Patent Grant
11223016
The present application is a U.S. National Stage of PCT/KR2017/010024 filed Sep. 13, 2017, which claims priority benefit of Korean Patent Application No. 10-2016-0128790, filed on Oct. 6, 2016 in the Korean Intellectual Property Office.
The present disclosure pertains to a composition for an active layer of organic photovoltaics and an organic photovoltaic comprising the same. More particularly, the present disclosure is concerned with an at least quaternary composition capable of providing efficient photovoltaic performance over a long period of time, with at least two donors and at least two low-molecular-weight fullerene acceptors introduced thereinto, and an organic photovoltaic comprising an active layer formed therefrom.
With the worldwide increase of energy consumption and the rapid expansion of transport means, such as automobiles, according to recent industrialization, the depletion of fossil energy resources, such as petroleum, coal, etc. has worsened. Furthermore, the use of fossil energy has caused environmental pollution problems such as greenhouse gas, etc. Hence, extensive interest has arisen in the development of clean energy substituting for conventional fossil energy sources. Further, intensive attention has been paid to the development of technologies capable of producing clean energy at low cost. Nowadays, electric power consumption is about 13 Terawatts (TW) and is predicted to increase to 30 TW or greater by 2050.
The sun is representative of such alternative energy sources and thus, solar cells are under the spotlight. A solar cell is an electrical device that directly converts the energy of light into electricity by the photovoltaic effect.
The world solar market has sharply increased by about 35 to 40% annually on average. Solar cells using crystalline silicon substrates predominate in the current solar cell market. For a brief description of the operating mechanism, when light is incident on a solar cell from the outside, the incident photoenergy excites a valance band electron in a p-type semiconductor to the conduction band and the excited electron generates an electron-hole pair inside the p-type semiconductor.
The electron in the electron-hole pair is transferred to the n-type semiconductor by the electric field present in p-n junction, supplying an electric current to the outside. The p-type semiconductor and the n-type semiconductor combine with each other to create a junction. In this regard, an excess of electrons present in the n-type semiconductor diffuse to the p-type semiconductor while an excess of holes present in the p-type semiconductor diffuses to the n-type semiconductor.
The vacant sites left behind the diffusion of electrons and holes are charged with cations and anions, respectively, like a battery. At the vicinity of the junction, a voltage from the cation to the anion is generated.
For the above-mentioned crystalline silicon-based solar cells, however, the cost of the substrate occupies a high portion in the total production cost and the need of intermittent and complicate processes, such as ingot-wafer-cell-module, etc., is a limitative barrier against securing profitability.
As one alternative to silicon-based solar cells, organic photovoltaics are also being actively studied. Solar organic cells employ conductive polymers that are of high electrical conductivity in spite of being organic materials, or organic semiconductor materials that can fabricated into semiconductor devices. As such, organic photovoltaics are expected to be used in so-called BIPV, which is installed at windows, walls, balconies, etc. in buildings, accounting for splendid appearance of the buildings as well as generating electricity. Having the advantage of being able to be fabricated in the form of thin films hundreds nm or less in thickness and being applicable to flexible structures, particularly, organic photovoltaics are suggested as a potential energy source for mobile information systems in the future and expected to find various applications.
In recent years, the introduction of fullerene (C60) into organic photovoltaics has made a swift progress. Steady development has been on technologies of increasing the efficiency of various organic thin-film solar cells by introducing single molecules such as CuPc, polymer materials such as PPV, P3HT, etc. into C60 or C60 derivatives.
Organic semiconductors used in an active layer of organic photovoltaics include organic single molecules and polymers. Organic single molecules are heated in a vacuum to consecutively form a donor layer and an acceptor. As for organic polymers, a solution containing donor and acceptor materials together is subjected to spin coating, inkjet printing, or screen printing to form a thin film.
When light is incident on an organic photovoltaic, a donor material absorbs a photon to create an electron-hole pair (“exciton”), which is an energy bulk in an excited state. The exciton diffuses toward arbitrary directions and separates into an electron and a hole at a boundary to the acceptor material. That is, an acceptor component with large electron affinity rapidly attracts the electron to induce charge separation. The hole remaining in the donor component layer migrates to the anode by the internal electric field formed by due to a difference in work function between opposite electrodes and by a concentration difference of accumulated charges while the electron travels the acceptor layer to the cathode and collected thereat. The charges thus collected finally flow as a current through an external circuit.
In this regard, the active layer has a bilayer structure of a donor (D) material and an acceptor (A) material (D/A bilayer) or a composite thin film ((D+A) blend), which is 100 nm thick in total, optionally with the interposition of buffer layers including a hole transport layer between the cathode and the active layer and an electron transport layer between the anode and the active layer. Particularly, the blend structure is also known as a “bulk-heterojunction (BHJ)” structure in which regions of each the donor material and the acceptor material are separated by 10 nanometers or less, resulting in the effect that the interface area between the donor and the acceptor increases several times greater compared to the bilayer structure. Therefore, the blend structure is known to increase the possibility of charge separation as well as serving to increasing light absorption efficiency due to micro light scattering.
In this context, for semiconductor polymers, research have been made of poly(p-phenylene vinylene) (PPV)-based components and polythiophene (PT) derivatives as donor materials. Polyfluorene (PF)-based components and copolymers thereof are also used as low-band gap donor components. These donor components must primarily have a light absorption wavelength range incident with the solar light spectrum and be superior in terms of electrical properties including the mobility of charges, etc. Meanwhile, fullerene (C60) or a derivative thereof (PCBM) is used as the acceptor material. Particularly, the derivatives of C60 in combination with semiconductor polymers are widely used as BHJ structural materials.
As a strategy for increasing the efficiency of organic photovoltaics using such a BHJ structure, a tandem structure in which two or more active layers are stacked has been developed. Reportedly, such active layers in a tandem structure are different in absorption region from each other and thus can absorb solar light in a reciprocally supplemental manner, with the consequent improvement of power conversion efficiency. However, when two or more active layers are consecutively stacked to fabricate a tandem structure, the lower active layer may be apt to be damaged. A fabrication process for alleviating this problem is also complicated. Hence, there is still a problem for commercialization.
In contrast to the above-mentioned tandem approach, recent research has reported that since the initial invention of bulk-heterojunction (BHJ) solar cells, new conjugated polymers and fullerene (or derivatives thereof) are combined to form an active layer whereby the organic photovoltaics can be improved in performance, specifically power conversion efficiency (PCE). There is a technique known to improve the performance of a solar cell in that a ternary composition that is prepared by additionally incorporating the basic binary composition composed of a polymer and fullerene with a different conjugated polymer donor component or a fullerene-based acceptor component is used as an active layer.
For instance, Korean Patent No. 2015-117361 A introduces a ternary active layer composition in which
poly[(4,8-bis-(2-ethylhexyloxy)-benzo[1,2-b:4,5-b′]dithiophen)-2,6-diyl-alt-(N-2-ethylhexylthieno[3,4-c]pyrrole-2,6-diyl]] (PBDTTPD), which is a polymer acting as a charge-bridge, is added to a binary active layer composition composed of poly(3-hexylthiophene (P3HT) as a polymer donor and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6)C61 (PC61BM), which is a fullerene derivative serving as a low-molecular-weight acceptor, stating that the solar cell is improved in power conversion efficiency although low in the low-molecular-weight acceptor content.
