Organic single-crystal composite oriented polymer film, method for producing the same, photoelectric device and use thereof

Abstract

The present invention provides an organic single crystal composite oriented polymer film, comprising an oriented polymer, which is a polymer fiber in which an organic polymer is aligned in one direction, and an organic single crystal tightly wrapping the polymer fiber, a method for producing the same, a photoelectric device, and its use. The present invention further provides a method for producing the composite film, which includes producing an oriented polymer film by a spatial confinement and oriented crystallization method, and growing an organic single crystal on the oriented polymer film by a solution method. The composite film produced using the method according to the present invention combines the larger heterojunction interface area and long-range order of a bulk heterojunction, achieving high carrier mobility and long exciton diffusion length while ensuring efficient dissociation of excitons. Compared with the organic single crystal composite disordered polymer, the polymer orientation further improves the long-range order of the system, resulting in a 27% decrease in fluorescence lifetime.

Description

[Technical Field]

[0001] The present invention belongs to the field of organic semiconductor technology, and more particularly to organic single-crystal composite orientation polymer films, methods for producing the same, photoelectric devices, and uses thereof. [Background technology]

[0002] An organic semiconductor bulk heterojunction is a composite structure formed by the contact of two or more organic semiconductor materials. Organic semiconductor bulk heterojunctions not only combine the electrical and optical properties of different organic semiconductors, but can also achieve properties not found in single-component organic semiconductors. For example, the built-in electric field formed at the heterointerface significantly improves the dissociation efficiency of photogenerated excitons, resulting in much higher performance for heterojunction-based photoelectric devices (e.g., solar cells, photodetectors) compared to single-component organic semiconductor photoelectric devices. However, the performance of photoelectric devices is limited. For example, in a planar heterojunction consisting of copper(II) phthalocyanine (CuPc) and a tetracarboxyperylene derivative, benzimidazole perylene (PTCBI), the exciton diffusion distance of CuPc is only 10-50 nm. As a result, excitons that cannot diffuse to the heterojunction interface recombine, resulting in a short-circuit current that is about half that of a bulk heterojunction device (F. Yang, M. Shtein, SR Forrest, Nature Materials, 4, 37 (2005)). Furthermore, carriers after dissociation may be trapped in defects within the system, leading to a decrease in device efficiency (H. Li, C. Fan, and W. Fu, Angewandte Chemie International Edition, 54, 956 (2015)). Therefore, an ideal high-performance photoelectric device requires a large heterojunction contact area, as well as sufficiently fast carrier movement and long exciton diffusion distances.

[0003] To achieve a large heterojunction contact area, organic photoelectric devices often employ a bulk heterojunction structure. In this bulk heterojunction, hole and electron transport materials (i.e., donors and acceptors) are mixed throughout the entire region, and the interface between them extends across the entire region. When the hole and electron transport materials come into close contact, a depletion layer is formed and an internal electric field is generated. Since the photogenerated excitons of the organic semiconductor need to dissociate into free charges due to the action of the internal electric field, the bulk heterojunction can increase the number of photogenerated excitons that reach the interface and dissociate within a limited diffusion distance, and further improve the overall photoelectric performance of De Beers, such as short-circuit current and photoresponse.

[0004] Currently, commonly used methods for manufacturing organic semiconductor bulk heterojunctions include blend solution spin coating and vapor phase co-deposition. These methods randomly separate phases to form a bulk heterojunction morphology in which two phases coexist. However, random phase separation often results in structures unfavorable to carrier movement, such as isolated island structures where one phase is completely surrounded by another, which is detrimental to carrier uptake by electrodes. Moreover, the structures obtained by these two methods are often amorphous or polycrystalline and contain many structural defects. Structural defects can form traps that capture carriers and excitons, and can also scatter carriers and excitons, hindering their movement, reducing the number of charges collected by electrodes, and potentially lowering the conversion efficiency and other properties of solar power generation.

