KR20170038397A - Solar cell of hybrid type and method for fabricating thereof - Google Patents

Abstract

A hybrid type solar cell is provided. Particularly, the solar cell has a hybrid shape where a perovskite semiconductor layer and a photoactive layer are combined. The photoactive layer may include a bulk heterojunction structure where an n-type polymer, an electron donor material, and an electron acceptor material are mixed. Accordingly, the electron mobility of a battery can be increased by additionally introducing an n-type polymer into the photoactive layer. In addition, optical sensitivity and FF in a near-infrared range can be improved through a structure where the perovskite semiconductor layer is bonded to the photoactive layer having improved electron mobility.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a hybrid solar cell and a method of manufacturing the hybrid solar cell.

The present invention relates to a solar cell, and more particularly, to a hybrid solar cell in which a photoactive layer including a perovskite semiconductor layer and an n-type polymer are combined, and a method of manufacturing the same.

As the need for environmentally friendly energy sources for the sustainable growth of human beings is emerging, the solar cell field has received great attention as a future energy source. Among them, the third generation solar cell is the most popular field recently due to its high absorption coefficient and easy process. Organic solar cell, which is the most representative of 3rd generation solar cells, is not only easy to fabricate devices by dissolving conjugated polymers with optically active substances in organic solvents, but also combines mechanical warpage and light weight. . As a result of these studies, organic solar cells have achieved a single efficiency of 10%, and materials having various light absorption regions ranging from visible light to infrared light have been developed. However, due to the low charge transfer of polymers, It is constrained.

In recent years, based on excellent electrical and optical characteristics, the organic hybrid perovskite shows a steep growth rate of up to 20% in only five years. This perovskite has high light absorption due to a direct transition band similar to an organic solar cell, and it can form a thin film having high crystallinity even by a simple solution process, Mobility and extremely low exciton binding energy. However, the high-performance perovskite developed to date has only the light absorbing ability in the visible light region, so that a significant portion of the sunlight corresponding to the infrared light region is not available. Therefore, in order to improve the performance of the current perovskite solar cell, to achieve the theoretical maximum performance and to increase the economic value, it is necessary to utilize a wider light absorption region.

In order to solve such a problem, recently, a method of combining a bulk hetero junction layer of an organic solar cell with perovskite has been reported. This method combines an organic solar cell having absorption in the infrared region and a perovskite solar cell having excellent absorption in the visible light region, and unlike the conventional tandem structure in series or parallel type, the two photoactive layers The process can be simplified and no current matching or voltage matching is required. However, the organic solar cell / perovskite-coupled solar cell reported so far still exhibits lower performance than the single perovskite solar cell due to the low charge mobility of the organic solar cell, and has been limited by many restrictions.

A problem to be solved by the present invention is to provide a solar cell capable of improving charge mobility and utilizing light in a wide light absorption region.

According to an aspect of the present invention, there is provided a semiconductor device including a first electrode, a second electrode disposed opposite to the first electrode, a perovskite semiconductor disposed between the first electrode and the second electrode, And a photoactive layer disposed between the perovskite semiconductor layer and the second electrode, wherein the photoactive layer is a bulk hetero junction in which an n-type polymer, an electron donor material, and an electron acceptor material are mixed, Type solar cell according to the present invention.

The n-type polymer may be a poly ((N, N'-bis (2-octyldodecyl) -naphthalene-1,4,5,8- 5'- (2,2'-bithiophene) (P (NDI2OD-T2)), polybenzimidazobenzonanthatroline (BBL), N, N'-difluorophenyl- Perylene tetracarboxylic diimide (DFPP), and polypyridoquinoxaline (polypyridoquinoxaline) may be used.

The electron donor material may be selected from the group consisting of 3,6-bis (5-bromothiophen-2-yl) -2,5-bis (2-hexyldecyl) pyrrole (3,4- (PDPP2T), poly-3-hexylthiophene (P3HT), poly-3-poly-3-octylthiophene (P3OT), polyparaphenylenevinylene (PPV) , Poly (2-methoxy, 5- (2-ethyl-hexyloxy) -1,4-phenylenevinylene) (MEHPPV) (MDMO-PPV), poly (2,1,3-benzothiadiazole-4,7-diyl (4,4-bis (2-ethylhexyl) -4H -Cyclopenta (2,1-b: 3,4-b`) dithiophene-2,6-diyl)) (PCPDTBT) and derivatives thereof.

