RU2554877C1 - Composition for producing organic photovoltaic cells based on phthalocyanines and analogues thereof - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: composition includes an electron-donor component and an electron-acceptor component. The electron-donor component is mono- or polynuclear phthalocyanine or naphthalocyanine or metal complexes thereof with a planar or sandwich structure. The electron-acceptor component of the composition is poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] having the structure:

.

Components are in the following ratio (wt %): electron-donor part - 1-5%, electron-acceptor part - 99-95%.

EFFECT: invention enables to obtain a composition capable of forming homogeneous solutions and has absorption in the wavelength range of 300-2500 nm.

4 cl, 5 ex

Description

Field of Technology:

The invention relates to the field of conversion of light energy into electrical energy, in particular to a composition for creating organic photovoltaic cells performing such a conversion.

The prior art:

To date, a large number of such compositions with various characteristics are known, their description is given in the following publications:

"Lighting porphyrins and phthalocyanines for molecular photovoltaics", M. Victoria Martınez-Dıaz at al., Cheme. Commyn., 2010, vol. 46, pp. 7090-7108;

"Photoinduced Electron Transfer and Excitation Energy Transfer in Directly Linked Zinc Porphyrin / Zinc Phthalocyanine Composite", Fuyuki Ito at al., J. Phys. Chem. A, 2006, vol. 110, pp. 12734-12742;

"Conjugated Polymer-Based Organic Solar Cells", Serap Gunes at al., Chem. Rev. 2007, vol. 107, p. 1324-1338.

The composition of these compositions includes phthalocyanines.

Closest to this invention are compositions for creating organic photovoltaic cells proposed in the patent: "Conductive polymeric ink composition and organic solar cell containing the same" / M-K. Kim, J.-N. Kim, J-H. Yoo, J.-N. Seong, N.-K. Lee (LG Chem, LTD.), Patent cooperation treaty application, No. WO 13169087 (publication date of the application: November 14, 2013). These compositions contain electron donor and electron withdrawing components. As an electron donor component, they include: poly (3-hexylthiophene) or polysiloxane carbazole, or polyaniline, or polyethylene oxide, or poly (1-methoxy-4- (2,5-phenylene-vinylene)), polyindole, polyvinyl carbazole or polyvinyl-pyrido-diazine or polyvinyl-naphthalene-isothiazole, polyphenylene sulfide, polyvinyl-pyridine, polythiophene, polyfluorene, polypyridine, and as an electron-withdrawing component are fullerenes, CdSe nanoparticles, carbon nanotubes, nanorods. The main disadvantage of the known composition is its dispersion, which leads to inconstancy and heterogeneity of the composition. In addition, this composition is insensitive to radiation in the near infrared range.

The task was to create such a composition that would be devoid of these drawbacks, in particular, formed homogeneous solutions and had absorption in the wavelength range from 300-2500 nm.

This problem was solved by the present invention. In the composition for creating organic photovoltaic cells, including the electron donor and electron withdrawing components, according to the invention, it contains mononuclear or polynuclear phthalocyanine or naphthalocyanine, or their metal complexes of planar or sandwich structure, and it contains poly as an electron withdrawing component [2- methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene] (MEN-PPV) structures:

in the following ratio of components (wt.%):

electron donor part: 1-5%,

electron withdrawing part: 99-95%.

As an electron donor component, the composition preferably contains substituted monophthalocyanines and their metal complexes structures

, где R=R′=Et, М=НН; или R=Н, R′=tBu, М=НН или R=R′=Bu, М=НН; или R=R′=Ph, М=Mg, Zn, Со, Ni, Cu; или R=Н, R′=tBu, М=Mg, Zn, Со, Ni, Cu, AlCl; или R=R′=Н, Et, Bu, Cl; М=EuOAc, ErOAc, LuOAc;

where R = R ′ = Et, M = HH; or R = H, R ′ = tBu, M = HH or R = R ′ = Bu, M = HH; or R = R ′ = Ph, M = Mg, Zn, Co, Ni, Cu; or R = H, R ′ = tBu, M = Mg, Zn, Co, Ni, Cu, AlCl; or R = R ′ = H, Et, Bu, Cl; M = EuOAc, ErOAc, LuOAc;

or naphthalocyanines and their metal complexes structures

, где R=R′=Ph, М=Mg; или R=Н, R′=tBu, М=Mg.

where R = R ′ = Ph, M = Mg; or R = H, R ′ = tBu, M = Mg.

