CN115394922A - Visible light transparent solar cell with high photon utilization efficiency and preparation method thereof - Google Patents
Visible light transparent solar cell with high photon utilization efficiency and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a visible light transparent solar cell with high photon utilization efficiency and a preparation method thereof. The cell comprises a broadband antireflection coating, a substrate, a first transparent electrode, a first transmission layer, an active layer, a second transmission layer, a second transparent electrode and a band-pass filter which are sequentially stacked; band pass filter is formed by low refracting index photonic crystal material layer and high refracting index photonic crystal material layer range upon range of in turn, the number of piles of low refracting index photonic crystal material layer is greater than the number of piles of high refracting index photonic crystal material layer, low refracting index photonic crystal material layer with the laminating of the transparent electrode of second sets up. By stacking the photonic crystal material layer with high and low refractive index and non-periodic thickness on the second transparent electrode, the integrated transparent electrode of the band-pass filter with high transmission of 400-700nm and total reflection performance of 700-1100nm in the whole visible light is obtained, so that the photon utilization efficiency and the color rendering index of the transparent solar cell are remarkably increased.
Description
Technical Field
The invention relates to the field of solar cells, in particular to a visible light transparent solar cell with high photon utilization efficiency and a preparation method thereof.
Background
Organic solar cells have advantages such as light weight, solution processability, inherent flexibility, transparency, and the like, and have received wide attention from researchers. In the past decade or more, enormous efforts including material design, morphology control, interface regulation and device engineering have resulted in energy conversion efficiencies approaching 20%. As an important extension of practical applications, transparent organic solar cells have unique advantages as building integrated photovoltaics, such as electrical building windows, automobile skylights, greenhouse roofs, wearable electronics, and the like. Perovskite (organic-inorganic hybrid, pure inorganic) solar cells are another novel thin film photovoltaic technology, and since 2009, the energy conversion efficiency reaches 25.7%, which is close to that of single crystal silicon solar cells, and meanwhile, the perovskite solar cells also have potential in transparent solar cell applications.
In recent years, a transparent organic solar cell having high photon utilization efficiency (energy conversion efficiency X average visible light transmittance) has been remarkably developed. Transparent solar cells with photon utilization efficiencies of 4.9% have been reported (Proceedings of the National Academy of Sciences of the United States of America,117 (2020) 21147-21154). Various strategies have been developed to build visible light, neutral color transparent organic solar cells for building integrated photovoltaic applications. Non-fullerene acceptor materials with strong near-infrared absorption but weak visible absorption were designed and developed and proved to be an effective strategy to improve the trade-off between energy conversion efficiency and color rendering index of transparent organic solar cells. Furthermore, adjusting the proportion of donor or acceptor materials in the active layer has proven to be an effective way to balance the electrical and optical properties. Visible light, neutral color transparent organic solar cells can also be efficiently fabricated using sequential deposition processing strategies. Recently, ternary and quaternary strategies have also been widely used to adjust the absorption and morphology of the relevant active layers to increase the energy conversion efficiency and adjust the color rendering index of transparent organic solar cells. In addition, the combination of optical engineering in the design of electrode materials and optical structures has also proven to be an effective method for adjusting the color rendering index.
These above-described results provide a number of ways to more efficiently distribute the internal light field across the device, thereby producing more visible light, particularly neutral colors, in human vision applications. To date, the problem of how to effectively utilize near infrared to achieve the efficiency of a visible light transparent solar cell while having high transparency in the visible light region has not been effectively solved. Therefore, an effective approach to solve this trade-off problem needs to be further explored to improve both the photovoltaic performance and the neutral color perception of transparent organic solar cells.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide a visible light transparent solar cell with high photon utilization efficiency and a method for manufacturing the same, which aims to solve the problem of low photon utilization efficiency of the conventional visible light transparent solar cell.
The technical scheme of the invention is as follows:
in a first aspect of the present invention, a visible light transparent solar cell with high photon utilization efficiency is provided, wherein the visible light transparent solar cell comprises a broadband antireflection coating, a substrate, a first transparent electrode, a first transmission layer, an active layer, a second transmission layer, a second transparent electrode, and a band-pass filter, which are sequentially stacked;
the broadband antireflection coating is formed by alternately laminating a high-refractive-index photonic crystal material layer and a low-refractive-index photonic crystal material layer, the number of layers of the low-refractive-index photonic crystal material layer is equal to that of the high-refractive-index photonic crystal material layer, and the high-refractive-index photonic crystal material layer is attached to the substrate;
the band-pass filter is formed by alternately laminating a low-refractive-index photonic crystal material layer and a high-refractive-index photonic crystal material layer, the number of layers of the low-refractive-index photonic crystal material layer is larger than that of the high-refractive-index photonic crystal material layer, and the low-refractive-index photonic crystal material layer is attached to the second transparent electrode.
Optionally, the low refractive index photonic crystal material is LiF or MgF 2 (ii) a The high-refractive-index photonic crystal material is TeO 2 、TiO 2 Or Ta 2 O 5 。
Optionally, in the broadband antireflection coating, the number of layers of the high refractive index photonic crystal material layer is 4 to 6, and the number of layers of the low refractive index photonic crystal material layer is 4 to 6.
