% to 100%). Permeation or absorption can be expressed as a percentage and depends on the absorbent properties of the material, the thickness or passage length through which the absorbing material passes, and the concentration of the absorbing material, whereby the absorbing material has a short path length and/or absorbent material. When the material is present in a low concentration, it may be possible for a material with absorptivity in the visible spectral region to still exhibit low absorption or high transmission.

As described herein and below, the photoactive materials in the 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%), instead exhibiting high absorption (eg, absorption peaks greater than 50%, greater than 60%, greater than 70%, or greater than 80%) in the near infrared and/or ultraviolet region. For some applications, absorption in the visible region can be as high as 70%. Various configurations of other materials, eg, substrates, optical layers, and buffer layers, may allow such materials to provide overall visible transparency, although these materials may exhibit some amount of visible absorption. For example, a thin film of a metal that exhibits visible absorption, such as, for example, Ag or Cu, may be included in the transparent electrode; When provided in a thin film construction, the overall transparency of the film can be high. Similarly, materials contained within an optical layer or buffer layer may exhibit absorption within the visible range, but the overall amount of visible light absorption may be low, provided at concentrations or thicknesses that provide visible transmission.

The visually transparent photovoltaic device 100 also includes a set of transparent electrodes 120 and 122 having a photoactive layer 140 disposed between the electrodes 120 and 122 . These electrodes, which may be fabricated using ITO, thin metal films, or other suitable visually transparent materials, provide electrical connections to one or more of the various layers shown. For example, thin films of copper, silver, or other metals may be suitable for use as visually transparent electrodes, even if these metals are capable of absorbing light within the visible band. However, thin films, for example, have a thickness of 1 nm to 200 nm (eg, 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 180 nm, about 185 nm, about 190 nm, or about 195 nm), the overall transmittance of the thin film in the visible band is high, for example, 30% greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, or greater than 90%. Advantageously, the thin metal film, when used as a transparent electrode, is highly absorptive or opaque to ultraviolet light by exhibiting a band gap that occurs in the ultraviolet band of the transparent conductive oxides of some semiconductors, such as a transparent electrode, for example , may exhibit lower absorption in the ultraviolet band than other semiconductor materials that may be useful as ITO. However, in some cases, since ultraviolet light can degrade certain materials, a transparent electrode that absorbs ultraviolet light can be used, for example, to screen at least a portion of the ultraviolet light from the underlying component.

A variety of deposition techniques can be used to create transparent electrodes, including vacuum deposition techniques, e.g., atomic layer deposition, chemical vapor deposition, physical vapor deposition, thermal evaporation, sputter deposition, epitaxy, and the like. can Solution based deposition techniques, such as spin-coating, may also be used in some cases. In addition, transparent electrodes can be patterned using techniques known in the art of microfabrication, including lithography, lift off, etching, and the like.

The buffer layers 130 and 132 and the photoactive layer 140 can be used to enforce the electrical and optical properties of photovoltaic devices. Such a layer may be a single layer of material or may include multiple sub-layers as appropriate for the particular application. Thus, the term “layer” is not intended to denote a single layer of a single material, but may include multiple sub-layers of the same or different materials. In some embodiments, a tandem device configuration comprising, for example, multiple heterojunctions, by repeating the buffer layer 130 , the photoactive layer(s) 140 , and the buffer layer 132 in a stacked configuration. (tandem device configuration) is provided. In some embodiments, the photoactive layer(s) include electron donor materials and electron acceptor materials, also referred to as donors and acceptors. Although these donors and acceptors are visibly transparent, they absorb outside the visible wavelength band, providing the device's photoactive properties.

Useful buffer layers include electron transport layers, electron blocking layers, hole transport layers, hole blocking layers, exciton blocking layers, optical spacers, physical buffer layers, charge recombination layers, or those that act as a charge generating layer. The buffer layer may be of any suitable thickness to provide the desired cushioning effect and may optionally be present or absent. Useful buffer layers, if present, can be between 1 nm and 1 μm thick. Fullerene materials, carbon nanotube materials, graphene materials, metal oxides such as molyddenum oxide, titanium oxide, zinc oxide, etc., polymers such as poly(3,4-ethylene) A variety of materials can be used as the buffer layer, including deoxythiophene), polystyrene sulfonic acid, polyaniline, and the like, copolymers, polymer mixtures, and small molecules such as vatocuproin. The buffer layer may be applied using a deposition process (eg, thermal evaporation) or a solution processing method (eg, spin coating).

1B shows an overview of examples of various single connection configurations for photoactive layer 140 . Optionally, the photoactive layer 140 may correspond to a mixed donor/acceptor (giant heterojunction) configuration, a planar donor/acceptor configuration, a planar and mixed donor/acceptor configuration, or a gradient donor/acceptor configuration. A variety of materials can be used as the photoactive layer 140 , for example, a material that absorbs in the ultraviolet or near infrared bands but minimally in any case in the visible band. In this way, photoactive materials can be used to generate electron-hole pairs for actuating external circuits by absorption of ultraviolet and/or near infrared rays, leaving visible light relatively undisturbed, thereby providing visible transmittance. As shown, the photoactive layer 140 may include a planar heterojunction, eg, separate donor and acceptor layers. The photoactive layer 140 may alternatively comprise a planar-mixed heterojunction structure, eg, separate acceptor and donor layers and a mixed donor-acceptor layer. The photoactive layer 140 may alternatively include mixed heterojunction structures comprising fully mixed acceptor-donor layers or those comprising mixed donor-acceptor layers in various relative concentration gradients.

The photoactive layer can have any suitable thickness and can have any suitable concentration or composition of the photoactive material to provide a desired level of transmittance and ultraviolet/near infrared absorption properties. Examples of the thickness of the photoactive layer may range from about 1 nm to about 1 μm, from about 1 nm to about 300 nm, or from about 1 nm to about 100 nm. In some cases, the photoactive layer can be made from individual sub-layers or mixtures of layers to provide suitable photovoltaic power generation properties, as shown in FIG. 1B . The various configurations shown in FIG. 1B can be used and depend on the particular donor and acceptor materials used to provide advantageous photovoltaic power generation. For example, some donor and acceptor combinations may benefit from certain configurations, while other donor and acceptor combinations may benefit from other specific configurations. Suitable photovoltaic power generation properties can be provided by providing the donor material and the acceptor material in any ratio or concentration. For mixed layers, the relative concentration of donor to acceptor is optionally from about 20 to 1 to about 1 to 20. Optionally, the relative concentration of donor to acceptor is optionally from about 5 to 1 to about 1 to 5. Optionally, the donor and acceptor are present in a ratio of 1 to 1.

In various embodiments, a visually transparent photovoltaic device 100 includes a transparent electrode 120 , a photoactive layer 140 and a transparent electrode 122 , including any one or more substrates 105 , an optical layer 110 , (112), and (114), and the buffer layers (130) and (132) may optionally be included or excluded.

As described more fully herein, embodiments of the present invention provide diaminodifluoro boron-based organic dyes for one or more buffer layers, optical layers, and/or photoactive layers, and related diamino dioxyboron dioxygen-based organic dyes. Contains organic dyes. Such compounds may include suitably functionalized versions for modification of the electrical and/or optical properties of the core structure. As an example, the disclosed compounds may contain functional groups that decrease absorption properties in the visible wavelength band between 450 nm and 650 nm and increase absorption properties in the NIR band at wavelengths greater than 650 nm.

For example, the disclosed visually transparent photoactive compounds are, in some embodiments, useful as electron donor photoactive materials and can be paired with suitable electron acceptor photoactive materials to provide photoactive layers useful in photovoltaic devices. Optionally, the disclosed visually transparent photoactive compounds are useful as electron acceptor photoactive materials and can be paired with suitable electron donor photoactive materials to provide photoactive layers useful for photovoltaic devices. Examples of donor and acceptor materials are U.S. Provisional Patent Applications Nos. 62/521,154, 62/521,158, 62/521,160, 62/521,211, 62/521,214, each filed on June 16, 2017. and 62/521,224, which are incorporated herein by reference in their entirety.

In an embodiment, the chemical structure of a disclosed photoactive compound is incorporated into a material by functionalizing it with one or more directing groups, e.g., electron donating groups, electron withdrawing groups, or substitutions for or with a core metal atom. It can provide desirable electrical properties. For example, in some embodiments, the photoactive compound is functionalized with an amine group, phenol group, alkyl group, phenyl group, or other electron donating group to improve the ability of the material to act as an electron donor in an optoelectronic device. As another example, in some embodiments, a photoactive compound can be functionalized with a cyano group, halogen, sulfonyl group, or other electron withdrawing group to improve the ability of a material to act as an electron acceptor in a photovoltaic device.

In embodiments, the photoactive compound is functionalized to provide the desired optical properties. For example, in some embodiments, photoactive compounds can be functionalized with extended conjugates to redshift the absorption profile of the material. It will be appreciated that conjugation can refer to the delocalization of a pi molecule to a molecule and can be characterized by altering single and multiple bonds in the molecular structure. For example, functionalization to prolong electron conjugation may involve fusing one or more aromatic groups into the molecular structure of the material. Other functionalizations that may provide extended conjugation include, for example, alkene functionalization with vinyl groups, aromatic or heteroaromatic functionalizations, for example carbonyl functionalization with acyl groups, sulfonyl functionalization, nitro functionalization, cyano functionalization, and the like. It will be appreciated that various molecular functionalizations can affect both optical and electrical properties of photoactive compounds.

It will be appreciated that device functionality may be affected by the shape of the active layer in the solid state. Separation of electron donors and acceptors into distinct domains, with dimensions on the scale of exciton diffusion lengths and large interfacial regions, can be advantageous for achieving high device efficiencies. Advantageously, it is possible to control the shape of the material by adjusting the molecular skeleton of the photoactive material. For example, the introduction of functional groups as described herein can have a significant impact on the morphology of materials in the solid state, regardless of whether such modifications affect the energetic or electronic properties of the material. Such morphological modifications can be observed in pure materials and when special materials are combined with the corresponding donor or acceptor. Functionalities useful for controlling conformation include the addition of alkyl chains, conjugated linkers, fluorinated alkanes, macro groups (such as tert-butyl, phenyl, naphthyl or cyclohexyl) as well as excessive portions of the out-of-plane structure of the molecule. including, but not limited to, more complex coupling processes designed to inhibit crystallization.

In embodiments, other molecular structural properties may provide desirable electrical and optical properties in the photoactive compound. For example, in some embodiments, a photoactive compound may represent a portion of a molecule that can be characterized as electron donating while other portions of the molecule can be characterized as electron accepting. Without wishing to be bound by any theory, a molecule comprising alternating electron donating and electron accepting sites may redshift the absorption properties of the molecule compared to a similar molecule lacking alternating electron donating and electron accepting sites. For example, alternating electron donating and electron accepting sites can be reduced or otherwise create a lower energy gap between the most occupied molecular orbital and the least occupied molecular orbital. Organic donor and/or acceptor groups may be useful as R-group substituents, such as in any aryl, aromatic, heteroaryl, heteroaromatic, alkyl, or alkenyl group, in the optically transparent photoactive compounds described herein. .

,

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는 강력한 수용체 그룹으로 고려될 수 있다. 유기 수용체 그룹의 예는

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를 포함하며, 이는 중간 수용체 그룹으로 고려될 수 있다. 유기 수용체 그룹의 예는

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를 포함하며, 이는 보다 약한 수용체 그룹으로 고려될 수 있다. 나타낸 유기 수용체 그룹의 경우, R^A는 예를 들면, 임의로, 수소 또는 알킬일 수 있다. 또한, 물결선은 나타낸 구조가 다른 소구조에 연결된 위치를 나타낸다.

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can be considered as a strong receptor group. Examples of organic acceptor groups are

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, which can be considered a weaker receptor group. For the indicated organic acceptor groups, R ^A can, for example, optionally be hydrogen or alkyl. Also, the wavy line indicates the position where the structure shown is connected to other substructures.

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를 포함하며, 이는 강력한 공여체 그룹으로 고려될 수 있다. 유기 공여체의 예는

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를 포함하며, 이는 중간의 공여체 그룹으로 고려될 수 있다. 유기 공여체 그룹의 예는

,

,

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를 포함하며, 이는 보다 약한 공여체 그룹으로 고려될 수 있다. 나타낸 유기 공여체 그룹의 경우, R^D는 예를 들면, 임의로, 수소 또는 알킬일 수 있다. 또한, 물결선은 나타낸 구조가 다른 소구조에 연결된 위치를 나타낸다.Examples of organic donor groups are

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,

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, which can be considered a weaker donor group. For the organic donor groups shown, R ^D can, for example, optionally be hydrogen or alkyl. Also, the wavy line indicates the position where the structure shown is connected to other substructures.

In embodiments, the photoactive compound may exhibit a symmetric structure, eg, a structure having two or more points of symmetry. Symmetric structures may include those in which the core groups are functionalized on opposite sides by the same group or two of the same core group are fused or otherwise bonded to each other. In other embodiments, the photoactive compound may exhibit an asymmetric structure, eg, a structure with less than two points of symmetry. Asymmetric structures may include those in which the core group is functionalized on the opposite side by a different group, or in which two different core groups are fused or otherwise bonded to each other.

When the material described herein is incorporated as a photoactive layer in a transparent photovoltaic device as an electron donor or electron acceptor, the layer thickness can be adjusted to change the device output, absorption, or transmittance. For example, increasing the donor or acceptor layer thickness may increase light absorption within such layers. In some cases, increasing the concentration of donor/acceptor material in a donor or acceptor layer may similarly increase light absorption within this layer. However, in some embodiments, the concentration of the donor/acceptor material is controlled, for example, when the active material layer comprises a pure or substantially pure layer of donor/acceptor material or a pure or substantially pure mixture of donor/acceptor material. It may not be possible. Optionally, the donor/acceptor material may be provided in a solvent or suspended in a carrier such as a buffer layer material, in which case the concentration of the donor/acceptor material may be adjusted. In some embodiments, the donor layer concentration is selected that maximizes the current produced. In some embodiments, the receptor layer concentration is selected that maximizes the current produced.

However, charge collection efficiency may decrease with increasing donor or acceptor thickness due to increased “travel distance” relative to the charged carrier. Thus, a compromise can be made between increased absorption and decreased charge collection efficiency with increasing layer thickness. Accordingly, it may be advantageous to select a material as described herein having a high absorption coefficient and/or concentration that allows for increased light absorption per thickness. In some embodiments, a donor layer thickness is selected that maximizes the current produced. In some embodiments, the acceptor layer thickness is selected that maximizes the current produced.

In addition to the individual photoactive layer thicknesses formed from the materials described herein, the thickness and composition of other layers in the transparent photovoltaic device may also be selected to enhance absorption within the photoactive layer. Other layers (buffer layers, electrodes, etc.) are typically selected based on their optical properties (refractive index and extinction coefficient) in the context of the thin film device stack and the resulting optical cavity. For example, the near-infrared absorbing photoactive layer may be positioned within the peak of the optical field for the near-infrared wavelength, where it absorbs to maximize the absorption and current obtained by the device. This can be achieved by spacing the photoactive layer at an appropriate distance from the electrode using a second photoactive layer and/or optical layer as a spacer. A similar scheme can be used for ultraviolet absorbing photoactive layers. In many cases, the longer wavelength optical field peak will also be located further away from the more reflective transparent electrode of the two transparent electrodes compared to the shorter wavelength optical field peak. Thus, when using separate donor and acceptor photoactive layers, the more red absorbing (longer wavelength) material is placed further away from the more reflective electrode, and the bluer absorbing (shorter wavelength) material is used with the reflective electrode. The donor and acceptor can be selected to be located closer to the .

In some embodiments, an optical layer can be included to increase the strength of the optical field at a wavelength at which the donor increases the current produced by the donor layer by increasing absorption of light within the donor layer. In some embodiments, the optical layer can be included to increase the intensity of the optical field at a wavelength at which the receptor absorbs within the receptor layer to increase light absorption, thereby increasing the current produced by the receptor layer. In some embodiments, optical layers can be used to improve the transmittance of the stack by reducing visible absorption or visible reflection. Further, the electrode material and thickness may be selected to enhance absorption outside the visible range within the photoactive layer, while preferentially transmitting light within the visible range.

Optionally, enhancing the spectral coverage of visually transparent photovoltaic devices is achieved with the use of a multi-cell series stack of visually transparent photovoltaic devices, referred to as tandem cells, which, as described with reference to FIG. 130 , photoactive layer 140 , and buffer layer 132 may be included as multiple stacked distances. Such constructions include one or more photoactive layers, which are typically separated by, for example, a combination of buffer layer(s) and/or thin metal layers. In this configuration, the current generated in each subcell flows continuously to the opposite electrode, so that the net current in the cell is limited by, for example, the lowest current generated by a particular subcell. do. The open circuit voltage (VOC) is equal to the sum of the VOCs of the subcells. By combining sub-cells fabricated with different donor-acceptors that absorb in different regions of the solar spectrum, significant improvements in efficiency associated with single connected cells can be achieved.

Further description relating to materials used in one or more of the photoactive layer and the buffer layer, including the donor layer and/or the acceptor layer, is provided below.

2 is a simplified plot showing exemplary visually transparent photovoltaic device absorption as a function of solar spectrum, human eye sensitivity, and wavelength. As shown in FIG. 2 , the embodiment of the present invention uses a photovoltaic structure with low absorption within the visible wavelength band of about 450 nm to about 650 nm, but absorbs within the UV and NIR bands, that is, outside the visible wavelength band, to enable transparent photovoltaic operation. The ultraviolet band or ultraviolet region may, in embodiments, be described as a light wavelength between about 200 nm and 450 nm. It will be appreciated that solar radiation useful at basal levels may have a limited amount of ultraviolet radiation less than about 280 nm, so in some embodiments, the ultraviolet band or ultraviolet region can be described as a wavelength of light between about 280 nm and 450 nm. will be able The near-infrared band or near-infrared region may, in embodiments, be described as a wavelength of light between about 650 nm and 1400 nm. The various compositions described herein can exhibit absorption comprising a NIR peak with a maximum absorption intensity in the visible region that is smaller than in the NIR region.