In addition, Korean Patent No. 1549659 discloses an organic photovoltaic in which a ternary composition comprising one polymer donor and two fullerene adducts as an acceptor is used as an active layer. According to the patent document, it is stated that the addition of an additional low-molecular-weight acceptor component to the binary basic active layer composition can improve power conversion efficiency without degrading the short-circuit current density (Jsc) and the fill factor (FF).
The foregoing ternary composition is advantageous in view of broadening the light absorption band, improving the nanomorphology of the blend, increasing the open-circuit voltage (VOC), and/or boosting the charge transfer. Particularly, ternary organic photovoltaics based on the efficient non-crystalline polymer host (e.g., poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]]; PTB7) are reported to exhibit a power conversion efficiency of about 10%, which would meet commercialization requirements.
Besides the demand for high power conversion efficiency, it is also critical to preserve an optimized morphology of the pristine active layer during the operation of the organic photovoltaic. The domains of the polymer and fullerenes grow during operation due to their thermodynamic instability at elevated temperatures, which is a major degradation mechanism limiting the commercialization viability of the organic photovoltaics. Particularly at outdoor operating temperatures exceeding the glass transition temperature (Tg) of typical polymers, both non-crystalline polymers and fullerene derivatives are readily clustered, accompanying a reduction in the interfacial areas and an increase in the percolation threshold for charge carrier transport.
As such, research into an increase in the lifespan of organic photovoltaics mainly by altering the stack structure or by aggregating or coalescing fullerene electron acceptor is ongoing.
However, the above-mentioned conventional techniques, particularly, the ternary composition (2D & 1A or 1D & 2A) in which an additional polymer donor component or low-molecular-weight acceptor component is incorporated into a basic binary active layer composition composed of a polymer donor component and a low-molecular-weight fullerene acceptor is still required for advance in photovoltaic performance or in maintaining photovoltaic performance over a long period of time.
The present disclosure aims to provide an at least quaternary composition that is used in an active for organic photovoltaics and capable of exhibiting better photovoltaic efficiency over a longer period of time compared to conventional binary and ternary active layer compositions.
A first aspect of the present disclosure provides an at least quaternary composition for use in an active layer of an organic photovoltaic, the composition comprising:
(I) a first and a second donor component that absorb light to create an exciton and donate the electron separated from the exciton formed; and (II) a first and a second low-molecular-weight fullerene acceptor component that receive the electron donated by the donor component,
wherein, the first donor component is a material having a bandgap of 1.1 to 2.5 eV,
the second donor component is a material having a LUMO (lowest unoccupied molecular orbital) identical to or lower than that of the first donor component,
the first low-molecular-weight fullerene acceptor component has a cascade energy level structure with the second donor component and the second donor component has a HOMO (highest occupied molecular orbital) identical to or higher than that of the first low-molecular-weight fullerene acceptor component, and
the second low-molecular-weight fullerene acceptor component has a cascade energy level structure with the first low-molecular-weight fullerene component and a LUMO higher than the HOMO of the first low-molecular-weight acceptor component.
According to an illustrative embodiment, the component (I) and the component (II) are contained at a mass ratio of 1:1 to 1:3 in the at least quaternary composition, the content of the first donor component in the component (I) ranges from 1 to 99% by mass, and the content of the first low-molecular-weight in the component (II) ranges from 1 to 99% by mass.
According to a second aspect of the present disclosure, provided is an organic photovoltaic comprising:
a pair of electrodes including a cathode and an anode different in work function from each other; and
an at least quaternary active layer disposed between the pair of electrodes and comprising
(I) a first and a second donor component that absorb light to create an exciton and donate the electron separated from the exciton formed; and (II) a first and a second low-molecular-weight fullerene acceptor component that receive the electron donated by the donor component,
wherein, the first donor component is a material having a bandgap of 1.1 to 2.5 eV,
the second donor component is a material having a LUMO (lowest unoccupied molecular orbital) identical to or lower than that of the first donor component,
the first low-molecular-weight fullerene acceptor component has a cascade energy level structure with the second donor component and the second donor component has a HOMO (highest occupied molecular orbital) identical to or higher than that of the first low-molecular-weight fullerene acceptor component, and
the second low-molecular-weight fullerene acceptor component has a cascade energy level structure with the first low-molecular-weight fullerene component and a LUMO higher than the HOMO of the first low-molecular-weight acceptor component.
In an illustrative embodiment, the LUMO of the second donor component may be higher than the LUMO of the first low-molecular-weight fullerene acceptor component.
In an illustrative embodiment, the LUMO of the second donor component may be identical to or lower by up to 50% than that of the first donor component and may be higher by at least 0.3 eV than that of the first low-molecular-weight fullerene acceptor component.
In an illustrative embodiment, the HOMO of the second donor component may be higher by at least 0.3 eV than that of the first low-molecular-weight fullerene acceptor component.
In an illustrative embodiment, the second low-molecular-weight fullerene acceptor component may have LUMO lower than that of the first donor component.
In an illustrative embodiment, the LUMO of the second low-molecular-weight fullerene acceptor component may be higher by up to 50% than the HOMO of the first low-molecular-weight fullerene acceptor component and may be lower by at least 0.3 eV than the LUMO of the first donor component.
In an illustrative embodiment, the HOMO of the second low-molecular-weight fullerene acceptor component may be lower than the LUMO of the first low-molecular-weight fullerene acceptor component.
In an illustrative embodiment, the HOMO of the second low-molecular-weight fullerene acceptor component may be lower by up to 50% than the LUMO of the first low-molecular-weight fullerene acceptor component.
According to an illustrative embodiment, the second donor component may have a bandgap of 1.2 to 2.6 eV.
According to an illustrative embodiment, the first low-molecular-weight fullerene acceptor component and the second low-molecular-weight fullerene acceptor component may each have a bandgap of 1.5 to 2.5 eV.
According to an illustrative embodiment, the first donor component may be poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]]; PTB7).
In an illustrative embodiment, the second donor component may be a polymer material including poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT).
In an illustrative embodiment, the first low-molecular-weight fullerene acceptor component may be [6,6]-phenyl C71butyricacidmethylester (PC71BM).
In an illustrative embodiment, second low-molecular-weight fullerene acceptor component may be [6,6]-phenyl C61 butyricacidmethylester (PC61BM).
In an illustrative embodiment, the organic photovoltaic may have a power conversion efficiency of at least 6% after thermal treatment at 65° C. or higher for one year.
In an illustrative embodiment, the point at which the power conversion efficiency (PCE) of the organic photovoltaic has fallen to 60% of the pristine value (T60) may be at least one year.
In an illustrative embodiment, the organic photovoltaic, the first donor component and the low-molecular-weight fullerene acceptor component may range in nanocrystallite size from 34 to 40 Å and from 18 to 21 Å, respectively, after the organic photovoltaic is thermally treated at 65° C. or higher for 100 hours.
According to an illustrative embodiment, the at least quaternary composition may have a pristine hole mobility (μh)/electron mobility (μe) ratio of from 0.8 to 2.
