TWI689562B - Inverted organic photovoltaic and method of manufacturing the same - Google Patents

Abstract

The present invention provides an inverted organic photovoltaic, comprising a conductive substrate, an electron-transporting layer (ETL), an active layer, a hole transport layer, and a counter electrode layer, wherein the ETL comprises a glucose-based biopolymer as a surface modifier. The present invention further provides a method of manufacturing the aforesaid inverted organic photovoltaic. The glucose-based biopolymer are easily accessible and are much more economical as compared to commonly used PFN/PEI-based interfacial materials. More importantly, the present invention enables 9.47% and 6.34% enhancement in PCE for the representative fullerene- and NFA-based BHJ systems (PTB7-Th:PC₇₁BM and PBDB-T:ITIC), respectively, as compared to the control devices comprising an unmodified ETL.

Description

Trans organic solar photovoltaic and its manufacturing method

The invention relates to a photoelectric device and a manufacturing method thereof, in particular to a photoelectric device using natural biological materials and a manufacturing method thereof.

So far, various projects of photosensitive (photoactive) materials, interface materials, and electrode materials have obviously helped to advance the performance of organic photovoltaics (OPVs). Due to the power conversion efficiency (PCE) exhibited by OPV Over 15%, OPV shows huge commercial potential. Therefore, some scientists have recently shifted their research focus to the development of environmentally friendly materials and processing methods with better economic benefits to promote the sustainable development of green energy technologies. For example, the recent green-solvent-processable OPV has aroused extensive research interest, because it can not only reduce the environmental impact of the device manufacturing process to a considerable extent, but also provide more cost-effective Of manufacturing methods. Since non-fullerene-based acceptors (NFAs) have better solution processability than traditional fullerene acceptors in non-halogenated solvents, the recently booming NFA seems to promote OPV progress.

In addition to the advancement of photoactive layers, the field is also highly eager to explore compatible and practical interface materials with environmentally friendly manufacturing capabilities. At present, it has been proved that the appropriate modified intermediate layer or introduced into the middle The layer can improve the charge collection efficiency and carrier selectivity in the device, because it can achieve better energy-level alignment at the organic/metal interface, and in some cases, due to the opposite interface The improved compatibility makes it possible to promote a more ideal type of bulk-heterojunction (BHJ) layer. So far, various solution-processable interface materials have been developed to improve OPV performance, including transition metal oxides, self-assembled layers, polyelectrolytes, non-conjugated organic materials, and organic-inorganic hybrid materials. Among them, due to conjugated polymerization [(9 ,9-bis(3'-(N,N-dimethylamine)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)](PFN) group derivative And non-conjugated polyethyleneimine (PEI)-based analogues are light, thin, and low temperature solution processable, so they are the most commonly used materials. For example, Huang et al. developed a series of water/alcohol soluble PFN-based polymers as a viable intermediate layer to improve the overall performance of derived OPV.

The main object of the present invention is to provide an organic solar photovoltaic comprising a glucose-based biopolymer as an intermediate layer. Glucose is usually stored as a polymer in plants or animals, which is the most abundant and important monosaccharide. In this way, the development of glucose-derived polymers in solar photovoltaic devices becomes very important. However, due to the inherent structural characteristics of common glucose-based polymers, they are generally insoluble in water or partially soluble in water or common organic solvents. Therefore, the simple solution-based process technology based on these polymers to manufacture them into high-quality films poses a huge challenge and hinders glucose-based biopolymers in photovoltaic devices. widely used.

The main object of the present invention is to provide an organic solar photovoltaic, which includes an easily accessible and more economical natural polymer intermediate layer, and furthermore, compared to the conventional technology, a polymer solar cell using a common glucose-based polymer, The polymer intermediate layer of the present invention has more Excellent solution processability and film forming ability.

To achieve the foregoing objective, the present invention provides a trans organic solar photovoltaic, which includes: a conductive substrate, an electron transport layer (ETL), an active layer, a hole transport layer, and a counter electrode layer; wherein, The electron transport layer includes a glucose-based biopolymer as a surface modifier.

In a preferred embodiment, the glucose-based biopolymer is dissolved in a solvent, and the solvent includes water, dimethyl sulfoxide (DMSO), or a combination thereof.

In a preferred embodiment, the glucose-based biopolymer is selected from the group consisting of methyl cellulose, chitosan, and dextrin.

In a preferred embodiment, the total surface energy of the glucose-based biopolymer is greater than 55 mN/m.

In a preferred embodiment, the electron transport layer is selected from the group consisting of titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin dioxide (SnO ₂ ), and zinc stannate (Zn ₂ SnO ₄ ).

In a preferred embodiment, the conductive substrate includes a conductive material selected from indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), indium-tin composite oxide (ITO) , Fluorine-doped tin oxide (FTO), zinc oxide (ZnO), zinc oxide-gallium trioxide (ZnO-Ga ₂ O ₃ ) and zinc oxide-aluminum oxide (ZnO-Al ₂ O ₃ ) group.

In a preferred embodiment, the active layer is a bulk heterojunction (BHJ) layer.

In a preferred embodiment, the bulk heterojunction layer is a fullerene-based or non-fullerene acceptor-based (NFA-based) layer.

In a preferred embodiment, the bulk heterojunction layer includes PTB7-Th: PC ₇₁ BM blend or PBDB-T: ITIC blend.

In a preferred embodiment, the weight ratio of the PTB7-Th:PC ₇₁ BM blend is 1:05 to 1:3.

In a preferred embodiment, the weight ratio of the PBDB-T:ITIC blend is 1:0.5 to 1:2.

In a preferred embodiment, the hole transport layer is selected from 2,2',7,7'-4-[N,N-bis(4-methoxyphenyl)amino]-9,9'- Spiro-OMeTAD, polydioxyethylthiophene: styrenesulfonic acid (PEDOT: PSS), N,N'-bis(3-methylphenyl)-N,N'-diphenyl- [1,1'-biphenyl]-4,4'-diamine (TPD), polytrihexyl polythiophene (P3HT), vanadium pentoxide (V ₂ O ₅ ), nickel oxide (NiO), graphite dilute (graphene), molybdenum sulfide (MoS ₂ ), molybdenum selenide (MoSe ₂ ), polyalkylthiophene (polyalkyl-thiophene) and molybdenum trioxide (MoO ₃ ).

In a preferred embodiment, the counter electrode layer includes a material selected from the group consisting of gold, silver, rubidium, palladium, nickel, molybdenum, aluminum, and alloys thereof.