[0005] To achieve high carrier mobility and long exciton diffusion distances, organic optoelectronic devices must employ long-range ordered structures. The most ideal long-range ordered structure is one in which the lattice is periodically arranged and grain boundaries are absent, i.e., a single crystal. Single crystals have fewer structural defects and are more favorable to exciton diffusion and carrier transport than amorphous or polycrystalline materials. Furthermore, they reduce the number of excitons that move to the interface and the number of carriers collected at the electrodes, which translates to improved performance of the optoelectronic device, such as carrier mobility. Currently, methods for producing low-molecular-weight organic semiconductor single crystals include poor solvent diffusion, solvent evaporation, and cold precipitation. However, crystals obtained by these methods are often bulky with considerable thickness, and carriers do not have time to migrate to electrodes during their lifetime. This leads to serious recombination of photogenerated carriers, which limits the performance improvement of related optoelectronic devices. Meniscus coating and printing methods (G. Giri, E. Verploegen, and SCB Mannsfeld, Nature, 480, 504 (2011); H. Minemawari, T. Yamada, and H. Matsui, Nature, 475, 364 (2011)) allow for the growth of film-like single crystals on a substrate. However, in order to increase the heterojunction interface area, it is necessary to grow crystals on an uneven substrate surface. Irregularities exceeding the thickness of the crystal inhibit the progress of crystallization, and rough surfaces increase the nucleation sites, sometimes resulting in only polycrystalline material being obtained (W. Shao, H. Dong and W. Hu, Chemical Science, 2, 590 (2011)).

[0006] On the other hand, in the case of polymeric organic semiconductors, the crystallization process involves multiple chain structural transitions, resulting in multiple potential barriers and making it difficult even to obtain single crystals (JALim, F.Liu, and S.Ferdous, Materials Today, 13,14 (2010)). Currently, attempts to construct long-range ordered organic polymer semiconductors are focused on forming oriented structures, including solution shearing and mechanical friction methods. However, in the solution shearing method, the polymer forms nuclei at the gas-liquid interface, and the resulting polymer film is clearly oriented only on the surface, with the side closer to the base being almost isotropic (D.Wu, M.Kaplan, and HWRo, Chemistry of Materials. 30, 1924 (2018)). The mechanical friction method has high operational demands, as it requires not only repeated friction of specific design equipment but also the induction of orientation of organic polymer semiconductors using highly oriented polytetrafluoroethylene (PTFE) as a substrate (L. Biniek, S. Pouget, and D. Djurado, Macromolecules, 47, 3871 (2014)). Moreover, after the polymer is oriented, oriented undulations are formed on the polymer surface, increasing surface roughness. As a result, the edges of solution droplets shrink unevenly during subsequent film-like low-molecular-weight single crystal growth. In addition, the high roughness promotes local nucleation, which is unfavorable for single crystal formation and compound growth of single crystal arrays.

[0007] As mentioned above, currently, organic semiconductor optoelectronic devices can only consider one of two properties: a large heterojunction contact area or long-range order, and it is difficult to achieve both. Due to the self-limiting properties of single crystals, they tend to form regular convex polyhedral shapes to minimize system energy and cannot easily sink into another phase to form a ridged surface. Therefore, it is somewhat difficult to realize a structure that combines the large interface area and long-range order of bulk heterojunctions. One viable method is to orient two organic semiconductor polymers together in a blend solution to form a bulk heterojunction, but oriented polymer semiconductors have grain boundaries, and their long-range order does not match that of single crystals. On the other hand, since low-molecular-weight single-crystal films are usually composed of band-shaped crystals with a width on the micron scale, the heterojunction formed by two types of low-molecular-weight single crystals becomes a planar heterojunction, with a limited interface area, and photogenerated excitons cannot sufficiently diffuse to the interface and dissociate. Therefore, composite structures of low-molecular-weight single crystals and oriented polymers are expected to maximize the long-range order of the system while simultaneously forming a large heterojunction contact area, thereby achieving excellent photoelectric performance.