Further optionally, in the broadband antireflection coating, the number of layers of the high refractive index photonic crystal material layer is 4, the number of layers of the low refractive index photonic crystal material layer is 4, and the high refractive index photonic crystal material is TeO 2 And the low-refractive-index photonic crystal material is LiF.
Optionally, in the bandpass filter, the number of layers of the low refractive index photonic crystal material layer is 9 to 13, and the number of layers of the high refractive index photonic crystal material layer is 8 to 12.
Further optionally, in the band pass filter, the number of layers of the low refractive index photonic crystal material layer is 9, the number of layers of the high refractive index photonic crystal material layer is 8, the low refractive index photonic crystal material is LiF, and the high refractive index photonic crystal material is TeO 2 。
Optionally, the active layer is a heterojunction structure composed of an electron donor material and an electron acceptor material, wherein the electron donor material is selected from polymer materials, and the electron acceptor material is selected from at least one of non-fullerene materials.
Further optionally, the polymer material is PM6, PTB7-Th or PBDB-T; the non-fullerene material is Y-series receptors (such as BTP-eC9, L8-BO, Y6, Y1), ITIC series receptors (such as ITIC, ITIC-4F, IT-M) and IEICO-4F; the mass ratio of the electron donor material to the electron acceptor material is in the range (0.2-1.2) to 1.2, such as 0.2:1.2, 0.4, 1.2, 0.6, 1.2, and 1.2.
Still further optionally, the polymer material is PM6, the non-fullerene material is both BTP-eC9 and L8-BO, and the mass ratio of PM6, BTP-eC9 and L8-BO is 0.8.
In a second aspect of the present invention, a method for manufacturing a visible light transparent solar cell with high photon utilization efficiency is provided, wherein the method comprises the following steps:
providing a substrate, wherein the substrate is provided with a first surface and a second surface which are oppositely arranged, and the first surface is provided with a first transparent electrode;
forming a broadband anti-reflection coating on the second surface;
forming a first transmission layer on the first transparent electrode;
forming an active layer on the first transport layer;
forming a second transport layer on the active layer;
forming a second transparent electrode on the second transport layer;
forming a band pass filter on the second transparent electrode;
the broadband antireflection coating is formed by periodically and alternately laminating a high-refractive-index photonic crystal material layer and a low-refractive-index photonic crystal material layer, the number of layers of the low-refractive-index photonic crystal material layer is equal to that of the high-refractive-index photonic crystal material layer, and the high-refractive-index photonic crystal material layer is attached to the substrate;
the band-pass filter is formed by non-periodically and alternately laminating a low-refractive-index photonic crystal material layer and a high-refractive-index photonic crystal material layer, the number of layers of the low-refractive-index photonic crystal material layer is larger than that of the high-refractive-index photonic crystal material layer, and the low-refractive-index photonic crystal material layer is attached to the second transparent electrode.
Has the beneficial effects that: the invention provides a novel band-pass filter integrated transparent electrode, a visible light neutral transparent solar cell with high photon utilization efficiency and a preparation method thereof, wherein the novel band-pass filter integrated transparent electrode comprises a high-refractive-index photonic crystal material layer, a low-refractive-index photonic crystal material layer and a transparent electrode; by stacking the aperiodic photonic crystal material layers with high refractive index and low refractive index on the transparent electrode, the novel band-pass filter integrated transparent electrode with the performance of high transmission of 400-700nm, total reflection of 700-900nm and even total reflection of 700-1100nm in the whole visible light is obtained. The band-pass filter integrated transparent electrode can remarkably increase the photon utilization efficiency and the color rendering index of the transparent solar cell in a transparent photovoltaic device, and further promotes the commercialization process of the transparent solar cell.
Drawings
Fig. 1 is a schematic structural diagram of a transparent organic solar cell according to embodiment 1 of the present invention.
Fig. 2 is a schematic structural diagram of a transparent organic solar cell according to embodiment 2 of the present invention.
FIG. 3 is a normalized absorption curve of the electron donor material PM6, the electron acceptor material BTP-eC9, and L8-BO of a single component in the examples.
FIG. 4 is a graph comparing glass transmittance to broadband antireflection coating integrated glass transmittance.
Fig. 5 is a graph of transmittance of an ultra-thin silver transparent cathode of 12nm thickness compared to transmittance of a band pass filter integrated silver transparent cathode.
Fig. 6 compares the photovoltaic performance of a transparent organic solar cell with an ultra-thin silver transparent cathode of 12nm thickness with a transparent solar cell with a bandpass filter integrated with a silver transparent cathode. (a) a current density-voltage characteristic curve; (b) an external quantum efficiency curve; (c) a transmittance curve; (d) CIE1931 chromaticity diagram coordinate; (e) Photograph of live-action taken of transparent solar cell and (f) statistical comparison of photon utilization efficiency of this document with reported references.