Another object of the present invention is to provide a method for manufacturing the above-mentioned trans organic solar photovoltaic, which includes: a. coating an electron transport layer on a conductive substrate, and then coating a glucose-based biopolymer Forming an intermediate layer as a surface modifier; b. forming an active layer on the intermediate layer; c. depositing a hole transfer layer on the active layer; and d. depositing a relative layer on the hole transfer layer Electrode layer.

In a preferred embodiment, the glucose-based biopolymer is selected from the group consisting of methyl cellulose, chitosan, and dextrin.

In a preferred embodiment, the electron transport layer is selected from titanium dioxide, zinc oxide, A group consisting of tin dioxide and zinc stannate.

In a preferred embodiment, the conductive substrate includes a conductive material selected from the group consisting of indium oxide, tin oxide, indium-tin composite oxide, fluorine-doped tin oxide, zinc oxide, and zinc oxide-three The group consisting of gallium oxide and zinc oxide-alumina.

In a preferred embodiment, the active layer is a piece of heterogeneous junction layer.

In a preferred embodiment, the bulk heterojunction layer is a fullerene-based or non-fullerene-receptor base layer.

In a preferred embodiment, the hole transport layer is selected from 2,2',7,7'-4-[N,N-bis(4-methoxyphenyl)amino]-9,9'- Spirobifluorene, polydioxyethylthiophene: styrenesulfonic acid, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1'-biphenyl] -4,4'-diamine, polytrihexyl polythiophene, vanadium pentoxide, nickel oxide, graphite dilute, molybdenum sulfide, molybdenum selenide, polyalkylthiophene and molybdenum trioxide.

Therefore, the present invention provides a trans organic solar photovoltaic, which includes a glucose-based biopolymer as a modified intermediate layer of an electron transport layer. Due to the modification of side groups and configuration, the glucosyl derivatives used in the present invention have good solubility in water or dimethyl sulfoxide. More importantly, the glucose-based biopolymer is easier to obtain and more economical than the commonly used PFN-based/PEI-based interface materials. The electron transport layer film with the glucose-based biopolymer as a surface modifier exhibits a uniform pattern, which is attributed to the good structural planarity and solution processability of the glucose-based biopolymer. The glucose-based biopolymer used in the present invention reveals the ability to promote the aggregation of photovoltaic components grown on top of it to produce a more ideal BHJ type. Compared with a control device containing unmodified ETL, the present invention can be applied to a representative fullerschiki (ie PTB7-Th: PC ₇₁ BM) and a non-fullerschler acceptor-based BHJ system (ie PBDB-T: ITIC)'s PCE increased by 9.47% and 6.34%.

100‧‧‧trans organic solar photovoltaic

10‧‧‧Conductible substrate

20‧‧‧Electron transfer layer

21‧‧‧Surface modifier

30‧‧‧Active layer

40‧‧‧Electron tunnel transmission layer

50‧‧‧counter electrode layer

FIG. 1 is a perspective schematic view of a preferred embodiment of the present invention.

2 is a schematic view of the structure of the glucose-based biopolymer in a preferred embodiment of the present invention.

FIG. 3 is an optical simulation diagram of a device according to a preferred embodiment of the present invention. The electron transport layer of the device uses (a) bare zinc oxide, (b) zinc oxide/methyl cellulose, and (c) zinc oxide/several Butanan and (d) zinc oxide/dextrin; simulated field intensity distribution |E| ² is normalized to the incident field intensity at normal incidence as a function of wavelength.

FIG. 4 is a transmission spectrum of a film according to a preferred embodiment of the present invention and its real photo (inset). The film is based on the glucose-based biopolymer, and the film has a thickness of 10 nm.

FIG. 5 shows (a) photoelectric spectrum (PES) and (b) ultraviolet photoelectric spectrum (UPS) of the glucose-based biopolymer/zinc oxide sample prepared on a silica substrate according to a preferred embodiment of the present invention.

FIG. 6 is an atomic force microscope (AFM) image of the glucose-based biopolymer/ZnO film according to a preferred embodiment of the present invention, wherein the top is a phase diagram, and the bottom is a topography diagram.

7 is a preferred embodiment of the present invention using different glucose-based biopolymers as the intermediate layer of fullerene-based trans organic solar photovoltaic (a) JV curve, (b) dark current curve, (c) J _ph -V _eff characteristic curve and (d) standardized EQE curve.

FIG. 8 is a JV curve diagram of a non-fullerene acceptor-based trans organic solar photovoltaic using ZnO/PFN or ZnO/methyl cellulose as an electron transport layer in a preferred embodiment of the present invention.

9 is a preferred embodiment of the present invention using ZnO/PFN or ZnO/methyl cellulose as the electron transport layer of non-fullerene acceptor-based trans organic solar photovoltaic (a) dark current curve and (b) J _ph -V _eff characteristic curve graph.

10 is an atomic force microscope (AFM) image of PTB7-Th: PC ₇₁ BM blend film grown on bare zinc oxide, chitosan, methyl cellulose and dextrin layers according to a preferred embodiment of the present invention. Among them, the top is the phase diagram, and the bottom is the topography.

11 is a two-dimensional GIWAXS (Grazing-Incidence Wide-Angle X-ray Scattering of the PTB7-Th: PC ₇₁ BM blend grown on different electron transport layers according to a preferred embodiment of the present invention )Figure.

FIG. 12 shows (a) a one-dimensional line tangent diagram and (b) normalized diagram corresponding to the PTB7-Th (100) peak and PC ₇₁ BM peak in the in-plane direction of a preferred embodiment of the present invention.

FIG. 13 is the corresponding (a) one-dimensional line tangent and (b) normalization of the PTB7-Th (100) peak and PC ₇₁ BM peak in the out-of-plane direction of a preferred embodiment of the present invention. Figure.

FIG. 14 is an azimuth distribution diagram of the PTB7-Th (100) signal of the PTB7-Th:PC ₇₁ BM blend film according to a preferred embodiment of the present invention, where the left side is a planar direction and the right side is a non-planar direction.

15 is a schematic diagram of a BHJ (this example is PTB7-Th: PC ₇₁ BM) type grown on a ZnO electron transport layer and grown on the glucose-based biopolymer according to a preferred embodiment of the present invention.

FIG. 16 is an optical simulation of a preferred embodiment of the trans organic solar photovoltaic device of the present invention, which is based on the calculated distribution of exciton generation rate in the PTB7-Th:PC ₇₁ BM blend layer of the device.

FIG. 17 is an optical modeling simulation of a preferred embodiment of the present invention, which is an optical modeling simulation of the current density and active layer thickness of the device described in FIG. 16.

