RU2592743C1 - Photovoltaic energy converter based on complexes of phthalocyanines and analogues thereof - Google Patents

Abstract

FIELD: physics.

SUBSTANCE: invention relates to converting light energy into electrical one. Photovoltaic energy converter as active layer comprises semiconducting polymers as explicit components, mono- or polynuclear phthalocyanine or naphthalocyanines, or their metal complexes of planar or sandwich structure as electron-donating components.

EFFECT: invention allows to exclude necessity of using complex multilayer structure.

6 cl

Description

Field of Technology:

The invention relates to the field of conversion of light energy into electrical energy, in particular, the invention can be classified as a photoconverter (photoresistor), created on the basis of organic semiconductor materials. The main component of the photoelectric converter are phthalocyanines - heterocyclic molecules from the class of synthetic dyes.

The prior art:

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

"Light-Harvesting and Energy-Transfer System Based on Self-Assembling Perylene Diimide-Appended Hexaazatriphenylene", Tsutomu Ishi-I at al., Org. Lett., 2005, vol. 7, No. 15, pp. 3175-3178;

"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, pp. 1324-1338.

The prior art devices are described in the following patents:

Patent No. 2532841, authors: Yamada Seiji, GOTO Yoshio, TOKITA Yuiti "Electrode with immobilized protein and its manufacturing method and functional element and method of its manufacture." This patent proposes a method for manufacturing an electrode with an immobilized protein by immobilizing cytochrome c552, a derivative or variant thereof, on a gold electrode so that the hydrophobic part of the cytochrome, derivative or variant thereof is located opposite the gold electrode. Cytochrome c552, its derivative or variant, and a gold electrode are connected to each other using a self-organizing monolayer located between them. After the formation of a self-organizing monolayer on a gold electrode, the gold electrode is immersed in a solution containing cytochrome c552, its derivative or variant, a buffer solution, and from 10 mM to 30 mm inclusive of potassium chloride to bind cytochrome c552, its derivative or variant with a gold electrode using a self-organizing monolayer located between them. Also proposed is an electrode obtained by the above method. A method for manufacturing a functional element of a photoelectric converter is proposed. The method includes the steps of forming an electrode with an immobilized protein by immobilization of a cytochrome c552 cytochrome, derivative or variant thereof on a gold electrode. A functional element of the photoelectric converter obtained by the above method is also proposed. The proposed group of inventions provides an increase in the stability of an electrode with an immobilized protein while maintaining the electron transfer ability of the cytochrome c552, its derivative or variant for long-term continuous use.

Patent No. 2528397, authors: Tsui Weihong "Photovoltaic module with stabilized polymer." The invention relates to a photovoltaic device containing a metal component and a polyvinyl butyral layer located in contact with the specified metal component, and a protective substrate located in contact with the specified polyvinyl butyral layer. The polyvinyl butyral layer contains 1H-benzotriazole or a salt of 1H-benzotriazole.

RF patent No. 2444087, authors: Strebkov Dmitry Semenovich, Zadde Vitaliy Viktorovich “Semiconductor photoelectric converter and method for its manufacture”. The invention relates to the design and manufacturing technology of optoelectronic devices, namely semiconductor photoelectric converters. The invention provides an increase in efficiency and a decrease in the cost of manufacturing photovoltaic converters, consisting of many microphototransducers.

RF patent No. 2436191, authors: Gudovskikh Alexander Sergeevich, Malevskaya Alexandra Vyacheslavovna, Zadiranov Yuri Mikhailovich, Andreev Vyacheslav Mikhailovich "Cascade photoelectric converter with nanostructured antireflection coating." The cascade photoelectric converter with a nanostructured antireflection coating is made on the basis of the multilayer semiconductor structure AlGaInP / GaInP / Ga (In) As / Ge. The photoelectric transducer contains rear and front ohmic contacts and a multilayer nanostructured antireflection coating formed on the front surface of the structure in places free of ohmic contacts, consisting of three layers: SiO ₂ with a thickness of 70-80, Si ₃ N ₄ with a thickness of 25-35 nm and TiO _x where x = 1.8-2.2, a thickness of 20-30 nm. The cascade photoelectric converter has an increased efficiency and low reflection coefficient in the short-wave and long-wave regions of the solar spectrum.