Detailed Description
The present invention provides a visible light transparent solar cell with high photon utilization efficiency and a method for manufacturing the same, and the present invention is further described in detail below in order to make the objects, technical solutions and effects of the present invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The embodiment of the invention provides a visible light transparent solar cell with high photon utilization efficiency, which comprises a broadband antireflection coating, a substrate, a first transparent electrode, a first transmission layer, an active layer, a second transmission layer, a second transparent electrode and a band-pass filter, wherein the broadband antireflection coating, the substrate, the first transparent electrode, the first transmission layer, the active layer, the second transmission layer, the second transparent electrode and the band-pass filter are sequentially stacked;
the broadband antireflection coating is formed by alternately laminating a high-refractive-index photonic crystal material layer and a low-refractive-index photonic crystal material layer, the number of layers of the low-refractive-index photonic crystal material layer is equal to that of the high-refractive-index photonic crystal material layer, and the high-refractive-index photonic crystal material layer is attached to the substrate;
band pass filter is formed by low refracting index photonic crystal material layer and high refracting index photonic crystal material layer range upon range of in turn, the number of piles of low refracting index photonic crystal material layer is greater than the number of piles (aperiodic range) of high refracting index photonic crystal material layer, low refracting index photonic crystal material layer with the laminating of second transparent electrode sets up.
In this embodiment, the broadband antireflection coating is composed of high and low refractive index photonic crystal materials alternately stacked periodically, and the bandpass filter is composed of high and low refractive index photonic crystal materials alternately stacked non-periodically.
In this embodiment, by introducing the optical structure of the band-pass filter, the band-pass filter has a high transmittance of 400-700nm in the whole visible light range, and the optical performance and color rendering index of total reflection of 700-1100nm are close to 100, so that the transmittance of the integrated transparent solar cell in the visible light range is improved due to the multilayer optical interference effect, that is, the average visible light transmittance is improved, and meanwhile, the total reflection characteristic of near infrared light enables near infrared light to be reflected back to the active layer to generate more photocurrents, that is, the short-circuit current is improved, so that the photon utilization efficiency and the color rendering index of the transparent solar cell are improved, and further commercialization of the transparent solar cell for visible light is facilitated.
First, the visible light transparent solar cell in this embodiment may be a visible light transparent organic solar cell (the active layer material is an organic material), or may be a visible light transparent perovskite solar cell (the active layer material is an organic-inorganic hybrid material or an inorganic material). In addition, the visible light transparent solar cell in this embodiment may be a visible light transparent solar cell with an upright structure, or may be a visible light transparent solar cell with an inverted structure.
When the transparent solar cell of visible light is just putting the transparent solar cell of visible light of structure, first transparent electrode is transparent anode, first transmission layer is the hole transport layer, the transparent electrode of second is transparent cathode, the second transmission layer is electron transport layer, promptly just putting the transparent solar cell of visible light of structure including range upon range of broadband antireflection coating, basement, transparent anode, hole transport layer, active layer, electron transport layer, transparent cathode and the band-pass filter that sets up in proper order.
Work as during the transparent solar cell of visible light is the transparent solar cell of the structure of inverting, first transparent electrode is transparent cathode, first transport layer is electron transport layer, the transparent electrode of second is transparent anode, first transport layer is the hole transport layer, promptly the transparent solar cell of the structure of inverting includes the broadband antireflection coating, basement, transparent cathode, electron transport layer, active layer, hole transport layer, transparent anode and the band pass filter that stack gradually the setting.
The present invention will be described in detail below by taking a visible light transparent organic solar cell of a front-mounted structure as an example.
Fig. 2 is a schematic structural diagram of a visible light transparent organic solar cell with a front-mounted structure according to an embodiment of the present invention. As shown in fig. 2, the visible light transparent organic solar cell includes: a broadband antireflection coating 1, a substrate comprising a transparent anode (the transparent anode is arranged on one surface of the substrate far away from the broadband antireflection coating) 2, a hole transport layer 3, an active layer 4, an electron transport layer 5, a transparent cathode 6 and a band-pass filter 7;
the broadband antireflection coating 1 is formed by alternately laminating a high-refractive-index photonic crystal material layer 12 and a low-refractive-index photonic crystal material layer 11, the number of layers of the low-refractive-index photonic crystal material layer 11 is equal to that of the high-refractive-index photonic crystal material layer 12, and the high-refractive-index photonic crystal material layer 12 is attached to the substrate 2 containing the transparent anode;
In this embodiment, the low refractive index photonic crystal material refers to a photonic crystal material having a refractive index of less than 1.4. In one embodiment, the low refractive index photonic crystal material is LiF or MgF 2 ；
In this embodiment, the high refractive index photonic crystal material refers to a photonic crystal material having a refractive index greater than 1.8. In one embodiment, the high refractive index photonic crystal material is TeO 2 、TiO 2 Or Ta 2 O 5 。
Further in one embodiment, the low refractive index photonic crystal material is LiF and the high refractive index photonic crystal material is TeO 2 。
In one embodiment, in the broadband antireflection coating, the number of layers of the high refractive index photonic crystal material layer is 4 to 6, and the number of layers of the low refractive index photonic crystal material layer is 4 to 6. By stacking different layers of materials with high and low refractive indexes and adjusting the thickness, the broadband antireflection coating can be obtained due to the interference effect of the multilayer thin film. The broadband antireflection coating obtained by vacuum deposition has excellent optical properties and structural stability.
In one embodiment, the number of layers of the high refractive index photonic crystal material layer is 4, the number of layers of the low refractive index photonic crystal material layer is 4, and the high refractive index photonic crystal material is TeO 2 The low-refractive index photonic crystal material is LiF. Using the broadband antireflection coating, it is possible toThe broadband antireflection transmission spectrum distribution of the 400-1000nm is realized.