The detailed description and technical content of the present invention will now be described in conjunction with the drawings. Furthermore, the drawings in the present invention are not necessarily drawn according to actual proportions for the convenience of explanation. The drawings and their proportions are not intended to limit the scope of the present invention, and will be described here first.

Unless otherwise defined, all technical and scientific terms in this document have the same meaning as understood by those with ordinary knowledge in the technical field to which the present invention belongs. As used in this application, the following terms have the following meanings.

Unless otherwise stated, "or" in this article means "and/or". As referred to herein, "comprising or including" means not excluding the presence or addition of one or more other components, steps, operations, and/or elements. "One" means that the grammatical object of the thing is one or more (ie, at least one). Similarly, the terms "include", "include", "include", "include", and "have" described herein can also be substituted for each other without limitation. The singular forms "one", "one", "one" and "the" mentioned in this article and the scope of the patent application include plural references. Terms in this article such as: "one", "the", "one or more", "plural" and "at least one" can be substituted for each other.

Please refer to "Figure 1", which shows a schematic perspective view of a preferred embodiment of the present invention.

The present invention is a trans organic solar photovoltaic (trans OPV) 100, which includes: a conductive substrate 10, an electron transport layer (ETL) 20, an active layer 30, a hole transport layer 40, and a relative Electrode layer 50; wherein, the electron transport layer 20 includes a glucose-based biopolymer as a surface modifier 21. Furthermore, the present invention also relates to a trans-form as described above A method of organic solar photovoltaic 100, which includes: a. coating an electron transport layer 20 on a conductive substrate 10, and then coating a glucose-based biopolymer to form an intermediate layer as a surface modifier 21; b Forming an active layer 30 on the intermediate layer; c. depositing a hole transfer layer 40 on the active layer 30; and d. depositing a counter electrode layer 50 on the hole transfer layer 40.

As used herein, "conductible substrate 10" refers to a substrate that has the effect of conducting electricity. Preferably, a conductive material can be used in combination with a substrate. In a preferred embodiment, the conductive material includes a transparent conductive oxide, wherein the conductive material is selected from a conductive polymer, indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), Indium-tin composite oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide, ZnO-Ga ₂ O ₃ and ZnO-Al ₂ O ₃ ; however, the present invention is not limited to these. In a preferred embodiment, the substrate can be selected from various transparent or translucent materials, such as but not limited to: glass or polymer. In a preferred embodiment, the conductive substrate 10 serves as the bottom electrode of the trans organic solar photovoltaic 100.

The "electron transport layer (ETL) 20" mentioned herein refers to a layer with high electron mobility. Specifically, the electron transport layer 20 can be an active element in the trans organic solar photovoltaic 100. The electrons separated by layer 30 are transferred to an electrode. In a preferred embodiment, the electron transport layer 20 includes a metal oxide material, such as but not limited to: titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin dioxide (SnO ₂ ), and zinc stannate (Zn ₂ SnO ₄ ) etc. Preferably, the electron transport layer 20 further includes a surface modifier 21 (also called interface material), and the surface modifier 21 includes a glucose-based biopolymer.

As used herein, "glucose-based biopolymer" refers to a polymer that includes a group of carbohydrates. The carbohydrate is composed of six carbon atoms and has an aldehyde group at one end. It is classified as cyclic hemiacetal in the form of aldehyde hexose. In general, glucose has isomeric repeating units, called "α-type" and "β-type". The main features distinguishing the "α-" and "β-" configurations are shown in Figure 2, where "α-" indicates that the hydroxyl group attached to C-1 and the -CH ₂ OH group on C-5 are located in the ring The opposite side of the plane (ie, trans arrangement, trans ), and "β-" indicates that the hydroxyl group attached to C-1 and the -CH ₂ OH group on C-5 are on the same side of the ring plane (ie, cis Arrangement, cis ). Common glucose-based polymers include cellulose, starch, and chitin. Due to their inherent structural characteristics, they are generally insoluble in water or partially soluble in water or common organic solvents. In a preferred embodiment, the glucose-based biopolymer included in the present invention is selected from the group consisting of methyl cellulose, chitosan, and dextrin. In a preferred embodiment, the glucose-based biopolymer is dissolved in a solvent, and the solvent includes water, dimethyl sulfoxide (DMSO), or a combination thereof. In a more preferred embodiment, the total surface energy of the glucose-based biopolymer is greater than 55mN/m, such as but not limited to: 55.1mN/m, 55.5mN/m, 56mN/m, 56.5mN/m, 57mN/ m, 57.5mN/m, 58mN/m, 58.5mN/m, 59mN/m, 59.5mN/m, 60mN/m, 60.5mN/m, 61mN/m, 61.5mN/m, 62mN/m, 62.5mN/ m, 63mN/m, 63.5mN/m, 64mN/m, 64.5mN/m, 65mN/m, 65.5mN/m, 66mN/m, 66.5mN/m, 67mN/m, 67.5mN/m, 68mN/m , 68.5mN/m, 69mN/m, 69.5mN/m, 70mN/m, 70.5mN/m, 71mN/m, 71.5mN/m, 72mN/m, 72.5mN/m, 73mN/m, 73.5mN/m , 74mN/m, 74.5mN/m, 75mN/m, 75.5mN/m, 76mN/m, 76.5mN/m, 77mN/m, 77.5mN/m, 78mN/m, 78.5mN/m, 79mN/m, 79.5mN/m, 80mN/m, 80.5mN/m, 81mN/m, 81.5mN/m, 82mN/m, 82.5mN/m, 83mN/m, 83.5mN/m, 84mN/m, 84.5mN/m, 85mN/m, 85.5mN/m, 86mN/m, 86.5mN/m, 87mN/m, 87.5mN/m, 88mN/m, 88.5mN/m, 89mN/m, 89.5mN/m or 90mN/m. It should be noted that these glucose-based biopolymers are not only environmentally friendly, but because of their rich availability in the environment, they are more economical than other intermediate layers commonly used in OPVs. Methyl cellulose can be made from cellulose, the aforementioned cellulose can be easily extracted from plants; chitosan can be extracted from the exoskeleton of crustaceans (such as crabs or shrimps); hydrolysate of dextrin starch, the aforementioned starch Mainly stored in cereals. Therefore, the manufacturing cost of these glucose-based biopolymers is very low. For example, using the world-renowned Sigma-Aldrich company (sigma-aldrich) as a comparison, chitosan (Aldrich company product number 448869), methyl cellulose ( Sigma's product number M7140) and dextrin (Sigma's product number D2131) are respectively $USD 65.5/50g, $USD 47.25/100g and $USD 42.25/500g; commonly used polymer intermediate layers such as: The price of fluorene conjugated polymer PFN (polyfluorene, Aldrich product number 900954-DOF) is $USD>1,000/g, the price of polyethyleneimine PEI (Aldrich company product number 408727) is $USD 79.50/100ml and PEIE ( Polyethylenimine ethoxylated, Aldrich product number 306185) is priced at $USD 98/100g; the price of these glucose-based biopolymers is cheaper than that of commonly used polymer interlayers.