[0008] There are currently several attempts to construct long-range ordered bulk heterojunctions between organic small molecule single crystals and polymer semiconductors. In the literature (J. Ren, S. Meng, and X. Guo, Journal of the American Chemical Society, 142, 1630 (2020)), inspired by the fact that crystals can be embedded in organic gel fibers in the mineralization phenomenon of living organisms, C is used in a poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV) gel. 60 MEH-PPV gel fibers are uniformly embedded inside the crystal obtained by growing C 60The crystals maintain their long-range order. However, the guest embedding content of the long-range ordered bulk heterojunctions constructed by this method is limited, mostly less than 1 wt%, and the obtained C 60 The crystals have a three-dimensional hexagonal bipyramidal shape of about 100 μm, and when constructing devices, electrodes can only be randomly deposited on certain positions on the crystal via a mask plate, making them highly uncontrollable and inconvenient to operate. In the literature (H.Li, G.Xue, and J.Wu, Chinese Chemical Letters, 28, 2121 (2017)), perylene bisimide (PBI) derivative fibers are dispersed on a base beforehand, and then a single crystal array of 6,13-bis(triisopropylsilylethynyl)-pentacene (Tips-pentacene) is grown on it using droplet-pinned crystallization (DPC). The single crystals grow in accordance with the undulations of the fibers, forming a large contact area and creating a long-range ordered bulk heterojunction. However, since the PBI fibers are randomly dispersed on the base by the spin-coating method, their surface irregularities are relatively small and uniform, and they do not significantly affect the subsequent growth of Tips-pentacene crystals. Furthermore, the fibers produced in this way do not exhibit clear orientation, and the crystallinity of the PBI fibers used in the literature is poor. The long-term order of the system can be further improved by selecting and oriented a crystalline polymer semiconductor.

[0009] From the above, it is clear that conventional technologies cannot produce the long-range ordered bulk heterojunction films described above, and there are mainly four challenges: 1) The polymer crystallization process is complex and involves a transformation of the multi-chain conformation, making it difficult to achieve better orientation with existing methods for producing oriented polymer organic semiconductors. 2) Oriented polymer organic semiconductors are formed by the aggregation of fibers of different thicknesses and widths, resulting in a rough surface. The undulations exceeding the crystal thickness hinder the growth of single crystals, while the rough surface increases nucleation sites, making it easier to form polycrystalline crystals. 3) Due to the self-limiting properties of single crystals, they tend to form regular convex polyhedral topography to minimize system energy, making it difficult to easily form an undulating surface that embeds polymer fibers. 4) The selection of the growth system and solvent is limited to ensure that the solvent used to grow the single crystal in the subsequent solution method does not dissolve the oriented fibers pre-dispersed on the base. Therefore, obtaining an ideal long-range ordered bulk heterojunction film composed of an ideal low-molecular-weight organic semiconductor single crystal and an oriented polymer organic semiconductor is a major technical challenge and a significant obstacle to the realization of high-performance organic optoelectronic devices. [Overview of the project] [Problems that the invention aims to solve]

[0010] In contrast to the shortcomings of the prior art, the present invention provides an organic single-crystal composite oriented polymer film, a method for producing the same, a photoelectric device, and its use, which can form a heterojunction that achieves both a larger heterojunction interface area and long-range order in bulk heterojunctions, ensuring efficient exciton dissociation while realizing high carrier mobility and a long exciton diffusion distance. Compared to a short-range ordered bulk heterojunction obtained by spin-coating, the fluorescence lifetime of the long-range ordered bulk heterojunction of the present invention is reduced by 81% in a composite film produced using the method of the present invention. Compared to a bulk heterojunction made of an organic single-crystal composite disordered polymer semiconductor, the present invention improves the long-range order of the system by oriented the polymer and reduces the fluorescence lifetime by 27%, thereby demonstrating that the organic single-crystal composite oriented polymer semiconductor film structure has the potential to improve the performance of photoelectric devices. [Means for solving the problem]

[0011] To achieve the above objectives, the technical solutions of the present invention are as follows.

[0012] A composite oriented polymer film comprising an oriented polymer, which is a polymer fiber formed by the unidirectional arrangement and growth of an organic polymer, and an organic single crystal, wherein the polymer fibers are of different lengths and arranged in the same direction, and the organic polymer molecular chains also have a certain crystalline arrangement. The principle of polymer fiber growth is that the organic molecular chains form a fiber form through crystallization, and then the fibers grow in the same direction, although the direction in which the fibers grow and the direction of the molecular chains may be the same or different. The organic single crystal tightly encloses the polymer fiber. Furthermore, "tightly encloses" means that the organic semiconductor single crystal grows in close contact with the surface of the polymer fiber.

[0013] Furthermore, the aforementioned tight wrapping is detected by observing whether the surface microtopography of the organic single crystal is undulating, and by observing whether there is a depression at the bonding surface between the organic single crystal and the oriented polymer. The depression refers to a depression in which the sample height is lower than the edge position in a width range where the edge sample heights on both sides are approximately the same, within a narrow width range (usually 100 nm or less).