RF patent №2502156, authors: Legotin Sergey Aleksandrovich, Krasnov Andrey Andreevich, Legotina Nina Gennadevna, Tyukhov Igor Ivanovich, Prikhodko Natalya Illarionovna, Korolchenko Aleksey Sergeevich, Simakin Viktor Vasilievich, Murashev Viktor Nikolaevich, Abdullaev Oleg Raufovich “Silicon with photovoltaic converter” method of its manufacture. " The present invention relates to the field of silicon multi-junction photovoltaic converters (PECs) of solar cells. According to the invention, the creation of a "comb" design of the photoelectric converter is proposed, which allows to realize in its diode cells the maximum possible volume of the space charge region of pn junctions, in which the collection of minority charge carriers occurs most efficiently. A design and a method for manufacturing this design of a comb silicon single crystal multi-junction photoelectric converter are proposed. This invention allows to increase the efficiency of photovoltaic converters up to 32%.

Patent No. 2450294, authors: Endo Sokhmei, Hayashibe Kazuya, Nagai Tooru, Hidet Ikuhiro, Suzuki Tadao, Nishimura Kimitaka, Shirasagi Toshihiko “Optical device, method for manufacturing a master copy used in the manufacture of an optical device, and photoelectric converter”. An optical device has many structures with elevated or recessed areas located with a short pitch equal to or shorter than the wavelength of visible light on the surface of the base. Structures form many rows in the form of arched paths on the surface of the base and form a configuration of a quasi-hexagonal lattice. The structure is in the form of an elliptical cone or a truncated elliptical cone having a major axis in a direction along arcuate paths. A method of manufacturing a master copy for use in manufacturing an optical device includes a first step in which a substrate is prepared with a resist layer formed on the surface; the second stage, which forms a latent image by periodically irradiating the resist layer with a laser beam during rotation of the substrate and the relative movement of the laser beam in the radial direction relative to the rotation of the substrate; and a third step in which a resist configuration is formed on the surface of the substrate by developing a resist layer. EFFECT: improved anti-reflection and packing density of structures.

Closest to this invention is a photovoltaic device proposed in the patent: WO 2011/148176. In this patent, as described, the photovoltaic device is a complex multilayer structure involving sequential deposition of layers. In addition, in these materials there is no mention of the composition of the composition, in which poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene] is always present in combination with one of the listed electron-donating components (mono- or polynuclear phthalocyanine, or naphthalocyanine, or their metal complexes of planar or sandwich structure) in a certain quantitative ratio, which allows to achieve the claimed technical result. Moreover, in WO 2011/148176, the applicants attributed poly [2-methoxy-5- (2-ethylhexyloxy) -1,4-phenylenevinylene] (MEH-PPV) (p. 10 line 34) and phthalocyanines (page 11 line 3) to organic donors, which does not allow their joint use as a composition, the necessary condition for which is the presence of both electron-donating and electron-withdrawing components.

The main disadvantage of the claimed photovoltaic devices is their complex multilayer design, providing for sequential deposition of layers.

These shortcomings are deprived of our proposed photoelectric energy converter based on complexes of phthalocyanines and their analogues. The problem was solved by the present invention. Photoelectric energy converter, contains an active (working) layer. According to the invention, a composition of the following composition is used as an active (working) layer: semiconducting polymers as electron-withdrawing components, mononuclear or polynuclear phthalocyanines, or naphthalocyanines, or their metal complexes of planar or sandwich structure as an electron-donating component in the following ratio of components (wt.% ): electron-donating part: 1-5%, electron-withdrawing part: 99-95%.

The photoelectric energy converter may further comprise additives of fullerenes and / or nanowires, and / or ionic liquids, and / or graphene, and / or metal oxides to increase the efficiency of the active layer. Moreover, the percentage of additives can vary over a wide range (from 0.01 to 10%).

Metal electrodes can be used as contacts, one of the contacts can be made in the form of a grid or be transparent, for example, from plexiglass or polyethylene terephthalate (PET).