In the broadband antireflection coating of the embodiment, the optimal thicknesses of the low refractive index photonic crystal material layer and the high refractive index photonic crystal material layer can be obtained by using a simulated annealing optimization algorithm of optical thin film design software, so that the broadband antireflection transmission spectrum distribution of 400-1000nm is realized. It should be noted that, the thicknesses of the photonic crystal material layers with different low refractive indexes are different, and the thicknesses of the photonic crystal material layers with different high refractive indexes are different, and a better thickness is optimized through software to obtain the functions required to be realized.
In one embodiment, the number of layers of the low refractive index photonic crystal material layer is 9 to 13 and the number of layers of the high refractive index photonic crystal material layer is 8 to 12. The number of stacked layers is selected to be more than 8 pairs, so that the transmission spectrum distribution of high transmittance of 400-700nm and total reflection of 700-1100nm can be realized.
In one embodiment, in the bandpass filter, the number of layers of the low refractive index photonic crystal material layer is 9, the number of layers of the high refractive index photonic crystal material layer is 8, the low refractive index photonic crystal material is LiF, and the high refractive index photonic crystal material is TeO 2 . The number of stacked layers is about 8, so that high transmittance of 400-700nm is realized, the loss of cost is reduced while the total reflection transmission spectrum distribution of 700-900nm is realized, and the stacked photonic crystal material is easy to fall off due to excessive number of stacked layers, so that the structure is unstable.
In the bandpass filter of the present embodiment, the optimal thicknesses of the low refractive index photonic crystal material layer 71 and the high refractive index photonic crystal material layer 72 can be obtained by using a simulated annealing optimization algorithm of optical thin film design software, so as to realize a transmission spectrum distribution of high transmittance of 400-700nm and total reflection of 700-1100 nm. It should be noted that, the thicknesses of the photonic crystal material layers with different low refractive indexes are different, and the thicknesses of the photonic crystal material layers with different high refractive indexes are different, and the optimal thickness is optimized through software to obtain the functions to be realized.
Specifically, the preliminarily determined formula of the low refractive index photonic crystal material layer and the high refractive index photonic crystal material layer stacked in the bandpass filter is:
η L d L ＝η H d H ＝λ 0 /4
wherein eta L 、η H Respectively, a low refractive index photonic crystal material (such as LiF) and a high refractive index photonic crystal material (such as TeO) 2 ) Refractive index of (d) L 、d H A low refractive index photonic crystal material layer (such as LiF layer) and a high refractive index photonic crystal material layer (such as TeO layer), respectively 2 Layer) thickness, λ 0 Is the center reference wavelength. The passband center reference wavelength, the passband wavelength width and the stopband wavelength width of the bandpass filter can be adjusted through simulation design through the multi-layer thickness of the low refractive index photonic crystal material layer and the high refractive index photonic crystal material layer so as to adapt to different solar cell systems.
In one embodiment, the active layer is a heterojunction structure of an electron donor material selected from a polymeric material and an electron acceptor material selected from at least one of a non-fullerene material.
In one embodiment, the polymeric material is one or more of PM6, PTB7-Th, and PBDB-T, among others.
In one embodiment, the non-fullerene material is one or more of the Y-series receptors (BTP-eC 9, L8-BO, Y6, Y1), the ITIC series (ITIC, ITIC-4F, IT-M), and IEICO-4F, among others.
In one embodiment, the mass ratio of the electron donor material to the electron acceptor material is in the range of (0.2-1.2) 1.2, such as 0.2, 1.2, 0.4, 0.6, 12, 0.8, 1.2 and 1.2. The absorption of the electron donor material is distributed in a visible light region, and the absorption strength of the electron donor material in the active layer in the visible light region can be regulated and controlled through proportion regulation, so that the average visible light transmittance and the energy conversion efficiency of the device are balanced.
In one embodiment, the electron donor material is PM6, the electron acceptor material is both BTP-eC9 and L8BO, and the mass ratio of PM6, BTP-eC9 and L8-BO is 0.8. Under the condition, the obtained solar cell has more excellent visible light transmittance and energy conversion efficiency.
Wherein, the chemical structural formula of PM6 is:
wherein, the chemical structural formula of BTP-eC9 is as follows:
wherein the chemical structural formula of L8-BO is as follows:
in one embodiment, the thickness of the active layer is 65-180nm, and the transmittance in the visible light region (the thinner the transmittance is higher) can be effectively adjusted to meet different practical application requirements by adjusting the thickness of the active layer.
Further in one embodiment, the polymer material is PM6, the non-fullerene material is both BTP-eC9 and L8-BO, the mass ratio of PM6, BTP-eC9 and L8-BO is 0.8. Under the condition, the obtained visible light transparent organic solar cell has higher photon utilization efficiency.
In this embodiment, the active layer may be prepared by spin coating an active layer solution. In one embodiment, the active layer solution preparation process is: the active layer solution is obtained by dissolving the electron donor material and the electron acceptor material in a solvent such as chlorobenzene, and adding an additive such as 1, 8-diiodooctane, the additive being 0.5% by volume of the active layer solution. Wherein the purpose of adding the additive is to optimize the morphology of the active layer.