[0014] Furthermore, the aforementioned tight enveloping is detected by measuring the recess depth at the bonding surface between the organic single crystal and the oriented polymer. The recess depth is the difference in height between the lowest position of the recess and the edge position of the recess. If the polymer fibers are not embedded in the organic single crystal, the bottom surface of the organic single crystal is flat or only has growth steps, and there is no recess, i.e., the recess depth is 0 nm. Therefore, 10 recesses at the bonding surface between the organic single crystal and the oriented polymer may be randomly selected, and the average value of their depths may be measured.

[0015] Furthermore, if the recess depth is 5 nm or more, it is considered that the organic single crystal is growing firmly in contact with the oriented polymer.

[0016] In this case, a sample of the bonding surface between the organic single crystal and the oriented polymer may be produced by spin-coating an aqueous polyvinyl alcohol solution onto the upper surface of the organic single crystal composite oriented polymer film at a rotation speed of 2000 rpm for 30 seconds, and then peeling off the polyvinyl alcohol after drying to expose the bonding surface.

[0017] An organic single crystal is a single crystal formed by growing an organic semiconductor on a polymer fiber. In the present invention, the organic semiconductor is an organic semiconductor molecule whose molecular formula, molecular structure, and molecular weight are clearly fixed. Preferably, the organic semiconductor is one or more selected from linear benzo compounds and their derivatives, linear heterobenzo compounds and their derivatives, benzothiophene compounds and their derivatives, perylene and its derivatives, and fullerene and its derivatives.

[0018] Furthermore, the organic semiconductor may be 6,13-bis(triisopropylsilylethynyl)pentacene (Tips-pentacene), 6,13-bis(triisopropylsilylethynyl)-5,7,12,14-tetraazapentacene (Tips-TAP), or 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene (C8-BTBT), or fullerene (C8-BTBT). 60 ), or perylene. The derivative is formed in which some atoms or groups of atoms in the molecule of a compound are substituted with other atoms or groups of atoms. For example, Tips-pentacene is a derivative of pentacene.

[0019] In the present invention, the organic polymer grown as an oriented polymer is an organic semiconductor molecule having a molecular weight distribution, in which a series of monomer units are linked together, and is preferably a polymer formed by polymerizing a linear conjugated homopolymer, a donor-acceptor alternating copolymer, or a low molecular weight organic semiconductor. The low molecular weight organic semiconductor usually refers to a low molecular weight of less than 1000 with a clearly defined molecular weight and structural formula, for example, 2,2'-((2Z,2'Z)-((4,4,9,9-tetrahexyl-4,9-dihydro-s-indaseno[1,2-b:5,6-b']dithiophene) (2,7-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-dilidene))dimalononitrile, IDIC), (2,2'-((2Z,2'Z)-((4,4,9,9-tetrahexyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile, IDIC), (2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro[1,2,5]thiadiazolo[3, 4e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-dylidene))dimalononitrile) ((2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro[1,2,5]thiadiazolo[3,4e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g ]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro1H-indene-2,1-diylidene))dimalononitrile), Y5), 2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(metanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-dylidene) )dimalononitrile(2,2'-((2Z,2'Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno [2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylyliden e))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile, Y6), etc., are linked directly or via conjugated linkage units such as carbon-carbon double bonds and thiophene rings. Polymers formed from low molecular weight organic semiconductors include PZ1(poly[(2,2'-((2Z,2'Z)-((4,4,9,9-tetrahexadecyl-4,9-dihydro-s-indaseno[1,2-b:5,6-b ']dithiophene-2,7-diyl)bis-(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene)) dimalononitrile-alt-2,5-thiophene)], poly[(2,2'-((2Z,2'Z)-((4,4,9,9-tetrahexadecyl-4,9-dihydro-s-indaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis-(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene)) dimalononitrile-alt-2,5-thiophene)]), PY-IT(poly[(2,2'-((2Z,2'Z)-((12,13-Bis(2-octyldodecyl)-3,9-diundecyl-12,13-dihydro[1,2,5]thiadiazolo[3,4e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]-indole-2,10-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-dylidene))dimalononitrile-alt This includes poly[(2,2'-((2Z,2'Z)-((12,13-bis(2-octyldodecyl)-3,9-diundecyl-12,13-dihydro[1,2,5]thiadiazolo[3,4e]thieno[2'',3'':4',5']thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]-indole-2,10-diyl)bis(methanylylidene))bis(3-oxo-2,3-dihydro-1H-indene-2,1-diylidene)) dimalononitrile-alt-2,5-thiophene)]), etc.