Preferably, as an electron-donating component, the composition contains aryl or alkyl substituted bi- and polynuclear phthalocyanines or their metal complexes of the structure:

, где R=Н, R′=tBu, М=НН, n=1; или R=Н, R′=tBu, М=Mg, n=1; или R=Н, R′=tBu, М=Zn, n=1; или R=R′=Bu, М=НН, n=1; или R=R′=Bu, М=Mg, n=1; или R=R′=Bu, М=Zn, n=1; R=Н, R′=tBu, М=НН, n=2; или R=Н, R′=tBu, М=Mg, n=2; или R=R′=Ph, М=Mg, n=1; или R=R′=Ph, М=Mg, n=2;

where R = H, R ′ = tBu, M = HH, n = 1; or R = H, R ′ = tBu, M = Mg, n = 1; or R = H, R ′ = tBu, M = Zn, n = 1; or R = R ′ = Bu, M = HH, n = 1; or R = R ′ = Bu, M = Mg, n = 1; or R = R ′ = Bu, M = Zn, n = 1; R = H, R ′ = tBu, M = HH, n = 2; or R = H, R ′ = tBu, M = Mg, n = 2; or R = R ′ = Ph, M = Mg, n = 1; or R = R ′ = Ph, M = Mg, n = 2;

or

, где n=1 или 2;

where n = 1 or 2;

or

, где R=R′=Н, PrO, Bu; или R=Н, R′=^tBu; М=Mg, Zn, Со, Ni, Cu.

where R = R ′ = H, PrO, Bu; or R = H, R ′ = ^t Bu; M = Mg, Zn, Co, Ni, Cu.

Preferably, as an electron-donating component, the composition contains phthalo- or naphthalocyanines of sandwich lanthanides

, где Ln=Eu, Dy, Er, Lu; R=R′=Et, Bu; или R=Н, R′=^tBu;

where Ln = Eu, Dy, Er, Lu; R = R ′ = Et, Bu; or R = H, R ′ = ^t Bu;

or

, где Ln=Eu, Dy, Er, Lu; R=Ph, PhO;

where Ln = Eu, Dy, Er, Lu; R = Ph, PhO;

or

, где Ln=Eu, Lu; R=Н, Cl;

where Ln = Eu, Lu; R = H, Cl;

or

, где Ln=Lu;

where Ln = Lu;

or

, где Ln=Eu, Er, Lu; R=Et, Bu;

where Ln = Eu, Er, Lu; R = Et, Bu;

or

, где R=R′=Bu; или R=Н, R′=^tBu; R¹=Н, Cl, Bu;

where R = R ′ = Bu; or R = H, R ′ = ^t Bu; R ¹ = H, Cl, Bu;

or

, где R=Cl, Bu;

where R = Cl, Bu;

or

, где R=R′=Bu; или R=Н, R′=^tBu; X=Н, СН₂ОН; Ln=Eu, Lu;

where R = R ′ = Bu; or R = H, R ′ = ^t Bu; X = H, CH ₂ OH; Ln = Eu, Lu;

or

or

, где R=R′=Bu; или R=Н, R′=^tBu; M=2H, LuOAc; Ln=Eu, Lu;

where R = R ′ = Bu; or R = H, R ′ = ^t Bu; M = 2H, LuOAc; Ln = Eu, Lu;

or

, где Ln=Eu, Dy, Lu;

where Ln = Eu, Dy, Lu;

or

, где R=R′′=Н; R′′′=^tBu;

where R = R ′ ′ = H; R ′ ′ ′ = ^t Bu;

or

The conductive properties of the proposed composite materials are provided by polyaniline or single-walled carbon nanotubes. Lasers and LEDs of the UV, visible and near infrared ranges were used as radiation sources, and universal high-precision measuring sources, oscilloscopes, and sensors with a light or sound signal were used to record (indicate) the response of photovoltaic compositions.

The claimed composition based on phthalocyanines and their analogues is sensitive to electromagnetic radiation from UV, visible and near infrared ranges and is capable of generating an electric current (EMF) when exposed to it. It is important that when exposed to a surface on which an electrically conductive composition based on phthalocyanines is applied a signal of visible, ultraviolet or near infrared radiation, the composition is capable of generating an electrical signal. At the same time, near-infrared radiation is more preferred, which allows the use of the claimed compositions in the daytime.