In one embodiment, the hole transport layer is made of poly (3, 4-ethylenedioxythiophene)) Poly (styrenesulfonic acid) (abbreviated to PEDOT: PSS) and molybdenum trioxide (abbreviated to MoO) 3 ) One or more of (a).
In one embodiment, the hole transport layer has a thickness of 20 to 100nm.
In one embodiment, the material of the electron transport layer is one or more of 2, 9-bis (3- ((3- (dimethylamino) propyl) amino) propyl) -3,3' - (1, 3,8, 10-tetraanthraono [2,1,9-def:6,5,10-d ' e ' f ' ] diisoquinoline (abbreviated as PDINN), poly [ (9, 9-bis (3 ' - (N, N-dimethylamino) propyl) fluorenyl-2, 7-diyl) -ALT- [ (9, 9-di-N-octylfluorenyl 2, 7-diyl) -bromide (PFN-Br), and zinc oxide (abbreviated as ZnO).
In one embodiment, the electron transport layer has a thickness of 1nm to 50nm.
In one embodiment, the material of the transparent anode is metal (such as silver) or metal oxide (such as ITO, FTO, AZO, etc.), but is not limited thereto.
In one embodiment, the material of the transparent cathode is metal (e.g., silver) or metal oxide (e.g., ITO, FTO, AZO, etc.), but is not limited thereto.
In one embodiment, the transparent cathode has a thickness of 50 to 300nm.
Further in one embodiment, the material of the transparent cathode is silver, and the thickness of the transparent cathode is 12nm.
In one embodiment, the substrate is a glass substrate or a plastic substrate such as Polydimethylsiloxane (PDMS), polyester (PET), and polyethylene naphthalate (PEN).
The embodiment of the invention provides a preparation method of the visible light transparent solar cell with high photon utilization efficiency, which comprises the following steps:
providing a substrate, wherein the substrate is provided with a first surface and a second surface which are oppositely arranged, and the first surface is provided with a first transparent electrode;
forming a broadband anti-reflection coating on the second surface;
forming a first transmission layer on the first transparent electrode;
forming an active layer on the first transport layer;
forming a second transport layer on the active layer;
forming a second transparent electrode on the second transport layer;
forming a band pass filter on the second transparent electrode;
the broadband antireflection coating is formed by periodically and alternately laminating a high-refractive-index photonic crystal material layer and a low-refractive-index photonic crystal material layer, the number of layers of the low-refractive-index photonic crystal material layer is equal to that of the high-refractive-index photonic crystal material layer, and the high-refractive-index photonic crystal material layer is attached to the substrate;
the band-pass filter is formed by non-periodic alternate stacking of a low-refractive-index photonic crystal material layer and a high-refractive-index photonic crystal material layer, the number of layers of the low-refractive-index photonic crystal material layer is larger than that of the high-refractive-index photonic crystal material layer, and the low-refractive-index photonic crystal material layer is attached to the second transparent electrode.
For a detailed description of the layers, see above, no further details are given here.
In one embodiment, the broadband antireflection coating may be prepared by vacuum thermal evaporation.
In one embodiment, the bandpass filter can be prepared by vacuum thermal evaporation.
The invention is further illustrated by the following specific examples.
Example 1
Fig. 1 is a schematic structural diagram of the transparent organic solar cell in this embodiment. As shown in fig. 1, the transparent organic solar cell of the present embodiment includes: an ITO glass substrate 1, a hole transport layer 2, an active layer 3, an electron transport layer 4 and a transparent cathode 5.
The transparent organic solar cell of the present example was prepared as follows:
(1) The ITO glass is sequentially subjected to ultrasonic cleaning for 15 minutes in an ultrasonic cleaning machine by using deionized water, acetone and ethanol, and then is dried by using nitrogen;
(2) PSS solution is coated on the ITO surface of the ITO glass in a spinning mode, the rotating speed is 3500 revolutions per second, the time is 30 seconds, and then annealing is carried out for 15 minutes at the temperature of 150 ℃ on a heating table to obtain a hole transport layer with the thickness of 30 nm;
(3) And (3) introducing the prepared ITO glass with the hole transport layer into a glove box in a nitrogen atmosphere, and spin-coating an active layer solution on the hole transport layer at the spin-coating speed of 5000 revolutions per second for 30 seconds to obtain an active layer with the thickness of 120nm. The active layer is a binary system, the electron donor material is PM6, the electron acceptor material is BTP-eC9, and the mass ratio is 1.2; the preparation process of the active layer solution comprises the following steps: dissolving PM6 and BTP-eC9 in chlorobenzene, and adding additive 1, 8-diiodooctane (the volume ratio is 0.5%);
(4) Further, in a binary system, an electron donor material is PM6, an electron acceptor material is BTP-eC9, the mass ratio is 0.8: PM6 and BTP-eC9 were dissolved in chlorobenzene and additive 1, 8-diiodooctane (0.5% by volume) was added. Spin-coating the active layer solution on the hole transport layer at a spin-coating speed of 5000 rpm for 30 seconds to obtain an active layer with a thickness of 120nm;
(5) Further, in a binary system, an electron donor material is PM6, an electron acceptor material is BTP-eC9, the mass ratio is 0.5: PM6 and BTP-eC9 were dissolved in chlorobenzene and additive 1, 8-diiodooctane (0.5% by volume) was added. Spin-coating the active layer solution on the hole transport layer at a spin-coating speed of 5000 rpm for 30 seconds to obtain an active layer with a thickness of 120nm;
(6) Further, in a ternary system, an electron donor material is PM6, an electron acceptor material is BTP-eC9, another electron acceptor material is L8-BO, the mass ratio is 0.8: PM6, BTP-eC9 and L8-BO were dissolved in chlorobenzene and the additive 1, 8-diiodooctane (0.5% by volume) was added. Spin-coating the active layer solution on the hole transport layer at a spin-coating speed of 5000 revolutions per second for 30 seconds to obtain an active layer with a thickness of 120nm;
(7) Further, in a ternary system, an electron donor material is PM6, an electron acceptor material is BTP-eC9, the other electron acceptor material is L8-BO, the mass ratio is 0.5: PM6, BTP-eC9 and L8-BO were dissolved in chlorobenzene and additive 1, 8-diiodooctane (0.5% by volume) was added. Spin-coating the active layer solution on the hole transport layer at a spin-coating speed of 5000 revolutions per second for 30 seconds to obtain an active layer with a thickness of 120nm;
FIG. 3 is a graph showing the absorption distribution curves of a single-component thin film of an electron donor material and an electron acceptor material, wherein the absorption distribution of the electron donor material is in a visible light region, and the absorption intensity of the electron donor material PM6 in the active layer in the visible light region can be regulated and controlled by adjusting the proportion, so that the average visible light transmittance and the energy conversion efficiency of the device are balanced.