According to the present disclosure, at least quaternary composition (or blend) prepared simply by mixing at least two different donor components and at least two different low-molecular-weight fullerene acceptor components, all of which satisfy particular energy absorption requirements, at a particular ratio is used as an active layer in an organic photovoltaic, resulting in broadening the absorption spectrum, promoting exciton dissociation and charge transport, and retaining optimized morphology.
As such, the at least quaternary active layer composition (or blend) for an active layer of an organic photovoltaic, according to the present disclosure, can provide a novel platform that can stably maintain superb photovoltaic parameters or performance over a long period of time. In particular, the enhancement of stability is attributed to the fact that the donor components and the low-molecular-weight fullerene acceptor components in the at least quaternary composition are restricted from phase separating from each other and undergoing domain growth and can be applied to organic photovoltaics which are thus expected to be broadly commercialized.
in the thin layers of the organic photovoltaic comprising the quaternary active layer for different incident wavelengths;
The present invention may be embodied by the following description. The following to description is to be understood as disclosing embodiments of the present invention, and the present invention is not necessarily limited thereto.
Furthermore, the appended drawings are used to understand embodiments of the present invention and are not construed as limiting the present invention, and details of individual constituents may be properly understood by specific purposes in the related description as will be described below
The terms and terminologies used herein may be defined as follows.
Herein, the terms “donor” and “acceptor” are intended to mean material having a high ionization potential (donor) and a material having high electron affinity (acceptor), respectively. That is, a material to donate an electron comes into contact with a strongly electron accepting material to allow the dissociation of excitons into free charge carriers.
As used herein, the term “short-circuit current (Isc)” means a flowing current at a voltage of 0 between the opposite ends of the solar cell. Since the current is attributed to the generation and collection of charges created by light, a short-circuit current and a light-generated current photovoltaic are identical to each other for an ideal solar cell. As such, a short-circuit current accounts for a maximum current that can be achieved in a solar cell and is determined by the elements shown in the following Mathematical Formula 1:
Isc∝εA*εED*εCT*εCC Mathematical Formula 1
wherein, εA represents light absorption efficiency, εED represents for exciton diffusion efficiency, εCT represents charge transport efficiency, and εCC represents charge collection efficiency.
The term “open-circuit voltage (VOC)” refers to a voltage occurring across the opposite ends of a solar cell at zero current and corresponds to the maximum voltage available from the solar cell.
The term “fill factor (FF)” refers to the ratio of maximum obtainable power to the product of the open-circuit voltage and short-circuit current, as defined in the following Mathematical Equation 1, and corresponds to a maximum area rectangle that can be filled under the current-voltage curve.
“power conversion efficiency” is the most important factor representing the performance of a solar cell and is the ratio of output energy to the input energy from the sun, as defined in the following Mathematical Equation 2:
As used herein, the term “bandgap” refers to a difference between HOMO and LUMO in a given organic component (polymer and/or low-molecular-weight).
It will be understood that when an element is referred to as being “on” another element, it can be directly on the other element or intervening elements may be present therebetween. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
Similarly, the expressions “under”, “beneath”, “below” should also be understood as a relative concept for positions.
As a rule, an organic photovoltaic may be briefly represented as the basic structure of metal/active layer/metal. As shown, a structure in which a substrate, a lower electrode layer (cathode), an active layer, and an upper electrode layer (anode) are formed in the order from the bottom is provided. Incidence of light on an organic photovoltaic creates a positive charge (hole) and a negative charge (electron) in the active layer, and the electron moves to the upper electrode layer disposed on the active layer while the hole is directed to the lower electrode layer under the active layer. In detail, when a donor component in the active layer absorbs a photon, an electron is transferred from HOMO to LUMO, creating an exciton in an excited state. According to an illustrative embodiment, the donor component is an organic material in a broad sense and may be particularly a polymer material.
Next, the dissociation of the created exciton into an electron and a hole is accompanied. The acceptor component in the active layer has LUMO lower than that of the donor component. When the exciton created in the donor component reaches an interface with the acceptor component during diffusion in arbitrary directions, the acceptor component attracts the electron to induce charge separation. In this regard, the hole remaining in the donor component migrates to the cathode while the electron existing in the acceptor component travels toward the anode.
In addition, the exciton has a high binding energy due to a low dielectric constant of the donor component. In order to overcome such binding energy, a LUMO energy level difference of at least about 0.3 eV, particularly at least about 0.5 eV should be required for inducing the charge dissociation of excitons.
To this end, there is a need for minimizing loss at the interfaces between the active layer and the electrodes, securing a path through which electrons and holes separated in the active layer can move to the electrodes without forming a short circuit, and making the mobility of charges (electrons and holes) smooth in each of the donor component and the acceptor component.
With reference to
In the embodiment depicted, the lower electrode layer is a cathode and may be made of a transparent material, for example, TCO (transparent conductive oxide). Examples of TCO include indium tin oxide, indium zinc oxide, gallium zinc oxide, aluminum zinc oxide, and a combination thereof. Typically, the lower electrode layer (for example, ITO) may be provided in the form of a coating on the substrate (for example, glass substrate).
Meanwhile, the upper electrode layer is an anode which may be made of Ni, Al, Ag, Au, Co, Pd, Cu, etc. alone or in combination. According to circumstances, the upper electrode layer may be a deposited film of the elements.
For the inverted-type organic photovoltaic depicted, the work function of the upper electrode layer (anode) should be high enough to match with the HOMO energy level of the donor component while the work function of the lower electrode layer (cathode) should be low enough to match with the LUMO energy level of the acceptor (that is, there is a difference in work function between the electrodes). For an upper electrode layer made of a metal having a high work function, such as Au or Ag, the use of TCO having a high work function (for example, about 4.7 eV in ITO) in a lower electrode may cause a mismatch with the LUMO level of the acceptor. In consideration of this event, the lower electrode layer may be modified with a thin film made of an electron conductive (hole blocking) material (for example, ZnO, TiOx, etc.) to ensure the matching.
According to an illustrative embodiment, the lower and the former electrode layer may be each formed using LPCVD (low pressure chemical vapor deposition), PECVD, ALD (atomic layer deposition), sputtering, electron-beam evaporation, thermal evaporation, etc., but the present disclosure is not limited thereto.
The thickness of the active layer may be selected within a suitable numerical scope in consideration of the donor component and kinds of the low-molecular-weight acceptor component used, light absorption amount, charge (hole and electron) mobility, etc. and may range, for example, from about 50 to 300 nm, particularly from about 70 to 200 nm, and more particularly from about 90 to 150 nm, but is not limited thereto. When the thickness of the active layer is below or exceeds particular levels, the light absorption area or the charge mobility is reduced, resulting in lowering the efficiency of the organic photovoltaic. Hence, it may be advantageous to select the thickness within the above-mentioned range.
In order to enhance the power conversion efficiency thereof, the solar cell may further comprise a charge transport layer such as a hole transport layer and/or an electron transport layer. For instance, a poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) layer having the repeating unit represented by the following General Formula 1 may be formed to modify the surface of the cathode (e.g., ITO):
PFN is a conjugated polymer dissolvable in a solvent such as methanol and can provide the effect of improving the power conversion efficiency by increasing charge transport potential and reducing recombination between holes and electrons.