An important feature of the claimed invention is that when using it, it is necessary to have sensors capable of responding to the emerging electric current. For example, a light bulb or LED may light up.

To ensure the connection between the sensor and the claimed composition, sensitive to electromagnetic radiation and capable of generating EMF upon its exposure, electrically conductive polymers or electrically conductive polymer compositions are most satisfied. As a flexible substrate, you can use fabric, in particular textile. It is capable of maintaining flexible properties after coating with compositions of electrically conductive polymers based on phthalocyanines and their analogues and is suitable for placement on humans, animals or inanimate objects.

To achieve the photovoltaic effect, it is preferable to use laser radiation, while devices that emit visible light (bulbs, photodiodes) appear to be the most promising for detecting (indicating) the response.

The invention is illustrated by the following examples.

Example 1

A saturated solution is prepared in methylene chloride (or tetrahydrofuran, toluene) containing MEN-PPV and substituted monophthalo or naphthalocyanines, structures

, где R=R′=Et, М=НН; или R=Н, R′=tBu, М=НН или R=R′=Bu, М=НН; или R=R′=Ph, М=Mg, Zn, Со, Ni, Cu; или R=Н, R′=tBu, М=Mg, Zn, Со, Ni, Cu, AlCl; или R=R′=Н, Et, Bu, Cl; М=EuOAc, ErOAc, LuOAc;

where R = R ′ = Et, M = HH; or R = H, R ′ = tBu, M = HH or R = R ′ = Bu, M = HH; or R = R ′ = Ph, M = Mg, Zn, Co, Ni, Cu; or R = H, R ′ = tBu, M = Mg, Zn, Co, Ni, Cu, AlCl; or R = R ′ = H, Et, Bu, Cl; M = EuOAc, ErOAc, LuOAc;

or

, где R=R′=Ph, М=Mg; или R=Н, R′=tBu, М=Mg или их металлокомплексов.

where R = R ′ = Ph, M = Mg; or R = H, R ′ = tBu, M = Mg or their metal complexes.

The composition is dried, thus obtaining a mixture of components in a mass ratio: 99% - MEN-PPV and 1% phthalocyanine.

Example 2

The composition was prepared as in example 1, but instead of substituted monophthalo or naphthalocyanines or their metal complexes, aryl or alkyl substituted bi and polynuclear phthalocyanines or their metal complexes of the structure were used:

, где R=Н, R′=tBu, М=НН, n=1; или R=Н, R′=tBu, М=Mg, n=1; или R=Н, R′=tBu, М=Zn, n=1; или R=R′=Bu, М=НН, n=1; или R=R′=Bu, М=Mg, n=1; или R=R′=Bu, М=Zn, n=1; R=Н, R′=tBu, М=НН, n=2; или R=Н, R′=tBu, М=Mg, n=2; или R=R′=Ph, М=Mg, n=1; или R=R′=Ph, М=Mg; n=2;

where R = H, R ′ = tBu, M = HH, n = 1; or R = H, R ′ = tBu, M = Mg, n = 1; or R = H, R ′ = tBu, M = Zn, n = 1; or R = R ′ = Bu, M = HH, n = 1; or R = R ′ = Bu, M = Mg, n = 1; or R = R ′ = Bu, M = Zn, n = 1; R = H, R ′ = tBu, M = HH, n = 2; or R = H, R ′ = tBu, M = Mg, n = 2; or R = R ′ = Ph, M = Mg, n = 1; or R = R ′ = Ph, M = Mg; n is 2;

or

, где n=1 или 2;

where n = 1 or 2;

or

, где R=R′=Н, PrO, Bu; или R=Н, R′=^tBu; М=Mg, Zn, Со, Ni, Cu, в массовом соотношении: 95% - МЕН-PPV и 5% - фталоцианина.

where R = R ′ = H, PrO, Bu; or R = H, R ′ = ^t Bu; M = Mg, Zn, Co, Ni, Cu, in a mass ratio: 95% - MEN-PPV and 5% - phthalocyanine.

Example 3

The composition was prepared as in example 1, but instead of substituted monophthalo or naphthalocyanines or their metal complexes, phthalo or naphthalocyanines of sandwich lanthanides were used.