The “active layer” described herein refers to an organic material used in the trans organic solar photovoltaic 100 to absorb light energy. In a preferred embodiment, the active layer included in the present invention is a bulk heterojunction (BHJ) layer. In a preferred embodiment, the active layer included in the present invention is a BHJ layer, and the BHJ layer is a fullerene-based or non-fullerene acceptor group. based, NFA-based) layer, wherein the BHJ layer may be a blend or a non-blend, and the aforementioned blend is, for example but not limited to, a binary blend or a ternary blend. The fullerene-based BHJ blend includes PTB7-Th: PC ₇₁ BM, P3HT: PCPDTBT: PC ₆₁ BM or PTB7-Th: p -DTS(FBTTH ₂ ) ₂ : PC ₇₁ BM; and the non-fullerene acceptor The blend of body-based BHJ includes PBDB-T: FDICTF, PBDB-T: DICTF, or PBDB-T: ITIC; however, the present invention is not limited to these. In a preferred embodiment, the active layer of the present invention includes a PTB7-Th:PC ₇₁ BM blend as a fullerene BHJ layer, and the weight ratio of the PTB7-Th:PC ₇₁ BM blend is 1:05 to 1:3, for example: 1:05, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1: 2.7, 1:2.8, 1:2.9 or 1:3. In a preferred embodiment, the active layer of the present invention includes a PBDB-T:ITIC blend as a non-fullerene acceptor-based BHJ layer, and the weight ratio of the PBDB-T:ITIC blend is 1: 0.5 to 1:2, for example: 1:05, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1: 1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9 or 1:2. In a preferred embodiment, the active layer included in the present invention may further include an additive, such as but not limited to: alkane thiol (1,8-diiodooctane, 1,8-diiodooctane, DIO) Or 1-chloronaphthalene (1-Chloronaphthalene, 1-CN).

The "hole transport layer (HTL) 40" described herein refers to a layer that has a high hole mobility in a solar cell and has a low energy barrier at the interface with the opposing electrode layer 50, which is easy to inject into holes. In a preferred embodiment, the hole transfer layer 40 comprises a material selected from 2,2',7,7'-4-[N,N-bis(4-methoxyphenyl) Amino]-9,9'-spiro-fluorene (Spiro-OMeTAD), polydioxyethylthiophene: styrenesulfonic acid (PEDOT: PSS), N,N'-bis(3-methylphenyl)-N ,N'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (TPD), polytrihexyl polythiophene (P3HT), vanadium pentoxide (V ₂ O ₅ ), A group consisting of nickel oxide (NiO), graphene, molybdenum sulfide (MoS), selenium sulfide (MoSe), polyalkyl-thiophene, and molybdenum trioxide (MoO ₃ ).

The "counter electrode layer (Counter electrode layer) 50" mentioned herein means that an electrode layer is usually a highly conductive molecule. In a preferred embodiment, the counter electrode layer 50 includes a material selected from platinum, copper, aluminum, indium, ruthenium, rhodium, iridium, osmium, gold, silver, rubidium, palladium, nickel, molybdenum, A group consisting of carbon, conductive polymers and their compositions and alloys. In a preferred embodiment, the counter electrode layer 50 includes a material selected from the group consisting of gold, silver, rubidium, palladium, nickel, molybdenum, aluminum, and alloys thereof.

As used herein, "coating/coating" refers to the attachment of a single or multiple uniform films on an object. In a preferred embodiment, the trans organic solar photoelectric device 100 of the present invention uses ultra-thin coating technology, where the coating method is, for example but not limited to, spin coating, slot coating ( Slit coating), spin plus slit coating (Spin plus slit coating), etc.

"Deposition" as used herein refers to the technique of depositing a material on the surface of a substance to make a thin film. In a preferred embodiment, the trans organic solar photovoltaic device 100 of the present invention uses an electrodeposition method or a chemical deposition method; however, the deposition method of the present invention is not limited to these.

Hereinafter, the present invention will be further described with detailed descriptions and implementations. However, it should be understood that these implementations are only used to help understand the present invention more easily, not to limit the scope of the present invention.

[Example]

A. Method

(1) Material

The polymer donors "PTB7-Th" and "PBDB-T" were purchased from Canadian supplier 1-Material and can be used without further purification. Chitosan (Aldrich product number 448869), methyl cellulose (Sigma company product number M7140) and dextrin (Sigma product No. D2131) was purchased from Sigma-Aldrich, and can be used without further purification.

(2) Manufacture of trans organic solar photovoltaic devices

Preparation of the conductive substrate: firstly, the ITO glass substrate is washed with detergent, and then washed with deionized water, acetone and isopropanol for 15 minutes respectively. Then, the ITO glass substrate (referred to as ITO substrate for short) was dried with nitrogen and then subjected to plasma treatment for 10 minutes.

Preparation of the electron transport layer: 0.1 g of zinc acetate was dissolved in 1 mL of 2-methoxyethanol and 28 μL of ethanolamine to prepare a ZnO precursor. The ZnO precursor solution was spin-coated on the ITO glass substrate, and annealed in air at 200°C for 30 minutes to form a ZnO electron transport layer to obtain an ITO glass substrate/ETL (or ZnO ETL).

Surface modification of the electron transport layer: As mentioned above, the main obstacle to the application of glucose-based biopolymers in photovoltaic devices is their poor solution processability. In order to overcome this problem, the examples herein reasonably select chitosan, methyl cellulose and dextrin as the preferred implementations. Chitosan, methyl cellulose and dextrin precursor solutions are prepared by combining 0.1 g/mL chitosan, methyl cellulose and dextrin with a small amount of acetic acid, water and dimethyl sulfoxide (DMSO) ) Dissolve together in water. The chitosan, methyl cellulose and dextrin precursor solution was spin-coated on the ZnO electron transport layer in air, and then annealed in air at 130°C for 15 minutes, but the dextrin system was at 150°C Anneal in air for 10 minutes. Note that the natural polymers used in the examples (ie chitosan, methyl cellulose and dextrin) have a decomposition temperature higher than 250°C. Therefore, the electron transport layer is surface-modified by chitosan, methyl cellulose or dextrin, and forms an ETL/glucose-based biopolymer layer, namely "ZnO/chitosan", "ZnO/ "Methyl cellulose" or "ZnO/dextrin". In this embodiment, the ETL that has not undergone surface modification is referred to as a comparative example of ETL, that is, "bare ETL" or "bare ZnO" in the comparative example.