3 provides a schematic illustration of a schematic energy level for the operation of an example of an organic photovoltaic device, eg, a visually transparent photovoltaic device 100 . For example, within such photovoltaic devices, various photoactive materials may exhibit electron donor or electron acceptor properties, depending on the type of material used for the buffer layer, electrode, etc. and their molecular properties. As shown in Figure 3, each donor and acceptor material has a maximum occupied molecular orbital (HOMO) and a lowest unoccupied molecular orbital (LUMO). The transition of electrons from HOMO to LUMO may be provided by absorption of a photon. The energy between the HOMO and LUMO (HOMO-LUMO gap) of a material roughly represents the energy of the material's optical bandgap. For electron donor and electron acceptor materials useful as the transparent photovoltaic devices provided herein, the HOMO-LUMO gaps for the electron donor and electron acceptor materials preferably fall outside the energy of photons in the visible region. For example, the HOMO-LUMO gap may be in the ultraviolet region or the near infrared region depending on the photoactive material. It will be appreciated that while HOMO is comparable to the valence band in a conventional conductor or semiconductor, LUMO is comparable to the conduction band in a conventional conductor or semiconductor.

The narrow absorption spectrum of many organic molecules, such as organic semiconductors, can make it difficult to absorb the entire absorption spectrum using a single molecular species. Thus, electron donor and acceptor molecules are usually paired to provide complementary absorption spectra and increase the spectral coverage of light absorption. In addition, the donor and acceptor molecules are selected such that their energy levels (HOMO and LUMO) lie favorably with respect to each other. Differences in the LUMO levels of the donor and acceptor provide a driving force for the dissociation of electron-hole pairs (excitons) produced in the donor, whereas differences in the HOMO levels of the donor and acceptor produce electron-holes on the acceptor. It provides the driving force for the separation of the pair (excitons). In some embodiments, it may be useful for an acceptor to have high electron mobility in order to efficiently transport electrons to an adjacent buffer layer. In some embodiments, it may be useful for the donor to have high hole mobility to efficiently transport holes to the buffer layer. Also, in some embodiments, it has been found that VOC is directly proportional to the difference between the LUMO of the acceptor and the HOMO of the donor, thus increasing the difference in the LUMO level of the acceptor and the HOMO level of the donor to increase the open circuit voltage (VOC). It can be useful to do This donor-acceptor pairing within the photoactive layer can be achieved by combining one of the materials described herein with a different visually transparent photoactive compound described herein or a completely separate material system, as described below with reference to FIG. 6 . This can be achieved by properly pairing with complementary materials that are available.

The buffer layer adjacent the donor, commonly referred to as the anode buffer layer or hole transport layer, is at the HOMO level or valence band (in the case of inorganic materials) of the buffer layer to transport holes from the donor to the anode (transparent electrode) energy landscape ( energy landscape) to align with the HOMO level of the donor. In some embodiments, it may be useful for the buffer layer to have high hole mobility. A buffer layer adjacent to an acceptor, commonly referred to as a cathode buffer layer or electron transport layer, is such that the LUMO level or conduction band of the buffer layer (in the case of inorganic materials) energy lands to transport electrons from the acceptor to the cathode (transparent electrode). The selection is made to align with the LUMO level of the receptor within the landscape. In some embodiments, it may be useful for a buffer layer to have high electron mobility.

4A, 4B, 4C, and 4D provide plots showing examples of absorption bands for different electron donor and electron acceptor configurations useful in visually transparent photovoltaic devices. In Figure 4a, the donor material exhibits absorption in the NIR, while the acceptor material exhibits absorption in the UV. Figure 4b shows an alternative configuration, where the donor material exhibits absorption in the UV while the acceptor material exhibits absorption in the NIR.

Figure 4c shows a further configuration, where both the donor and acceptor materials show absorption in the NIR. As shown in the figure, the solar spectrum exhibits a significant amount of useful radiation in the NIR with only a relatively small amount in the ultraviolet, making the configuration shown in FIG. 4C useful for obtaining large amounts of energy from the solar spectrum. It is contemplated that other embodiments are contemplated in which both the donor and acceptor materials exhibit absorption within the NIR, as shown in FIG. 4D in which the acceptor is blue shifted with respect to the donor, as opposed to the configuration shown in FIG. 4C where the donor is blue shifted with respect to the acceptor you will know

The present invention also provides a method of making a visually transparent photovoltaic device, for example a visually transparent photovoltaic device 100 . For example, FIG. 5 provides an overview of a method 500 for making a visually transparent photovoltaic device in accordance with some embodiments. The method 500 begins at block 505 , where a transparent substrate is provided. It will be appreciated that useful transparent substrates include visually transparent substrates such as glass, plastic, quartz, and the like. Flexible and rigid substrates are useful in various embodiments. Optionally, the transparent substrate is provided with one or more optical layers preformed on the upper and/or lower surfaces.

At block 510 , one or more optical layers are optionally formed on or over the transparent substrate, eg, over and/or under the surface of the transparent substrate. Optionally, one or more optical layers are formed on another material, such as an intervening layer or material, such as a transparent conductor. Optionally, one or more optical layers are positioned visibly adjacent to and/or in contact with the transparent substrate. It will be appreciated that the formation of the optical layer is optional and may not include an optical layer adjacent to and/or in contact with the transparent substrate in some embodiments. The optical layer may be formed by one or more chemical vapor 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 vapor deposition methods, such as For example, it can be formed using a variety of methods including, but not limited to, thermal evaporation, electron beam evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, ion beam deposition, and electrospray deposition. . It will be appreciated that useful optical layers include optically transparent optical layers. Useful optical layers may include those that provide one or more optical properties including, for example, anti-radiation properties, wavelength selective reflection or distributed Bragg reflection properties, refractive index matching properties, encapsulation, and the like. Useful optical layers optionally include optical layers that are transparent to ultraviolet and/or near infrared light. However, depending on the configuration, some optical layers may optionally provide passive infrared and/or ultraviolet absorption. Optionally, the optical layer can include a visually transparent photoactive compound described herein.

At block 515, a transparent electrode is formed. As described above, the transparent electrode may be an indium tin oxide thin film or other transparent conductive film, such as a metal thin film (eg, Ag, Cu, etc.), a metal thin film (eg, Ag, Cu, etc.) and a dielectric material. , or a multilayer stack comprising a conductive organic material (eg, a conductive polymer, etc.). It will be appreciated that the transparent electrode may include an electrode that is visually transparent. The transparent electrode may be formed using one or more deposition processes including vacuum deposition techniques, for example, atomic layer deposition, chemical vapor deposition, physical vapor deposition, thermal evaporation, sputter deposition, epitaxy, and the like. Solution based deposition techniques, such as spin-coating, may also be used in some cases. In addition, transparent electrodes can be patterned using microfabrication techniques such as lithography, lift-off, etching, and the like.

At block 520 , one or more buffer layers are formed, for example, on the transparent electrode. The buffer layer may be formed by one or more chemical vapor 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 vapor deposition methods, such as For example, it may be formed using a variety of methods including, but not limited to, thermal evaporation, electron beam evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, ion beam deposition, and electrospray deposition. It will be appreciated that useful buffer layers may include visually transparent buffer layers. Useful buffer layers can include those that act as electron transport layers, electron blocking layers, hole transport layers, hole blocking layers, optical spacers, physical buffer layers, charge recombination layers, or charge generating layers. In some cases, the disclosed visually transparent photoactive compounds may be useful as buffer layer materials. For example, the buffer layer optionally comprises a visually clear photoactive compound described herein.

At block 525 , one or more photoactive layers are formed on, for example, a buffer layer or a transparent electrode. As mentioned above, the photoactive layer may comprise an electron acceptor layer of an electron donor and an acceptor and an electron donor layer or a co-deposited layer. Useful photoactive layers include those comprising a visually clear photoactive compound described herein. The photoactive layer may be formed by one or more chemical vapor 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 vapor deposition methods, such as For example, it may be formed using a variety of methods including, but not limited to, thermal evaporation, electron beam evaporation, molecular beam epitaxy, sputtering, pulsed laser deposition, ion beam deposition, and electrospray deposition.

In some instances, visually transparent photoactive compounds useful for the photoactive layer may be deposited using vacuum deposition techniques, such as thermal evaporation. Vacuum deposition may occur in a vacuum chamber, for example, at a pressure of ^{about 10 -5} Torr to about 10 ^{-8 Torr.} In one example, vacuum deposition may occur at a pressure ^{of about 10 -7 Torr.} As indicated above, various deposition techniques can be applied. In some embodiments, thermal evaporation is used. Thermal evaporation may include heating the material source to be deposited (ie, a visually transparent photoactive compound) at a temperature of 200°C to 500°C. The temperature of the material source may be selected to achieve a thin film growth rate of from about 0.01 nm/s to about 1 nm/s. For example, a thin film growth rate of 0.1 nm/s can be used. This growth rate is useful for producing thin films with thicknesses of about 1 nm to 500 nm over the course of minutes to hours. It will be appreciated that various properties of the material being deposited (eg, molecular weight, volatility, thermal stability) can adjust or affect the source temperature or the maximally useful source temperature. For example, the thermal decomposition temperature of the material being deposited may limit the maximum temperature of the source. As another example, highly volatile deposited materials require lower source temperatures to achieve target deposition rates compared to less volatile materials, which may require higher source temperatures to achieve target deposition rates. can do. As the material being deposited evaporates from the source, it may be deposited on a surface (eg, substrate, optical layer, transparent electrode, buffer layer, etc.) at a lower temperature. For example, the surface may have a temperature of from about 10°C to about 100°C. In some cases, the temperature of the surface may be actively controlled. In some cases, the temperature of the surface may not be actively controlled.

At block 530 , one or more buffer layers are optionally formed, for example, on the photoactive layer. The buffer layer formed at block 530 may be formed similarly to those formed at block 520 . It will be appreciated that blocks 520 , 525 , and 530 may be repeated one or more times to form a multilayer stack of materials including, for example, a photoactive layer, and, optionally, various buffer layers.

At block 535 , a second transparent electrode is formed, for example, in a buffer layer or a photoactive layer. The second transparent electrode may be formed in block 515 using techniques applicable to the formation of the first transparent electrode.

At block 540 , one or more additional optical layers are optionally formed, for example at the second transparent electrode.

It should be understood that the specific steps shown in FIG. 5 provide a specific method of making a visually 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 shown above in a different order. Furthermore, the individual steps shown in FIG. 5 may include a number of sub-steps that may be performed in various orders as appropriate to the individual steps. Additionally, additional steps may be added or removed depending on the particular application. It will be appreciated that many variations, modifications, and alternatives are possible.

Method 500 can optionally be extended to correspond to a method for generating electrical energy. For example, a method of generating electrical energy may include providing a visually transparent photovoltaic device, eg, by manufacturing a visually transparent photovoltaic device according to method 500 . A method of generating electrical energy may also include exposing a visually transparent photovoltaic device to visible, ultraviolet and/or near infrared light, for example, for the generation of electrical energy, as described above with reference to FIG. 3 , electron-holes. It can drive the formation and separation of pairs. A visually transparent photovoltaic device can include a photoactive material, a buffer material, and/or a visually transparent photoactive compound described herein as an optical layer.

6 provides plots showing general absorption properties and/or donor/acceptor behavior for different classes of photoactive compounds. A visually transparent photoactive layer useful in a visually transparent photovoltaic device may comprise one or more photoactive compounds of the different classes shown. For example, the photoactive compounds described herein can be incorporated into a visually transparent photoactive layer as an acceptor compound along with other photoactive compounds of the class shown in FIG. 6 .

In some instances, the boron-dipyrromethene (BODIPY)-based compounds described herein can be incorporated into a visually transparent photoactive layer as a donor or acceptor compound in combination with other photoactive compounds of the class shown in FIG. 6 . As an example, when a boron-dipyrromethene (BODIPY)-based compound is used as an electron donor photoactive material, it is paired with an electron acceptor photoactive material from the class shown in FIG. 6 as a counterpart to form a photoactive layer useful in photovoltaic devices. can provide Similarly, when boron-dipyrromethene (BODIPY)-based compounds are used as electron acceptor photoactive materials, they are paired with electron donor photoactive materials from the class shown in FIG. 6 as their counterparts to form photoactive layers useful in photovoltaic devices. can provide

In some cases, the disclosed photoactive compounds may fall within the indicated acceptor-donor-acceptor structure (ADA) and may be useful as electron acceptor photoactive materials that absorb near infrared light, as counterpart electron donor photoactive materials from the class shown in FIG. They can be paired to provide a useful photoactive layer for a photovoltaic device.

As another example, the phthalocyanines described herein can be incorporated into a visually transparent photoactive layer as a donor or acceptor compound along with other photoactive compounds of the class shown in FIG. 6 . For example, when phthalocyanine is used as the electron donor photoactive material, it can be paired with an electron acceptor photoactive material from the class shown in FIG. 6 as a counterpart to provide a useful photoactive layer in a photovoltaic device. Similarly, when phthalocyanine is used as an electron acceptor photoactive material, it can be paired with an electron donor photoactive material from the class shown in FIG. 6 as a counterpart to provide a useful photoactive layer for a photovoltaic device.

As a general example, the compounds described herein can be incorporated into a visually transparent photoactive layer as an acceptor compound along with other donor photoactive compounds of the class shown in FIG. 6 . For example, when a compound is used as an electron acceptor photoactive material, it can be paired with an electron donor photoactive material from the class shown in FIG. 6 as a counterpart to provide a useful photoactive layer for a photovoltaic device. As another general example, the compounds described herein can be incorporated into a visually transparent photoactive layer as a donor compound along with other acceptor photoactive compounds of the class shown in FIG. 6 . For example, when a compound is used as an electron donor photoactive material, it can be paired with an electron acceptor photoactive material from the class shown in FIG. 6 as a counterpart to provide a useful photoactive layer for a photovoltaic device.

As a general example, TAPC, or a derivative thereof, can be used as the electron donor that absorbs UV. As another general example, fullerenes or fullerene derivatives may optionally be used as electron acceptors that absorb UV. As another general example, cyanine salts can be used as electron donors that absorb near infrared rays. In another general example, molecules having a donor-acceptor-donor structure (D-A-D) may be useful as electron donor photoactive materials or electron acceptor photoactive materials that absorb near infrared rays. As another general example, molecules having an acceptor-donor-acceptor structure (A-D-A) may be useful as electron acceptor photoactive materials that absorb near infrared rays. Examples of acceptor groups and donor groups for the D-A-D and A-D-A structures are described above. In some cases, the different classes shown may exhibit overlapping absorption characteristics (ie, spectral ranges). However, it may be desirable to select corresponding photoactive compounds that have absorption characteristics from different spectral regions, do not have overlapping absorption characteristics, or have different peak absorption wavelengths.

,

,

,

,

, 또는

를 갖는다. 구현예에서, 각각의 X는 독립적으로 S, N, 또는 C―R이다. 구현예에서, 각각의 L 그룹은 독립적으로 단일 결합이거나 치환되거나 비치환된 알킬렌 그룹, 치환되거나 비치환된 아릴렌 그룹, 또는 치환되거나 비치환된 헤테로아릴렌 그룹으로부터 선택된 2가 연결 그룹이다. 구현예에서, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다.Visibly transparent photoactive compounds useful as photoactive materials, buffer materials, and/or optical layers include boron-dipyrromethene-based compounds, such as difluoroboron-based organic dyes, and related boron dioxygen-based organic dyes. contains dyes. In some instances, the photoactive compound exhibits a maximum near-infrared absorption intensity greater than the maximum visible-light absorption intensity and has the formula

,

,

,

,

, or

has In embodiments, each X is independently S, N, or C-R. In embodiments, each L group is independently a single bond or a divalent linking group selected from a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group. In embodiments, each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted a heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.

,

, 또는

를 갖는 것을 제조하기 위한 합성 반응식(scheme)의 예를 제공한다. 동일한 분자식이나 상이한 구조적 구성(즉, 구조 이성체)의 화합물이 도 7a와 도 7b 사이의 차이에 의해 대조되는 바와 같이, 형성될 수 있음을 알 수 있을 것이다. 도 7a를 참조하면, 많은 상이한 치환이 반응물

에 대해 이루어짐으로써, 예를 들면, 수득되는 최종 생성물내 붕소-함유 환에 대해 5-원 환 펜던트(pendant)가

, 예를 들면,

,

,

, 또는

과 같은, 파라 치환된 페닐 그룹 외에의 다른 구조물로 치환될 수 있음을 알 수 있을 것이다. 유사하게, 도 7b를 참조하면, 많은 상이한 치환이 펜던트 페닐 또는 티오펜을 가하는 반응에 대해 이루어져 식별되는 최종 반응 생성물이 형성될 수 있음을 알 수 있을 것이다. 예를 들면, 치환은 치환된 페닐 환(예컨대, 알킬 치환된, 할로겐 치환된, 알콕시 치환된 등)을 포함할 수 있다. 다른 펜던트 환 구조, 예를 들면, 나프틸 그룹, 페난트릴 그룹, 안트릴 그룹 등을 유사하게 가할 수 있다. 또한, 붕소-질소 환에 융합된 환 구조를 개질시키기 위해, 디시아노 나프틸렌, 디시아노 티오펜 등과 같은 다른 구조가 도 7a의 1,2-디시아노벤젠 출발 반응물에 대해 치환될 수 있다. 붕소-질소 환, 예를 들면, 벤조인돌 또는 나프토인돌, 티에노피롤 등에 융합된 환 구조를 개질시키기 위해, 도 7b의 인돌에 대한 유사한 치환이 또한 이루어질 수 있다. 표 1은 약칭 식별자(ID)와 함께 디플루오로 붕소-계 유기 염료의 예를 제공한다.7a and 7b show a visually transparent photoactive compound, for example, the chemical formula

,

, or

Examples of synthetic schemes for preparing those having It will be appreciated that compounds of the same molecular formula or different structural composition (ie structural isomers) may be formed, as contrasted by the difference between FIGS. 7A and 7B . Referring to Figure 7a, many different substitutions are made for the reactants.