, где Ln=Eu, Dy, Er, Lu; R=R′=Et, Bu; или R=Н, R′=^tBu;

where Ln = Eu, Dy, Er, Lu; R = R ′ = Et, Bu; or R = H, R ′ = ^t Bu;

or

, где Ln=Eu, Dy, Er, Lu; R=Ph, PhO;

where Ln = Eu, Dy, Er, Lu; R = Ph, PhO;

or

, где Ln=Eu, Lu; R=Н, Cl;

where Ln = Eu, Lu; R = H, Cl;

or

, где Ln=Lu;

where Ln = Lu;

or

, где Ln=Eu, Er, Lu; R=Et, Bu;

where Ln = Eu, Er, Lu; R = Et, Bu;

or

, где R=R′=Bu; или R=Н, R′=^tBu; R¹=Н, Cl, Bu;

where R = R ′ = Bu; or R = H, R ′ = ^t Bu; R ¹ = H, Cl, Bu;

or

, где R=Cl, Bu;

where R = Cl, Bu;

or

, где R=R′=Bu; или R=Н, R′=^tBu; X=Н, CH₂OH; Ln=Eu, Lu;

where R = R ′ = Bu; or R = H, R ′ = ^t Bu; X = H, CH ₂ OH; Ln = Eu, Lu;

or

or

, где R=R′=Bu; или R=Н, R′=^tBu; М=2Н, LuOAc; Ln=Eu, Lu;

where R = R ′ = Bu; or R = H, R ′ = ^t Bu; M = 2H, LuOAc; Ln = Eu, Lu;

or

, где Ln=Eu, Dy, Lu;

where Ln = Eu, Dy, Lu;

or

, где R=R′′=Н; R′′′=^tBu;

where R = R ′ ′ = H; R ′ ′ ′ = ^t Bu;

or

, в массовом соотношении: 98% - МЕН-PPV и 2% - фталоцианина.

, in a mass ratio: 98% - MEN-PPV and 2% - phthalocyanine.

Example 4

The composition was prepared as in example 1, but single-walled nanotubes (SWCNT, Aldrich) were additionally added (concentration in the range 0.1-5 wt.%).

Example 5

The composition was prepared as in example 1, but additionally added polyaniline (concentration in the range of 0.1-5 wt.%).

Single-walled nanotubes (SWCNT, Aldrich) and polyaniline were used in examples 4 and 5 to improve their conductive properties.

The compositions obtained in examples 1-5 were used as follows:

1. The composition was applied by watering on a layer of fabric (textile, parachute, Bologna, etc.), previously coated with a layer of cathode material.

2. The composition was applied by watering on a solid surface (glass, ceramic, plastic (flexible polymer)), previously coated with a layer of electrode material.

In both methods, after drying, the surface of the composition was covered with an Ag paste network (Kontaktol), or with a transparent PO electrode (hard - on glass or flexible - on a polymer carrier).

Upon contact of the laser radiation with the composition material, the response was recorded in the form of an increase in voltage (measured in nV and% of the initial (background) instrument voltage):

SAMPLE 1

Structure:

Plastic / graphite, paste (“Contactol”) / MEN-PPV: tBuPcAlCl / Ag paste (“Contactol”), where tBuPcAlCl has the structure:

, где R=Н, R′=tBu, М=AlCl.

where R = H, R ′ = tBu, M = AlCl.

Response:

0) noise value - 30 nV;

1) red laser:

max, value - 200 nV (570%);

slew rate - about 20 nV / s (67%) [107 nV for 5 s (260%)];

2) blue laser:

Max. value - 190 nV (530%));

slew rate - about 35 nV / s (120%) [98 nV for 5 s (220%)];

3) blue LED:

Max. value - 140 nV (370% o);

slew rate - about 18 nV / s (60%) [90 nV for 5 s (200%)].

Contact distance: 2.5 cm.

Complete relaxation time: less than 10 s.

SAMPLE 2

Structure:

Textile fabric / SWCNT (Aldrich) / MEN-PPV: tBuPcAlCl / Ag paste (Kontaktol)

Response:

0) noise value - 25 nV;

1) red laser:

Max. value - 215 nV (760%);

slew rate - about 18 nV / s (72%) [90 nV for 5 s (260%)];

2) blue laser:

Max. value - 120 nV (380%);

slew rate - about 30 nV / s (120%) [101 nV for 5 s (300%)];

3) blue LED:

Max. value - 180 nV (620%);

slew rate - about 24 nV / s (96%) [120 nV for 5 s (380%)].