Preparation of the active layer: using the representative fullerene group (containing PTB7-Th: PC ₇₁ BM blend) BHJ system and non-fullerene acceptor group (containing PBDB-T: ITIC blend) BHJ system As an example of the light activation system. Dissolve 0.5 mg/mL PFN in methanol containing 2 vol% acetic acid to prepare a PFN precursor solution, and spin coat it on the surface-prepared or non-surface-prepared surface prepared in a nitrogen-filled glove box On the ETL of sex. The PTB7-Th: PC ₇₁ BM blend (weight ratio 1:1.5) precursor solution was prepared in chlorobenzene (CB) with DIO added (CB/DIO=97/3, v/v), the PBDB-T: ITIC blend (weight ratio 1:1) precursor solution was prepared in chlorobenzene with added DIO (CB/DIO=99.5/0.5, v/v). All these precursor solutions were vigorously stirred in a nitrogen-filled glove box at 60°C for 8 hours. The thickness of the BHJ layer spin-coated on the ELT layer is 80-90 nm. For this non-fullerene acceptor-based BHJ system, the spin-coated film was placed in a nitrogen-filled glove box and further annealed at 90°C for 10 minutes.

Preparation of the hole transfer layer and the opposite electrode layer: under high vacuum (<10 ^-6 Torr) environment, thermal deposition of MoO ₃ and Ag with 8-nm and 100-nm thickness, respectively, to complete the top electrode, equipment The effective area is 10 mm ² .

Finally, the device is made of ITO glass substrate/ZnO/glucose-based biopolymer/BHJ/MoO ₃ /Ag of the trans organic solar photovoltaic, and the corresponding thickness of each layer is 110nm, 30nm, 10nm, 80nm, 8nm And 100nm.

(3) Photoelectric characteristics

The current-voltage ( JV ) characteristics of the trans-organic solar photoelectric cell were measured by the Newport LCS-100 simulator under AM 1.5G illumination (100mW/cm ² ), and the computer-controlled Keithley 2400 power supply measurement unit instrument ( source measurement unit, SMU) for recording.

A silicon photodiode sensor with a KG-5 filter is used to correct the illumination intensity. During the illumination period (QE-R, Guangyan Technology Co., Ltd.), the external quantum efficiency (EQE) was recorded using the monochromatic light of the xenon lamp, and the standard single crystal silicon solar photovoltaic cells of 300nm to 800nm were used to correct the light intensity of each wavelength.

(4) Type characteristics

For surface energy analysis, the contact angle was further measured. AFM images were acquired in a tap mode using a multifunctional atomic force microscope (AFM) system with a Nanoscope three-dimensional controller (digital instrument). The silicon cantilever (PPP-SEIHR probe, Nanosensor) has a spring constant of 15N/m and a resonance frequency of 130kHz.

Grazing-Incidence Wide-Angle X-ray Scattering (GIWAXS) data measurement was performed at the National Synchrotron Radiation Research Center (NSRRC) in Taiwan. The beam BL17A1 has a wavelength of 1.321Å.

By atmospheric photoelectron spectrometer (atmospheric photoelectron spectroscopy, PES, RIKEN AC2) and ultraviolet photoelectron spectrometer (ultraviolet photoelectron spectrometer, UPS) measurement prepared on SiO ₂ substrate surface-modified ETL (ie, ZnO/glucose-based biopolymer) or the function function (WF) of the surface-unmodified ETL (ie, bare ZnO). The aforementioned UPS measurement system uses a Thermo VG-Scientific brand windowless He emission light source, which provides a He(I) emission system of 21.2 eV. A passing energy of 20 eV was used, and the extraction angle of the photoelectrons was set to 90°.

(5) Optical modeling

Transfer matrix formalism (TMF) is used for optical simulation. The refraction wavelength composite index ( n = h + i c (1)) of each material was measured by ellipsometry. Based on the imaginary part ( c ) and real part ( n ) of the refractive index of each layer, the fractions of light absorption, reflection, and transmission in each layer can be calculated. For organic solar photovoltaics, the optical model is based on the device composed of ITO glass substrate/ZnO/glucose-based biopolymer/BHJ/MoO ₃ /Ag, and the corresponding thickness of each layer is 110nm, 30nm, 10nm, 80nm, 8nm and 100nm.

Calculate the electric field distribution based on the assumption of 100% internal quantum efficiency (IQE) and AM1.5 intensity spectrum (ASTM G173-03), and follow Petterson's report "Photofilm Construction of Organic Thin Film Solar Photovoltaic Devices in 1999". In the model. In addition, the current density was calculated on the assumption of 100% internal quantum efficiency and AM1.5 intensity spectrum (ASTM G173-03). The results are shown in Fig. 3. The measured EQE spectrum was divided by the simulated absorption spectrum of the BHJ layer in the completed device to obtain internal quantum efficiency.

B. Results

(1) Characteristics of the glucose-based biopolymer membrane

The structural formulas of chitosan (A), methyl cellulose (B) and dextrin (C) are as follows. Chitosan (A) and methyl cellulose (B) composed of β-glucose The monomer has amine groups and methyl functional groups, so that chitosan (A) and methyl cellulose (B) have better solution processability than the original cellulose. Methyl cellulose (B) has good compatibility with water, and chitosan (A) can also be dissolved in water with the help of a small amount of acetic acid. On the other hand, dextrin (C), which has a typical hydroxyl functional group on the glucose monomer, is composed of α-type glycosidic bonds and shows better solubility than virgin cellulose in DMSO.

Due to the inherently good structural planarity and solution processability, chitosan, methyl cellulose and dextrin show good film-forming ability and high optical transparency (as shown in Fig. 4). Good potential for OPV applications. Therefore, considering the insulating properties of chitosan, methyl cellulose and dextrin, this embodiment aims to use chitosan, methyl cellulose and dextrin as the electron transport layer (ZnO) in trans organic solar photovoltaic The surface modifier of ZnO has been determined to have defects and poor compatibility with the components in organic solar photovoltaics, so it may not be conducive to the formation of the ideal BHJ type. The glucose-based biopolymers used in this example have different functional groups. This feature may induce the formation of interfacial dipoles to affect the function function of ZnO. Therefore, first, the photoelectron spectroscopy was used to examine the properties of ZnO/glucose-based biopolymers. Total function. The results are shown in Fig. 5, and the observed changes in the functional function are negligible, indicating that their function plays a secondary role in mediating the functional function of the metal oxide.