The electron acceptor material fullerenes (fullerene), 6,6- phenylene -C ₆₁ - butyl rigs Acid methyl ester _{(PCBM (C 61)),} PCBM (C 60), PCBM (C 70), PCBM (C 71), _{PCBM (C 76), PCBM (} C 80), PCBM (C 82), indene-C60 bisadduct (ICBA) and 6,6-phenyl-butyl -C61- rigs Acid cholesteryl the fullerene is selected from the ester (PCBCR) derivative, Polybenzimidazole, perylene, and the like may be used.

And a hole transport layer disposed between the first electrode and the perovskite semiconductor layer.

The hole transport layer may comprise at least one of poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (PANI / CSA) polyaniline / poly PANI / PSS) and polyaniline / dodecylbenzene sulfonic acid (PANI / DBSA) at least one of the conductive polymer, molybdenum oxide (MoOx), vanadium oxide is selected from (V ₂ O _5), nickel oxide (NiO), and tungsten oxide ( WOx). ≪ / RTI >

And an electron transport layer disposed between the photoactive layer and the second electrode.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming a first electrode on a substrate; forming a perovskite semiconductor layer on the first electrode; forming a photoactive layer on the perovskite semiconductor layer And forming a second electrode on the photoactive layer, wherein the photoactive layer is a bulk heterojunction structure of an n-type polymer, an electron donor material, and an electron acceptor material. A method of manufacturing a solar cell can be provided.

The step of forming the photoactive layer includes the steps of: preparing a mixture by dissolving the n-type polymer, the electron donor and the electron acceptor material in an organic solvent, and applying the mixture to the perovskite semiconductor layer, To form a photoactive layer.

The organic solvent may be selected from the group consisting of chlorobenzene, dichlorobenzene, chloroform, diphenyl ether (DPE), diiodoctane (DIO), dimethylacetamide, DMAC) and N-methyl-2-pyrrolidone (NMP).

The organic solvent may include 1 to 10% by weight of diphenyl ether or diiodoctane based on the total weight of the organic solvent.

And forming a hole transport layer between the first electrode and the perovskite semiconductor layer.

And forming an electron transport layer between the photoactive layer and the second electrode.

The present invention can improve the external quantum efficiency and the performance of the battery by increasing the electron mobility of the cell by additionally introducing the n-type polymer into the photoactive layer.

Further, through the structure in which the perovskite semiconductor layer is combined with the photoactive layer having improved electron mobility, the photo sensitivity and the low fill factor (FF) can be improved in the near-infrared region.

However, the effects of the present invention are not limited to those mentioned above, and other effects not mentioned can be clearly understood by those skilled in the art from the following description.

1 is a cross-sectional view illustrating a structure of a hybrid type solar cell according to an embodiment of the present invention.
2 (a) to 2 (b) are schematic and sectional SEM images showing the structure of the solar cell manufactured in Example 1 of the present invention.
3 (a) to 3 (f) are TEM images and AMF images of the photoactive layer prepared in Example 1 of the present invention and Comparative Examples 1 to 2.
4 (a) to 4 (b) are graphs showing absorption coefficient and charge mobility measurement results of the photoactive layer prepared in Example 1 of the present invention and Comparative Examples 1 to 2. FIG.
5 (a) to 5 (c) are graphs showing current-voltage measurement results of the solar cell manufactured in Example 1 of the present invention and Comparative Examples 1 to 2.
6 (a) to 6 (c) show the photoelectric conversion efficiency (PCE), the fill factor (FF) and the external quantum efficiency (EQE) of the solar cell manufactured in Example 1 of the present invention and Comparative Examples 1 to 2 ). Fig.
7A to 7B are graphs showing current-voltage characteristics and external quantum efficiency according to the mixing ratio of the electron donor polymer and the electron acceptor polymer material of Example 1. FIG.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. Rather, the intention is not to limit the invention to the particular forms disclosed, but rather, the invention includes all modifications, equivalents and substitutions that are consistent with the spirit of the invention as defined by the claims. Like reference numerals throughout the specification denote like elements.