A photovoltaic energy converter typically comprises a substrate onto which the aforementioned active layer is applied. For example, solid or flexible surfaces, a fabric impregnated with a composition forming an active layer, can be used as a substrate.

Device operation:

The device contains electrodes for removing electric charge. The device is capable of operating in one of two operating modes - a photoelectric converter or photo resistance. In the first mode of operation, when the surface of the device (active layer) is irradiated with a beam of light (or other radiation), photons of this radiation excite complexes entering the active layer, which leads to a potential difference between the places where the electrodes are embedded and an electric current to circuit into which said converter is included. Thus, the energy of the stream (for example, light) is converted into electrical energy. In the second mode of operation, the device is included in an electric circuit of direct or alternating current, when the surface of the device (active layer) is irradiated with a beam of light (or other radiation), photons of this radiation excite complexes entering the active layer, which leads to the generation of additional charge carriers and as a consequence, a change in the electrical resistance of the device, which, in turn, leads to a change in the current in the circuit into which said photoresistor is included.

The composition consisting of phthalocyanines and their analogues, indicated in this application, is more versatile, can be applied to any rigid or flexible material (microchip, pin structure, contacts, polymer, dielectric, textile material), and a combination with polymeric materials gives the claimed composition such properties as flexibility and elasticity are parameters that are one of the main ones in the technologies for creating modern electronic devices and devices. In addition, homogeneous solutions of the proposed composition have absorption in the wavelength range from 300-2500 nm, in contrast to the composition mentioned in WO 2011/148176, which makes it possible to use the claimed compositions for detecting signals in a wide spectral range. The conductivity of the proposed composite materials can be improved by the addition of fullerenes and / or nanowires, and / or ionic liquids, and / or graphene, and / or metal oxides, which also distinguishes them from the prototype compositions and compositions proposed in WO 2011/148176.

The use of phthalocyanines as the main components of the photoelectric converter in the present patent has the following reasons.

In the absorption spectra of metal phthalocyanines there are two intense bands in the wavelength range of 300-400 nm (Soret band) and in the wavelength range of 650-700 nm (Q band). The shape and position of the peaks in the absorption spectra can vary depending on the nature of the peripheral substituents and the central metal ion, as well as on the structure of the structures themselves. Due to the high absorption coefficients, films with a thickness of 30 Å are already visible to the naked eye. In addition, the spectra of most PCMs have three other absorption bands in the UV region. They are indicated by the symbols N (36400 cm ^-1 - wave number, 275 nm - wavelength), L (40800 cm ^-1 , 245 nm) and C (47600 cm ^-1 , 210 nm). Thus, phthalocyanine molecules can actively absorb electromagnetic radiation over a wide range of wavelengths.

Electrochemical and spectral studies show that the π-system is an electronic buffer that can both receive and give electrons with the formation of charged particles. The charge carriers here are holes, the formation of which is described by the scheme РсМ-е ^- → РсМ ⁺ .

Inside the phthalocyanine molecule, a positive charge is distributed between all atoms of the π-system, which is a single potential well for the electron. The movement of a hole along a stack of molecules is limited by the activation energy of electron hopping from a neutral molecule to an oxidized one.

The physical properties of phthalocyanines allow the use of this type of molecule to create multilayer structures and compositions. As a flexible substrate, you can use fabric, in particular textile. They are capable of maintaining flexible properties after coating with conductive pastes with the subsequent creation of an active working layer of the proposed composites based on polymers and phthalocyanines or their analogues and are suitable for placement on people, animals or inanimate objects.

For ease of recording the effect, it is preferable to use laser radiation to significantly increase the observed response. One of the simple and obvious methods of detection is the use of a threshold detector in combination with a photo-emitting device (for example, an LED) to indicate that the response has exceeded a threshold value.

The invention is illustrated by the following examples.

In examples 1, 2, planar, 3, 4 sandwich-like, 5, 6 bi- and polynuclear, including articulated by spacers, 7, 8 functionally substituted phthalocyanines or related compounds were used.

The conductivity of the proposed composite materials was improved by the addition of fullerenes and / or nanowires, and / or ionic liquids, and / or graphene, and / or metal oxides.