Surface-modified ETL (ie, ZnO/glucose-based biopolymer) imparts surface energy and morphological characteristics. The surface-modified ETL plays an important role in the development of the active layer (ie, the BHJ layer) grown on top of it. The total surface energy ( _γtotal ) of the surface-modified ETL was measured using contact angle goniometry in combination with the Wu model. The aforementioned Wu model refers to the publication “By Surface Energy Control to Improve Polymerization” published by Bulliard X. et al. in 2010 Solar cell performance", using distilled water and glycerin as the detection liquid for contact angle (θ) measurement. Basically, the total surface energy ( _γtotal ) is equal to the sum of dispersing energy ( _γdispersive ) and polar energy ( _γpolar ). The corresponding data of the samples of the examples are summarized in Table 1. As mentioned above, both ZnO/chitosan film (64.77mN m ^-1 ) and ZnO/methylcellulose film (59.41mN m ^-1 ) produce higher total surface than bare ZnO (55.23mN m ^-1 ) Yes, it is because ZnO/chitosan membrane and ZnO/methyl cellulose membrane have higher hydrophobic properties. It is worth noting that due to the increased compatibility at the interface, a higher total surface energy indicates easier adhesion to the organic material in contact. The total surface energy (55.18mN m ^-1 ) of the ZnO/dextrin film is comparable to bare ZnO, which is due to the hydroxyl functional groups mainly composed in dextrin.

Considering the effect of the surface texture of the prepared film on its surface energy, a tapping atomic force microscope (AFM) was used to study the shape of the sample of this example. FIG. 6 shows the AFM morphology and phase diagram of the ZnO/glucose-based biopolymer membrane of the present invention. As shown in the figure, the ZnO/glucose-based biopolymer membrane of the present invention is very uniform, in which severe phase separation is not clearly observed. The estimated root mean square (RMS) surface roughness of bare ZnO, ZnO/chitosan, ZnO/methyl cellulose, and ZnO/dextrin were 1.23, 1.62, 0.72, and 1.00 nm, respectively. Films containing methyl cellulose produce the smoothest surface with the best uniformity, exhibiting its excellent film-forming ability.

As mentioned above, glucose has isomeric repeating units. The glucose system of dextrin is polymerized by α-type connection, and methyl cellulose is polymerized by β-type connection. Due to steric hindrance and hydrogen bonding, alpha-glucose-based biopolymers usually have a coiled backbone and spring-like disks Around. Conversely, the β-glucose-based biopolymer has a straighter skeleton, so compared to the α-glucose-based biopolymer, the β-glucose-based biopolymer is beneficial to provide a more extended structure. In addition, the better linearity of β-type glucose-based biopolymers can allow a large number of hydrogen bonds to be formed between OH groups on adjacent chains to produce dense stacked patterns to form a continuous layered structure like fibers. Therefore, compared with the α-type glucose-based biopolymer having a coil spring structure (eg, dextrin in this embodiment), the β-type glucose-based biopolymer having a layered structure (eg, methyl fiber in this embodiment) Element) prefers to produce a smoother membrane surface. Although chitosan belongs to β-type glucose-based biopolymer, however, it exhibits the largest surface roughness among the glucose-based biopolymers used in this example, which is due to the amine group in addition to the aforementioned configuration factors It also played a key role in the resulting chain stacking pattern.

(2) Performance of the trans organic solar photovoltaic

Next, the efficacy of the glucose-based biopolymer as a ZnO surface modifier in the trans-organic solar photovoltaic was examined, in which the BHJ layer of the representative PTB7-Th: PC ₇₁ BM blend was first used as the light activation system. The measured JV curve under AM 1.5G illuminance is shown in Fig. 7, and the relevant solar photoelectric parameters such as: open circuit voltage ( V _oc ), short circuit current ( J _sc ) and fill factor ( FF ) are summarized in Table 2. For convenience, the device using bare ZnO ETL in this embodiment is represented by a ZnO device, and the device using a glucose-based biopolymer interlayer is corresponding to its chitosan device, methyl cellulose device or dextrin device. Said. It is worth noting that for the BHJ layer of the PTB7-Th: PC ₇₁ BM blend, the ZnO device modified with PFN (ie, a comparative example using bare ZnO ETL) did not show significantly improved performance, which may be Because PFN has partial solubility in non-polar solvents.

The ZnO surface modifiers used in this example affect the performance of their trans organic solar photovoltaic in different ways. The methylcellulose device exhibited the best performance with a PCE of 9.25%, V _oc of 0.794V, J _sc of 17.08 mA/cm ² and FF of 68.2, while the comparative example ZnO device (ie bare ZnO) produced performance _{PCE: 8.45%, V oc:} 0.793V, J sc: 16.67mA / cm 2 and FF: 63.9.

The difference in PCE changes generally shows the structure-performance relationship of these glucose-based biopolymers, because these glucose-based biopolymers have different membrane types and different functional side group effects. However, as mentioned above, after coating these glucose-based biopolymers, the ZnO function function has not changed. Therefore, it is speculated that the film quality and film type including the intermediate layer and the BHJ layer have a key influence on the performance results. As previously disclosed, the methylcellulose film with the smoothest film surface allows the trans-photovoltaic device containing it to exhibit the highest PCE. As shown in FIG. 7(b), in all the device examples, the chitosan device has the largest dark current, indicating that relatively more charge recombination occurs in the chitosan device. However, it should be noted that such a large dark current indicates that the device Conductive polymers or interfacial doping can be formed.

In order to further detect the behavior of charge recombination in the device of this embodiment, the photocurrent density ( J _ph ) is plotted in FIG. 7(c) as a function of the effective voltage ( V _eff ) of the device of this embodiment. The aforementioned J _ph is calculated from J _ph = J _L - J _D , where J _L and J _D represent the current density measured under AM 1.5G illumination and darkness, respectively, and V _{eff is} defined as V _eff = V ₀ - V _bias , where V ₀ is the voltage when J _ph is 0, and V _bias is the bias applied. Generally speaking, J _ph will approach saturation value ( J _sat ) in the high bias region, indicating the state of completely dissociating the charge and being swept away by the high internal electric field. Therefore, J _ph,SC /J _ph,sat ratio represents the product of exciton dissociation probability under short-circuit condition, and J _ph,max /J _ph,sat ratio represents the product of charge collection probability under maximum power output condition. Therefore, the J _ph /J _sat ratio under external bias between the short-circuit condition and the maximum power output condition can be evaluated as the combined product of charge dissociation and collection probability. When V _{eff is the} same as 0.1 eV, the probabilities of the aforementioned ZnO device, chitosan device, methyl cellulose and dextrin device are 0.63, 0.57, 0.70 and 0.66, respectively. Higher values of the methyl cellulose and the dextrin device indicate better charge dissociation and collection probability.