The present invention can provide a hybrid type solar cell in which a perovskite semiconductor layer and a photoactive layer of a bulk heterojunction structure are combined. Specifically, the hybrid type solar cell includes a perovskite semiconductor layer disposed on the first electrode, an electron donor material, an electron acceptor material And a n-type polymer, and a second electrode disposed on the photoactive layer.

1 is a cross-sectional view illustrating a structure of a hybrid type solar cell according to an embodiment of the present invention. A manufacturing method of the hybrid type solar cell of the present invention will be described with reference to FIG.

First, a step of forming the first electrode 100 on the substrate 10 may be performed. The substrate 10 may be a substrate having transparency for efficient light incidence. For example, a transparent inorganic substrate selected from a glass substrate, a quartz substrate, and a sapphire (Al ₂ O ₃ ) substrate, or a polyethylene terephthalate Polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polypropylene (PP), polyimide (PI), polystyrene And a transparent organic substrate selected from a combination of the above.

In the present invention, the first electrode 100 serves as an anode, and a material having a work function larger than that of the second electrode 500 may be used. Specifically, the first electrode 100 may be formed of a transparent conductive oxide layer or a conductive polymer. The transparent conductive oxide layer may be formed of, for example, indium tin oxide (ITO), fluorine doped tin oxide (FTO), indium zinc oxide (IZO), zinc oxide- Gallium oxide (ZnO-Ga ₂ O ₃ ) or zinc oxide-aluminum oxide (ZnO-Al ₂ O ₃ ). The conductive polymer may be, for example, polythiophene, polyacetylene, polypyrrole, polyaniline, poly (3,4-ethylenedioxythiophene) / poly (4- At least one selected from polyaniline / camphorsulfonic acid (PANI / CSA), polyaniline / poly (4-styrenesulfonate) (PANI / PSS) and polyaniline / dodecylsulfonic acid (PANI / DBSA) It can be either.

The first electrode 100 may be formed on the substrate 10 by an electron beam evaporation method, a sputtering method, or a thermal evaporation method. Do not.

The step of forming the hole transport layer 150 on the first electrode 100 may be performed before the step of forming the perovskite semiconductor layer 200 on the first electrode 100 .

The hole transport layer 150 may be configured such that holes separated from the photoactive layer 300 are transported to the first electrode 100 through the perovskite semiconductor layer 200. Specifically, the hole transport layer 150 may be formed of poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate), PEDOT / PSS ), Polyaniline / camphorsulfonic acid (PANI / CSA) polyaniline / poly (4-styrenesulfonate, PANI / PSS), polyaniline / dodecylbenzenesulfonic acid , PANI / DBSA) and at least one selected from at least one of the conductive polymer, molybdenum oxide (MoOx), vanadium oxide (V ₂ O _5), nickel oxide (NiO), and tungsten oxide (WOx) is selected from derivatives thereof The step of forming the hole transport layer 150 on the first electrode 100 may be performed by a dip coating method, a spin coating method, a spray coating method, coating method, a bar coating method, a doctor blade (doctor b but is not limited to, at least one method selected from lade method, inkjet printing method, screen printing method and gravure printing method.

Thereafter, a step of forming the perovskite semiconductor layer 200 on the first electrode 100 may be performed. The perovskite semiconductor layer 200 may be formed on the hole transport layer 150 when the hole transport layer 150 is formed on the first electrode 100. Referring to FIG.