(8) Preparing a PDNN solution with the concentration of 1 milligram per milliliter, using methanol as a solvent, and spin-coating the PDNN solution on an active layer to be used as an electron transport layer, wherein the rotating speed is 3000 revolutions per second, and the time is 30 seconds to obtain the electron transport layer with the thickness of 10 nm;
(9) And transferring the device with the electron transport layer subjected to spin coating into a vacuum coating machine to thermally evaporate a silver transparent cathode at the evaporation rate of 3 angstroms per second and the thickness of 12nm, thereby preparing the traditional transparent solar cell.
Example 2
Fig. 2 is a schematic structural diagram of the transparent organic solar cell of the present embodiment. As shown in fig. 2, the transparent organic solar cell of the present embodiment includes: the broadband antireflection coating 1 (is formed by periodically and alternately laminating a high-refractive-index photonic crystal material layer 11 and a low-refractive-index photonic crystal material layer 12, the number of layers of the high-refractive-index photonic crystal material layer 11 and the low-refractive-index photonic crystal material layer 12 is 4), the ITO glass substrate 2, the hole transmission layer 3, the active layer 4, the electron transmission layer 5, the transparent cathode 6 and the band-pass filter 7 (is formed by non-periodically and alternately laminating a high-refractive-index photonic crystal material layer 71 and a low-refractive-index photonic crystal material layer 72, the number of layers of the high-refractive-index photonic crystal material layer 71 is 8, and the low-refractive-index photonic crystal material layer 71 is a low-refractive-index photonic crystal material layerThe number of layers of crystalline material layer 72 is 9). Wherein the high refractive index photonic crystal material is TeO 2 And the low-refractive index photonic crystal material is LiF.
The preparation steps of the transparent organic solar cell of the embodiment are as follows:
(1) The ITO glass is sequentially subjected to ultrasonic cleaning for 15 minutes in an ultrasonic cleaning machine by using deionized water, acetone and ethanol, and then is dried by using nitrogen;
(2) The cleaned ITO glass is transferred into a vacuum coating machine, and a low-refractive index photonic crystal material LiF and a high-refractive index photonic crystal material TeO are vacuum-evaporated on the glass surface of the ITO glass 2 And obtaining a LiF layer and TeO through the optimization design of a film design software simulated annealing optimization algorithm 2 The thicknesses of the layers, the thicknesses of the low-high refractive index material layers alternately stacked from bottom to top (i.e., in a direction away from the glass surface), are 115nm, 27nm, 22nm, 134nm, 13nm, 35nm, 32nm, and 16nm in this order, the LiF layer and the TeO layer 2 The evaporation rate of the layer is respectively 2 angstroms per second and 3 angstroms per second, so that the broadband antireflection coating is prepared;
(3) Putting the ITO surface of the ITO glass sheet subjected to vacuum thermal evaporation with the broadband antireflection coating into a plasma cleaning machine for cleaning for 3 minutes, then spin-coating PEDOT on the ITO surface, namely PSS solution, at the rotating speed of 3500 revolutions per second for 30 seconds, and then annealing for 15 minutes on a heating table at the temperature of 150 ℃ to obtain a hole transport layer with the thickness of 30 nm;
(4) And (3) introducing the prepared ITO glass with the hole transport layer into a glove box in a nitrogen atmosphere, and spin-coating an active layer solution on the hole transport layer at the spin-coating speed of 5000 revolutions per second for 30 seconds to obtain an active layer with the thickness of 120nm. The active layer is a ternary system, the electron donor material is PM6, the electron acceptor material is BTP-eC9 and L8-BO, and the mass ratio is 0.8; the preparation process of the active layer solution comprises the following steps: dissolving PM6, BTP-eC9 and L8-BO in chlorobenzene, and adding additive 1, 8-diiodooctane (the volume ratio is 0.5%);
(5) Preparing a PDINN solution with the concentration of 1 milligram per milliliter, using methanol as a solvent, and then spin-coating the PDINN solution on an active layer to be used as an electron transport layer, wherein the rotating speed is 3000 revolutions per second, and the time is 30 seconds, so that the electron transport layer with the thickness of 10nm is obtained;
(6) Transferring the ITO glass which is spin-coated with the electron transport layer into a vacuum coating machine to thermally evaporate a silver transparent cathode, wherein the evaporation rate is 3 angstroms per second, and the thickness is 12nm;