In this regard, the additionally formed layer may range in thickness from about 5 to 20 nm, particularly from about 7 to 15 nm, and more particularly from 9 to 12 nm.
According to an illustrative embodiment, a hole transport layer, for example, a MoO3 layer may be introduced on the anode (for example, Ag layer) and may have a thickness of about 1 to 10 nm and particularly about 2 to 7 nm. The numeral ranges supposed above are illustrative, but do not limit the present disclosure.
According to an embodiment, the composition for forming an active layer comprises: a donor component creating an exciton in response to light absorption and donating an electron dissociated from the created exciton; and a low-molecular-weight fullerene acceptor composition accepting the electron donated from the donor component. In greater detail, the composition for forming an active layer is an at least quaternary composition (or blend) which comprises, in consideration of absorption profiles and cascade energy levels, at least two donor components (first donor and second donor); and at least two low-molecular-weight fullerene components (first and second low-molecular-weight acceptor) as acceptor components.
It is a noticeable feature of the embodiment that an exceptional improvement can be brought about into the lifespan characteristic as well as the photovoltaic performance (or parameter) in the solar cell, compared to conventional binary or ternary active layers, by employing two donor components (D) and two low-molecular-weight fullerene components (A). As such, a combination of at least two donor components and at least two low-molecular-weight fullerene acceptor components can effectively alleviate the phenomenon of degrading the stability of the device, such as the phase separation of the blend, upon long-term operation.
Without being bound by any theory, a blend for the active layer is thermodynamically unstable at high temperatures such that the domains of the donor component and the low-molecular-weight fullerene acceptor grow during the operation of the organic photovoltaic, thus causing degradation. In particular, at outdoor operating temperatures, which often exceed the glass transition temperature of typical polymers, both non-crystalline polymers and fullerene derivatives are readily clustered accompanying reduction in the donor (D)-acceptor (A) interfacial areas and increase in the percolation threshold for charge carrier transport.
In contrast to typical binary or ternary compositions, the additionally added donor component and/or low-molecular-weight fullerene acceptor component acts as a morphology stabilizer to provide parameters to control blending and separation behaviors of the components, thereby arresting the morphology at its optimum. For example, the incorporation of an additional low-molecular-weight fullerene acceptor component restricts the diffusion of other low-molecular-weight fullerene acceptor components, thus controlling domain growth in the BHJs, with no requirement of additional chemical modification or post-treatment.
As such, employment of two or more kinds of each of the donor component and the low-molecular-weight acceptor, which are different in energy level, results in broadening the absorption spectrum, providing superb light absorptivity and high exciton dissociation rate, and facilitating transport kinetics as well as retaining optimized morphology. Hence, the active layer with the components exhibits improved photovoltaic performance (efficiency) and is highly stable even during operation at high temperatures for a long period of time, which would be advantageous for prolong the lifespan.
In one embodiment, the donor component (I) and the low-molecular-weight fullerene acceptor component (II) may be used at a mass ratio of about 1:1 to about 1:3, particularly about 1:1 to about 1:2, and more particularly about 1:1 to about 1:1.5. The reason why a mass ratio between component (I) and component (II) is controlled into a particular range is to increase the efficiency of the solar cell and maintain thermal stability thanks to the minimization of morphological alteration. It would be advantageous to select within the above-mentioned range.
Of the at least quaternary active layer composition, the donor component (I) may comprise the first donor component at a content of about 1 to 99% by mass, particularly about 30 to 95% by mass, and more particularly about 40 to 80% by mass. When the content of the first donor component in the entire donor component (I) is below or exceeds particular levels, there may occur the problem that the solar cell degrades in efficiency. Therefore, it is preferred that the content be adjusted within the above-mentioned range.
According to one embodiment, the at least quaternary active layer composition is based on a binary composition of a basic donor component (hereinafter referred to as “first donor component”) and a basic low-molecular-weight fullerene acceptor component (hereinafter referred to as “first low-molecular-weight acceptor component”) plus at least on donor component (hereinafter referred to as “second donor component”) and at least one low-molecular-weight acceptor component (hereinafter referred to as “second low-molecular-weight acceptor component”).
In one embodiment, the first donor component may be a polymer material and may be typically a material having a bandgap of about 1.1 to 2.5 eV and more typically about 1.2 to 2.3 eV. According to an illustrative embodiment, the material meeting the bandgap requirement may be poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b′]dithiophene-2,6-diyl][3-fluoro-2-[(2 ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] (PTB7) having the repeating unit represented by the following General Formula 2:
PTB7 has an optical bandgap of about 1.65 eV. In addition to PTB7, examples of materials (particularly polymers) available as the first donor component are listed in Table 1, below.
In this context, BTT-DPP, DPP-TT-T, and PCPDTBT may each have the repeating units represented by the following General Formulas 3 to 5, respectively:
As the first donor component, materials satisfying the above-mentioned requirements may be used alone or in combination. As such, a material having a particular bandgap, when used as the first donor component, can absorb a large number of photons, thus potentially allowing higher power conversion efficiency.
In an illustrative embodiment, a polymer for use as the first donor component may have a molecular weight (Mw) of about 10,000 to 500,000, particularly about 15,000 to 400,000, and more particularly about 20,000 to 350,000 and may be appropriately selected in general consideration of kinds of polymers, desired energy levels or bandgaps, desired crystal properties in the active layer, etc.
Meanwhile, the second donor component may have, for example, cascade energy levels with respect to the first donor component and may be thus a material having LUMO identical to or lower than that of the first donor component. By way of example, the LUMO of the second donor component may be reduced to up to about 50%, particularly about 20 to 45%, and more particularly about 30 to 35% of the LUMO of the first donor component.
Given to the second donor component with respect to the first donor component, the above-mentioned energy level can advantageously allow the smooth energy flow between the donor components.
In an illustrative embodiment, the second donor component may be the polymer poly[N-9′-heptadecanyl-2,7-carbazole-alt-5,5-(4′,7′-di-2-thienyl-2′,1′,3′-benzothiadiazole)] (PCDTBT) having the repeating unit represented by the following General Formula 6:
In addition, examples of the polymers available as the second donor component include PCDTBT, F8TBT, PPV, MDMO-PPV, MEH-PPV, P3HT, PBDTTT-CF, F8BT, PSBTBT, PBTTPD, and TQ1, which may be used alone or in combination. In this context, MDMO-PPV, MEH-PPV, and P3HT have the repeating units represented by the following General Formulas 7 to 9:
In this regard, the second donor component may typically range in bandgap from about 1.2 to 2.6 eV and more typically from about 1.4 to 2.5 eV. For example, PCDTBT, MEH-PPV, and P3HT have respective optical bandgaps of about 1.86 eV, about 2.11 eV, and about 1.95 eV.
In an illustrative embodiment, a polymer for use as the second donor component may have a molecular weight (Mw) of about 10,000 to 500,000, particularly about 15,000 to 400,000, and more particularly about 20,000 to 350,000 and may be appropriately selected in general consideration of kinds of polymers, desired energy levels or bandgaps, desired morphological properties in the active layer, etc. In one illustrative embodiment, the LUMO of the second donor component may be higher than that of the first low-molecular-weight fullerene acceptor component, for example, by at least about 0.3 eV and particularly by about 0.31 to 0.35 eV.