[0020] Preferably, the organic polymer is poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c These include ']dithiophene-4,8-dione'), (Poly[(2,6-(4,8-bis(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b']dithiophene))-alt-(5,5-(1',3'-di-2-thienyl-5',7'-bis(2-ethylhexyl)benzo[1',2'-c:4',5'-c']dithiophene-4,8-dione)], PM6), PY-IT, etc.

[0021] Preferably, the organic single crystal composite aligned polymer film further comprises a substrate on which the blended polymer is aligned and grown in one direction.

[0022] The substrate may be a rigid substrate such as a glass plate, a silicon wafer, a metal oxide (AlO X ITO, FTO)) or the like, or may be a flexible substrate such as a polyimide (PI), polyethylene terephthalate (PET), mica sheet or the like, and the substrate is not dissolved or corroded by the solvent used in the manufacturing process.

[0023] In order to facilitate the subsequent growth of the organic single crystal, the substrate may be modified; preferably, the substrate is a substrate modified with a silane group-containing self-assembled molecule, a phosphate group-containing self-assembled molecule, or a thiol group-containing self-assembled molecule.

[0024] Preferably, the substrate is a substrate modified with cross-linked poly(methylmethacrylate) (c-PMMA) or benzocyclobutene (divinyltetramethyldisiloxane-bis(benzocyclobutene), BCB).

[0025] The present invention further provides a simple manufacturing method for an aligned polymer film, which uses an organic solvent oriented crystallization process that is solid at room temperature to place a polymer solute within the space of a thin layer for restricted crystallization, and aligns the polymer one-dimensionally on a substrate via a flow field during the solidification process. The substrate herein may be a substrate in the narrow sense, and the substrate is a glass plate, a silicon wafer, a metal oxide (AlO XThe substrate may be a rigid substrate such as ITO or FTO, or a flexible substrate such as polyimide (PI), polyethylene terephthalate (PET), or mica sheet. The substrate may be modified with silane group-containing self-assembling molecules, phosphate group-containing self-assembling molecules, or thiol group-containing self-assembling molecules. The substrate may also be a substrate in a broad sense; that is, when applied to a semiconductor device, the substrate may have electrodes and a transport layer, and polymer fibers can be oriented and grown on the transport layer. The oriented polymer film produced by the present invention has good orientation over the entire thickness range compared to the solution shear method or mechanical friction method, does not require multiple operations with a specific mold, and can be widely applied to a variety of substrates.

[0026] When manufacturing an oriented polymer film using the aforementioned spatial restriction and orientation crystallization method, an integrated apparatus comprising a motor, a threaded rod, a ball nut, a jig, and a temperature gradient hot stage is employed. The output shaft of the motor is connected to the threaded rod, the threaded rod is screwed into the ball nut, the jig is used to clamp the substrate, the temperature gradient hot stage is positioned parallel to the threaded rod, the jig is fixedly connected to the ball nut, and the jig is placed on the temperature gradient hot stage. The motor rotates the threaded rod, the ball nut moves along the threaded rod, and the jig moves from a high-temperature region to a low-temperature region on the temperature gradient hot stage, that is, the substrate moves from a high-temperature region to a low-temperature region. Therefore, the movement speed of the jig is equal to the movement speed of the substrate and equal to the solidification rate of the organic polymer in the organic polymer solution. The temperature gradient hot stage may be a Kofler melting point meter, and the substrate is placed on the temperature gradient hot stage. The size of the substrate is preferably not greater than the size of the hot stage, but preferably a square with side lengths of 1 to 1.5 cm.