As mentioned above, the improvement in performance is also related to the change of the BHJ layer type, because the improvement of the BHJ layer type can promote the dissociation of the photoexcitons in the aforementioned device. This phenomenon can also be reflected by the corresponding standardized EQE spectra of the aforementioned devices. As shown in FIG. 7(d), the devices of all the examples showed good photoreactions at 300~800nm, but the methylcellulose devices and dextrin devices showed stronger at ~410nm and ~700nm. reaction.

In order to further verify the applicability of the present invention to different types of BHJ systems, in the representative non-fullerene receptor group PBDB-T: ITIC blend system, the best performing methylcellulose in this example was further used Surface modified ZnO ETL. The results are shown in Fig. 8 and Table 2. The methylcellulose device showed excellent PCE of 9.89%, V _oc of 0.873V, J _sc of 16.93 mA/cm ² and FF of 66.9, better than the comparative example Performance (ie ZnO/PFN device, PCE: 9.30%; V _oc : 0.866V; J _sc : 16.84 mA/cm ² ; FF : 63.8). This result clearly shows that ZnO ETL modified with methyl cellulose is generally suitable for different types of BHJ systems. However, unlike the BHJ system of PTB7-Th: PC ₇₁ BM blends, the methyl cellulose intermediate layer can improve the performance of devices containing it by better mediating the interface electronic properties at the ZnO/BHJ interface Performance, as shown in Figure 9.

(3) Type of BHJ active layer

As described above, in the case of the BHJ system using the PTB7-Th:PC ₇₁ BM blend, the stronger PCE can be traced back to the BHJ pattern induced by the glucose-based biopolymer intermediate layer. First, AFM was used to study the types of the blends in the examples. FIG. 10 shows the PTB7-Th: PC ₇₁ BM blend film grown on Comparative Example (ie, bare ZnO ETL) and Example (ie, ETL modified with glucose-based biopolymer surface), respectively AFM image with similar appearance. As shown in the figure, all the sample samples show interpenetrating network active layers, but have different surface textures and roughness. The surface roughness RMS of the BHJ layer grown on the bare ZnO ETL film, chitosan ETL film, methyl cellulose ETL film and dextrin ETL film were 1.34, 1.28, 1.30 and 1.31 nm, respectively. Such subtle changes may result from the unique nano-scale phase separation.

In order to further explore the molecular stacking characteristics and stacking orientation of the BHJ film in the examples and comparative examples, GIWAXS was used to detect the morphological characteristics of the BHJ film. FIG. 11 is a two-dimensional GIWAXS diagram of an example and a comparative example, in which both the in-plane and out-of-plane directions are observed to correspond to the PTB7-Th layered accumulation ( 100) Peak, and a ring signal was observed at q = ~1.3Å ^-1 belonging to the aggregate of PC ₇₁ BM. It is worth noting that the stacking pattern of the embodiment using the glucose-based biopolymer intermediate layer did not track significant changes.

Further analyze the half-peak full amplitude (FWHM) of the one-dimensional profile, PTB7-Th and PC ₇₁ BM extracted from the aforementioned two-dimensional map and their corresponding corresponding pole maps. Figures 12 and 13 show the detailed crystalline properties of PTB7-Th:PC ₇₁ BM blends grown on different ETLs. The relevant crystallization parameters are summarized in Table 3 (planar direction) and Table 4 (non-planar direction). As shown in Figure 12, when the peak value q _y =1.33Å ^-1 is PC ₇₁ BM, the diffraction peak of q _y =0.30Å ^-1 is designated as the PTB7-Th(100) signal, and the PTB7-Th(100) The signal is related to the layered stacking interval of 36.1Å. PTB7-Th and PC ₇₁ BM's half-peak full amplitude analysis is shown in Figure 12 and Figure 13, and PTB7-Th's azimuthal-angle pole plot (azimuthal-angle pole plot) is shown in Figure 14. It can be clearly observed that the BHJ membrane of the BHJ membrane in the embodiment device using the ZnO ETL modified with glucose-based biopolymer surface (ie, ZnO/chitosan, ZnO/methyl cellulose, or ZnO/dextrin) The crystallite size and stacking orientation have been enhanced. It is shown that the glucose-based biopolymers used in the examples can promote the BHJ pattern, which is the result of improving the interface compatibility and roughness as described above, as shown in FIG. 15. Note that given that PC ₇₁ BM and PTB7-Th have strong light capture in the short-wavelength region of 300-400nm and the long-wavelength region of 700-800nm, respectively, the increased light observed at the peaks of ~410nm and ~700nm can be observed The reaction (as shown in Fig. 7(d)) is attributed to their enhanced crystallization and stacking orientation, respectively. This enhanced crystallinity is conducive to the generation of photoexcitons and subsequent dissociation/transportation of charges.

(4) The light field inside the trans organic solar photovoltaic

In order to further clarify other factors outside the pattern, its contribution to the improvement of J _sc observed in the example device using the glucose-based biopolymer intermediate layer, based on PTB7-Th: PC ₇₁ BM blend The BHJ system performs optical modeling simulation. As shown in FIGS. 16 and 3, the simulated field strength (|E| ² ) in the foregoing device is a wavelength function under the device of the embodiment shown in the figure. The results show that the example device containing an intermediate layer of glucose-based biopolymer exhibits an enhanced field strength in the long wavelength region (>700 nm) inside the active layer, which can be said to prove the slight enhancement observed at the long wavelength EQE. Such enhancement is directly helpful to increase the total generation rate of the active layer (as shown in FIG. 16), confirming that a higher J _sc is observed in the methyl cellulose device than in the ZnO device.

As shown in FIG. 17, the decrease in current density due to the decrease in the thickness of BHJ can be alleviated in the embodiment device including the glucose-based biopolymer intermediate layer. By moving the current density curve to a thinner active layer area, high-performance translucent OPV can be achieved with the help of using these glucose-based biopolymer intermediate layers.