(7) The band pass filter was vapor deposited on a silver transparent cathode. The specific preparation steps of the band-pass filter are as follows: vacuum evaporation of low-refractive-index photonic crystal material LiF and high-refractive-index photonic crystal material TeO on surface of silver transparent cathode 2 The structure of the material is [ LiF/TeO ] 2 ] 8 LiF, and obtaining a LiF layer and TeO through optimization of a film design software simulated annealing optimization algorithm 2 The thicknesses of the layers, from bottom to top (i.e., in the direction away from the surface of the silver transparent cathode), of the alternately stacked low and high refractive index material layers are 145.90nm, 89.90nm, 149.20nm, 93.70nm, 150.30nm, 93.80nm, 150.30nm, 93.90nm, 151.20nm, 94.70nm, 152.10nm, 96.30nm, 154.40nm, 99.70nm, 162.80nm, 106.50nm and 84.30nm in this order, and a transmission spectrum distribution of high transmittance at 400-700nm and total reflection at 700-1100nm is obtained. Thus, the preparation of the transparent solar cell with high photon utilization efficiency based on the band-pass filter integrated transparent cathode is completed.
FIG. 4 is a graph comparing glass transmittance to transmittance of a broadband antireflection coated integrated glass, with the thicknesses of the specific layers summarized in Table 1 below.
TABLE 1 summary of layer thicknesses for broadband ARC
Fig. 5 is a graph comparing the transmittance of an ultra-thin silver transparent cathode of 12nm thickness to the transmittance of a bandpass filter integrated silver transparent cathode, the thickness of the specific layers being summarized in table 2 below.
TABLE 2 summary of thickness of layers of integrated transparent cathode of band pass filter
The transparent organic solar cell prepared in example 1 was tested for electrical properties under am1.5g simulated sunlight with an illumination intensity of 100 milliwatts per square centimeter, and the optimal photon utilization efficiency was obtained at an active layer thickness of 75nm, with the following transparent organic solar cell performance parameters: the short circuit current density is 17.44 milliamperes per square centimeter, the open circuit voltage is 0.853 volts, the fill factor is 74.93 percent, and the energy conversion efficiency is 11.15 percent. The optical performance of the relevant devices is tested by using an ultraviolet-visible spectrophotometer, the average visible light transmittance is 29.71%, the CIE1931 color coordinate is (0.281, 0.293) and the color rendering index is 80.27, and the photon utilization efficiency is 3.31% by calculation.
The electrical properties of the transparent organic solar cell prepared in example 2 were tested under am1.5g simulated sunlight at an illumination intensity of 100 milliwatts per square centimeter, and at an active layer thickness of 65nm, a short circuit current density of 16.00 milliamps per square centimeter, an open circuit voltage of 0.851 volts, a fill factor of 73.75%, and an energy conversion efficiency of 10.04% were obtained. Testing the optical performance of a related device by using an ultraviolet visible light spectrophotometer to obtain that the average visible light transmittance is 51.37 percent, the CIE1931 color coordinate is (0.309, 0.338) and the color rendering index is 86.45, calculating to obtain the photon utilization efficiency to be 5.16 percent, wherein the photon utilization efficiency value is the highest value when the average visible light transmittance exceeds 50 percent in the reported literature; at a thickness of 75nm of the active layer, a short circuit current density of 17.97 milliamps per square centimeter, an open circuit voltage of 0.854 volts, a fill factor of 74.54%, and an energy conversion efficiency of 11.44% were obtained. The optical performance of related devices is tested by an ultraviolet-visible spectrophotometer, the average visible light transmittance is 46.79%, the CIE1931 color coordinates are (0.305, 0.336) and the color rendering index is 85.39, the photon utilization efficiency is 5.35% through calculation, and the photon utilization efficiency value is the highest value in reported documents. When the thickness of the active layer is 140nm, the obtained short-circuit current density is 23.21 milliamperes per square centimeter, the open-circuit voltage is 0.853 volts, the filling factor is 76.29 percent, and the energy conversion efficiency is 15.10 percent. The optical performance of related devices is tested by an ultraviolet-visible spectrophotometer, the average visible light transmittance is 25.08%, the CIE1931 color coordinates are (0.278, 0.309) and the color rendering index is 77.97, the photon utilization efficiency is 3.79% by calculation, and the energy conversion efficiency value in the reported literature is the highest value when the average visible light transmittance exceeds 25%.
Fig. 6 is a comparison of the photovoltaic performance of the transparent organic solar cell with the band pass filter integrated transparent electrode, in which the mass ratio of the electron donor material, the electron acceptor material and the other electron acceptor material is 0.8 and the thickness of the active layer is 75nm, in the ternary system, the transparent organic solar cell with the ultrathin film silver transparent cathode having the thickness of 12nm is as follows. Included are (a) current density-voltage characteristics; (b) an external quantum efficiency curve; (c) a transmittance curve; (d) CIE1931 chromaticity diagram coordinates; (e) A photograph of a live view of a transparent solar cell and (f) a photon utilization efficiency statistical chart of this document and the reported references. It can be seen from the figure that the integration of the bandpass filter structure can effectively improve the photon utilization efficiency and the color rendering index of the transparent organic solar cell.