The perovskite semiconductor layer may be a conventional perovskite semiconductor material. Perovskite has AMX ₃ (A, M: cation, X: anion) chemical formula and is a material showing semiconductor, nonconductor and superconducting phenomenon. The perovskite semiconductor layer in the present invention may be an organometallic halogen compound having a molecular formula C _n H _{2n + 1} NH ₃ MX ₃ . In this case, n is an integer of 1 to 20, and M is a group consisting of Pb, Sn, Ti, Nb, Zr, and Ce. And X may be halogen, fluorine (F), iodine (I), bromine (Br) and chlorine (Cl). But are not limited to, for example, CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbBr ₃ , CH ₃ NH ₃ PbI ₂ Cl or CH ₃ NH ₃ PbI ₂ Br. Since the perovskite semiconductor layer 200 has a high extinction coefficient in an exponential unit, the perovskite semiconductor layer 200 can exhibit an excellent light collecting effect and the photoelectric conversion efficiency of the solar cell to which the perovskite semiconductor layer 200 is applied can be improved. The perovskite semiconductor layer 200 may be formed by a conventional perovskite deposition method. For example, a solution process, a spin coating process, a chemical vapor deposition process, or a physical vapor deposition process may be used. have.

Then, the photoactive layer 300 may be formed on the perovskite semiconductor layer 200. The photoactive layer 300 may be a bulk heterojunction structure of an n-type polymer, an electron donor material, and an electron acceptor material. The photoactive layer 300 may function as a photoelectric conversion layer that absorbs light incident on the solar cell and separates excitons generated from the electron donor material into electrons and holes to generate current.

The electron donor material contained in the photoactive layer 300 may be an organic material that absorbs light. In an embodiment of the present invention, the electron donor material may include an organic material capable of effectively absorbing light in the near infrared range. . Specifically, the electron donor material may be at least one selected from the group consisting of 3,6-bis (5-bromothiophen-2-yl) 2H, 5H) -dione (5-bromothiophen-2-yl) -2,5-bis (2-hexyldecyl) pyrrolo [ -dione, PDPP2T), poly-3-hexylthiophene (P3HT), poly-3-octylthiophene (P3OT), polyparaphenylene vinylene poly-p-phenylenevinylene (PPV), poly (9,9'-dioctylfluorene), poly (2-methoxy, 5- (2-ethylhexyloxy) 4-phenylenevinylene, MEHPPV), poly (2-methyl, 5- (3 ', 7'-dimethyloctyl) Oxy-1,4-phenylene vinylene, MDMO-PPV), poly (2, 3, 2,1-b: 3,4-b`) dithiophene-2,6-dicarboxylic acid, Di (4-bis (2-ethylhexyl) -4H-cyclopenta (2,1-b: 3,4-b ') d at least one conjugated polymer selected from the group consisting of indium-2,6-diyl), PCPDTBT, and derivatives thereof.

The electron acceptor material contained in the photoactive layer 300 may be an organic material capable of receiving electrons from the electron donor material. Specifically, the electron acceptor material is a fullerene (fullerene), (6,6) - phenyl -C ₆₁ - butyl rigs Acid methyl ester _{(6,6-phenyl-C 61 -butyricacid} -methylester, PCBM (C 61)), PCBM (C ₆₀ ), PCBM (C ₇₀ ), PCBM (C ₇₆ ), PCBM (C ₈₀ ), PCBM (C ₈₂ ), indene-C60 bisadduct (1 ', 1'',4' among -di [1,4] methanonaphthaleno [5,6] fullerene-C60, ICBA) and 6,6-phenyl-butyl -C61- rigs Acid cholesteryl ester _{(6,6-phenyl-C 61 -butyricacidcholesterylester} , PCBCR) Any one selected from a fullerene derivative, polybenzimidazole (PBI), and perylene can be used. In one embodiment of the present invention, the mixing ratio of the electron donor material and the electron donor material may be in the range of 1: 1 to 1: 5 in terms of mass ratio. However, since the conditions optimized for each material are different, It can be adjusted by mixing ratio to show optimized performance.