For example, a 5-membered ring pendant to the boron-containing ring in the final product obtained is

, For example,

,

,

, or

It will be appreciated that it may be substituted with a structure other than a para-substituted phenyl group, such as Similarly, referring to FIG. 7B , it will be seen that many different substitutions can be made for the reaction adding pendant phenyl or thiophene to form the identified final reaction product. For example, substitution can include a substituted phenyl ring (eg, alkyl substituted, halogen substituted, alkoxy substituted, etc.). Other pendant ring structures such as a naphthyl group, a phenanthryl group, an anthryl group, and the like can be similarly added. In addition, in order to modify the ring structure fused to the boron-nitrogen ring, other structures such as dicyano naphthylene, dicyano thiophene, etc. may be substituted for the 1,2-dicyanobenzene starting reactant of FIG. 7A . Similar substitutions for the indole of Figure 7b can also be made to modify the ring structure fused to a boron-nitrogen ring, for example, benzoindole or naphthoindole, thienopyrrole, and the like. Table 1 provides examples of difluoroboron-based organic dyes with abbreviated identifiers (IDs).

8 provides exemplary normalized absorption spectra for a number of compounds in Table 1, wherein these compounds show strong absorption in the near infrared with some absorption in the ultraviolet and minimal absorption in the visible band.

A sample photovoltaic device was installed using a number of the transparent photoactive compounds in Table 1 and tested for photovoltaic efficiency. Two device configurations, generally installed as shown in FIG. 1A , with a transparent photoactive compound used as the donor molecule with _{C 60} used as the acceptor, were used for testing purposes. In one configuration, two transparent electrodes were used to create a fully transparent device. In the second configuration, one transparent electrode (indium tin oxide) was used and one opaque electrode was used. The device installed according to the second configuration showed opacity due to the presence of the opaque electrode, but the behavior was tested by illuminating the device through a transparent electrode. Some clear photoactive compounds were used in both configurations to provide comparative results. The results are summarized in Table 2, where AVT is the mean visible transmission (for transparent cells), J _sc is the short circuit current density, V _OC is the open circuit voltage, and FF is the charge factor (together with Comparison of maximum power to theoretical power at open circuit voltage and short circuit current).

As an example, a transparent photovoltaic device using a visually transparent photoactive compound identified as D-10 with an opaque configuration was installed as follows. An anode buffer layer about 8 nm thick was deposited over the visually transparent substrate and the 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 comprising _{C 60} as acceptor was deposited over the donor layer. A cathode buffer layer about 5 nm thick was deposited over the acceptor layer. Finally, an opaque aluminum layer about 80 nm thick was deposited as the top electrode. Cells were illuminated and performance monitored. 9 provides an example of data for a D-10 photovoltaic cell, showing current density as a function of voltage.

It will be appreciated that further customizations can be made to the visually transparent photoactive compounds provided herein, for example, by substituting a functionalized oxygen atom for fluorine bonded to a boron atom. 10 provides an overview of a synthetic route for boron dioxygen-based compounds using reactions involving boron difluoride-based compounds and catechols. It will be appreciated that the boron difluoride-based compounds described herein may be substituted for those shown in FIG. 10 . It will also be appreciated that other reactants, such as other dixhydroxy aromatic derivatives (eg, 2,3-dihydroxynaphthalene), may be substituted for catechol. 11 provides an alternative synthetic scheme for forming boron dioxide-based compounds by a reaction involving a methoxy substituted compound and BCl _{3 .} Table 3 provides examples of boron dioxide-based organic dyes with abbreviated identifiers (IDs). 12 shows that compound D-3 shows slightly less absorption in the visible band than compound D-1, but shows a similar absorption profile, difluoroboron-based compound D-1 and boron dioxygen-based compound D- Comparative data showing the absorption spectra for 3 are provided.

, 또는

를 갖는 구조를 갖는 구조들을 나타낼 수 있는 구조를 가질 수 있다. 구현예에서, 각각의 X는 독립적으로 S, N, 또는 C―R이다. 구현예에서, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 예를 들면, 붕소 및 인접한 질소 원자를 포함하는 환은 5-원 또는 6-원 환, 예를 들면, 티아졸 환, 벤젠 환, 피리딘 환, 이미다졸 환, 피롤 환, 티오펜 환, 나프탈렌, 피렌, 인돌, 벤조티오펜, 벤즈이미다졸, 벤조티아졸, 또는 트리아진 환에 융합될 수 있다. 도 13은 융합된 가시적으로 투명한 광활성 화합물을 형성하기 위한 합성 반응식을 제공한다. 3개의 티오펜 융합된 가시적으로 투명한 광활성 화합물(I-33, I-34, 및 I-35)에 대한 흡수 스펙트럼은 도 14에 나타낸다. 페닐 치환된(I-33) 및 3급-부틸-페닐 치환된 (I-35) 융합된 화합물에 대한 스텍트럼은 가시 대역에서 거의 흡수하지 않는 양호한 스펙트럼 특성을 나타낸다. 티오펜 치환된 융합된 화합물 I-34에 대한 스펙트럼은 보다 넓은 흡수 특징을 나타내지만, 가시 대역에서 여전히 현저하게 적은 흡수를 나타낸다.Difluoro boron-based visually transparent photoactive compounds and boron dioxygen-based visually transparent photoactive compounds have a ring structure in which a ring comprising boron and an adjacent nitrogen atom is fused, e.g., a maximum greater than the maximum visible light absorption intensity. Represents the near-infrared absorption intensity and chemical formula

, or

It may have a structure that can represent structures having a structure having . In embodiments, each X is independently S, N, or C-R. In embodiments, each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted a heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. For example, a ring containing boron and adjacent nitrogen atoms is a 5-membered or 6-membered ring, such as a thiazole ring, a benzene ring, a pyridine ring, an imidazole ring, a pyrrole ring, a thiophene ring, naphthalene, pyrene , to an indole, benzothiophene, benzimidazole, benzothiazole, or triazine ring. 13 provides a synthetic scheme to form a fused visually transparent photoactive compound. Absorption spectra for three thiophene fused, visually clear photoactive compounds (I-33, I-34, and I-35) are shown in FIG. 14 . The spectra for the phenyl substituted (I-33) and tert-butyl-phenyl substituted (I-35) fused compounds show good spectral properties with little absorption in the visible band. The spectrum for the thiophene substituted fused compound I-34 shows broader absorption characteristics, but still significantly less absorption in the visible band.

An example of a photovoltaic device was set up using a phenyl substituted thiophene fused, visually clear photoactive compound identified as I-35 and the opaque configuration was set up as follows. An anode buffer layer about 8 nm thick was deposited over the visually transparent substrate and the indium tin oxide (ITO) transparent conductor. An about 20 nm thick layer of I-35 as a donor was deposited over the anode buffer layer. An about 30 nm thick layer comprising _{C 60} as acceptor was deposited over the donor layer. A cathode buffer layer about 5 nm thick was deposited over the acceptor layer. Finally, an opaque aluminum layer about 80 nm thick was deposited as the top electrode. Cells were illuminated and performance monitored. 15 provides an example of data for an I-35 photovoltaic cell, showing current density as a function of voltage.

As any modification to the fused visually clear photoactive compound, a reduction in molecular weight may be advantageous. For example, D-33, D-34, D-35, I-33, I-34, and I-35 represent a molecular weight in excess of 600 amu. Reducing molecular weight may improve the use of visually transparent photoactive compounds in the formation of visually transparent photovoltaic devices, as lower molecular weight compounds have higher volatility and can be more readily deposited using vacuum deposition techniques. The molecular weight is reduced to less than 600 amu by removal of the side-group to form compounds D-36, D-37, D-38, I-36, I-37, and I-38. Since some synthetic techniques may use sublimation for purification purposes, lower molecular weights may also be advantageous for synthetic purposes. 16 provides an overview of a synthetic scheme for producing compounds with reduced molecular weight.

,

, 또는

를 가질 수 있다. 임의로, 각각의 A1은 독립적으로 하나 이상의 R 그룹 치환체를 포함하는 융합되거나 융합되지 않은 방향족 또는 헤테로방향족 그룹이다. 임의로, 각각의 A2는 독립적으로 하나 이상의 R 그룹 치환체를 포함하는 융합되거나 융합되지 않은 방향족 또는 헤테로방향족 그룹이다. 임의로, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다.A further configuration for a visually transparent photoactive compound may include a bis structure wherein two boron-nitrogen containing rings are included in the compound. For example, a visually transparent photoactive compound may exhibit a maximum near-infrared absorption intensity greater than the maximum visible-light absorption intensity, and

,

, or

can have Optionally, each A1 is independently a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents. Optionally, each A2 is independently a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents. Optionally, each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted heteroaromatic group group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.

For example, each A1 is optionally one or more thiazole ring, benzene ring, pyridine ring, imidazole ring, pyrrole ring, thiophene ring, naphthalene, pyrene, indole, benzothiophene, benzimidazole, benzothiazole, or an unsubstituted or R substituted ring group including a triazine ring. Optionally, each A2 independently comprises a 5- or 6-membered aromatic or heteroaromatic ring comprising one or more R group substituents. Optionally, each A2 is independently one or more thiazole ring, benzene ring, pyridine ring, imidazole ring, pyrrole ring, thiophene ring, naphthalene, pyrene, indole, benzothiophene, benzimidazole, benzothiazole, or unsubstituted or R substituted ring groups including triazine rings.

,

,

,

,

,

,

,

, 또는

를 가질 수 있으며, 각각의 X는 독립적으로 S, N, 또는 C―R이고, 각각의 A3는 독립적으로 하나 이상의 R 그룹 치환체를 포함하는 방향족 또는 헤테로방향족 그룹이다.In a further example, the visually transparent photoactive compound is

,

,

,

,

,

,

,

, or

, each X is independently S, N, or C-R, and each A3 is independently an aromatic or heteroaromatic group comprising one or more R group substituents.

Table 4 provides examples of specific compounds having a bis configuration, and Figures 17, 18, 19, 20, and 21 provide examples of synthetic schemes to form compounds having a bis configuration.

The absorption spectrum of the photoactive compound identified as D-56 is shown in FIG. 22 together with the absorption spectrum of D-1 for comparison. D-56 shows a wider and slightly blueshifted low energy absorption peak in the near infrared, but still shows low absorption in the visible band.

BODIPY-based compounds (also referred to herein as BODIPY compounds) can be used as donor materials and can be paired with a number of useful acceptor materials. For example, a visually transparent photovoltaic device can contain a BODIPY-based donor material and an acceptor material containing a fullerene (eg, C60, C70, or a combination thereof).

In some embodiments, the donor material comprises one or more BODIPY compounds as described herein, and the acceptor material is a nickel dithiolate (NDT) compound, dicyano-indandione (DiCN), benzothiadiazole (BT). , benzo- bis -thiadiazole (BBT), diketopyrrolopyrrole diphenylthiethylamine (DPP-DPTA), naphthalenetetracarboxylic diimide (NTCDI), bisimide coronene (CBI), fluoranthene, chola Nullene, phthalocyanine, naphthalocyanine, or combinations thereof. Examples of useful NDT compounds include those described herein. Examples of useful DiCN, BT, BBT, and DPP-DPTA include, but are not limited to, those described herein. Examples of useful NTCDI, CBI, fluoranthene, and coranulene include, but are not limited to, those described herein. Examples of useful phthalocyanines and naphthalocyanines include, but are not limited to, those described herein.

In some embodiments, the acceptor material comprises DiCN, BT, BBT, DPP-DPTA, NTCDI, fluoranthene, or combinations thereof. In some embodiments, the receptor material comprises NDT. In some embodiments, the acceptor material comprises CBI, coranulene, phthalocyanine, naphthalocyanine, or a combination thereof.

In certain instances, the donor material contains a BODIPY compound and the acceptor material also contains a BODIPY compound. In this example, the receptor BODIPY can be functionalized with an electron withdrawing group or an acceptor moiety, as described herein. BODIPY compounds functionalized in this way when paired with a donor material such as NDT, DiCN, BT, BBT, DPP-DPTA, phthalocyanine, or naphthalocyanine can also be used as acceptor material.

Visibly transparent photoactive compounds useful as photoactive materials, buffer materials, and/or optical layers include donor-acceptor (near-IR DA) molecules that absorb near infrared light. As used herein, the term “donor-acceptor molecule” refers to compounds having different moieties that provide different relative electron withdrawing or electron donating properties. For example, a donor-acceptor molecule comprises a donor moiety that provides electron donating properties and an acceptor moiety that provides electron withdrawing properties. In general, a donor-acceptor molecule may comprise a first moiety that provides relatively more electron donating properties and a second moiety that provides relatively less electron donating properties. In other words, the donor-acceptor molecule may comprise a first moiety that provides relatively more electron withdrawing properties and a second moiety that provides relatively less electron withdrawing properties. A donor-acceptor molecule may also be referred to as a "push-pull" molecule 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. For example, a push-pull molecule may have a donor-acceptor-donor structure or an acceptor-donor-acceptor structure. In some embodiments, a push-pull molecule may have a strong or very strong donor moiety on one side of the double bond or conjugated moiety and a strong or very strong acceptor moiety on the opposite side of the double bond or conjugated system. can have The push-pull molecules described herein include those that behave as electron acceptors in photovoltaic devices. The donor-acceptor molecules described herein include those that behave as electron acceptors in photovoltaic devices. Although DA molecules can include both acceptor donor moieties and acceptor moieties, they are important acceptor materials when paired with a donor material as described herein (eg, nickel dithiolate, BODIPY, or other donor material). can be used as Examples of near-IR DA molecules include, but are not limited to, dicyano-indandione, benzo-bis -thiadiazole, benzothiadiazole, diketopyrrolopyrrole diphenylthienylamine, and derivatives thereof.

In some embodiments, the active layer comprises an acceptor having structures A-D-A, wherein each "A" moiety is an acceptor moiety and a "D" moiety is a donor moiety. As a non-limiting example, each "A" moiety can be independently selected from:

,

,

,

,

,

,

, 및

,

,

,

,

,

,

,

, and

,

The "D" moiety may be selected from:

,

,

,

,

,

,

,

,

, 및

,

,

,

,

,

,

,

,

,

, and

,

where R ^D is hydrogen or alkyl, and the wavy line indicates the position where the structure shown is linked to another structure.

In some embodiments, the active layer comprises an acceptor having structures D-A-D, wherein each "D" moiety is a donor moiety and the "A" moiety is an acceptor moiety. As a non-limiting example, each "D" moiety can be independently selected from:

,

, 및

,

,

, and

,

The "A" moiety may be selected from:

,

,

,

,

,

,

, 및

,

,

,

,

,

,

,

, and

,

where R ^A is hydrogen or alkyl, and the wavy line indicates the position where the structure shown is linked to another structure.

Dicyano-indandione (DiCN) and its derivatives (dicyano-indandione indacenodithiophene, dicyano-indandione dithienocarbazole, dicyano-indandione, anthradithiophene, dicyano-indandione boron- Dipyrromethene, dicyano-benzo[ b ]thiophen-3( 2H )-one 1,1-dioxide) can be used as an acceptor in the devices described herein. For example, ITIC (ie , 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexyl Phenyl)-dithieno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene) in organic photovoltaic devices Although it has demonstrated good performance as a non-fullerene acceptor, it has not been used before in transparent photovoltaic devices. Dicyano-indandione typically exhibits an absorption maximum in the near infrared.

Examples of DiCN structures include those according to Formula I:

(I).

(I).

Optionally, Y is F, Cl, Br, alkoxy, alkyl, or aryl in the compound of formula (I). Optionally, n is an integer from 0 to 5 in the compound of formula (I). Optionally, X is _{C(CN) 2} , O, S, C(O), or SO ₂ in compounds of formula (I). Optionally, Ar is aryl, such as phenyl, thiethyl, thiazolyl, and the like.

An example of a fused pi system is an anthra[1,9-bc :5,10- b'c' ]dithiophene radical (eg , anthra[1,9- bc :5,10- b'c' ]dithiophene -1,6-diyl); 4,9-dihydro- s -indaceno[1,2- b :5,6- b' ]dithiophene radical (eg , 4,9-dihydro- s -indaceno[1,2- b : 5,6- b′ ]dithiophene-2,7-diyl); Unsubstituted and substituted 5 H 5-a dithieno [3,2-b: 2 ', 3'-h] carbazole is a radical (e. G., 5-methyl -5 H - in dithieno [3,2 -b:2',3'-h]carbazole-2,8-diyl); unsubstituted and 4-substituted 4H -dithieno[3,2- b :2′,3′- d ]pyrrole radicals (eg , 4-methyl- 4H -dithieno[3,2- b: 2 ', 3'- d] pyrrol-2,6-diyl or 4- (4-methylphenyl) -4 H - rowing dt [3,2- b: 2', 3'- d] pyrrole -2 ,6-diyl); dithieno[3,2- b :2',3'- d ]thiophene radical (eg , dithieno[3,2- b :2',3'- d ]thiophene-2,6- diyl); thieno[3,2- b ]thiophene radicals (eg , thieno[3,2- b ]thiophene-2,6-diyl). Optionally, the fused pi system comprises groups unsubstituted or substituted, for example, with aryl, alkyl, heteroaryl, halo, and the like.

In some embodiments, the pi system fused in the compound of formula (I) is selected from:

, 및

,

, and

,

wherein R ^D can optionally be hydrogen or alkyl.

In some embodiments, the pi system fused in the compound of formula (I) is selected from:

, 및

,

, and

,

wherein R ^D can optionally be hydrogen or alkyl.

In some embodiments, the pi system fused in the compound of formula (I) is selected from:

,

,

,

, 및

.

,

,

,

, and

.

wherein R ^D can optionally be hydrogen or alkyl.

DiCN compounds also include unfused pi systems and those with asymmetric structures (with fused or unfused pi systems). In some embodiments, the DiCN compound has a structure according to Formula II versus Formula II:

(II).

(II).

Optionally, Y is F, Cl, Br, alkoxy, alkyl, or aryl in the compound of formula (I). Optionally, n is an integer from 0 to 5 in the compound of formula (II). Optionally, t is 1 or 2 in the compound of formula (II). Optionally, X is C(CN) ₂ , O, S, C(O), or SO ₂ in the compound of Formula II. Optionally, Ar is aryl in the compound of formula II, for example phenyl, thiethyl, thiazolyl, and the like. Optionally, each Z is independently H or a radical having the formula:

,

,

where the wavy line represents the point of attachment to the pi system and X, Y, Ar, and n are as defined above.