Contact distance: 3 cm.

Complete relaxation time: less than 10 s.

SAMPLE 3

Structure:

Oilcloth fabric / SWCNT, (Aldrich) / MEN-PPV: tBuPcAlCl / polyaniline / Ag paste (“Contactol”)

Response:

0) noise value - 35 nV;

1) red laser:

Max. value - 350 nV (900%);

slew rate - about 30 nV / s (86%) [150 nV for 5 s (330%)];

2) blue laser:

poppy. value - 105 nV (200%);

slew rate - about 15 nV / s (43%) [72 nV for 5 s (110%)];

3) blue LED:

Max. value - 210 nV (500%);

slew rate - about 25 nV / s (71%) [110 nV for 5 s (214%)].

Contact distance: 1.75 cm.

Complete relaxation time: less than 10 s.

Measuring equipment

1. Universal high-precision source meter: Keithley 2612A System Sourcemeter;

2. Red laser (650 nm);

3. Blue laser (405 nm, 20 mW);

4. Blue LED (450 nm, 100 mW full power).

The resulting response indicates the possibility of using this composition for organic photovoltaic cells.

Claims (4)

1. A composition for creating organic photovoltaic cells, including an electron-donating component and an electron-withdrawing component, characterized in that it contains mono or polynuclear phthalocyanine or naphthalocyanine or their metal complexes of planar or sandwich structure, and as an electron-withdrawing component, poly [2- methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene], structures:

in the following ratio of components, wt.%:
electron donor part: 1-5%,
electron withdrawing part: 99-95%. 2. The composition according to p. 1, characterized in that as an electron-donating component it contains substituted monophthalocyanines and their metal complexes of the structure:

where R = R ′ = Et, M = HH; or R = H, R ′ = tBu, M = HH or R = R ′ = Bu, M = HH; or R = R ′ = Ph, M = Mg, Zn, Co, Ni, Cu; or R = H, R ′ = tBu, M = Mg, Zn, Co, Ni, Cu, AlCl; or R = R ′ = H, Et, Bu, Cl; M = EuOAc, ErOAc, LuOAc;
or naphthalocyanines and their metal complexes structures:

where R = R ′ = Ph, M = Mg; or R = H, R ′ = tBu, M = Mg. 3. The composition according to p. 1, characterized in that as an electron-donating component it contains aryl or alkyl substituted bi- and polynuclear phthalocyanines or their metal complexes of the structure:

where R = H, R ′ = tBu, M = HH, n = 1; or R = H, R ′ = tBu, M = Mg, n = 1; or R = H, R ′ = tBu, M = Zn, n = 1; or R = R ′ = Bu, M = HH, n = 1; or R = R ′ = Bu, M = Mg, n = 1; or R = R ′ = Bu, M = Zn, n = 1; R = H, R ′ = tBu, M = HH, n = 2; or R = H, R ′ = tBu, M = Mg, n = 2; or R = R ′ = Ph, M = Mg, n = 1; or R = R ′ = Ph, M = Mg, n = 2;
or

where n = 1 or 2;
or

where R = R ′ = H, PrO, Bu; or R = H, R ′ = ^t Bu; M = Mg, Zn, Co, Ni, Cu. 4. The composition according to p. 1, characterized in that as an electron-donating component it contains phthalo- or naphthalocyanines of lanthanides of a sandwich structure structure:

where Ln = Eu, Dy, Er, Lu; R = R ′ = Et, Bu; or R = H, R ′ = ^t Bu;
or

where Ln = Eu, Dy, Er, Lu; R = Ph, PhO;
or

where Ln = Eu, Lu; R = H, Cl;
or

where Ln = Lu;
or

where Ln = Eu, Er, Lu; R = Et, Bu;
or

where R = R ′ = Bu; or R = H, R ′ = ^t Bu; R ¹ = H, Cl, Bu;
or

,

where R = Cl, Bu;
or

,

where R = R ′ = Bu; or R = H, R ′ = ^t Bu; X = H, CH ₂ OH; Ln = Eu, Lu;
or

;
or

where R = R ′ = Bu; or R = H, R ′ = ^t Bu; M = 2H, LuOAc; Ln = Eu, Lu;
or

where Ln = Eu, Dy, Lu;
or

where R = R ′ ′ = H; R '''= ^t Bu;
or

.