In examples 1, 3, 5, 7, an electrically conductive polymer (MEH-PPV) was used

In examples 2, 4, a polymer was used ((polythiophene)

In examples 6, 8, a polymer ((polyaniline) was used

In all examples, the following ratio of components (wt.%) Was observed:

electron donor part: 1-5%,

electron withdrawing part: 99-95%.

Methylene chloride, tetrahydrofuran or toluene were used as solvents.

Example 1

A composition is prepared containing (including) a polymer (MEH-PPV) and phthalocyanine or related planar compounds dissolved in methylene chloride (or tetrahydrofuran, toluene), suitable for application to surfaces and objects.

Example 2

A composition is prepared containing (including) a polymer (polythiophene), ionic liquids and phthalocyanine or metallophthalocyanine (or related compounds) of planar structure, dissolved in methylene chloride (or tetrahydrofuran, toluene), suitable for application to surfaces and objects.

Example 3

A composition is prepared containing (including) an electrically conductive polymer (MEH-PPV) and a metal phthalocyanine (or related compounds) sandwich structure dissolved in methylene chloride (or tetrahydrofuran, toluene), suitable for application to surfaces and objects.

Example 4

A composition is prepared containing (including) a polymer (polythiophene), nanowires, fullerene, C ₆₀ and metallophthalocyanine (or related compounds) of a sandwich structure, dissolved in methylene chloride (or tetrahydrofuran, toluene), suitable for application to surfaces and objects.

Example 5

A composition is prepared containing (including) a polymer (MEH-PPV) and a binocular spacer-type metallophthalocyanine (or related compound) dissolved in methylene chloride (or tetrahydrofuran, toluene), suitable for application to surfaces and objects.

Example 6

A composition is prepared containing (including) a polymer (polyaniline), graphene and metallophthalocyanine (or related compounds) of the binuclear spacer type, dissolved in methylene chloride (or tetrahydrofuran, toluene), suitable for application to surfaces and objects.

Example 7

A composition is prepared containing (including) an electrically conductive polymer (MEH-PPV) and functionally substituted phthalocyanines (or related compounds - porphyrins, porphyrazines or naphthalocyanines) of various structures and their metal complexes, dissolved in methylene chloride (or tetrahydrofuran, toluene), suitable for application to surfaces and objects.

Example 8

A composition is prepared containing (including) a polymer (polyaniline), metal oxide (TiO ₂ ) and functionally substituted phthalocyanines (or related compounds - porphyrins, naphthalocyanines) dissolved in methylene chloride (or tetrahydrofuran, toluene), suitable for application to the surface and items.

The compositions obtained in examples 1-8 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 electrode 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 coated with a conductive paste or a transparent ITO electrode (hard - on glass or flexible - on a polymer carrier).

Upon contact of laser radiation with the composition material, the response of one of two types was recorded:

1) Photoresistive response - consisting in a change in electrical resistance

2) Photovoltaic response - consisting in the occurrence (or increase) created by the sample photo EMF.

The claimed device was implemented on the example of 3 samples, the characteristics of which are presented below:

SAMPLE 1

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%);

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

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

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:

Max. 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 (655 nm, 100 mW);

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

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

Claims (6)

1. The photoelectric energy converter contains an active layer, characterized in that it contains semiconducting polymers as an electron-withdrawing component, mononuclear or polynuclear phthalocyanines, or naphthalocyanines, or their metal complexes of planar or sandwich structure as an electron-donating component as an active (working) layer. 2. The photovoltaic energy converter according to claim 1, characterized in that it further comprises additives of fullerenes and / or nanowires, and / or ionic liquids, and / or graphene, and / or metal oxides to increase the efficiency of the active layer. 3. The photovoltaic energy converter according to claim 1, characterized in that it contains contacts, which are used as conductive pastes or as contacts, it contains metal electrodes. 4. The photovoltaic energy converter according to claim 3, in which one of the contacts is made in the form of a grid. 5. The photovoltaic energy converter according to claim 3, wherein one of the contacts is transparent. 6. The photovoltaic energy converter according to claim 3, wherein one or both contacts are applied by coating on hard or flexible surfaces.