Examples of pi systems present in compounds of formula II include fused pi systems, such as anthra[1,9-bc :5,10- b'c' ]dithiophene radicals (eg , anthra[1,9 - bc :5,10- b'c' ]dithiophene-1,6-diyl); 4,9-dihydro- s -indaceno[1,2- b :5,6- b' ]dithiophene radical (eg , 4,9-dihydro- s -indaceno[1,2- b : 5,6- b′ ]dithiophene-2,7-diyl); Unsubstituted and substituted 5 H 5-a dithieno [3,2-b: 2 ', 3'-h] carbazole is a radical (e. G., 5-methyl -5 H - in dithieno [3,2 -b:2',3'-h]carbazole-2,8-diyl); unsubstituted and 4-substituted 4H -dithieno[3,2- b :2′,3′- d ]pyrrole radicals (eg , 4-methyl- 4H -dithieno[3,2- b: 2 ', 3'- d] pyrrol-2,6-diyl or 4- (4-methylphenyl) -4 H - rowing dt [3,2- b: 2', 3'- d] pyrrole -2 ,6-diyl); dithieno[3,2- b :2',3'- d ]thiophene radical (eg , dithieno[3,2- b :2',3'- d ]thiophene-2,6- diyl); thieno[3,2- b ]thiophene radicals (eg , thieno[3,2- b ]thiophene-2,6-diyl).

Examples of pi systems present in compounds of formula II include unfused moieties such as triphenylamine radicals (eg , N -phenyl-di(phen-4,1-diyl)amine), thiophenylamine radicals (eg , N -methyl-di(thiophen-2,5-diyl)amine and N -phenyl-(phen-4,1-diyl)-(thiophen-2,5-diyl)-amine) amine radicals comprising; Biphenyl radical (e.g., 1,1'-4,4'-diyl bipen), thiophene radical (e.g., thiophene-2,5-diyl), a phenylene radical (e.g., pen-1, 4-diyl).

Optionally, fused and unfused pi systems include groups unsubstituted or substituted with, for example, aryl, alkyl, heteroaryl, halo, and the like.

In some embodiments, the pi system in the compound of Formula II is selected from:

, 및

,

, and

,

wherein R ^D can optionally be hydrogen or alkyl.

In some embodiments, the pi system in the compound of Formula II is selected from:

, 및

,

, and

,

wherein R ^D can optionally be hydrogen or alkyl.

In some embodiments, the pi system in the compound of Formula II is selected from:

,

,

,

, 및

.

,

,

,

, and

.

wherein R ^D can optionally be hydrogen or alkyl.

23-28 provide examples of synthetic schemes for preparing symmetric and asymmetric DiCN compounds, including compounds according to Formulas I and II. As shown in Figure 23, for example, 2-(3-oxo-2,3-dihydro-1 H -inden-1-ylidene)malononitrile (cat. No. 1080-74-6) is optionally Condensation with a number of di- and tri-aldehydes in the presence of reagents such as acetic anhydride can give symmetric DiCN compounds. Asymmetric DiCN compounds can be prepared by using mono-functional aldehydes as shown in FIG. 24 . Other methods are also described, for example, in J. Am. Chem. Soc. , 2017 , 139, 7148-7151; Adv. Mater. 2016 , 28, 4734; and Adv. Mater. 2015 , 27, 1170 can be used for DiCN preparation. For example, ITIC (Cat No. 1664293-06-4), ITIC-M Isomer (Cat No. 2047352-80-5; 2047352-83-8; 2047352-86-1), ITIC-TH (Cat No. 1889344-13) -1), and a number of DiCN compounds, including ITIC-2F (catalog no. 2097998-59-7), are commercially available.

Tables 5-9 provide non-limiting examples of DiCN compounds with abbreviated identifiers (IDs).

The DiCNs and derivatives thereof described herein may optionally be characterized as "acceptor-donor-acceptor" molecules. In embodiments, DiCN and its derivatives can behave as receptors in transparent photovoltaic cells. Such molecules can absorb NIR and can be characterized as non-fullerene acceptors when used in some cases with high efficiency in organic photovoltaic devices. In embodiments, such materials may be useful in translucent PV devices with very high efficiency, for example, when a DiCN-type acceptor is paired with one or more donors that absorb at a blue-shifted position with respect to DiCN. This blue-shifted absorption may be partially within the visible spectrum. However, this severely limits the transmittance. Highly transparent devices can be achieved by pairing the DiCN material with either a UV-selective donor molecule (similar to FIG. 4b ), or a NIR-selective donor that is redshifted to DiCN (similar to FIG. 4d ).

DiCN compounds can be used as acceptor materials and can be paired with many useful donor materials. In some embodiments, 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. do. 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, but are not limited to, those described herein. This application is incorporated herein by reference in its entirety. In some embodiments, the donor material contains BODIPY, phthalocyanine, naphthalocyanine, or a combination thereof.

In some embodiments, DiCN and its derivatives can be formed in the photoactive material layer by solution processing techniques. However, DiCN and its derivatives may, in embodiments, be established as "acceptor-donor-acceptor" molecules. In an embodiment, the central donor core may correspond to a large fused aromatic ring with pendant alkyl chains, providing solubility for solution phase processing. Advantageously, embodiments of DiCN and its derivatives may not include pendant alkyl chains or other thermally labile branched or solubilizing functional groups of this nature, which will result in lower molecular weight structures with relatively improved evaporation. can Advantageously, these and other “donor-acceptor-donor” molecules can be processed using gas phase deposition techniques, such as thermal evaporation.

29 and 30 provide exemplary normalized absorption spectra for DiCN compounds. A sample photovoltaic device was installed 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 anode buffer layer about 8 nm thick was deposited over the visually transparent substrate and the indium tin oxide (ITO) transparent conductor. An about 10 nm thick layer of CuPc as the donor was deposited over the anode buffer layer. An about 10 nm thick layer containing DiCN A-16 as acceptor was deposited over the donor layer. A cathode buffer layer about 5 nm thick was deposited over the acceptor layer. Finally, an opaque aluminum layer about 80 nm thick was deposited as the top electrode. Cells were illuminated and performance monitored. 15 provides an example of data for an A-16 photovoltaic cell, showing current density as a function of voltage.

Benzo- bis -thiadiazole compounds (BBT) including benzo(1,2-c:4,5-c)bis((1,2,5)-thiadiazole) and other BBTs having the structure can be used in the devices described herein. BBT is typically used as a receptor in the devices described herein. In some embodiments, BBT may be used as a donor. BBT typically exhibits maximum absorption in the near infrared.

Since BBT is a strong electron withdrawing group, when it is covalently bound to a strong electron donating group, such as an amine, the resulting charge transfer state absorption is in the infrared region of the spectrum. This allows the fabrication of optoelectronic devices that do not absorb light within the visible part of the spectrum. BBT also sublimes easily under vacuum and can provide better visible transmittance and more neutral colors in photovoltaic devices that are transparent than other receptors.

In some embodiments, the BBT compound has a structure according to Formula IIIa, IIIb, or IIIc:

(IIIa)

(IIIb)

(IIIc).

(IIIa)

(IIIb)

(IIIc).

Optionally, each of R ₁ , R ₂ , R ₃ , and R ₄ consists of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl in the compounds of Formulas IIIa, IIIb, and IIIc independently selected from the group. optionally, A ₁ and A ₂ is independently selected from the group consisting of alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclylene in the compounds of Formulas IIIa, IIIb, and IIIc. Optionally, X is selected from the group consisting of O, S, Se, and Te in the compounds of Formulas IIIa, IIIb, and IIIc.

_{In some embodiments, R 1} , R ₂ , R ₃ , and R ₄ in a compound of Formula IIIa, Formula IIIb, and/or Formula IIIc are independently selected from:

,

, 및

.

,

, and

.

_{In some embodiments, A 1 in} a compound of Formula IIIb or IIIc and A ₂ is independently selected from arylene and heteroarylene. _{In some embodiments, A 1 in} a compound of Formula IIIb or IIIc and A ₂ is a thiophene radical (eg , thiophene-2,5-diyl). In some such embodiments, each of R ₁ , R ₂ , R ₃ , R ₄ is aryl (eg , phenyl).

In some embodiments, the benzothiadiazole compound has a structure according to Formula IVa, Formula IVb, or Formula IVc:

(IVa)

(IVb)

(IVc).

(IVa)

(IVb)

(IVc).

Optionally, each of R ₁ , R ₂ , R ₃ , and R ₄ in the compounds of Formulas IVa, IVb, and Formula IVc consists of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl. independently selected from the group. optionally, A ₁ and A ₂ is independently selected from the group consisting of alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclylene in the compounds of Formulas IVa, IVb, and IVc. Optionally, X is selected from the group consisting of O, S, Se, and Te in the compounds of Formulas IVa, IVb, and IVc.

In some embodiments, in compounds of Formula IVa, Formula IVb, and/or Formula IVc, R ₁ , R ₂ , R ₃ , and R ₄ are independently selected from:

,

, 및

.

,

, and

.

_{In some embodiments, A 1 in} a compound of Formula IVb or IVc and A ₂ is independently selected from arylene and heteroarylene. _{In some embodiments, A 1 in} a compound of Formula IIIb or IIIc and A ₂ is a thiophene radical (eg , thiophene-2,5-diyl). In some such embodiments, each of R ₁ , R ₂ , R ₃ , R ₄ is aryl (eg , phenyl).

The structure can be easily modified by selecting the linker (group A) and their substitution with an aliphatic or aromatic group (group R). In addition, the X group may be selected from O, N, S, Se, or combinations thereof. BBT can be used as a receptor (in a mixed layer or a pure layer) or transport layer within the following device configurations.

32 provides examples of synthetic schemes for preparing BT compounds and BBT compounds, including compounds according to Formula IIIa, Formula IIIb, Formula IIIc, Formula IVa, Formula IVb, and Formula IVc. For example, 4,7-dibromobenzo[c]-1,2,5-thiadiazole (product number 15155-41-6) is a star in a Stille-type coupling reaction. Reactions with nyl thiophenes can provide thiophene-substituted BT and BBT compounds. Other methods are also described, for example, in Chem. Mater. 2011 , 23, 5484-5490 can be used in the preparation of BT and BBT. Table 10 provides non-limiting examples of BT and BBT compounds along with abbreviated identifiers.

BT compounds and BBT compounds can be used as acceptor molecules and can be paired with a number of useful donor materials. In some embodiments, the acceptor material contains BT, BBT, or a derivative thereof, and the donor material is a boron-dipyrromethene (BODIPY) compound, a phthalocyanine, naphthalocyanine, a nickel dithiolate (NDT) compound, or a compound thereof include combinations. 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, but are not limited to, those described herein. In some embodiments, the donor material contains BODIPY, phthalocyanine, naphthalocyanine, or a combination thereof.

Diketopyrrolopyrrole diphenylthienylamine (DPP-DPTA) and its derivatives can be used as receptors in the devices described herein. DPP-DPTA is characterized by a donor-acceptor-donor structure, and depending on the specific DPP-DPTA can exhibit maximum absorption in the near-infrared and visible regions.

In some embodiments, diketopyrrolopyrrole diphenylthienylamine is a compound according to Formula V:

(V).

(V).

_{Optionally, R 1 in} the compound of formula V and R ₂ is independently selected from the group consisting of alkyl, cycloalkyl. optionally, A ₁ and A ₂ is independently selected from the group consisting of alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclylene. Non-limiting examples of DPP-DPTA compounds and DPP-DPTA derivatives are shown in Table 11. In some embodiments, the DPP-DPTA derivative is isoindigo, eg, compound C-1. 33 shows examples of absorption spectra for photoactive compounds, such compounds absorb more in the visible region than may be desirable for some visually transparent photovoltaic device embodiments.

,

, 또는

를 갖는다. 구현예에서, 각각의 M은 독립적으로 금속, 예를 들면, Fe, Co, Ni, Cu, Zn, Mo, Pd, 또는 Pt이다. 구현예에서, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 알케닐 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다. 구현예에서, 각각의 A는 독립적으로 하나 이상의 R 그룹 치환체를 갖는 융합된 폴리사이클릭 환 그룹이다.Visibly transparent photoactive compounds useful as photoactive materials, buffer materials, and/or optical layers include metal dithiolene complexes. In some instances, the photoactive compound exhibits a maximum near-infrared absorption intensity greater than the maximum visible-light absorption intensity and has the formula

,

, or

has In embodiments, each M is independently a metal, eg, Fe, Co, Ni, Cu, Zn, Mo, Pd, or Pt. In embodiments, each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fusion an aromatic group, a substituted or unsubstituted heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, or a substituted or unsubstituted alkoxy group. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group. In an embodiment, each A is independently a fused polycyclic ring group having one or more R group substituents.

,

,

,

, 또는

)에 융합된 환 구조로의 치환을 가능하게 함으로써, 예를 들면, 반응물

에 대해 많은 상이한 치환을 행할 수 있음을 알 수 있을 것이다. 유사하게, 도 34b를 참고하면, 상이한 최종 생성물을 형성하기 위해 많은 상이한 치환을 시아노 그룹에 대해 행할 수 있음을 알 수 있을 것이다. 예를 들면, 치환은 페닐 환(예컨대, 알킬 치환된, 할로겐 치환된, 알콕시 치환된, 등), 융합된 환 구조를 포함할 수 있다. 다른 펜던트 환 구조, 예를 들면, 나프틸 그룹, 페난트릴 그룹, 아세나프틸 그룹 등을 유사하게 가할 수 있다.34A and 34B provide examples of synthetic schemes for preparing visually transparent photoactive compounds. Referring to Figure 34a, so that the final product obtained is different, the phenyl ring pendant to the dithione is replaced with a structure of another structure, for example, a phenyl ring having more substituents than at a different position, or both the phenyl ring Other substituents of, for example, dithione (e.g. ,

,

,

,

, or

) by enabling substitution with a ring structure fused to, for example, a reactant

It will be appreciated that many different substitutions can be made for . Similarly, referring to FIG. 34B , it will be seen that many different substitutions can be made to the cyano group to form different end products. For example, substitution can include phenyl rings (eg , alkyl substituted, halogen substituted, alkoxy substituted, etc.), fused ring structures. Other pendant ring structures, for example, a naphthyl group, a phenanthryl group, an acenaphthyl group, and the like can be similarly added.

Table 12 provides examples of metal dithione complexes along with their abbreviated identifiers (IDs).

35 provides exemplary normalized absorption spectra for a number of compounds in Table 12, which shows that these compounds exhibit strong absorption in the near infrared with some absorption in the ultraviolet and minimal absorption in the visible band. indicates

Sample photovoltaic devices were installed using a number of the clear photoactive compounds in Table 12 and tested for photovoltaic efficiency. Two device configurations, generally installed as shown in FIG. 1A , with a transparent photoactive compound used as the photoactive layer or buffer layer, were used for testing purposes. In one configuration, two transparent electrodes were used to create a fully transparent device. In the second configuration, one transparent electrode (indium tin oxide) was used and one opaque electrode was used. Although the device installed according to the second configuration exhibited opacity due to the presence of the opaque electrode, the photovoltaic behavior was tested by illuminating the device through the transparent electrode.

As an example, a transparent photovoltaic device using a visually transparent photoactive compound identified as N-1 having an opaque configuration was installed as follows. A cathode buffer layer about 8 nm thick was deposited over the visually transparent substrate and the indium tin oxide (ITO) transparent conductor. An about 15 nm thick layer of subphthalocyanine (SubPc) dye as a donor was deposited over the anode buffer layer. An about 30 nm thick layer of compound N-1 as the acceptor was deposited over the donor layer. A cathode buffer layer about 5 nm thick was deposited over the acceptor layer. Finally, an opaque aluminum layer about 80 nm thick was deposited as the top electrode. Cells were illuminated and performance monitored. 36 provides an example of data for an N-10 photovoltaic cell, showing current density as a function of voltage.

Another example of a transparent photovoltaic device was installed using a nickel dithiolate complex as a buffer layer in an opaque configuration. An about 10 nm thick cathode buffer layer comprising compound N-1 was deposited over a visually transparent substrate and an indium tin oxide (ITO) transparent conductor. As the photoactive layer, an about 60 nm thick layer comprising _{C 60 was deposited over the buffer layer.} An anode buffer layer about 20 nm thick was deposited over the acceptor layer. Finally, an opaque aluminum layer about 80 nm thick was deposited as the top electrode. Cells were illuminated and performance monitored. 37 provides an example of data for a photovoltaic cell, showing current density as a function of voltage.

Metal dithiolates can be used as receptor materials and can be paired with a number of useful materials. In some embodiments, for example, the acceptor material comprises one or more metal dithiolates and the donor material is a boron-dipyrromethene (BODIPY) compound, phthalocyanine, naphthalocyanine, dicyano-indandione (DiCN), benzo thiadiazole (BT), benzo- bis -thiadiazole (BBT), diketopyrrolopyrrole diphenylthiethylamine (DPP-DPTA), or a combination thereof. Examples of useful BODIPY compounds include, but are not limited to, those described herein. Examples of useful DiCN, BT, BBT, and DPP-DPTA include, but are not limited to, those described herein. Examples of useful phthalocyanines and naphthalocyanines include, but are not limited to, those described herein. In some embodiments, the donor material comprises a BODIPY compound, a phthalocyanine, a naphthalocyanine, or a combination thereof. In some embodiments, the donor material comprises DiCN, BT, BBT, or DPP-DPTA.

In certain instances, the acceptor material contains a metal dithiolate and the donor material also contains a metal dithiolate. In this example, the donor metal dithiolate may be functionalized with one or more donor groups, such as the strong, moderate, and weak donor groups described above. Metal dithiolates functionalized in this way can also be used with acceptor materials such as BODIPY, phthalocyanine, naphthalocyanine, DiCN, BT, BBT, or DPP-DPTA, naphthalenetetracarboxylic diimide (NTCDI), bisimide coro When paired with nene (CBI), fluoranthene, coranulene, fullerene (eg , C60 or C70), or combinations thereof, it can be used as the donor material. Examples of useful NTCDI, CBI, fluoranthene, and coranulene include, but are not limited to, those described herein.