In one embodiment, the first low-molecular-weight fullerene acceptor component may have a cascade energy level structure with respect to the donor component (particularly, the second donor component). In this context, the HOMO of the second donor component may be in an energy level identical to or higher than that of the first low-molecular-weight fullerene acceptor component. By way of example, the HOMO of the second donor component may be higher than that of the first low-molecular-weight fullerene acceptor component by at least about 0.3 eV and particularly by about 0.31 to 0.35 eV. Given to the second donor component with respect to the first low-molecular-weight fullerene acceptor component, the energy level can advantageously allow the smooth energy flow therebetween.
In an illustrative embodiment, the first low-molecular-weight fullerene acceptor component may be [6,6]-phenyl C71butyricacidmethylester(PC71BM) represented by the following General Formula 10, C60, C70, C84, PC61BM, ICBA, ICMA, or [6,6]-Thienyl C61 butyric acid methyl ester, which may be used alone or in combination:
In one embodiment, the first low-molecular-weight fullerene acceptor component may typically range in optical bandgap from about 1.5 to 2.5 eV and more typically from about 1.7 to 2.3. eV. For instance, PC71BM has an optical bandgap of about 1.96 eV.
According to one embodiment, the second low-molecular-weight fullerene acceptor component forms a cascade energy level structure with respect to the first low-molecular-weight fullerene acceptor component and may have a LUMO higher than the HOMO of the first low-molecular-weight fullerene acceptor component. In addition, the second low-molecular-weight fullerene acceptor component may have a LUMO lower than that of the first donor component.
According to an illustrative embodiment, the LUMO of the second low-molecular-weight fullerene acceptor component may be higher by about up to 50% (particularly about 20 to 45% and more particularly about 30 to 35%) than the HOMO of the first low-molecular-weight fullerene acceptor component and may be lower by about 0.3 eV and particularly by about 0.31 to 0.35 eV than the LUMO of the first donor component.
In the low-molecular-weight acceptor component (II), the first low-molecular-weight fullerene acceptor component may be present at a content of about 1 to 99% by mass, particularly about 20 to 90% by mass, and more particularly about 40 to 80% by mass. When the content of the first low-molecular-weight fullerene acceptor component is below or exceeds certain levels, the lifespan of the solar cell may degrade due to the morphological alteration. Therefore, it would be advantageous that the content be adjusted within the above-mentioned range.
In an illustrative embodiment, concrete examples of the second low-molecular-weight fullerene acceptor component include [6,6]-phenyl C61butyricacidmethylester(PC61BM) represented by the following General Formula 11, C60, C70, C84, ICBA, ICMA, [6,6]-Thienyl C61 butyric acid and methyl ester, which may be used alone or in combination:
The second low-molecular-weight fullerene acceptor component may typically range in optical bandgap from about 1.5 to 2.5 eV and more typically from about 1.7 to 2.3. eV. For example, the optical bandgap of PC61BM is about 2.1 eV.
In an illustrative embodiment, the HOMO of the second low-molecular-weight fullerene acceptor component may be lower than the LUMO of the first low-molecular-weight fullerene acceptor component. By way of example, the HOMO of the second low-molecular-weight fullerene acceptor component may be lower by about up to about 50% (particularly about 20 to 45% and more particularly about 30 to 35%) than the LUMO of the first low-molecular-weight fullerene acceptor component.
When the quaternary composition is introduced into the active layer in a typical organic photovoltaic, particularly with the use of a polymer material as a donor component, any coating method, such as spin coating, dip coating, bar coating, inkjet printing, etc. may be applied without particular limitations thereto.
For the coating, the above-mentioned at least four components may be dissolved in an organic solvent. As the organic solvent, for example, chlorobenzene, chloroform, para-xylene, dichlorobenzene, trichlorobenzene, hexane, and THF may be used alone or in combination. Of the solvents exemplified above, chlorobenzene may be advantageous because of the attainment of higher photovoltaic efficiency (in detail, EQE). The organic solvent may be used in an amount of about 1 to 4% by mass, based on the total mass of the quaternary donor and acceptor components, particularly in an amount of about 1.2 to 3.5% by mass, and more particularly in an amount of about 1.5 to 3% by mass. However, the amount ranges are illustrative, and various amounts of the solvent may be used unless any problem with the coating is present.
According to an illustrative embodiment, the composition may further comprise diiodooctane (e.g., 1,8-diiodooctane), diiodohexane (e.g., 1,6-diiodohexane), octanethiol (e.g., 1,8-octanedithiol), dibromooctane (e.g., 1,8-dibromooctane), 1-chloronaphthalene), 1-methylnaphthalene, and a combination thereof as an additive to induce the formation of an optimum continuous morphology. In this regard, the amount of the available additive component may range from about 1 to 7% by mass, particularly about 1.5 to 6% by mass, and more particularly about 2 to 5% by mass.
The at least quaternary active layer composition provided according to the embodiment exhibits balanced charge carrier mobilities and, for example, the pristine composition may have an hole mobility (μh)/electron mobility (μe) ratio of about 0.8 to 2, particularly about 0.9 to 1.8, more particularly about 0.95 to 1.5, far more particularly about 1 to 1.4.
In an illustrative embodiment, the organic photovoltaics fabricated using as an active layer a composition of at least four components (the first and the second donor components and the first and the second low-molecular-weight fullerene acceptor components) grouped to have particular energy level properties as mentioned above (for example, optical bandgaps) may retain a power conversion efficiency of at least about 6.2% (in detail, at least about 6.25%, and more particularly at least 6.27%) after one month of operation at 65° C. or higher and at least about 6% (in detail, about 6.1%, and more particularly at least about 6.2%) after one year of operation at 65° C. or higher.
Moreover, the point at which the power conversion efficiency (PCE) has fallen (dropped) to 60% of the pristine (initial) value may be at least one year of operation, particularly at least 1.5 years, and more particularly about 2 years. The solar cell can retain at least about 70%, particularly at least about 72%, and more particularly at least about 75% of the pristine PCE. As described, the at least quaternary active layer composition can bring about an improvement in long-term stability at high temperatures. In contrast, when a binary composition is used, the power conversion efficiency decreases to a level of down to about 3.4%.
Without being bound by any theory, it is supposed that such improvements in the stability might be achieved by restricting the growth of the domains to suppress phase separation between the polymer and the low-molecular-weight fullerene. In a particularly illustrative embodiment, after an organic photovoltaic fabricated using the composition for the active layer is thermally treated at 65° C. or higher for 100 hours, the first donor component (particularly a polymer material) and the low-molecular-weight fullerene acceptor component may range in nanocrystallite size from about 34 to 40 Å (particularly about 35 to 39 Å, and more particularly about 36 to 38 Å) and from about 18 to 21 Å (particularly about 18.5 to 20.5 Å, and more particularly about 19 to 20 Å), respectively.
Furthermore, the organic photovoltaic can attain good resistance to power conversion efficiency loss even after operation in more severe conditions, for example, at about 120° C.
As described in the foregoing, the BHJ platform comprising the active layer according to the present disclosure can provide a new approach to the maintenance of high efficiency over a long period of time and can be applied to outdoor organic photovoltaics without any problems.
Hereinafter, the present disclosure will be described in detail with reference to examples. These examples are only for illustrating the present invention more specifically, and it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples.