The photoactive layer 300 of the present invention includes the n-type polymer as well as the electron donor material and the electron acceptor material. The n-type polymer is a material having a high charge mobility, which moves electrons transferred from the electron blocking material to move the electron mobility of the photoactive layer 300, thereby improving battery performance and power conversion efficiency have. Specifically, the n-type polymer is a poly ((N, N'-bis (2-octyldodecyl) -naphthalene-1,4,5,8-bis (dicarboxyimide) Bis (2-octyldodecyl) -naphthalene-1,4,5,8-bis (dicarboximide) -2 (2,2'-bithiophene) , 6-diyl) -alt-5,5'- (2,2'-bithiophene), P (NDI2OD-T2), polybenzimidazobenzophenanthroline (BBL) N, N'-diperfluorophenyl-3,4,9,10-perylenetetracarboxylic diimide (DFPP), and polypyridoquinoxaline ). In one embodiment of the present invention, the n-type polymer includes P (NDI2OD-T2) having a high electron mobility of 0.45 to 0.85 m ² / Vs Can be used.

Specifically, the step of forming the photoactive layer 300 on the perovskite semiconductor layer 200 may include the steps of dissolving the n-type polymer, the electron donor material, and the electron acceptor material in an organic solvent to prepare a mixture And applying the mixture to the perovskite semiconductor layer, followed by drying to form a photoactive layer.

First, a mixture can be prepared by dissolving the n-type polymer, the electron donor material, and the electron acceptor material in an organic solvent. In order to realize a solar cell with excellent performance, it is preferable that the photoactive layer 300 has an optimized bulk heterojunction structure. For this purpose, the n-type polymer, the electron donor material and the electron acceptor material may be effectively mixed The light emitting efficiency of the photoactive layer 300 can be further improved by using an organic solvent having an organic solvent.

Specifically, the organic solvent is selected from the group consisting of chlorobenzene (CB), dichlorobenzene (DCB), chloroform, diphenyl ether (DPE), diiodooctane ), Dimethylacetamide (DMAC), and N-methyl-2-pyrrolidone (NMP). More specifically, the organic solvent may include 1 to 10% by weight of diphenyl ether (DPE) or diiodooctane (DIO), based on the total weight of the organic solvent. In one embodiment of the present invention, the organic solvent may include 1 to 10% by weight of diphenyl ether (DPE) and 90 to 99% by weight of chlorobenzene (CB). The diphenyl ether (DPE) can form an even mixture of the n-type polymer, the electron donor material, and the electron acceptor material, thereby increasing the luminous efficiency of the photoactive layer 300. Specifically, this can be explained through the following examples and drawings.

Thereafter, a mixture in which the n-type polymer, the electron donor and the electron acceptor are dissolved in the organic solvent is coated on the perovskite semiconductor layer 200 and then dried to form a photoactive layer 300 can do. For example, the method of applying the mixture on the perovskite semiconductor layer 200 can be performed using a conventional polymer blend application method. For example, a spin coating method, an inkjet printing method, but is not limited to, ink-jet printing, screen printing, casting, doctor blade, and vacuum evaporation. .

After the mixture is applied, it is dried to form the photoactive layer 300 from which the organic solvent contained in the mixture is removed. The drying process may be a general organic solvent drying process, a high vacuum chamber drying process, or a drying process under a temperature atmosphere of about 80 ° C.

1, an electron transport layer 400 may be formed on the photoactive layer 300 before the second electrode 500 is formed on the photoactive layer 300. Referring to FIG. The electron transport layer 400 may efficiently transfer electrons generated in the photoactive layer 300 to the second electrode 500. The electron transport layer 400 may be formed of, for example, a metal oxide such as titanium oxide (TiO ₂ ) or zinc oxide (ZnO) doped with an n-type dopant, or a metal oxide such as a dipole layer such as PFN or PEI But are not limited thereto.

Then, a second electrode may be formed on the photoactive layer 300. When the electron transport layer 400 is formed on the photoactive layer 300, the second electrode 500 may be formed on the electron transport layer 400. The second electrode 500 serves as a cathode for collecting electrons generated in the photoactive layer 300, and a metal electrode can be used. Specifically, the second electrode 500 may be formed of, for example, aluminum (Al), gold (Au), platinum (Pt), silver (Ag), nickel (Ni), copper (Cu), palladium Tungsten (W), molybdenum (Mo), and a metal selected from one or more of these alloys.

The hybrid type solar cell of the present invention, which is manufactured through the above-described manufacturing method, includes the n-type polymer having a high charge mobility in the photoactive layer, thereby increasing the charge mobility of the photoactive layer. The efficiency can be improved.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the following examples.