Visibly transparent photoactive compounds useful as photoactive materials, buffer materials, and/or optical layers include, but are not limited to, naphthalenetetracarboxylic diimides, bisimide coronenes, fluoranthenes, coranulenes, and derivatives thereof. , including UV receptor molecules.

Naphthalenetetracarboxylic diimide (NTCDI) and its derivatives (including but not limited to 4,5,9,10-tetraamino-naphthalenetetracarboxylic diimide and imidazo naphthalenetetracarboxylic diimide) are disclosed herein. It is typically used as a receptor in the device described in However, in certain embodiments, NTCDI and/or derivatives thereof may be used as donors. Among other advantages, NTCDI is characterized by good transparency, maximum absorption in ultraviolet light, and ease of handling of the synthesis. NTCDI is useful in certain organic photovoltaic devices in addition to visually transparent photovoltaic devices.

A dimer of naphthalenedicarboximide can be linked via a group bridging two nitrogens (ie one nitrogen in each NTCDI monomer). The structure of the two components can be readily modified at the nitrogen position with various groups, for example, aliphatic or aromatic groups. The structure can be modified at the bay position with various groups, such as halide, aliphatic, or aromatic groups. Linkages between NTCDI monomers include, but are not limited to, direct N-N linkages and 1,4 phenylene diamine linkages. NTCDI may be used as a receptor (in a mixed or pure layer) or transport layer in the devices described herein.

Naphthalenedicarboximides absorb in the ultraviolet position of the electromagnetic spectrum, making them an attractive material class for visually transparent photovoltaic cells. Film morphology is very important in the photoactive layer. The three-dimensional shape of fullerness has been proposed to enable their high performance in devices. Therefore, it may be desirable to synthesize molecules with higher dimensionality to mimic these properties. Dimeric structures using planar chromophores are one way to achieve the desired number of dimensions.

Examples of NTCDI compounds include those according to formula (VI) and derivatives thereof:

(VI)

(VI)

Optionally, X ₁ , X ₂ , X ₃ , X ₄ are independently selected from the group consisting of aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl in the compound of formula VI. optionally, R ₁ and R ₂ is independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl in the compound of Formula VI.

Examples of NTCDI compounds also include those according to formula (VII) and derivatives thereof:

(VII)

(VII)

Optionally, each X is independently selected from the group consisting of F, Cl, Br, alkyl, alkoxy, and aryl in the compound of Formula VII. Optionally, each subscript n is independently 0, 1, 2, 3, 4, or 5 in the compound of Formula VII. Optionally, each Y is independently selected from the group consisting of H, alkyl, unsubstituted aryl, or substituted aryl in the compound of Formula VII. Optionally, each ring designated "Ar" is an independently selected aryl group in the compound of Formula VII.

Examples of NTCDI compounds also include compounds according to the following formula (VIII) and derivatives thereof:

(VIII)

(VIII)

Optionally, each X and each Y is independently selected from the group consisting of F, Cl, Br, alkyl, alkoxy, and aryl in the compound of Formula VIII. Optionally, the subscript n is independently 0, 1, 2, 3, 4, or 5 in the compound of Formula (VIII). Optionally, each subscript m is independently 0, 1, or 2 in the compound of Formula (VIII). Optionally, each ring designated "Ar" is independently an independently selected aryl group in the compound of Formula VIII.

Examples of NTCDI compounds include those according to the following formulas (IXa) and (IXb) and derivatives thereof:

(IXa)

(IXa)

(IXb)

(IXb)

Optionally, the bridging group (B) may be a direct covalent bond, an arylene linker, a heteroarylene linker, an alkylene linker, or a heteroalkylene linker in the compounds of formulas IXa and IXb. Optionally, each of X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , and X ₆ is H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, hetero in the compounds of Formulas IXa and IXb independently selected from the group consisting of cyclyl, and halogen. Optionally, each of R ₁ , R ₂ , R ₃ , and R ₄ in the compounds of Formulas IXa and IXb is selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl. independently selected.

In some embodiments, the acceptor material comprises an NTCDI compound or an NTCDI derivative and the donor material is a boron-dipyrromethene (BODIPY) compound, phthalocyanine, naphthalocyanine, nickel dithiolate (NDT) compound, dicyano-indandione (DiCN) ), benzothiadiazole (BT), benzo- bis -thiadiazole (BBT), diketopyrrolopyrrole diphenylthiethylamine (DPP-DPTA), or a combination thereof. 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 DiCN, BT, BBT, and DPP-DPTA include, but are not limited to, those described herein.

38 provides examples of synthetic schemes for preparing NTCDI compounds, including compounds according to Formula VI, Formula VII, Formula VIII, Formula IXa, and Formula IXb. For example, 1,4,5,8-naphthalenetetracarboxylic dianhydride (Product No. 81-30-1) is optionally in the presence of a base such as pyridine, diisopropylethyl amine, can be reacted with aromatic and aliphatic amines to give various NTCDI compounds. Other methods are also described, for example, in J. Org. Chem. 2007, 72 (21), 8070-8075. A number of NTCDI compounds, such as NDI-2OD-Br polymer (Cat No. 1100243-35-3) and NDI-2HD-2Br (Cat No. 1459168-68-3), are commercially available and in the apparatus provided herein. can be used

Tables 13-14 provide non-limiting examples of NTCDI compounds with abbreviated identifiers (IDs).

39 provides an exemplary normalized absorption spectrum for NTCDI E-1, indicating that the compound absorbs strongly in ultraviolet light with limited absorption in visible and near infrared light. A sample photovoltaic device was set up using NTCDI compound E-1 as the acceptor or cathode buffer. In the first example, E-1 was used as the acceptor and aluminum phthalocyanine chloride (ClAlPc) was used as the donor. An anode buffer layer about 8 nm thick was deposited over the visually transparent substrate and the indium tin oxide (ITO) transparent conductor. An about 15 nm thick layer of ClAlPc as the donor was deposited over the anode buffer layer. An about 10 nm thick layer containing NTCDI E-1 as the acceptor was deposited over the donor layer. A cathode buffer layer about 5 nm thick was deposited over the acceptor layer. Finally, a transparent layer of indium tin oxide with a thickness of about 50 nm was deposited as the top electrode. Cells were illuminated and performance monitored. 40A provides an example of data for an E-1 photovoltaic cell, showing current density as a function of voltage.

In a second example, E-1 was used in an intra-cell cathode buffer layer containing a fuller donor. About 5 nm thick cathode buffer layer containing NTCDI E-1 was deposited on the substrate. An about 60 nm thick layer of C60 (25%:75%) as donor was deposited over the cathode buffer layer. An anode buffer layer about 20 nm thick was deposited over the donor layer. Finally, an anode of about 50 nm thick indium tin oxide was prepared on top of the anode buffer layer. Cells were illuminated and performance monitored. 40B shows an example of data for an E-1 photovoltaic cell, showing current density as a function of voltage.

Bisimide coronene (CBI) and its derivatives are typically used as receptors in the devices herein. However, in certain embodiments, CBI and/or derivatives thereof may be used as donors in the device. Like NTCDI, CBI is characterized by maximum absorption in ultraviolet light. CBI has not previously been used in photovoltaic devices.

Examples of CBI compounds include those according to the following formulas (Xa) and (Xb) and derivatives thereof:

(Xa)

(Xa)

(Xb)

(Xb)

Optionally, each R is H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, and an electron-withdrawing group (such as CN, halogen, etc.) in compounds according to Formulas Xa and Xb. independently selected from the group consisting of

In some embodiments, the acceptor material contains a CBI compound or a CBI derivative and the donor material is a boron-dipyrromethene (BODIPY) compound, phthalocyanine, naphthalocyanine, nickel dithiolate (NDT) compound, dicyano-indandione (DiCN) ), benzothiadiazole (BT), benzo- bis -thiadiazole (BBT), diketopyrrolopyrrole diphenylthiethylamine (DPP-DPTA), or a combination thereof. 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, but are not limited to, those described herein. Examples of useful DiCN, BT, BBT, and DPP-DPTA include, but are not limited to, those described herein.

41 provides examples of synthetic schemes for preparing CBI compounds, eg, compounds according to Formulas Xa and Xb. For example, perylene (catalog: 198-55-0) can be replaced with N-substituted maleimides, such as N-methyl maleimide (cat: 930-88-1) and chloranyl (118-75). -2) can be thermally annealed to give the N-substituted CBI compound. Use tetracarboxy perylene or perylene-3,4,9,10-tetracarboxylic dianhydride (product number: 128-69-8) and replace the carboxy/anhydride group with, for example, the corresponding with variously-substituted amines. Additional functionality can be introduced by conversion to an amide. Other methods are also described, for example, in Chem Eur J. 2007, 13 (6), 1746-1753, for the preparation of CBI. Non-limiting examples of CBI compounds include CBI F-1 and CBI F-2 shown below.

(F-1)

(F-2)

(F-1)

(F-2)

Fluorantene and its derivatives are typically used as receptors in the devices described herein. However, in certain embodiments, fluoranthene and/or derivatives thereof may be used as donors in the device. Fluoranthenes are characterized by maximum absorption in ultraviolet light, synthetic handling, and tunable energy levels. Fluoranthenes have been used in certain organic photovoltaic devices, but have not previously been used in transparent photovoltaic devices.

Examples of fluoranthenes include fused imide structures:

.

.

The structure can be readily modified with various groups at the nitrogen position, for example, aryl groups, alkyl groups, and/or cycloalkyl groups. The structure may also be modified at the Ar position with halo, aryl, alkyl, cycloalkyl, and the like. The structure may also be modified with various groups at the X and Y positions, for example, halo, aryl, alkyl, cycloalkyl, and the like. Fluoranthene fused imides can be used as acceptor or donor (in mixed or pure layers) or transport layers in the device configurations described herein.

In some embodiments, the fluoranthene is a compound according to Formula XI or a derivative thereof:

(VI)

(VI)

Optionally, R is selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl in a compound according to formula (XI). Optionally, X and Y are H and E in the compound according to Formula XI - is independently selected from the group consisting of a withdrawing group (e.g., CN, halogen, etc.). optionally, Z ₁ and Z ₂ is independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl in a compound according to Formula XI.

In some embodiments, the acceptor material contains fluoranthene or a fluoranthene derivative, and the donor material is a boron-dipyrromethene (BODIPY) compound, phthalocyanine, naphthalocyanine, nickel dithiolate (NDT) compound, dicyano- indandione (DiCN), benzothiadiazole (BT), benzo- bis -thiadiazole (BBT), diketopyrrolopyrrole diphenylthiethylamine (DPP-DPTA), or a combination thereof. 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, but are not limited to, those described herein. Examples of useful DiCN, BT, BBT, and DPP-DPTA include, but are not limited to, those described herein.

42A and 42B provide examples of synthetic schemes for preparing fluoranthene compounds, for example compounds according to Formula XI. For example, 1,3-di(thiophen-2-yl)propan-2-one can be replaced with acenaphthenequinone (eg , 1,2-dioxo-1,2-dihydroacenaphthylene-5-carbonitrile) This can then be reacted with an N-substituted maleimide (eg, N-methyl maleimide) to provide the various N-substituted fused imide fluoranthenes. Other methods are also described, for example, in Org. Lett. 2010, 12 (23), 5522-5525. Non-limiting examples of fluoranthenes include fluoranthene G-1 and fluoranthene G-2 shown below.

(G-1)

(G-2)

(G-1)

(G-2)

A sample photovoltaic device was set up using fluoranthene G-1 as the acceptor and boron subphthalocyanine (B-SubPc) as the donor. An anode buffer layer about 8 nm thick was deposited over the visually transparent substrate and the indium tin oxide (ITO) transparent conductor. An about 20 nm thick layer of B-SubPc as the donor was deposited over the anode buffer layer. An about 10 nm thick layer containing fluoranthene G-1 as an acceptor was deposited over the donor layer. A cathode buffer layer about 5 nm thick was deposited over the acceptor layer. Finally, a transparent layer of indium tin oxide about 50 nm thick was deposited as the cathode. Cells were illuminated and performance monitored. 43 provides an example of data for a G-1 photovoltaic cell, showing current density as a function of voltage.

Coranulene and its derivatives are typically used as receptors in the devices described herein. However, in certain embodiments, coranulene and/or derivatives thereof may be used as donors in the device. Coranulene is characterized by maximum absorption in ultraviolet light. Coranulene has been used in certain organic photovoltaic devices, but has not previously been used in transparent photovoltaic devices.

Examples of coranulene include those according to the following formulas (XIIa) and (VIIb) and derivatives thereof:

(XIIa)

(XIIa)

(XIIb)

(XIIb)

Optionally, each R is H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, and an electron-withdrawing group (such as CN, halogen, etc.) in compounds according to Formulas XIIa and XIIb. independently selected from the group consisting of

In some embodiments, the acceptor material contains coranulene or a coranulene derivative and the donor material is a boron-dipyrromethene (BODIPY) compound, phthalocyanine, naphthalocyanine, nickel dithiolate (NDT) compound, dicyano-indandione ( DiCN), benzothiadiazole (BT), benzo- bis -thiadiazole (BBT), diketopyrrolopyrrole diphenylthiethylamine (DPP-DPTA), or a combination thereof. 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, but are not limited to, those described herein. Examples of useful DiCN, BT, BBT, and DPP-DPTA include, but are not limited to, those described herein.

44 provides examples of synthetic schemes for preparing coranulene, for example coranulene according to Formulas XIIa and XIIb. For example, acetaphthenequinone (product number: 82-86-0) is reacted with 1,3-bis(2-chlorophenyl)propan-2-one followed by norbornadiene to 7,10-bis (2-chlorophenyl)fluoranthene can be formed and then converted to the corresponding coranulene using a palladium catalyst. Alternatively, various N-substituted maleimides may be used in place of norbornadiene prior to the palladium-catalyzed coranulene formation step. Other methods can also be used, for example, ACS Omega , 2017 , 2, 8, 4964-4971, which may be used in the preparation of coranulene. Table 16 provides non-limiting examples of coranulene with abbreviated identifiers.

,

,

,

, 또는

를 갖는다. 구현예에서, 각각의 R 그룹은 독립적으로 수소, 할로겐, 시아노 그룹, 치환되거나 비치환된 알킬 그룹, 치환되거나 비치환된 방향족 그룹, 치환되거나 비치환된 융합된 방향족 그룹, 치환되거나 비치환된 헤테로방향족 그룹, 치환되거나 비치환된 융합된 헤테로방향족 그룹, 치환되거나 비치환된 아민 그룹, 또는 치환되거나 비치환된 알콕시 그룹이다. 구현예에서, 각각의 n은 0, 1, 2, 3, 4, 5, 6, 또는 7이다. 구현예에서, 각각의 X는 독립적으로 O, N-R, S, 또는 Se이다. 구현예에서, 각각의 A는 독립적으로 하나 이상의 R 그룹 치환체를 포함하는 융합되거나 융합되지 않은 방향족 또는 헤테로방향족 그룹이다. 임의로, 2개 이상의 R 그룹은 치환되거나 비치환된 환 그룹 또는 치환되거나 비치환된 융합된 환 그룹을 형성한다.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 squarin organic molecules. In some instances, the photoactive compound exhibits a maximum ultraviolet absorption intensity or a maximum near infrared absorption intensity greater than the maximum visible light absorption intensity and has the formula

,

,

,

, or

has In embodiments, each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted a heteroaromatic group, a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group. In embodiments, each n is 0, 1, 2, 3, 4, 5, 6, or 7. In embodiments, each X is independently O, NR, S, or Se. In embodiments, each A is independently a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents. Optionally, two or more R groups form a substituted or unsubstituted ring group or a substituted or unsubstituted fused ring group.

를 갖는 것들을 제조하기 위한 합성 반응식의 예를 제공한다. 반응물이

의 형태를 취할 수 있도록, 예를 들면, 티오펜의 3-위치에서 메틸 그룹의 메틸 그룹, 예를 들면, R 그룹 외의 다른 구조로의 치환을 가능하게 함으로써, 반응물

에 대해 많은 상이한 치환이 이루어질 수 있음을 알 수 있을 것이다. 추가적으로 또는 대안적으로, 반응물

은 예를 들면, 티오펜 환 상의 3- 또는 4-위치에서 하나 이상의 R 그룹으로 작용화됨으로써, 반응물이

의 형태를 취할 수 있도록 한다. 예를 들면, 치환된 또는 비치환된 알킬 그룹 또는 치환된 또는 비치환된 방향족 그룹을 다른 것들 외에도 R 그룹에 대해 사용할 수 있다. 이러한 방식으로, 다양한 상이한 치환된 테트라시아노 퀴노이달 티오펜 화합물을 도 45에서의 반응식을 따라서 생성시킬 수 있다. 표 17은 약칭 식별자(ID)와 함께 테트라시아노 퀴노이달 티오펜 화합물의 예를 제공한다.Figure 45 is a photoactive compound that is visually clear, for example, the formula, which may be referred to herein as a tetracyano quinoidal thiophene compound;

Examples of synthetic schemes for preparing those having reactant

For example, by allowing the substitution of a methyl group at the 3-position of the thiophene with a structure other than a methyl group, for example the R group, the reactant may take the form of

It will be appreciated that many different substitutions can be made for . Additionally or alternatively, the reactants

is functionalized with one or more R groups, for example in the 3- or 4-position on the thiophene ring, so that the reactants are

to take the form of For example, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group may be used for the R group in addition to others. In this way, a variety of different substituted tetracyano quinoidal thiophene compounds can be generated according to the scheme in FIG. 45 . Table 17 provides examples of tetracyano quinoidal thiophene compounds with an abbreviated identifier (ID).

46 provides an exemplary normalized absorption spectrum for compound O-1 in Table 17, indicating that the compound exhibits strong absorption in the near infrared with limited absorption in the ultraviolet and visible bands.