Fabrication of Organic Photovoltaic
PCDTBT (molecular weight (Mw): 57,000, 1-Material), PTB7 (Mw: of 115,000, 1-Material), PC71BM (>99%, Nano-C), and PC61BM (>99.5%, Nano-C) were used as received. The device fabrication was based on the protocol optimized for the PTB7-based binary organic photovoltaic. First, each of various amounts (x mg, 0<x<10 mg) of PCDTBT was dissolved in 970 μL of chlorobenzene (anhydrous, 99.8%, Sigma-Aldrich) and magnetically stirred at 80° C. for 72 hours. PTB7 (10-x mg), PC61BM (y mg, 0<y<15 mg), PC71BM (15-y mg) and 30 μL of 1,8-diiodooctane (DIO, 98%, Sigma-Aldrich) were mixed with the fully blended PCDTBT solution, followed by magnetic stirring at 50° C. for 24 hours.
A solution of 0.5 mg/ml PFN (1-Material) and 2 μL/mL acetic acid in methanol was applied onto ITO-coated glass and dried for 1 hour at room temperature. The binary blend (b-BHJ blend), the ternary blend (t-BHJ blend), and the quaternary blend (q-BHJ blend) were each applied onto the top of the PFN layer by spin coating to form an active layer with a fixed thickness of 90±5 nm. The solvent was dried overnight in a vacuum chamber before top electrode deposition. An 8-nm-thick layer of MoO3 and a 100-nm-thick layer of Ag were then thermally evaporated through a shadow mask.
The active area of the devices (0.116 cm2) was defined by the overlap between the top and bottom electrodes. The complete organic photovoltaics were sealed in a nitrogen-filled glove box using an encapsulation glass immediately after the top electrode deposition.
The internal energy levels of the inverted-type organic photovoltaic fabricated using the quaternary blend among the prepared active layer compositions are depicted in
Evaluation of Film Using Active Layer Composition Inclusive of Donor and Acceptor
As shown in
Photoluminescence (PL) Spectrum Analysis
An experiment was conducted in order to examine effects of the incorporation of PCDTBT into PTB7 on light emission properties. The resulting emission spectra are depicted in
As shown in the figure, when PCDTBT was mixed with PTB7 at a composition ratio of at PTB7:PCDTBT=0.5:0.5, the emission intensity from PCDTBT (centered at 705 nm) decreased while the PTB7 emission (centered at 770 nm) increased. This PL emission change strongly indicates the effective energy transfer from PCDTBT to PTB7. On the other hand, when the low-molecular-weight fullerene acceptor component was mixed in the PTB7:PCDTBT blend (e.g., PTB7:PCDTBT:PCIIBM=0.5:0.5:1.5), the PL emission peaks from both PCDTBT and PTB7 were distinctively quenched.
With reference to
Moreover, the optical response was even further enhanced in the ultraviolet range (<380 nm) when the second acceptor PC61BM was added. This optical response implied that the quaternary organic photovoltaic is better at harnessing broadband solar energy (UV-Vis-near-infrared (NIR)) than the binary and ternary blends.
Optical Simulation Test
To investigate the optical response of the organic photovoltaics to the solar spectrum, an optical simulation was made on the basis of the T-matrix method, followed by calculating the internal optical E-field distribution in the organic photovoltaics having multilayer structures. A test was conducted to examine whether the optical simulation results agreed with the experimental spectra. Using the optical constants (i.e., n and k values) of the materials, absorption spectra of the multi-layer stack structure were calculated based on extraction of the transmission (T) and reflection (R) at each of the interfaces between different layers. The T and R values were obtained by calculating series of matrix components composed of the Fresnel complex reflection and transmission at the interface. Then, the average energy dissipation rate Qj (x, λ) in the jth layer at incident wavelength λ and at the position x in the thin layers was found
wherein, ε0 is the free space permittivity, subscript j denotes the jth layer, c is the speed of light in the free space, and Ej(x) is the optical E-field at the position x. Qj(x,λ) can be translated into the effective absorption of the jth layer.
in the thin layers of the organic photovoltaic comprising the quaternary active layer for different incident wavelengths.
In this regard,
Under AM 1.5G condition, it is possible to calculate the exciton generation rate G(x, λ), using the energy dissipation rate in the layers as in the following Mathematical Formula 4:
wherein h is the Planck constant.
The total exciton generation rate, Gex(x), can be calculated such that Gex(x), =∫Gj(x,λ)dλ, which, in turn, provides the expected exciton generation rate in the active layer, Gex. It was found that Gex=∫090 nmGex(x)dx=1.21×1028 m−3 s−1 for the quaternary organic photovoltaic under AM 1.5G condition, which is in a good agreement with the experimentally measured value of (1.006±0.224)×1028 m−3 s−1.
Test for Composition-Dependent Color Tunability of BHJ Blend
The device was tested for absorption spectrum and color tunability by controlling PTB7/PCDTBT and PC71BM/PC61BM ratios in the quaternary BHJ layers and the results are depicted in
As can be seen, the color of the device can be tuned by controlling contents of the components in the quaternary composition. Such color tunability is particularly advantageous for aesthetic applications such as colorful building-integrated photovoltaics (BIPVs) or luminescent smart windows.
Test for Optimization of Composition for Organic Photovoltaic Comprising Quaternary Active Layer
Selection of Optimum Solvent
To find the optimized composition of the organic photovoltaics provided with the quaternary active layer, the ratio of donors in the mixture was varied on the basis of the best binary donor-acceptor (D-A) ratio of 1:1.5 (by mass), in such a way that PTB7:PCDTBT:PC71BM=1-x:x:1.5 (wherein 0≤x≤1). Results for optimum solvents with different solvent compositions are depicted in
As can be seen, chlorobenzene was regarded as a good solvent for the reference PTB7:PC71BM blend.
Optimization of Composition of Blend for Active Layer in Organic Photovoltaic
It was more practical to find the optimized composition by varying the relative amounts of the two donor components while keeping the amount of the acceptor fixed because this strategy yielded more possibilities for designing the optical and morphological properties of the active layer than did an alternative strategy involving varying the amounts of the acceptors. On the basis of the optimum composition 1:1.5 (by mass) of the binary donor-acceptor (D-A), experiments were carried out by varying the composition of the other components.
As apparent from
When combined, the foregoing results show a maximum PCE at x=0.1.
After the composition of the donor components were optimized, PC61BM was introduced as an additional acceptor component to further improve performance and establish quaternary D-A BHJs. In addition, this approach facilitated controlling the nanoscale morphology of the quaternary BHJ. It can be conjectured that the additional donor (D) and acceptor (A) would interfere with the formation of either crystalline grains of donor polymers Or aggregated domains of acceptor fullerenes. Accordingly, the phase separation would be effectively controlled by the morphology to derive long-term and thermal stability.
The ratio of the acceptors in the mixture were varied while fixing the overall donor-to-acceptor ratio such that PTB7:PCDTBT:PC71BM:PC61BM=0.9:0.1:1.5-y:y (0≤y≤1.5)
It is also notable that the quaternary organic photovoltaic exhibited enhanced external quantum efficiency (EQE) spectra compared with those of the ternary and binary organic photovoltaics, as depicted in
Parameters associated with capabilities of photon absorption and exciton dissociation in active layers were obtained from the Jph-Veff characteristics depicted in
In the table, Jph was obtained from JL-JD and Jsat, Gmax and P(E,T) denote the saturation current density, maximum exciton generation rate, and charge dissociation probability, respectively.