[Example]

Example 1 : containing an n-type polymer The photoactive layer  Manufacture of deployed solar cells

As shown in FIG. 2 (a), ITO was coated on a glass substrate by sputtering to form a first electrode, and a hole transporting layer thin film in which PEDOT: PSS and VOx were mixed was formed on the substrate. On the hole transport layer (CH ₃ NH ₃₎ to form a perovskite teucheung consisting of PbI _3. Then, an organic solvent in which a small amount of diphenyl ether (DPE) was added to chlorobenzene (CB) was prepared, and PDPP2T (PDPP-TT), an electron acceptor material PC ₇₁ BM, and an n-type polymer P (NDI2OD-T2) (product name: N2200) was dissolved. The mixing ratio of the mixture was 1: 0.5, 1: 1, 1: 1.5, 1: 2 and 1: 3 in PDPP2T: PC ₇₁ BM. Specifically, in the case of 1: 3, 4 mg of PDPP2T as an electron donor polymer and 12 mg of PC ₇₁ BM as an electron acceptor polymer were mixed, and 1 mg of n-type polymer was added.

The mixture was coated on the perovskite layer and then dried to form a photoactive layer. The thickness of the photoactive layer was 60 nm, 100 nm, 140 nm, and 170 nm, respectively, for each sample. An n-type doped titanium oxide (TiO ₂ ) thin film was formed on the photoactive layer to form an aluminum (Al) electrode. A sectional SEM image of the manufactured solar cell is shown in Fig. 2 (b).

Comparative Example 1: Photoactive layer (1) containing no n-type polymer [

All the steps were carried out in the same manner as in Example 1, except that chlorobenzene (CB) alone was used as the organic solvent without mixing the n-type polymer in forming the photoactive layer.

Comparative Example 2: Photoactive layer 2 containing no n-type polymer (2)

All the steps were carried out in the same manner as in Example 1, except that n-type polymers were not mixed when the photoactive layer was formed.

3 (a) to 3 (f) are TEM images and AMF images of the photoactive layer prepared in Example 1 of the present invention and Comparative Examples 1 to 2.

3 (a) and 3 (d) show a photoactive layer prepared by using chlorobenzene alone as an organic solvent in Comparative Example 1, PDPP2T as an electron donor polymer and PC ₇₁ BM as an electron donor polymer are not mixed well, It can be confirmed that they are united. 3 (b) and FIG. 3 (e) which are TEM images of Comparative Example 2, when an organic solvent in which a small amount of diphenyl ether is appropriately added to chlorobenzene is used, the electron acceptor polymer and the electron donor polymer are well- It can be confirmed that they are mixed. 3 (c) and 3 (f), which are TEM images of Example 1, when an organic solvent in which a small amount of diphenyl ether is appropriately added to chlorobenzene is used, not only electron acceptor polymers and electron donor polymers but also n Type polymer N2200 is also mixed well. Accordingly, when the photoactive layer of the present invention is formed, an appropriate amount of diphenyl ether is contained in the organic solvent in an amount ranging from 1% by weight to 10% by weight, thereby efficiently mixing the polymers constituting the photoactive layer.

4 (a) to 4 (b) are graphs showing absorption coefficient and charge mobility measurement results of the photoactive layer prepared in Example 1 of the present invention and Comparative Examples 1 to 2. FIG.

Referring to FIG. 4 (a), although the absorption degrees all have similar values, it can be seen that the value of the charge mobility varies according to the embodiment as shown in FIG. 4 (b). As a result, it can be seen that the electron mobility of the solar cell of the present invention is increased while introducing the n-type polymer into the photoactive layer. In addition, since the electrons generated in the perovskite semiconductor layer migrate to the upper aluminum electrode through the photoactive layer of the bulk heterojunction structure, the electron mobility of the organic photoactive layer affects the performance of the solar cell have.

5 (a) to 5 (c) are graphs showing current-voltage measurement results of the solar cell manufactured in Example 1 of the present invention and Comparative Examples 1 to 2.