In summary, the present invention provides a trans organic solar photovoltaic, which includes a glucose-based biopolymer as a modified intermediate layer of the electron transport layer. Due to the modification of side groups and configuration, the glucosyl derivatives used in the present invention have good solubility in water or dimethyl sulfoxide. More importantly, the glucose-based biopolymer is easier to obtain and more economical than the commonly used PFN-based/PEI-based interface materials. The electron transport layer film with the glucose-based biopolymer as a surface modifier exhibits a uniform pattern, which is attributed to the good structural planarity and solution processability of the glucose-based biopolymer. The glucose-based biopolymer used in the present invention reveals the ability to promote the aggregation of photovoltaic components grown on top of it to produce a more ideal BHJ type. Compared with a control device containing unmodified ETL, the present invention can be applied to representative fullerhyl groups (ie PTB7-Th: PC ₇₁ BM) and non-fullerhyl acceptor group-based BHJ systems (ie PBDB-T: ITIC) increased PCE by 9.47% and 6.34%.

The present invention has been described in detail above, but the above mentioned is only one of the preferred embodiments of the present invention, which cannot be used to limit the scope of implementation of the present invention, that is, any equivalent made according to the patent application scope of the present invention Changes and modifications should still fall within the scope of the patent of the present invention.

100‧‧‧trans organic solar photovoltaic

10‧‧‧Conductible substrate

20‧‧‧Electron transfer layer

21‧‧‧Surface modifier

30‧‧‧Active layer

40‧‧‧Electron tunnel transmission layer

50‧‧‧counter electrode layer

Claims (20)

A trans-organic photovoltaic (photovoltaic) comprising: a conductive substrate, an electron transport layer, an active layer, a hole transport layer, and a counter electrode layer; wherein the electron transport layer includes a glucose group (glucose-based) biopolymer as a surface modifier. The trans organic solar photovoltaic as described in item 1 of the patent application scope, wherein the glucose-based biopolymer is dissolved in a solvent, and the solvent includes water, dimethyl sulfoxide (DMSO) or a combination thereof. The trans organic solar photovoltaic as described in item 1 of the patent application scope, wherein the glucose-based biopolymer is selected from the group consisting of methyl cellulose, chitosan, and dextrin. The trans organic solar photovoltaic as described in item 2 of the patent application scope, wherein the total surface energy of the glucose-based biopolymer is greater than 55 mN/m. The trans organic solar photovoltaic as described in item 2 of the patent application scope, wherein the electron transport layer is selected from titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin dioxide (SnO ₂ ) and zinc stannate (Zn ₂ SnO ₄ ). The trans organic solar photovoltaic as described in item 2 of the patent application scope, wherein the conductive substrate comprises a conductive material selected from the group consisting of indium oxide (In ₂ O ₃ ) and tin oxide (SnO ₂ ), indium-tin composite oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), zinc oxide-gallium oxide (ZnO-Ga ₂ O ₃ ) and zinc oxide-alumina (ZnO- Al ₂ O ₃ ). The trans organic solar photovoltaic as described in item 1 of the scope of the patent application, wherein the active layer is a bulk heterojunction layer. The trans organic solar photovoltaic as described in item 7 of the patent application scope, wherein the bulk heterojunction layer is fullerene-based or non-fullerene acceptor-based )Floor. The trans organic solar photovoltaic as described in item 8 of the patent application scope, wherein the bulk heterojunction layer comprises PTB7-Th: PC ₇₁ BM blend or PBDB-T: ITIC blend. The trans organic solar photovoltaic as described in item 9 of the patent application scope, wherein the weight ratio of the PTB7-Th:PC ₇₁ BM blend is 1:05 to 1:3. The trans organic solar photovoltaic as described in item 9 of the patent application scope, wherein the weight ratio of the PBDB-T:ITIC blend is 1:0.5 to 1:2. The trans organic solar photovoltaic as described in item 2 of the patent application scope, wherein the hole transfer layer is selected from 2,2',7,7'-4-[N,N-bis(4-methoxy Phenyl)amino]-9,9'-spiro-fluorene (Spiro-OMeTAD), polydioxyethylthiophene: styrenesulfonic acid (PEDOT: PSS), N,N'-bis(3-methylphenyl )-N,N'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (TPD), polytrihexyl polythiophene (P3HT), vanadium pentoxide (V ₂ O ₅ ), composed of nickel oxide (NiO), graphene, molybdenum sulfide (MoS ₂ ), molybdenum selenide (MoSe ₂ ), polyalkyl-thiophene and molybdenum trioxide (MoO ₃ ) Group. The trans organic solar photovoltaic as described in item 2 of the patent application scope, wherein the counter electrode layer includes a material selected from the group consisting of gold, silver, rubidium, palladium, nickel, molybdenum, aluminum, and alloys thereof Group. A method for manufacturing a trans organic solar photovoltaic device as described in item 1 of the scope of patent application, which includes: a. coating an electron transport layer on a conductive substrate, and then coating a glucose-based biopolymer to form an intermediate layer as a surface modifier; b. forming an active layer on the intermediate layer; c. Depositing a hole transfer layer on the active layer; and d. depositing a counter electrode layer on the hole transfer layer. The method according to item 14 of the patent application scope, wherein the glucose-based biopolymer is selected from the group consisting of methyl cellulose, chitosan, and dextrin. The method as described in item 14 of the patent application range, wherein the electron transport layer is selected from titanium dioxide (TiO ₂ ), zinc oxide (ZnO), tin dioxide (SnO ₂ ) and zinc stannate (Zn ₂ SnO ₄ ) The group formed. The method according to item 14 of the patent application scope, wherein the conductive substrate comprises a conductive material selected from the group consisting of indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ), indium- Tin composite oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), zinc oxide-gallium oxide (ZnO-Ga ₂ O ₃ ) and zinc oxide-alumina (ZnO-Al ₂ O ₃ ) Group. The method as described in item 14 of the patent application range, wherein the active layer is a bulk heterojunction layer. The method as described in item 18 of the patent application range, wherein the block heterojunction layer is a fullerene-based or non-fullerene acceptor-based layer. The method as described in item 14 of the patent application scope, wherein the hole transfer layer is selected from 2,2',7,7'-4-[N,N-bis(4-methoxyphenyl)amino ]-9,9'-spiro-fluorene (Spiro-OMeTAD), polydioxyethylthiophene: styrenesulfonic acid (PEDOT: PSS), N,N'-bis(3-methylphenyl)-N, N'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (TPD), polytrihexyl polythiophene (P3HT), vanadium pentoxide (V ₂ O ₅ ), oxidation A group consisting of nickel (NiO), graphene, molybdenum sulfide (MoS ₂ ), molybdenum selenide (MoSe ₂ ), polyalkyl-thiophene and molybdenum trioxide (MoO ₃ ).

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