Meanwhile, the enhancement of the fill factor (FF) would be attributed mainly to the balanced charge carrier mobilities when the fraction of PC61BM was increased.
The charge carrier mobilities were measured as follows.
The hole and electron mobilities of devices with different annealing durations were measured by the space-charge-limited current (SCLC) method using hole-only devices and electron-only devices, respectively. The device structure of the hole-only device was ITO/PEDOT:PSS/active layer/MoO3/Au while the electron-only device was composed of ITO/PFN/active layer/Al. The SCLC model is described by the following Mathematical Formula 5:
wherein ε0 is the vacuum permittivity (8.85×1012 F/m), εr is the relative dielectric constant of the polymer blends (assumed as 3), μ0 is the zero-field mobility, L is the thickness of the active layer, and β is the characteristic field constant. The experimentally obtained J-V characteristics were plotted as ln(Jd3/V2) vs. (V/d)0.5 to obtain μp through the slope and y-intercept value.
In relation thereto,
Ultimately, the PTB7:PCDTBT:PC71BM:PC61BM composition yielding the maximum PCE was experimentally found to be 0.9:0.1:1.2:0.3 (hereinafter, designated for quaternary organic photovoltaics).
The maximum PCE (8.42±0.12%) of the quaternary organic photovoltaic (q-OPV) was greater than those of other BHJ-OPVs including the 7.59±0.19% for the reference binary OPV made up of PTB7:PC71BM (b-OPV) and even the 8.20±0.08% for the optimized ternary OPV made up of PTB7:PCDTBT:PC71BM (t-OPV). The optimized quaternary composition was found to be responsible for the maximum Jsc and fill factor (FF), as shown in Table 3, below.
In addition,
The calculated Gmax agreed with the optically simulated value based on the E-field distribution in the active layer depicted in
Improvement of Stability in q-OPV Suppressing Early Loss in Performance
The q-OPV was beforehand confirmed to have sufficiently high efficiency and then examined for stability under elevated temperatures. The performance decay in OPVs is commonly characterized by two stages: (i) a drastic exponential decline in performance at an early stage of operation (known as burn-in loss period) and (ii) a subsequent gradual linear decay on a longer timescale.
As shown in the figures, b-, t- and q-OPVs operating at 65° C. were observed to display the expected exponential decays in photovoltaic parameters at the early stages of exposure (the average and standard deviation values obtained from more than 12 devices). The operating temperature is within the usual range of temperatures that outdoor applications of PVs are exposed to, and is comparable to or higher than the glass transition temperatures of typical conjugated polymers.
The thermal stress at such real OPV operating temperatures initially induces nanoscale grain growth rather than micron-size features. As a result, it was assumed that the nanoscale grain growth and structural disorder increase contributed mainly to the observed abrupt decrease in Jsc and FF. Compared with other parameters, VOC appeared to be nearly constant throughout the operation, which can be explained by the VOC being independent of the nano-grain growth.
Consequently, the q-OPV retained a PCE of up to 84.7% of the initial value even after 8 hours of operation, and this value was much higher than the corresponding 72.1% and 65.6% values for the t- and b-OPVs, respectively. Interestingly, a heat-dependent property showed that the performance decay of the b-OPV was accelerated at around 65° C. while the q-OPV displayed a better resistance to the decay even at elevated temperatures over 65° C., as shown in
The enhanced internal quantum efficiency (IQE) spectrum in the q-OPV was consistent with the J-V result regardless of the duration of the operation. In this regard, time-dependent IQE spectra and IQE-PCE characteristics are depicted in
Considering that IQE is associated with the internal carrier transport process (strongly governed by nanomorphology), the q-OPV was apparently superior in suppressing the undesirable nanoscale crystallization and aggregation of the donor polymers and fullerenes, respectively, in the early stages of the photovoltaic operation.
Then, to examine whether the nano-grain growth was impeded, 2D GIWAXS (two-dimensional grazing-incidence wide-angle X-ray scattering) analysis of the active layer measured at different operation times was carried out.
In this regard, 2D GIWAXS analysis was carried out according to the following procedure.
GIWAXS measurements were taken at the Pohang Accelerator Laboratory (PAL) using the 5 A beam line and the samples for measurements were prepared as follows:
The polymer-fullerene blends with different compositions of materials were applied onto ITO-glass/PFN substrate, followed by encapsulation in a nitrogen atmosphere before annealing. The angle of incident X-rays was 0.13° and the incident photon energy was 11.57 keV. To minimize air scattering, samples were mounted in a helium ambient chamber. The in-plane GIWAXS profiles were fitted to a superposition of four Pearson VII functions for organic materials peaks and one exponentially decaying profile for the background. The peaks were assigned based on Collins, B. A., Li, Z., Tumbleston, J. R., Gann, E., McNeill, C. R. & Ade, H. Absolute measurement of domain composition and nanoscale size distribution explains performance in PTB7:PC71BM solar cells. Adv. Energy Mater. 3, 65-74 (2013), which is incorporated by reference herein.
The 2D GIWAXS analysis results are depicted in
As shown in
In the figure and table, nano-grain sizes were calculated from the measured FWHM values and FF (0.94) by using the Scherrer equation.
With reference to Table 4 and
The increases in both hole mobility (μh) and electron mobility (βe) were suppressed for the quaternary device, but not for the binary and ternary devices (see
Raman Spectroscopy Analysis
To uncover the origin of the reduction in the nanoscale grain growth rate in the q-OPVs, the Raman spectroscopy technique was used to explore vibrational modes of molecules and provide insight into polymer ordering and domain segregation. Raman analysis was conducted according to the following procedure.
The samples for Raman measurement were prepared as they had been for GIWAXS measurement. The Raman measurement was conducted using an inVia Raman microscope (Renishaw). The excitation source was 532 nm laser, and an acquisition time was minimized as 1 sec to reduce the photo-degradation of the polymer-fullerene blends during measurement. In order to interpret the changes in the Raman spectrum at around 1450 cm−1, the first-principle calculations of PTB7 and PC71BM was performed by using the Plane-Wave Self-Consistent Field (PWscf) and PHonon codes of the Quantum ESPRESSO distribution with the projector-augmented wave (PAW) method and Perdew-Burke-Ernzerhof (PBE) exchange-correlation function. The energy cutoff of 50 Rydberg was used for the molecular structure relaxations and the Raman spectrum calculations.
Based on the experimental results, two vibrational normal modes were considered at 1457 cm−1 and 1441 cm−1 for PC71BM and PTB7, respectively.
As shown in
Long-term Stability and Thermal Stability of q-OPV
OPVs were characterized and tested for long-term stability as follows.