5 (a) to 5 (c), in the case of FIG. 5 (a) of Comparative Example 1, the current-voltage characteristic decreases as the thickness of the photoactive layer increases. On the other hand, c), the current-voltage characteristics are maintained regardless of the thickness of the photoactive layer. Accordingly, it can be seen that the electron mobility is improved by adding the n-type polymer to the photoactive layer of the present invention. In comparison between FIG. 5 (a) and FIG. 5 (b) of Comparative Example 2, it was confirmed that the current-voltage characteristics were somewhat improved when diphenylether (DPE) was included as a solvent in the formation of the photoactive layer .

FIGS. 6 (a) to 6 (c) are graphs showing the power conversion efficiency (PCE), fill factor (FF) of the solar cell manufactured in Example 1 of the present invention and Comparative Examples 1 to 2, ) And an external quantum efficiency (EQE) measurement result.

6A to 6B, in the case of the solar cell of Comparative Example 1, the thickness of the thin film increases and the photoelectric conversion efficiency (PCE) and the fill factor (FF) slightly decrease sharply at 100 nm or more Can be confirmed. On the other hand, the photovoltaic conversion efficiency (PCE) and the fill factor (FF) are not greatly reduced even when the thickness of the thin film is increased in the case of the solar cell manufactured in Example 1 of the present invention having a high electron mobility, . It can also be seen that the solar cell produced in Example 1 of the present invention exhibits a fill factor (FF) of about 80, which is a very high value. This may be due to the very high charge mobilities of the present invention reaching 10 ² cm ² V ^-1 S ^-1 due to the n-type polymer introduced into the photoactive layer.

FIG. 6 (c) is a comparison of the external quantum efficiency (EQE) of the cell in the near-infrared region. It shows that the solar cell, the perovskite semiconductor layer in which only the conventional perovskite semiconductor layer is disposed, It can be seen that the structure in which the photoactive layer including the n-type polymer of the present invention and the perovskite semiconductor layer are combined has the highest external quantum efficiency (EQE) value as compared with the solar cell having the photoactive layer bonded thereto. As a result, the hybrid solar cell of the present invention can drastically solve the low fill factor (FF) and low-near-infrared light sensitivity of conventional organic solar cells / perovskite-coupled solar cells, It is expected to be used in related fields.

7A to 7B are graphs showing current-voltage characteristics and external quantum efficiency according to the mixing ratio of the electron donor polymer and the electron acceptor polymer material of Example 1. FIG. Specific values are shown in Table 1 below.

V _OC (V) J _SC (mAcm ^-2 ) FF PCE (%) RPM 1: 0.5 0.71 5.07 0.50 1.80 800 1: 1 0.67 12.81 0.59 5.06 800 1: 1.5 0.66 15.02 0.64 6.34 1200 1: 2 0.65 15.58 0.64 6.48 1200 1: 3 0.64 17.87 0.64 7.32 1500

Referring to FIG. 7 (a), it can be seen that the current voltage characteristics are improved when the electron acceptor polymer PC ₇₁ BM is more mixed than PDPP 2 T (TT) used as the electron donor polymer. Also, referring to FIG. 7 (b), it can be seen that the external quantum efficiency is high when the electron acceptor polymer is mixed at the same wavelength. That is, in the embodiment of the present invention, the polymer used as the electron donor material and the electron acceptor material has an effect of improving the mixing ratio of each material to 1: 3 compared to other mixing ratios. The mixing ratio of the electron donor material and the electron donor material may vary depending on the type of polymer used in the examples.

It should be noted that the embodiments of the present invention disclosed in the present specification and drawings are only illustrative of specific examples for the purpose of understanding and are not intended to limit the scope of the present invention. It will be apparent to those skilled in the art that other modifications based on the technical idea of the present invention are possible in addition to the embodiments disclosed herein.