In conclusion, the method improves the photon utilization efficiency and the color rendering index of the transparent organic solar cell by combining the proportion regulation of the electron donor material and the electron acceptor material in the active layer material and the synergistic effect of the band-pass filter integrated transparent electrode, and the result shows that the method can greatly improve the photon utilization efficiency of the traditional transparent solar cell. Finally, a transparent solar cell with the photon utilization efficiency reaching 5.35% is obtained, and is the highest value in the reported literature at present.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A visible light transparent solar cell with high photon utilization efficiency is characterized by comprising a broadband antireflection coating, a substrate, a first transparent electrode, a first transmission layer, an active layer, a second transmission layer, a second transparent electrode and a band-pass filter which are sequentially stacked;
the broadband antireflection coating is formed by alternately laminating a high-refractive-index photonic crystal material layer and a low-refractive-index photonic crystal material layer, the number of layers of the low-refractive-index photonic crystal material layer is equal to that of the high-refractive-index photonic crystal material layer, and the high-refractive-index photonic crystal material layer is attached to the substrate;
band-pass filter is formed by low refracting index photonic crystal material layer and high refracting index photonic crystal material layer range upon range of in turn, the number of piles on low refracting index photonic crystal material layer is greater than the number of piles on high refracting index photonic crystal material layer, low refracting index photonic crystal material layer with the laminating of second transparent electrode sets up.
2. The high photon utilization efficiency visible light transparent solar cell of claim 1, wherein the low index photonic crystal material is LiF or MgF 2 (ii) a The high-refractive index photonic crystal material is TeO 2 、TiO 2 Or Ta 2 O 5 。
3. The high photon utilization efficiency visible light transparent solar cell of claim 1, wherein the number of layers of the high refractive index photonic crystal material layer is 4-6 and the number of layers of the low refractive index photonic crystal material layer is 4-6 in the broadband antireflection coating.
4. The high photon utilization efficiency visible light transparent solar cell of claim 3, wherein the number of layers of high refractive index photonic crystal material layers in the broadband antireflection coating is 4, the number of layers of low refractive index photonic crystal material layers is 4, and the high refractive index light is emittedThe material of the sub-crystal is TeO 2 And the low-refractive-index photonic crystal material is LiF.
5. The high photon utilization efficiency visible light transparent solar cell of claim 1, wherein the number of layers of the low refractive index photonic crystal material layer in the bandpass filter is 9-13, and the number of layers of the high refractive index photonic crystal material layer is 8-12.
6. The high photon utilization efficiency visible light transparent solar cell of claim 5, wherein the bandpass filter has 9 layers of the low refractive index photonic crystal material layer, 8 layers of the high refractive index photonic crystal material layer, the low refractive index photonic crystal material is LiF, and the high refractive index photonic crystal material is TeO 2 。
7. The high photon utilization efficiency visible light transparent solar cell of claim 1, wherein the active layer is a heterojunction structure of an electron donor material and an electron acceptor material, the electron donor material is selected from a polymer material, and the electron acceptor material is selected from at least one of non-fullerene materials.
8. The high photon utilization efficiency visible light transparent solar cell of claim 7 wherein the polymer material is one or more of PM6, PTB7-Th and PBDB-T; the non-fullerene material is one or more of Y-series receptors, ITIC series receptors and IEICO-4F; the mass ratio of the electron donor material to the electron acceptor material is in the range of (0.2-1.2): 1.2.
9. The high photon utilization efficiency visible light transparent solar cell of claim 8, wherein the polymer material is PM6, the non-fullerene material is two of BTP-eC9 and L8-BO, and the mass ratio of PM6, BTP-eC9 and L8-BO is 0.8.
10. A method for preparing the visible light transparent solar cell with high photon utilization efficiency according to any one of claims 1 to 9, comprising the following steps:
providing a substrate, wherein the substrate is provided with a first surface and a second surface which are oppositely arranged, and the first surface is provided with a first transparent electrode;
forming a broadband anti-reflection coating on the second surface;
forming a first transmission layer on the first transparent electrode;
forming an active layer on the first transport layer;
forming a second transport layer on the active layer;
forming a second transparent electrode on the second transport layer;
forming a band pass filter on the second transparent electrode;
the broadband antireflection coating is formed by periodically and alternately laminating a high-refractive-index photonic crystal material layer and a low-refractive-index photonic crystal material layer, the number of layers of the low-refractive-index photonic crystal material layer is equal to that of the high-refractive-index photonic crystal material layer, and the high-refractive-index photonic crystal material layer is attached to the substrate;
the band-pass filter is formed by non-periodically and alternately laminating a low-refractive-index photonic crystal material layer and a high-refractive-index photonic crystal material layer, the number of layers of the low-refractive-index photonic crystal material layer is larger than that of the high-refractive-index photonic crystal material layer, and the low-refractive-index photonic crystal material layer is attached to the second transparent electrode.
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