또는

를 갖는 것들을 제조하기 위한 합성 반응식의 예를 제공한다. 반응물이

의 형태를 취할 수 있도록, 예를 들면, 티오펜의 3- 또는 4-위치에서 메틸 그룹의 메틸 그룹이외의 다른 구조, 예를 들면, R 그룹으로의 치환을 가능하게 함으로써, 많은 상이한 치환이 반응물

에 대해 이루어질 수 있음을 알 수 있을 것이다. 추가적으로 또는 대안적으로, 반응물이

의 형태를 취할 수 있도록, 반응물

은 하나 이상의 R 그룹으로, 예를 들면, 페닐 환의 3- 또는 4-위치에서 작용화될 수 있다. 예를 들면, 치환된 또는 비치환된 알킬 그룹 또는 치환된 또는 비치환된 방향족 그룹을 다른 것들 외에도 R 그룹에 대해 사용할 수 있다. 이러한 방식으로, 다양한 상이한 치환된 테트라시아노 인다센 화합물을 도 47에서의 반응식에 따라 생성시킬 수 있다. 표 18은 약칭 식별자(ID)와 함께 테트라시아노 인다센 화합물의 예를 제공한다.Figure 47 is a visually clear photoactive compound, for example, referred to herein as a tetracyano indacene compound, the formula

or

Examples of synthetic schemes for preparing those having reactant

Many different substitutions can be made in the reactants, for example by allowing the substitution of a methyl group at the 3- or 4-position of the thiophene with a structure other than the methyl group, for example the R group.

It can be seen that this can be done for Additionally or alternatively, the reactants

so that the reactant can take the form of

can be functionalized with one or more R groups, for example at the 3- or 4-position of the phenyl ring. For example, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group may be used for the R group in addition to others. In this way, a variety of different substituted tetracyano indacene compounds can be generated according to the scheme in FIG. 47 . Table 18 provides examples of tetracyano indacene compounds with an abbreviated identifier (ID).

을 갖는 것들을 제조하기 위한 합성 반응식의 예를 제공한다. 반응물이

의 형태를 취할 수 있도록, 예를 들면, 페닐 환 상의 3급 부틸의 3급 부틸 그룹 이외의 다른 구조, 예를 들면, R 그룹으로의 치환을 가능하게 함으로써, 많은 상이한 치환이 반응물

에 대해 이루어질 수 있음을 알 수 있을 것이다. 예를 들면, 치환된 또는 비치환된 알킬 그룹 또는 치환된 또는 비치환된 방향족 그룹을 다른 것들 외에도 R 그룹에 대해 사용할 수 있다. 이러한 방식으로, 다양한 상이한 치환된 카바졸 티아포르피린 화합물을 도 48에서의 반응식에 따라 생성할 수 있다. 표 19는 약칭 식별자(ID)와 함께 카바졸 티아포르피린 화합물의 예를 제공한다.Figure 48 is a visually clear photoactive compound, for example, referred to herein as a carbazole thiaporphyrin compound, the formula

Examples of synthetic schemes for preparing those having reactant

Many different substitutions can take the form of, for example, the substitution of a tertiary butyl on the phenyl ring with a structure other than a tertiary butyl group, for example an R group, so that many different substitutions can be made in the reactants.

It can be seen that this can be done for For example, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group may be used for the R group in addition to others. In this way, a variety of different substituted carbazole thiaporphyrin compounds can be generated according to the scheme in FIG. 48 . Table 19 provides examples of carbazole thiaporphyrin compounds with an abbreviated identifier (ID).

49 provides an exemplary normalized absorption spectrum for compound L-1 in Table 19, indicating that the compound shows strong absorption in the near infrared and ultraviolet bands with limited absorbance in the visible band.

를 갖는 것들을 제조하기 위한 합성 반응식의 예를 제공한다. 반응물이

의 형태를 취할 수 있도록, 예를 들면, 티오펜 환에서 R 그룹으로의 치환을 가능하게 함으로써, 많은 상이한 치환이 반응물

에 대해 이루어질 수 있음을 알 수 있을 것이다. 추가로 또는 대안적으로, 반응물

을 하나 이상의 R 그룹으로 작용화함으로써, 반응물이

의 형태를 취하도록 할 수 있다. 예를 들면, 치환된 또는 비치환된 알킬 그룹 또는 치환된 또는 비치환된 방향족 그룹을 다른 것들 외에도 R 그룹에 대해 사용할 수 있다. 이러한 방식으로, 다양한 상이한 치환된 디티오펜 스쿠아린 화합물을 도 50에서의 반응식에 따라 생성시킬 수 있다. 표 20은 약칭 식별자(ID)와 함께 디티오펜 스쿠아린 화합물의 예를 제공한다.50 is a chemically clear photoactive compound, which may be referred to herein as a dithiophene squarine compound, for example;

Examples of synthetic schemes for preparing those having reactant

Many different substitutions can take the form of, for example, a thiophene ring to an R group, so that many different substitutions can take the form of

It can be seen that this can be done for Additionally or alternatively, the reactants

By functionalizing with one or more R groups, the reactants are

can take the form of For example, a substituted or unsubstituted alkyl group or a substituted or unsubstituted aromatic group may be used for the R group in addition to others. In this way, a variety of different substituted dithiophene squarine compounds can be generated according to the scheme in FIG. 50 . Table 20 provides examples of dithiophene squarin compounds with abbreviated identifiers (IDs).

As shown in Figure 50, dithiophene squarin can be considered to have an electron donor/electron acceptor/electron donor structure.

In some embodiments, the donor material or acceptor material comprises one or more of a tetracyano quinoidal thiophene, tetracyano indacene, carbazole thiaporphyrin, or dithiophene squarin compound as described herein, wherein the counterpart Materials are nickel dithiolate (NDT) compound, dicyano-indandione (DiCN), benzothiadiazole (BT), benzo- bis -thiadiazole (BBT), diketopyrrolopyrrole diphenylthiethylamine (DPP) -DPTA), naphthalenetetracarboxylic diimide (NTCDI), bisimide coronene (CBI), fluoranthene, coranulene, phthalocyanine, naphthalocyanine, BODIPY compound, or a combination thereof. Examples of useful NDT compounds include, but are not limited to, those described herein. Examples of useful DiCN, BT, BBT, and DPP-DPTA include, but are not limited to, those described herein. Examples of useful NTCDI, CBI, fluoranthene, and coranulene include, but are not limited to, those described herein. Examples of useful BODIPY compounds include, but are not limited to, those described herein.

Visibly transparent photoactive compounds useful as photoactive materials, buffer materials, and/or optical layers include Al-containing phthalocyanines, Co-containing phthalocyanines, Cu-containing phthalocyanines, Fe-containing phthalocyanines, Pb-containing phthalocyanines, Mg-containing phthalocyanines, Mn -containing phthalocyanine, Ni-containing phthalocyanine, Pd-containing phthalocyanine, Pt-containing phthalocyanine, Si-containing, Sn-containing phthalocyanine, V-containing phthalocyanine, Zn-containing phthalocyanine, and derivatives thereof .

It will be appreciated that the optical and electrical properties of the material may be sensitive to the central metal. For example, the central metal may be Cu, Co, Ni, Zn, Mg, ClAl, SnCl ₂ , Pb, Pt, Pd, V, or the like. However, other metals may be useful with metal phthalocyanine-based materials, and substitution of different metals for nickel may result in changes to the absorption profile and/or donor/acceptor behavior. It can also bond oxygen and other protecting groups to the central metal.

Certain metal phthalocyanines and naphthalocyanines have been found to exhibit “n-type” (high electron mobility) properties. It may be advantageous to offset the HOMO level of these molecules with respect to the donor, thereby allowing exciton dissociation, allowing these materials to function better as acceptors in molecular photovoltaic devices. If the HOMO level of the parent n-type material is not deeper than that of the donor material, an electronegative substituent can be added to the parent molecule to change its HOMO level, thereby creating the desired HOMO level offset. This material can be replaced with a _{fullerance, for example C 60} , which is an acceptor material commonly used in molecular photovoltaic devices.

Suitable materials for the layer may comprise one or more phthalocyanines of formula (XIII):

(XIII)

(XIII)

where M is Sn, SnCl ₂ , SnO, Pb, Mg, Mn, AlCl, AlOH, GaCl, MnCl, SiCl ₂ , Si(OH) ₂ , PbCl ₂ , VO, Co, Fe, FeCl, Ni, TiO, and TiCl _{2 and each R 1} to R ₁₆ is independently selected from the group consisting of H, F, Cl, and an electron withdrawing group (eg, an electronegative organic ligand or other electronegative substituent). Examples of electron withdrawing groups include sulfonyl groups (eg, tosyl, triflyl, mesyl, etc.), haloalkyl groups (eg trifluoromethyl, trichloromethyl, etc.), cyano, sulfonates, nitro, and carboxylates. including, but not limited to.

Suitable materials for the layer may comprise one or more naphthalocyanines of formula (XIV):

(XIV),

(XIV),

where M is Sn, SnCl ₂ , SnO, Pb, Mg, Mn, AlCl, AlOH, GaCl, MnCl, SiCl ₂ , Si(OH) ₂ , PbCl ₂ , VO, Co, Fe, FeCl, Ni, TiO, and TiCl ₂ , and _{each of R 1} to R ₂₄ is independently selected from the group consisting of H, F, Cl, and an electron withdrawing group.

The compounds of formulas (XIII) and (XIV) are non-limiting examples of metal phthalocyanines and naphthalocyanines that can be included as materials in the active layer herein and have absorption peaks in the UV/NIR portion of the solar spectrum. The energy level of these materials can be modified by adding additional substituents (eg, electronegative substituents).

Specific examples of compounds within Formula XIII or Formula XIV are provided below as Formulas XV, XVI, and XVII:

(XV, SnPc)

(XV, SnPc)

(XVI; SnNcCl₂)

(XVI; SnNcCl ₂ )

(XVII; SnPcCl₂)

(XVII; SnPcCl ₂ )

SnPc and SnNcCl ₂ were used as donor materials in OPV whereas SnPcCl ₂ was found to have high electron mobility. All three materials absorb the UV/NIR portion of the solar spectrum. See FIG. 51 .

These new materials can be electrically inverted (top to bottom: top electrode, buffer layer (MoO ₃ ), donor, acceptor, buffer layer (ZnO), bottom electrode) or conventional (top to bottom: top electrode, buffer). layer (BCP), acceptor, donor, buffer layer (MoO ₃ ), bottom electrode) device structure. In the inverted device structure, electrons (holes) are collected at the lower (upper) electrode. In contrast, electrons (holes) are collected at the top (bottom) electrode in conventional device structures. The mentioned buffer layer is a non-limiting example. As those skilled in the art will appreciate, buffer layers other than those listed and known in the art may be included in alternative embodiments.

Experiments were performed using some of these new materials within an inverted device structure. ZnO and MoO ₃ were used as the bottom and top buffer layers, respectively. ITO and silver were used as the lower and upper electrodes, respectively. The absorption spectrum of SnNcCl2 is red-shifted compared to ClAlPc and is suitable for preparing transparent PVs. The VOC extracted from the SnNcCl ₂ /C60 cell (~0.2 V) is lower than its ClAlPc counterpart (~0.8 V). Therefore, in order to enable a larger VOC while maintaining its absorption spectrum, the SnNcCl ₂ molecule used as a material in the active layer herein can be modified. This can be achieved by adding an electronegative substituent to _{SnNcCl 2 .} See Figures 52-54.

Metal phthalocyanine (MPc) is commonly used as a donor material in OPV. However, MPc may have high electron mobility and potential to act as acceptor material in OPV. One example of such a material is SnPcCl ₂ . Unlike C ₆₀ , SnPcCl ₂ absorbs only the NIR portion of the spectrum. See FIG. 55 . Therefore, SnPcCl ₂ is a suitable acceptor material for the active layer herein and for making transparent PVs. The energy level of SnPcCl ₂ can be tuned by adding electronegative substituents to modulate its acceptor properties.

_{SnNcCl 2} and as donor and acceptor materials Transparent PVs using SnPcCl ₂ respectively were installed. Performance for these devices is shown in Figures 56 and 57.

Donor materials and n-type materials, and the n-type properties of phthalocyanines and naphthalocyanines are described in H. Peisert, M. Knupfer, T. Schwieger, GG Fuentes, D. Olligs, J. Fink, and Th. Schmidt, J. Appl. Phys. 2003 , 93, 9683-9692; H. Brinkmann, C. Kelting, S. Makarov, O. Tsaryova, G. Schnurpfeil, D. Wohrle, and D. Schlettwein, Phys. stat. sol. (a) 2008 , 205, 409-420; P. Sullivan, A. Duraud, l. Hancox, N. Beaumont, G. Mirri, JHR Tucker, RA Hatton, M. Shipman, and TS Jones, Adv. Energy Mater. 2011, 1, 352-355; B. Verreet, BP Rand, D. Cheyns, A. Hadipour, T. Aernouts, P. Heremans, A. Medina, CG Claessens, and T. Torres, Adv. Energy Mater. 2011, 1, 565-568; H. Gommans, T. Aernouts, B. Verreet, P. Heremans, A. Medina, CG Claessens, and T. Torres, Adv. Funct. Mater. 2009, 19, 3435-3439; and D. Song, H. Wang, F. Zhu, J. Yang, H. Tian, Y. Geng, and D. Yan, Adv. Mater. 2008 , 20, 2142-2144, B. Lim, GY Margulis, J.-H. Yum, EL Unger, BE Hardin, M. Gratzel, MD McGeheer, and A. Sellinger, Org. Lett. 2013, 15, 784-787; AN Cammidge, VHM Goddard, G. Will, DP Arnold, and MJ Cook, Tetrahedron Lett. 2009, 50, 3013-3016; P. Margaron, R. Langlois, and JE van Liert, J. Photochem. Photobiol. B: Biol. 1992, 14, 187-199; M. Hanack and M. Lang, Adv. Mater. 1994, 6, 819-833; and NB McKeown, J. Mater. Chem. 2000, 10, 1979-1995, all of which are incorporated herein by reference as if set forth in their entirety.

Suitable materials for the layers herein may include UV/NIR absorbing organic semiconductor materials modified by the addition of conjugated substituents. These new materials can be synthesized by adding conjugated substituents to donor or acceptor materials, such as phthalocyanines and naphthalocyanines, commonly used as organic semiconductors. Addition of the conjugate results in a red-shift of the absorption spectrum of the original molecule. Addition can adjust the absorption spectrum of a material that mainly absorbs UV/NIR with some absorption in the visible region, making it completely transparent in the visible region. Further examples of suitable materials include those of Formulas XVIII and XIX:

(XVIII) 또는

(XVIII) or

(XIX),

(XIX),

where M is Sn, SnCl ₂ , SnO, Pb, Mg, Mn, AlCl, AlOH, GaCl, MnCl, SiCl ₂ , Si(OH) ₂ , PbCl ₂ , VO, Co, Fe, FeCl, Ni, TiO, and is selected from the group consisting of TiCl _{2 ;} R ₁ is phenyl; subscript m is 1 to 5; subscript n is 1 to 5; the subscript o is 1 to 5; The subscript p is 1 to 5. In some embodiments, R ₂ , R ₃ , and R ₄ are also phenyl. Combinations of compounds of formula XVIII with compounds of formula XIX are also possible. Combinations of any two or more of the compounds herein are possible. Specific examples of compounds within Formulas XVIII and XIX are shown in Formulas XX, XXI, XXII, XXIII, XXIV, and XXV below:

(XX; ClAlPc);

(XX; ClAlPc);

(XXI);

(XXI);

(XXII);

(XXII);

(XXIII);

(XXIII);

(XXIV); 및

(XXIV); and

(XXV).

(XXV).

The phthalocyanine optionally has a structure according to Formula XXXII:

(XXXII), 여기서

(XXXII), where

M is a metal,

A ₁ , A ₂ , A ₃ , and A ₄ are each substituted or unsubstituted fused aromatic ring group, wherein A ₁ is from at least one of A ₂ , A ₃ , or A _{4 .} different numbers of fused rings. In this way, phthalocyanines can exhibit an asymmetric structure. Examples of asymmetric phthalocyanines of Formula XXXII include those of Formulas XXI, XXII, XXIII, XXIV, and XXV.

Examples of phthalocyanine synthesis are as follows.

Chemical Synthesis: Phthalonitrile, 4,5-dichlorophthalonitrile, 4-fluorophthalonitrile and tetrafluorophthalonitrile were sublimed for purification. Zinc(II) acetate, potassium fluoride, 18crown-6 and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), purchased at the highest available purity, were used without further purification. The solvent used for preparation (reagent grade) was dried, distilled and stored under anhydrous conditions. All syntheses were performed under high purity and dry nitrogen.

Phthalocyaninato zinc(II)(PcZn) DBU (0.76 g, 5 mmol) was mixed with sublimated phthalonitrile (0.64 g, 5 mmol) and anhydrous zinc(II) acetate in anhydrous n-pentanol (20 mL). (0.23 g, 1.25 mmol). The mixture was heated at reflux for 36 h. Methanol (50 mL) was added. The isolated product was washed with water and methanol and then treated with methanol overnight in a Soxhlet apparatus. Yield 0.54 g (75%). Thereafter, the dried PcZn was purified by zone sublimation at 10-7-10-6 mbar and 370°C.

Non-limiting examples of bases used are represented by formulas XXVI (DBU), XXVII (TBD), XXVIII (DBN), and XXIX (BEMP):

The synthesis of Pc can be performed as summarized in Scheme I:

Scheme I

The synthesis of Nc can be performed as summarized in Scheme II:

Scheme II

58 and 59, the inclusion of 1,2-dicyanobenzene with a metal source such as vanadium(III) chloride or zinc chloride provides a metal substituted phthalocyanine. The cyanobenzene starting material may also be further substituted (eg, with a thiophenyl group or other substituent). Table 21 provides additional non-limiting examples of phthalocyanine compounds that can be prepared via this method.

Accordingly, in some embodiments the phthalocyanine is a compound according to Formula XXXII or a derivative thereof:

(XXXII)

(XXXII)

Optionally, each X and each Y is independently selected from the group consisting of H, F, Cl, Br, alkoxy, alkyl, and aryl in the compound of Formula XXXII. Optionally, Z is selected from the group consisting of Cl, =O, and -OH in the compound of formula XXXII. Optionally M is a metal (eg , Cu, Fe, Co, Mn, Al, or Sn) in the compound of formula (XX).