10: substrate 100: first electrode
150: hole transport layer 200: perovskite semiconductor layer
300: photoactive layer 400: electron transport layer
500: Second electrode

Claims (13)

A first electrode;
A second electrode disposed opposite to the first electrode;
A perovskite semiconductor layer disposed between the first electrode and the second electrode; And
And a photoactive layer disposed between the perovskite semiconductor layer and the second electrode,
Wherein the photoactive layer is a bulk heterojunction structure in which an n-type polymer, an electron donor material, and an electron acceptor material are mixed. The method according to claim 1,
The n-type polymer may be a poly ((N, N'-bis (2-octyldodecyl) -naphthalene-1,4,5,8- 5'- (2,2'-bithiophene) (P (NDI2OD-T2)), polybenzimidazobenzonanthatroline (BBL), N, N'-difluorophenyl- (DFPP), and polypyridoquinoxaline. The hybrid type solar cell according to claim 1, wherein the material is at least one material selected from the group consisting of a perylene tetracarboxylic diimide (DFPP) and a polypyridoquinoxaline. The method according to claim 1,
The electron donor material may be selected from the group consisting of 3,6-bis (5-bromothiophen-2-yl) -2,5-bis (2-hexyldecyl) pyrrole (3,4- (PDPP2T), poly-3-hexylthiophene (P3HT), poly-3-poly-3-octylthiophene (P3OT), polyparaphenylenevinylene (PPV) , Poly (2-methoxy, 5- (2-ethyl-hexyloxy) -1,4-phenylenevinylene) (MEHPPV) (MDMO-PPV), poly (2,1,3-benzothiadiazole-4,7-diyl (4,4-bis (2-ethylhexyl) -4H (2, 1-b: 3,4-b ') dithiophene-2,6-diyl)) (PCPDTBT), and derivatives thereof, and a hybrid type Solar cells. The method according to claim 1,
The electron acceptor material fullerenes (fullerene), 6,6- phenylene -C ₆₁ - butyl rigs Acid methyl ester _{(PCBM (C 61)),} PCBM (C 60), PCBM (C 70), PCBM (C 71), Wherein the fullerene selected from PCBM (C ₇₆ ), PCBM (C ₈₀ ), PCBM (C ₈₂ ), indene-C ₆₀ bisadduct (ICBA) and 6,6-phenyl-C ₆₁ -butylic acid cholesteryl ester Wherein the material is at least one material selected from the group consisting of polybenzimidazole, polybenzimidazole, and perylene. The method according to claim 1,
And a hole transport layer disposed between the first electrode and the perovskite semiconductor layer. 6. The method of claim 5,
The hole transport layer may comprise at least one of poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (PANI / CSA) polyaniline / poly PANI / PSS) and polyaniline / dodecylbenzene sulfonic acid (PANI / DBSA) at least one of the conductive polymer, molybdenum oxide (MoOx), vanadium oxide is selected from (V ₂ O _5), nickel oxide (NiO), and tungsten oxide ( WOx). ≪ / RTI > The method according to claim 1,
And an electron transport layer disposed between the photoactive layer and the second electrode. Forming a first electrode on a substrate;
Forming a perovskite semiconductor layer on the first electrode;
Forming a photoactive layer on the perovskite semiconductor layer; And
And forming a second electrode on the photoactive layer,
Wherein the photoactive layer is a bulk heterojunction structure of an n-type polymer, an electron donor material, and an electron acceptor material. 9. The method of claim 8,
Wherein forming the photoactive layer comprises:
Dissolving the n-type polymer, the electron donor material, and the electron acceptor material in an organic solvent to prepare a mixture; And
Applying the mixture to the perovskite semiconductor layer, and then drying the mixture to form a photoactive layer. 10. The method of claim 9,
The organic solvent may be selected from the group consisting of chlorobenzene (CB), chloroform (CF), dichlorobenzene (DCB), diphenyl ether (DPE), diiodooctane (1-8 diiodo), dimethylacetamide Methyl-2-pyrrolidone (NMP). 2. The method of manufacturing a hybrid type solar cell according to claim 1, 10. The method of claim 9,
Wherein the organic solvent comprises 1 to 10% by weight of diphenyl ether based on the total weight of the organic solvent. 9. The method of claim 8,
And forming a hole transporting layer between the first electrode and the perovskite semiconductor layer. 9. The method of claim 8,
And forming an electron transporting layer between the photoactive layer and the second electrode.

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