The J-V characteristics of the OPVs were recorded using a source meter (Keithley 2400) under an Air Mass 1.5 Global (AM 1.5G) illumination with an intensity of 100 mWcm−2. White light was provided by a solar simulator (XES-301S, SAN-EI ELECTRIC) with a 300 W Xe lamp. The light source was carefully adjusted by using a silicon reference cell calibrated by the National Renewable Energy Laboratory (NREL). The EQE spectra were monitored using a K3100 Spectral IPCE Measurement System equipped with a 300 W Xe light source and monochromator (McScience). The IQE spectra were obtained based on IQE=EQE/(1-R-parasitic absorption), where the experimentally obtained spectral EQE and R values were used. The film absorption spectra of the active layers prepared on a quartz substrate were obtained using a Cary 5,000 UV-Vis-NIR spectrophotometer (Varian). For the thermal stability test, the devices with full encapsulation were stored on a digital hot plate preheated to a desired temperature (65 or 120° C.) in dark ambient conditions, and the photovoltaic performance was obtained repeatedly under AM 1.5G illumination (repeated cycles of dark thermal annealing and device testing at room temperature). It was assumed that the performance decay primarily resulted from the degradation within the active layer under the thermal stress because effects from other external factors (for example, exposure to oxygen or humidity) were minimized after encapsulation. All measurements were conducted using encapsulated devices under ambient conditions unless otherwise stated.
Following the drastic reduction in the performance of the devices at first use (for example, within about 1 day), their performances then exhibited a moderate decrease over a longer timescale of more than 30 days. It has been conjectured that the long-term performance decay mechanism (after 1 day) would differ from that within one day. Accordingly, the OPVs annealed for one day were assigned as a reference for long-term stability analysis. In contrast to the mechanism for the initial (about 1 day) decay, the main mechanism for the long-term decay in the photovoltaic performances would be the diffusion-limited phase separation driven by coalescence, which is a process governed by spinodal decomposition of the immiscible blends. To compare in detail the phase-separated morphologies in the BHJs, extraction was made of the correlation length scale from the blends, which is strongly associated with the overall domain size.
Calculation of numerical domain sizes was conducted as follows.
For the detailed analysis of the phase-separated morphology of the BHJ active layer, the domain size was extracted using image-analysis of the 2D distribution of the orientation angle of the phase ((p) measured by AFM. The tapping-mode phase images of the active layers were obtained using an XE-100 AFM (Park Systems). Considering that the difference in the phase angle is proportional to the compositional difference, it is instructive to quantify the spatial scale of the composition distribution using the pair-correlation function, g(r). This function may be defined by the following Mathematical Formula 6:
The function allows for a determination of the long-range order of the system. In the mathematical formula, r is the 2D coordinates in the system, the bracket denotes values averaged over the system, and
In
Of the drawings,
By applying the 2D phase value (φ(r)) to the pair-correlation function (g(r)), the correlation lengths in the x (Lcor,x) and y (Lcor,y) directions were obtained (
With reference to the figures, the correlation length was found to increase in both the x and y directions more prominently in the b-OPV than in the q-OPV. This result was supported by analyzing the 2D FFT patterns of the AFM phase image. As shown in
As a consequence of those analyses, the q-OPV was found to be advantageous in retaining a high PCE for the extremely extendable operation duration as can be seen in
In relation thereto,
In contrast to the foregoing results, the PCE of b-OPV fell to less than 80% of the reference PCE after this time period (see time-dependent VOC, Jsc and FF of b- and q-OPVs in
Interestingly, the notable inhibition of phase separation in the q-OPV also occurred in harsh temperature conditions. The q-OPV after one month at 120° C. retained 72.4% of its reference PCE, in contrast to a retention of only about 58.3% for the b-OPV (
Next, the overall average domain size (Hinter) was obtained from the calculated correlation length scale. In relation thereto, test results of long-term durability are depicted in
As can be seen in
The q-OPV also exhibited such beneficial features under the extremely harsh temperature condition (120° C.) as seen in
For the multi-component mixture (for example, having two or more D-A pairs), it is known that the difference between the diffusivities of each component induces a kinetic trapping effect that slows down the separation rate. For the q-OPV, the slowed-down phase separation also gave rise to a wider size distribution of nanodomains than did the b-OPV, which was also attributed to the greater difference between the diffusivities of the donor and the acceptor. This greater difference resulted in the kinetic trapping effect, which decreased the rate of phase separation. To compare the rates of phase separation of the b- and q-OPVs, the well-known kinetic model for the phase-separated domain governed by spinodal decomposition was employed such that Hinter(t)=Hinter(t0)+C(t−t0)1/3 (wherein C is the kinetic factor related to the Onsager mobility of the material and t0 is the reference time (chose here to be one day). As a result of the analysis, it was found that the C was 0.382 day−1/3 for the q-OPV, a value four times smaller than the 1.52 day−1/3 for the b-OPV.
Notably, the phase separation rate (Γe) can be derived from the relationship Γc=1/tc, wherein the characteristic timescale for the phase separation (tc) can be obtained from the relationship tc=t0+C−3 based on Hinter(t)=Hinter(t0)+[(t−t0)/(tc−t0)]1/3. Quantitatively, using the calculated C, it was found that the phase separation rate for the q-OPV was much slower than that for the b-OPV by a factor of 14.7 (for example, Γc: 0.053 day−1 for the q-OPV versus 0.779 day−1 for the b-OPV). It has been well known that the domain size and its growth rate are strongly associated with the photovoltaic performance. An additional work progress was made to numerically obtain the photovoltaic parameters that depend on the Hinter (influencing the exciton transport dynamics). To this end, the modified drift-diffusion equation for the charge carriers and the Poisson equation for the electric potential were utilized. From the numerical calculations, the time-dependent open-circuit voltage (VOC), short-circuit current density (Jsc), fill factor (FF), and power conversion efficiency (PCE) values can be obtained from the Hinter. The results are depicted in
In
As discussed above, the employed model could be statistically verified in analyzing the effect of the change in morphology on the photovoltaic parameters. Additional application was made of the model to anticipate the long-term (for example, one year) thermal stability of the q-OPV. By extrapolating the Hinter the photovoltaic parameters as well as the life expectancy of OPVs for such a long duration operation can be obtained.
Notably, it is strongly expected that the q-OPV will not reach the T60 point even after one year of operation, whereas the b-OPV was estimated to reach the T60 point within one month. Therefore, a highly extended life expectancy of more than several years can be anticipated for the q-OPV. The long-term stability of the q-OPV and its superior photovoltaic performances strongly suggest that this OPV can be used in outdoor applications with commercially acceptable quality.
While the present invention has been described with reference to the embodiments, it will be understood by a person skilled in the art that the present invention may be changed and modified without departing from the scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2016-0128790 | Oct 2016 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2017/010024 | 9/13/2017 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2018/066826 | 4/12/2018 | WO | A |
| Number | Date | Country |
|---|---|---|
| 20130027213 | Mar 2013 | KR |
| 20150072731 | Jun 2015 | KR |
| 20160027958 | Mar 2016 | KR |
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| International Search Report; PCT/KR2017/010024; dated 2017. |
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| Jiayu Qiu, et al.; Journal of Photopolymer Science and Technology; “Bulk-Hertojunction Solar Cells Based on Ternary Blend Active Layers ofPTB 7, PC61BM, and PC7 1BM”; vol. 28, No. 3; 2015. |
| Number | Date | Country | |
|---|---|---|---|
| 20200168801 A1 | May 2020 | US |