In some embodiments, the phthalocyanine is a compound according to Formula XXXIII, Formula XXXIV, Formula XXXV, or Formula XXXVI, or a derivative thereof:

(XXXIII)

(XXXIII)

(XXXIV)

(XXXIV)

(XXXV)

(XXXV)

(XXXVI)

(XXXVI)

Optionally, each R ₁ to R ₈ is a group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl in the compounds of Formula XXXIII, Formula XXXIV, Formula XXXV, and Formula XXXVI independently selected from Optionally, each X is independently selected from the group consisting of O, S, Se, and Te in the compounds of Formula XXXIII, Formula XXXIV, Formula XXXV, and Formula XXXVI. Optionally, M is a metal (eg, Cu, Co, Ni, Zn, Mg, ClAl, SnCl ₂ , Pb, Pt, or Pd) in the compounds of Formula XXXIII, Formula XXXIV, Formula XXXV, and Formula XXXVI.

60A and 60B and 61 provide exemplary normalized absorption spectra for phthalocyanines J-14, J-1, J-2, and J-3. The spectrum demonstrates that the compound exhibits strong absorption in the UV and near infrared.

In some embodiments, the donor material comprises phthalocyanine, naphthalocyanine, or a combination thereof, and the acceptor material is a boron-dipyrromethene (BODIPY) compound, a nickel dithiolate (NDT) compound, a dicyano-indandione (DiCN) ), benzothiadiazole (BT), benzo- bis -thiadiazole (BBT), diketopyrrolopyrrole diphenylthienylamine (DPP-DPTA), naphthalenetetracarboxylic diimide (NTCDI), bisimide coronene (CBI), fluoranthene, coranulene, or a combination thereof. 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 DiCN, BT, BBT, and DPP-DPTA include, but are not limited to, those described herein. Examples of useful NTCDI, CBI, fluoranthene, and coranulene include, but are not limited to, those described herein.

In some embodiments, the acceptor material comprises DiCN, BT, BBT, DPP-DPTA, or a combination thereof. In some embodiments, the acceptor material comprises NDT, NTCDI, fluoranthene, fullerene, or a combination thereof. In some embodiments, the receptor material comprises BODIPY, CBI, coranulene, or a combination thereof.

In certain instances, the donor material contains phthalocyanine or naphthalocyanine and the acceptor material also contains phthalocyanine or naphthalocyanine. In such instances, the acceptor phthalocyanine/naphthalocyanine may be functionalized with an electron withdrawing group or an acceptor group as described herein. Phthalocyanines and naphthalocyanines functionalized in this way can also be used as acceptor materials when paired with donor materials such as BODIPY, NDT, DiCN, BT, BBT, or DPP-DPTA.

Description of Inclusion by References and Variations

Patent documents including all references throughout this disclosure, for example, issued or granted patents or equivalents; Patent Application Gazette; and materials from non-patent literature documents or other sources are hereby incorporated by reference in their entirety, as if individually incorporated by reference.

All patents and publications mentioned in this disclosure are indicative of the state of the art to which this invention pertains. The references cited herein are hereby incorporated by reference in their entirety to indicate the state of the art, in some cases, such as their filing dates, and such information is provided, where necessary, to exclude specific embodiments in the prior art. (eg, to disclaim), it is intended to be used herein. For example, where compounds are claimed, it is to be understood that compounds known in the prior art are not intended to be encompassed by the claims, including the specific compounds disclosed in the references disclosed herein (particularly the referenced patent documents).

When groups of substituents are disclosed herein, it is to be understood that all individual members of all subgroups and classes that can be formed using such groups and substituents are separately disclosed. When Markush groups or other groupings are used herein, all individual members of groups and all possible combinations and subcombinations of groups are intended to be individually encompassed by this disclosure. As used herein, "and/or" means that the list includes one, all, or any combination of items in the list separated by "and/or"; For example, "1, 2 and/or 3" means "'1' or '2' or '3' or '1 and 2' or '1 and 3' or '2 and 3' or '1, 2 and 3'".

Any formulation or combination of ingredients described or exemplified may be used in the practice of the present invention unless otherwise indicated. Specific names of materials are intended to be illustrative, as it is known that those skilled in the art may name the same material differently. It will be appreciated that methods, device elements, starting materials, and synthetic methods other than those specifically exemplified may be used in the practice of the present invention without resorting to undue experimentation. All art-known functional equivalents of any such methods, device elements, starting materials, and synthetic methods are intended to be encompassed by the present invention. Where ranges, e.g., temperature ranges, time ranges, or composition ranges are provided in the specification, it is intended to be encompassed by the present disclosure, as well as all intermediate ranges and subranges, as well as all individual values subsumed within the range provided.

As used herein, “comprising” is synonymous with “comprising,” “comprising,” or “characterizing,” inclusive or open-ended and does not exclude additional, unrecited elements or method steps. does not As used herein, “consisting of” excludes any element, step, or ingredient not specified within the claimed element. As used herein, “consisting essentially of” does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claims. It is to be understood that any recitation herein of the term “comprising”, particularly in a description of components of a composition or description of an element of a device, includes compositions and methods consisting essentially of and consisting of the recited components or elements. The invention illustratively described herein may be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein.

The terms and expressions used are used as aspects of description and not of limitation, and there is no intention to use such terms and expressions of excluding any equivalents of the illustrated and described features or portions thereof, however, various modifications are claimed in this subject matter. It can be seen that it is possible within the scope of the invention. Accordingly, although the present invention has been specifically disclosed in terms of preferred embodiments and certain features, modifications and variations of the concepts herein disclosed may occur to those skilled in the art, and such modifications and variations are defined by the appended claims. It is to be understood as being considered to be within the scope of the present invention as such.

Claims (119)

A visually transparent photovoltaic device comprising:
a visibly transparent substrate;
a first visually transparent electrode coupled to the visually transparent substrate;
a second visually transparent electrode over the first visually transparent electrode;
A first visually transparent active layer between a first visually transparent electrode and a second visually transparent electrode, wherein the first visually transparent active layer comprises an acceptor material comprising a near-infrared absorbing photoactive compound; wherein the near infrared absorbing photoactive compound exhibits a first maximum near infrared absorption intensity and a first maximum visible light absorption intensity, wherein the first maximum near infrared absorption intensity is greater than the first maximum visible light absorption intensity. a visibly transparent active layer; and
a second visually transparent active layer between the first visually transparent electrode and the second visually transparent electrode, wherein the second visually transparent active layer has a second maximum absorption intensity in the near infrared and a second A visually transparent photovoltaic cell comprising a donor material exhibiting a maximum visible light absorption intensity, wherein the second maximum absorption intensity is greater than the second maximum visible light absorption intensity. Device. The photovoltaic device of claim 1 , wherein the donor material comprises a boron-dipyrromethene compound. The photovoltaic device of claim 1 , wherein the donor material comprises phthalocyanine or naphthalocyanine. The visually transparent photoactive layer of claim 1 , wherein the first visually transparent photoactive layer is coupled to the first visually transparent electrode or the first visually transparent photoactive layer is coupled to the second visually transparent electrode. photovoltaic device. The visually transparent photovoltaic device of claim 1 , wherein the first visually transparent photoactive layer and the second visually transparent photoactive layer correspond to separate, mixed, or partially mixed layers. The photovoltaic device of claim 1 , wherein the maximum near-infrared absorption by the acceptor material is redshifted with respect to the maximum near-infrared absorption by the donor material. The optically transparent photovoltaic device of claim 1 , wherein the maximum near-infrared absorption by the acceptor material is blueshifted with respect to the maximum near-infrared absorption by the donor material. The photovoltaic device of claim 1 , wherein the near-infrared absorbing photoactive compound comprises a donor-acceptor (near-IR DA) molecule that absorbs near infrared. 9. The method of claim 8, wherein the near-IR DA molecule is dicyano-indandione, dicyano-indandione derivatives, benzo- bis -thiadiazole, benzo- bis -thiadiazole derivatives, benzothiadiazole, benzothiadia A visually transparent photovoltaic device selected from the group consisting of sol derivatives, diketopyrrolopyrrole diphenylthienylamine, diketopyrrolopyrrole diphenylthienylamine derivatives, and combinations thereof. 10. The photovoltaic device of claim 9, wherein the near-IR DA molecule has a molecular weight of 200 amu to 1000 amu, 300 amu to 800 amu, or 400 amu to 600 amu. 10. The photovoltaic device of claim 9, wherein the dicyano-indandione has the following formula and derivatives thereof:

,
here,
Y is selected from the group consisting of F, Cl, Br, alkoxy, alkyl, and aryl;
each subscript n is independently 0, 1, 2, 3, or 4;
each X is independently selected from the group consisting of C(CN) ₂ , O, S, C(O), and SO _{2 ;}
Each ring denoted by "Ar" is an independently selected aryl group,
The fused pi system bridging group is unsubstituted or substituted (eg , with aryl, alkyl, heteroaryl, halo, etc.). 10. The photovoltaic device of claim 9, wherein the dicyano-indandione has the following formula and derivatives thereof:

,
here,
Z is independently H or a radical having the formula:

,
where the wavy line represents the point of attachment to the pi system,
Y is selected from the group consisting of F, Cl, Br, alkoxy, alkyl, and aryl;
each subscript n is independently 0, 1, 2, 3, or 4;
t is 1 or 2;
each X is independently selected from the group consisting of C(CN) ₂ , O, S, C(O), and SO _{2 ;}
each ring denoted by "Ar" is an independently selected aryl group,
The pi system bridging group is unsubstituted or substituted (eg , with aryl, alkyl, heteroaryl, halo, etc.). 10. The photovoltaic device of claim 9, wherein the dicyano-indandione is selected from the group consisting of:

and

. 10. The method according to claim 9, wherein the near-IR DA molecule is a dicyano-indandione or a dicyano-indandione derivative, and the donor material is a boron-dipyrromethene compound, phthalocyanine, naphthalocyanine, nickel dithiolate compound, benzo-bis - A visually transparent photovoltaic device comprising thiadiazole, benzothiadiazole, or a combination thereof. 10. The photovoltaic device of claim 9, wherein the benzo- bis -thiadiazole has the formula: or a derivative thereof:

,

, or

,
here:
each R ₁ , R ₂ , R ₃ , and R ₄ is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl;
A ₁ and A ₂ is 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. 10. The photovoltaic device of claim 9, wherein the benzothiadiazole has the formula: or a derivative thereof:

,

, or

,
here:
each R ₁ , R ₂ , R ₃ , and R ₄ is independently selected from the group consisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl;
A ₁ and A ₂ is 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. 10. The method of claim 9, wherein the near-IR DA molecule is benzo- bis -thiadiazole, benzo- bis -thiadiazole derivative, benzothiadiazole, or benzothiadiazole derivative, and the donor material is boron-dipyrromethene. A photovoltaic device that is visually transparent, comprising a compound, a phthalocyanine, a naphthalocyanine, a nickel dithiolate compound, or a combination thereof. 10. The photovoltaic device of claim 9, wherein the diketopyrrolopyrrole diphenylthienylamine has the formula: or a derivative thereof:

,
wherein R ₁ and R ₂ are independently selected from the group consisting of alkyl, cycloalkyl;
A ₁ and A ₂ is independently selected from the group consisting of alkylene, arylene, heteroarylene, cycloalkylene, and heterocyclylene. 10. The photovoltaic device of claim 9, wherein the diketopyrrolopyrrole diphenylthienylamine derivative is a compound of:

. 10. The method of claim 9, wherein the near-IR DA molecule is a diketopyrrolopyrrole diphenylthienylamine or a diketopyrrolopyrrole diphenylthienylamine derivative, and the donor material is a boron-dipyrromethene compound, phthalocyanine, naphthalocyanine, nickel dithiol acrylate compounds, benzo-non-scan-thiadiazole, benzo-thiadiazole, or a transparent photovoltaic device with visible combinations thereof. A visually transparent photovoltaic device comprising:
a visibly transparent substrate;
a first visually transparent electrode coupled to the visually transparent substrate;
a second visually transparent electrode over the first visually transparent electrode;
A first visually transparent active layer between a first visually transparent electrode and a second visually transparent electrode, wherein the first visually transparent photoactive layer comprises a boron-dipyrromethene-based compound, wherein The boron-dipyrromethene-based compound is a photoactive compound and exhibits a first maximum near-infrared absorption intensity and a first maximum visible light absorption intensity, wherein the first maximum near-infrared absorption intensity is greater than the first maximum visible light absorption intensity. a large, said first visually transparent active layer; and
a second visually transparent photoactive layer present between the first visually transparent electrode and the second visually transparent electrode and exhibiting a second maximum absorption intensity in near infrared or ultraviolet and a second maximum visible light absorption intensity in the near infrared or ultraviolet; , wherein the second visually transparent photoactive layer is greater than the second maximum visible light absorption intensity. The visually transparent photovoltaic device of claim 21 , wherein the second visually transparent photoactive layer comprises a second boron-dipyrromethene-based. The visually transparent photovoltaic device of claim 21 , wherein the second visually transparent photoactive layer comprises a naphthalene-tetracarboxylic diimide (NTCDI) compound. The visually transparent photovoltaic device of claim 21 , wherein the photoactive compound acts as an electron acceptor material and the second visually transparent photoactive layer comprises an electron donor material. The visually transparent photovoltaic device of claim 21 , wherein the photoactive compound acts as an electron donor material and wherein the second visually transparent photoactive layer comprises an electron acceptor material. The visually transparent photovoltaic device of claim 21 , wherein the first visually transparent photoactive layer and the second visually transparent photoactive layer independently have a thickness of 1 nm to 300 nm. The visually transparent photovoltaic device of claim 21 , wherein the first visually transparent photoactive layer and the second visually transparent photoactive layer correspond to separate, mixed, or partially mixed layers. The photovoltaic device of claim 21 , wherein the photoactive compound is visually transparent. 22. The visually transparent photoactive layer of claim 21, wherein the first visually transparent photoactive layer is coupled to the first visually transparent electrode or the first visually transparent photoactive layer is coupled to the second visually transparent electrode. photovoltaic device. 22. The photovoltaic device of claim 21, wherein the boron-dipyrromethene-based compound has the formula:

,
here,
the photoactive compound exhibits a first maximum near-infrared absorption intensity and a first maximum visible-light absorption intensity;
Each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, 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 two or more R groups are either a substituted or unsubstituted ring group or a substituted or unsubstituted fused group form a ring group,
wherein each X is independently S, N, or C-R. 31. The photovoltaic device of claim 30, wherein the boron-dipyrromethene-based compound has the formula:

or

. 32. The photovoltaic device of claim 31, wherein the boron-dipyrromethene-based compound has the formula:

or

. 31. The photovoltaic device of claim 30, wherein the boron-dipyrromethene-based compound has the formula:

,

,

, or

. 34. The photovoltaic device of claim 33, wherein the boron-dipyrromethene-based compound has the formula:

,

,

, or

. 31. The photovoltaic device of claim 30, wherein the boron-dipyrromethene-based compound has the formula:

or

. 22. The photovoltaic device of claim 21, wherein the boron-dipyrromethene-based compound has the formula:

,
here,
the photoactive compound exhibits a first maximum near-infrared absorption intensity and a first maximum visible-light absorption intensity;
Each L group is independently a single bond or a divalent 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 hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, substituted or unsubstituted heteroaromatic group, is a substituted or unsubstituted fused heteroaromatic group, a substituted or unsubstituted amine group, or a substituted or unsubstituted alkoxy group, or two or more R groups are a substituted or unsubstituted cyclic group or a substituted or unsubstituted fused to form a ring group,
each X is independently S, N, or C-R. 37. The photovoltaic device of claim 36, wherein the boron-dipyrromethene-based compound has the formula:

or

. 22. The photovoltaic device of claim 21, wherein the boron-dipyrromethene-based compound has the formula:

,
here,
the photoactive compound exhibits a first maximum near-infrared absorption intensity and a first maximum visible-light absorption intensity;
A1 is a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents;
each A2 is independently a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents;
Each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, 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, wherein at least two R groups are either a substituted or unsubstituted ring group or a substituted or unsubstituted fused group. to form a ring group. 39. The photovoltaic device of claim 38, wherein the boron-dipyrromethene-based compound has the formula:

,
here:
the photoactive compound exhibits a first maximum near-infrared absorption intensity and a first maximum visible-light absorption intensity;
A1 is a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents;
each A2 is independently a fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents;
Each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, 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, wherein at least two R groups are either a substituted or unsubstituted ring group or a substituted or unsubstituted fused group. to form a ring group. 40. The photovoltaic device of claim 39, wherein the boron-dipyrromethene-based compound has the formula:

. A visually transparent photovoltaic device comprising:
a visibly transparent substrate;
a first visually transparent electrode coupled to the visually transparent substrate;
a second visually transparent electrode over the first visually transparent photoactive layer;
A first visually transparent active layer between a first visually transparent electrode and a second visually transparent electrode, wherein the first visually transparent photoactive layer has the formula

comprising a photoactive compound having
[here,
the photoactive compound exhibits a first maximum near-infrared absorption intensity and a first maximum visible light absorption intensity, wherein the first maximum near-infrared absorption intensity is greater than the first maximum visible light absorption intensity;
M is a metal,
Each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aromatic group, 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 two or more R groups are a substituted or unsubstituted cyclic group or a substituted or unsubstituted fused group. to form a ring group], the first visually transparent active layer; and
a second visually transparent photoactive layer present between the first visually transparent electrode and the second visually transparent electrode and exhibiting a second maximum absorption intensity and a second maximum visible light absorption intensity in the near infrared or ultraviolet; , wherein the second visually transparent photoactive layer is greater than the second maximum visible light absorption intensity. The visually transparent photovoltaic device of claim 41 , wherein the second visually transparent photoactive layer comprises a boron-dipyrromethene-based compound. The visually transparent photovoltaic device of claim 41 , wherein the second visually transparent photoactive layer comprises phthalocyanine or naphthalocyanine. The visually transparent photovoltaic device of claim 41 , wherein the photoactive compound acts as an electron acceptor material and the second visually transparent photoactive layer comprises an electron donor material. The visually transparent photovoltaic device of claim 41 , wherein the photoactive compound acts as an electron donor material and the second visually transparent photoactive layer comprises an electron acceptor material. The visually transparent photovoltaic device of claim 41 , wherein the first visually transparent photoactive layer and the second visually transparent photoactive layer independently have a thickness of 1 nm to 300 nm. The visually transparent photovoltaic device of claim 41 , wherein the first visually transparent photoactive layer and the second visually transparent photoactive layer correspond to separate, mixed, or partially mixed layers. The photovoltaic device of claim 41 , wherein the photoactive compound is visually transparent. 42. The visually transparent photoactive layer of claim 41, wherein the first visually transparent photoactive layer is coupled to the first visually transparent electrode or the first visually transparent photoactive layer is coupled to the second visually transparent electrode. photovoltaic device. 42. The photovoltaic device of claim 41, wherein M is Fe, Co, Ni, Cu, Zn, Mo, Pd, or Pt. 42. The visually transparent photovoltaic device. 42. The photovoltaic device of claim 41, wherein the photoactive compound has the formula:

or

. 53. The photovoltaic device of claim 52, wherein the photoactive compound has the formula:

or

. 42. The photovoltaic device of claim 41, wherein the photoactive compound has the formula:

,

,

,

,

,

,

,

,

. 42. The photovoltaic device of claim 41, wherein the photoactive compound has the formula:

, wherein each A is independently a fused polycyclic ring group having one or more R group substituents. 56. The photovoltaic device of claim 55, wherein the photoactive compound has the formula:

,

,

,

, or

. 57. The photovoltaic device of claim 56, wherein the photoactive compound has the formula:

,

,

,

, or

. 42. The photovoltaic device of claim 41, wherein the photoactive compound has the formula:

. 59. The photovoltaic device of claim 58, wherein the photoactive compound has the formula:

or

. A visually transparent photovoltaic device comprising:
a visibly transparent substrate;
a first visually transparent electrode coupled to the visually transparent substrate;
a second visually transparent electrode above the first visually transparent electrode;
A first visually transparent active layer between a first visually transparent electrode and a second visually transparent electrode, wherein the first visually transparent photoactive layer has the formula

or

comprising a photoactive compound having
[here,
the photoactive compound exhibits a first maximum near-infrared absorption intensity and a first maximum visible light absorption intensity, wherein the first maximum near-infrared absorption intensity is greater than the first maximum visible light absorption intensity;
M is a metal,
Each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aromatic group, 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, wherein at least two R groups are a substituted or unsubstituted cyclic group or a substituted or unsubstituted forming a fused ring group], said first visually transparent active layer; and
a second visually transparent photoactive layer present between the first visually transparent electrode and the second visually transparent electrode and exhibiting a second maximum absorption intensity and a second maximum visible light absorption intensity in the near infrared or ultraviolet; , wherein the second visually transparent photoactive layer is greater than the second maximum visible light absorption intensity. A visually transparent photovoltaic device comprising:
a visibly transparent substrate;
a first visually transparent electrode coupled to the visually transparent substrate;
a second visually transparent electrode over the first visually transparent electrode;
A first visually transparent active layer between a first visually transparent electrode and a second visually transparent electrode, wherein the first visually transparent active layer is an acceptor material comprising an ultraviolet electron acceptor (UV acceptor) molecule. wherein the UV receptor-based material is a photoactive compound and exhibits a first maximum ultraviolet absorption intensity and a first maximum visible light absorption intensity, wherein the first maximum ultraviolet absorption intensity is the first maximum visible light absorption intensity a larger, said first visually transparent active layer; and
a second visually transparent active layer between the first visually transparent electrode and the second visually transparent electrode, wherein the second visually transparent active layer has a second maximum absorption intensity in the near infrared and a second A visually transparent photovoltaic cell comprising a donor material exhibiting a maximum visible light absorption intensity, wherein the second maximum absorption intensity is greater than the second maximum visible light absorption intensity. Device. 62. The photovoltaic device of claim 61, wherein the first maximum visible light absorption intensity is between 0.1% and 10% of the first maximum ultraviolet absorption intensity. 63. The photovoltaic device of claim 62, wherein the first maximum visible light absorption intensity is between 0.1% and 5% of the first maximum ultraviolet absorption intensity. 62. The visually transparent photovoltaic device of claim 61, wherein the first visually transparent photoactive layer and the second visually transparent photoactive layer are independently between 1 nm and 300 nm thick. 62. The visually transparent photovoltaic device of claim 61, wherein the first visually transparent photoactive layer and the second visually transparent photoactive layer correspond to separate, mixed, or partially mixed layers. 62. The photovoltaic device of claim 61, wherein the acceptor material is visually transparent. 62. The visually transparent photoactive layer of claim 61, wherein the first visually transparent photoactive layer is coupled to the first visually transparent electrode or the first visually transparent photoactive layer is coupled to the second visually transparent electrode. photovoltaic device. 62. The method according to claim 61, wherein the UV receptor-molecule is naphthalenetetracarboxylic diimide, naphthalenetetracarboxylic diimide derivative, bisimide coronene, bisimide coronene derivative, fluoranthene, fluoranthene derivative, coranulene, chola. A visually transparent photovoltaic device selected from the group consisting of nullene derivatives, and combinations thereof. 69. The photovoltaic device of claim 68, wherein the naphthalenetetracarboxylic diimide has the formula: or a derivative thereof:

,
here,
X ₁ , X ₂ , X ₃ , X ₄ are independently selected from the group consisting of aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl;
R ₁ and R ₂ is independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl. 69. The photovoltaic device of claim 68, wherein the naphthalenetetracarboxylic diimide has the formula: or a derivative thereof:

,
here:
each X is independently selected from the group consisting of F, Cl, Br, alkyl, alkoxy, and aryl;
each subscript n is independently 0, 1, 2, 3, 4, or 5;
each Y is independently selected from the group consisting of H, alkyl, unsubstituted aryl, or substituted aryl;
Each ring designated "Ar" is an independently selected aryl group. 69. The photovoltaic device of claim 68, wherein the naphthalenetetracarboxylic diimide has the formula: or a derivative thereof:

,
here:
each X and each Y is independently selected from the group consisting of F, Cl, Br, alkyl, alkoxy, and aryl;
subscript n is independently 0, 1, 2, 3, 4, or 5;
each subscript m is independently 0, 1, or 2;
Each ring designated "Ar" is an independently selected aryl group. 69. The photovoltaic device of claim 68, wherein the naphthalenetetracarboxylic diimide has the formula: or a derivative thereof:

, or

,
here:
The bridging group (B) is a direct covalent bond, an arylene linker, a heteroarylene linker, an alkylene linker, or a heteroalkylene linker,
each X ₁ , X ₂ , X ₃ , X ₄ , X ₅ , and X ₆ is independently from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, and halogen is selected as
each R ₁ , R ₂ , R ₃ , and R ₄ is independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl. 69. The photovoltaic device of claim 68, wherein the naphthalenetetracarboxylic diimide is selected from the group consisting of:

,

,

, and

. 69. The photovoltaic device of claim 68, wherein the bisimide coronene has the formula: or a derivative thereof:

or

,
here:
each R is independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, and an electron-withdrawing group (eg , CN, halogen, etc.). 69. The photovoltaic device of claim 68, wherein the fluoranthene has the formula: or a derivative thereof:

here:
R is selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl;
X and Y are independently selected from the group consisting of H and an electron-withdrawing group (eg , CN, halogen, etc.);
Z ₁ and Z ₂ is independently selected from the group consisting of H, aryl, heteroaryl, alkyl, alkenyl, alkynyl, cycloalkyl, and heterocyclyl. 69. The photovoltaic device of claim 68, wherein the fluoranthene is selected from the group consisting of:

and

. 69. The photovoltaic device of claim 68, wherein the coranulene has the formula: or a derivative thereof:

or

,
here:
each R is independently selected from the group consisting of H and an electron-withdrawing group (eg , CN, halogen, etc.). 69. The method of claim 68, wherein the donor material is boron-dipyrromethene compound, phthalocyanine, naphthalocyanine, nickel dithiolate compound, dicyano-indandione, benzothiadiazole, benzo- bis -thiadiazole, diketopyrrolopyrrole A photovoltaic device that is visually transparent, comprising diphenylthiethylamine, or a combination thereof. A visually transparent photovoltaic device comprising:
a visibly transparent substrate;
a first visually transparent electrode coupled to the visually transparent substrate;
a second visually transparent electrode over the first visually transparent electrode;
a first visually transparent active layer between a first visually transparent electrode and a second visually transparent electrode, wherein the first visually transparent photoactive layer has a first maximum near infrared or ultraviolet absorption intensity and a first a photoactive compound exhibiting a maximum visible light absorption intensity, wherein the first maximum near infrared or ultraviolet absorption intensity is greater than the first maximum visible light absorption intensity, wherein the photoactive compound is a tetracyanoquinoidal thiophene compound, tetracyano said first visually transparent active layer which is an indacene compound, a carbazole thiaporphyrin, or a dithiophene squarin compound; and
a second visually transparent photoactive layer present between the first visually transparent electrode and the second visually transparent electrode and exhibiting a second maximum absorption intensity and a second maximum visible light absorption intensity in the near infrared or ultraviolet; , wherein the second visually transparent photoactive layer is greater than the second maximum visible light absorption intensity. 80. The visually transparent photovoltaic device of claim 79, wherein the second visually transparent photoactive layer comprises a boron-dipyrromethene-based compound. 81. The visually transparent photovoltaic device of claim 79, wherein the second visually transparent photoactive layer comprises an ultraviolet receptor molecule. 81. The visually transparent photovoltaic device of claim 79, wherein the photoactive compound acts as an electron acceptor material and wherein the second visually transparent photoactive layer comprises an electron donor material. 81. The visually transparent photovoltaic device of claim 79, wherein the photoactive compound acts as an electron donor material and wherein the second visually transparent photoactive layer comprises an electron acceptor material. 80. The visually transparent photovoltaic device of claim 79, wherein the first visually transparent photoactive layer and the second visually transparent photoactive layer are independently between 1 nm and 300 nm thick. 80. The visually transparent photovoltaic device of claim 79, wherein the first visually transparent photoactive layer and the second visually transparent photoactive layer correspond to separate, mixed, or partially mixed layers. 80. The photovoltaic device of claim 79, wherein the photoactive compound is visually transparent. 80. The visibly transparent photoactive layer of claim 79, wherein the first visually transparent photoactive layer is coupled to the first visually transparent electrode or wherein the first visually transparent photoactive layer is coupled to the second visually transparent electrode. Transparent photovoltaic device. 80. The photovoltaic device of claim 79, wherein the photoactive compound is a tetracyano quinoidal thiophene compound. 80. The photovoltaic device of claim 79, wherein the photoactive compound is a tetracyano quinoidal thiophene compound having the formula:

,
here,
Each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, 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, wherein at least two R groups are either a substituted or unsubstituted ring group or a substituted or unsubstituted fused group. to form a ring group,
n is 0, 1, 2, 3, 4, 5, 6, or 7,
each X is independently O, NR, S, or Se. 91. The photovoltaic device of claim 89, wherein the photoactive compound has the formula:

,
here,
m is 0, 1, 2, 3, 4, or 5. 91. The photovoltaic device of claim 90, wherein the photoactive compound has the formula:

,

,

,

,

,

,

,

,

,

, or

. 92. The photovoltaic device of claim 91, wherein the photoactive compound has the formula:

. 80. The photovoltaic device of claim 79, wherein the photoactive compound is a tetracyano indacene compound. 80. The photovoltaic device of claim 79, wherein the photoactive compound is a tetracyano indacene compound of the formula:

or

,
here,
each A is an independently fused or unfused aromatic or heteroaromatic group comprising one or more R group substituents;
Each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, 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, wherein at least two R groups are either a substituted or unsubstituted ring group or a substituted or unsubstituted fused group. to form a ring group. 95. The photovoltaic device of claim 94, wherein the photoactive compound has the formula:

,

,

, or

. 80. The photovoltaic device of claim 79, wherein the photoactive compound is a carbazole thiaporphyrin compound of the formula:

,
here,
Each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, 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, wherein at least two R groups are either a substituted or unsubstituted ring group or a substituted or unsubstituted fused group. to form a ring group. 80. The photovoltaic device of claim 79, wherein the photoactive compound is a dithiophene squarine compound. 80. The photovoltaic device of claim 79, wherein the photoactive compound is a dithiophene squarine compound having the formula:

,
here:
Each R group is independently hydrogen, halogen, cyano group, substituted or unsubstituted alkyl group, substituted or unsubstituted aromatic group, substituted or unsubstituted fused aromatic group, 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, wherein at least two R groups are either a substituted or unsubstituted ring group or a substituted or unsubstituted fused group. to form a ring group. A visually transparent photovoltaic device comprising:
a visibly transparent substrate;
a first visually transparent electrode coupled to the visually transparent substrate;
a second visually transparent electrode over the first visually transparent electrode;
A first visually transparent active layer between a first visually transparent electrode and a second visually transparent electrode, wherein the first visually transparent active layer comprises a phthalocyanine-based material, wherein the phthalocyanine-based material is a photoactive compound and exhibits a first maximum near-infrared absorption intensity and a first maximum visible light absorption intensity, wherein the first maximum near-infrared absorption intensity is greater than the first maximum visible light absorption intensity; transparent active layer; and
a second visually transparent active layer present between the first visually transparent electrode and the second visually transparent electrode and exhibiting a second maximum absorption intensity in the near infrared or ultraviolet and a second maximum visible light absorption intensity in the near infrared or ultraviolet; , wherein the second maximum absorption intensity of visible light is greater than the maximum absorption intensity of visible light. 101. The visually transparent photovoltaic device of claim 99, wherein the second visually transparent photoactive layer comprises a second phthalocyanine-based material. 101. The visually transparent photovoltaic device of claim 99, wherein the second visually transparent photoactive layer comprises a boron-dipyrromethene-based compound. 101. The visually transparent photovoltaic device of claim 99, wherein the phthalocyanine-based material acts as an electron acceptor material, wherein the second visually transparent photoactive layer comprises an electron donor material. 101. The visually transparent photovoltaic device of claim 99, wherein the phthalocyanine-based material acts as an electron donor material, wherein the second visually transparent photoactive layer comprises an electron acceptor material. 101. The visibly transparent photoactive layer of claim 99, wherein the first visually transparent photoactive layer is coupled to the first visually transparent electrode or wherein the first visually transparent photoactive layer is coupled to the second visually transparent electrode. Transparent photovoltaic device. 101. The visually transparent photovoltaic device of claim 99, wherein the first visually transparent photoactive layer and the second visually transparent photoactive layer correspond to separate, mixed, or partially mixed layers. 101. The photovoltaic device of claim 99, wherein the phthalocyanine-based material is visually transparent. 101. The photovoltaic device of claim 99, wherein the phthalocyanine-based comprises a phthalocyanine. 108. The photovoltaic device of claim 107, wherein the phthalocyanine has the formula: or a derivative thereof:

here,
M is Sn, SnCl ₂ , SnO, Pb, Mg, Mn, AlCl, AlOH, GaCl, MnCl, SiCl ₂ , Si(OH) ₂ , PbCl ₂ , VO, Co, Fe, FeCl, Ni, TiO, and TiCl ₂ is selected from the group consisting of
each R ₁ to R ₁₆ is independently selected from the group consisting of H, F, Cl, and an electron withdrawing group. 108. The photovoltaic device of claim 107, wherein the phthalocyanine has the formula: or a derivative thereof:

here:
each X and each Y is independently selected from the group consisting of H, F, Cl, Br, alkoxy, alkyl, and aryl;
M is a metal;
Z is selected from the group consisting of Cl, =O, and -OH. 110. The photovoltaic device of claim 109, wherein M is selected from the group consisting of Cu, Fe, Co, Mn, Al, and Sn. 108. The photovoltaic device of claim 107, wherein the phthalocyanine has the formula: or a derivative thereof:

,

, or

,
here:
each R ₁ to R ₈ is independently selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl;
each X is independently selected from the group consisting of O, S, Se, and Te;
M is metal. 112. The photovoltaic device of claim 111, wherein M is selected from the group consisting of Cu, Co, Ni, Zn, Mg, ClAl, SnCl ₂ , Pb, Pt, and Pd. 101. The photovoltaic device of claim 99, wherein the phthalocyanine-based comprises naphthalocyanine. 114. The photovoltaic device of claim 113, wherein the naphthalocyanine has the formula: or a derivative thereof:

,
here,
M is Sn, SnCl ₂ , SnO, Pb, Mg, Mn, AlCl, AlOH, GaCl, MnCl, SiCl ₂ , Si(OH) ₂ , PbCl ₂ , VO, Co, Fe, FeCl, Ni, TiO, and TiCl ₂ is selected from the group consisting of
each R ₁ to R ₂₄ is independently selected from the group consisting of H, F, Cl, and an electron withdrawing group. 114. The photovoltaic device of claim 113, wherein the naphthalocyanine has the formula: or a derivative thereof:

here:
each R ₁ to R ₆ is independently selected from the group consisting of alkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, and heterocyclyl;
each X is independently selected from the group consisting of O, S, Se, and Te;
M is metal. 116. The photovoltaic device of claim 115, wherein M is selected from the group consisting of Cu, Co, Ni, Zn, Mg, ClAl, SnCl ₂ , Pb, Pt, and Pd. 101. The photovoltaic device of claim 99, wherein the phthalocyanine has the formula:

,
here,
M is a metal,
A ₁ , A ₂ , A ₃ , and A ₄ are each substituted or unsubstituted fused aromatic ring group, wherein A ₁ is from at least one of A ₂ , A ₃ , or A _{4 .} containing different numbers of fused rings. 118. The photovoltaic device of claim 117, wherein the phthalocyanine-based material comprises one or more compounds selected from the group consisting of:

,

,

,

, and

. 101. The photovoltaic device of claim 99, wherein the phthalocyanine-based material comprises at least one compound selected from the group consisting of:

,

,

,

,

,

,

,

,

,

,

,

,

,

,

, and

.

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