[0027] Specifically, the procedure is as follows: A desired mass of organic polymer and an organic solvent that is solid at room temperature are weighed, and the organic solvent is melted by heating at a temperature between its melting and boiling points to obtain an organic polymer solution. Next, a substrate is placed on a temperature gradient hot stage equipped with a jig, the organic polymer solution is aspirated and dropped onto the substrate, and another clean glass plate (other covers are also possible, and a transparent glass plate is selected for its ease of observation of the solvent solidification state) preheated on a hot stage at a temperature higher than the melting point of the organic solvent is quickly placed over the solution droplets. Preferably, the surface of the glass plate in contact with the organic polymer solution is modified with octadecyltrichlorosilane (OTS), and the glass plate is modified for easy removal so as to leave a complete film on the substrate without adhering an oriented polymer after the solvent and organic polymer have solidified. Here, the temperature of the initial placement position of the substrate is above the melting point of the organic solvent used. Then, an article pre-cooled at a low temperature (e.g., a tweezers head, a needle head, etc.) is brought into contact with the low-temperature side surface of the hot stage of a glass plate placed on a substrate, creating a gradient in which the temperature decreases vertically from the substrate to the glass plate placed on top of it, thereby nucleating and growing organic solvents in the liquid film on the surface of the upper glass plate under low-temperature induction. Preferably, once solvent nucleation is observed, the pre-cooled article used to induce nucleation is removed. Preferably, by pressing the glass plate with a weight of m≧100g, the thickness of the liquid film sandwiched between the glass plate and the substrate can be reduced, thereby reducing the thickness and roughness of the resulting polymer film, as well as enhancing the spatial limiting effect and facilitating the formation of an oriented structure and subsequent organic single crystal growth.

[0028] Subsequently, the motor is started, the threaded rod is rotated to move the ball nut, and the jig is moved at a constant speed toward the low-temperature region of the temperature gradient hot stage along with the substrate. During the growth of organic solvent crystals, the organic polymer solute is constantly extruded and concentrated in a very thin area near the substrate surface, and at the same time, orientation crystallization of the organic solvent occurs due to orientation movement on the temperature gradient hot stage, resulting in the polymer exhibiting a concentration decrease gradient from the low-temperature region to the high-temperature region of the temperature gradient hot stage. Therefore, due to the combined effect of the spatial limiting effect and the concentration gradient, the organic polymer gradually undergoes orientation crystallization from the high-temperature region to the low-temperature region in conjunction with the orientation crystallization of the organic solvent, and when the liquid film completely solidifies, a polymer semiconductor film oriented in one direction is finally obtained. Preferably, the movement speed of the jig controlled by the motor is 5 to 800 μm / s, i.e., the movement speed of the substrate is 5 to 800 μm / s.

[0029] Subsequently, the glass plate is peeled off, and the solidified liquid film is left in an environment below the melting point of the organic solvent or in a vacuum to sublimate the organic solvent, or the solid organic solvent is removed with an orthogonal solvent to obtain an oriented polymer film on the substrate. The orthogonal solvent is a solvent that dissolves the solid organic solvent but does not dissolve the manufactured organic polymer.

[0030] The aforementioned low-temperature pre-cooling is a relative concept; generally, if the temperature is lower than the melting point of the organic solvent, and the difference between the two temperatures is 80°C or more, the article is considered to have been pre-cooled at a low temperature.

[0031] To modify a glass plate with OTS, specifically, 8 μL of OTS is aspirated using a pipette gun in a glove box under a nitrogen atmosphere and injected into a 20 mL sample vial containing metaxylene. The OTS is completely transferred by aspirating several times. The sample vial is capped and shaken well before being removed from the glove box. After washing the glass plate with an alkaline solution, it is plasma-treated at 10% power for 120 seconds. The treated glass plate is placed in a PTFE petri dish, the prepared OTS solution is poured over it, and the dish is capped and allowed to stand in an atmospheric environment for 1-2 hours to react. After the reaction is complete, the glass plate is ultrasonically cleaned using chloroform to obtain the OTS-modified glass plate.

[0032] Herein, the organic polymer is an organic semiconductor molecule with a molecular weight distribution formed by connecting a series of monomer units, and is preferably a polymer formed by polymerizing a linear conjugated homopolymer, a donor-acceptor alternating copolymer, or a small-molecule organic semiconductor.

[0033] Preferably, the organic polymer is poly(3-hexylthiophene-2,5-diyl) (P3HT), PM6, PY-IT, or the like.

[0034] Based on the same inventive concept, the present invention further provides a method for preparing the above-mentioned organic single-crystal composite oriented polymer film, comprising the following steps: S1: preparing an oriented polymer film on a substrate by the above-mentioned space-limited and oriented crystallization method, wherein the concentration of the organic polymer solution therein is c. In order to prevent the oriented polymer fibers pre-dispersed at the bottom from having an excessively large roughness, and prevent such fibers from protruding high and hindering the growth of single crystals, the concentration of the polymer solution is preferably 0 < c ≤ 5 mg / mL, more preferably 2 ≤ c ≤ 4 mg / mL, except that the above-mentioned weight is used to thinly press the liquid film. S2: growing an organic single crystal on the oriented polymer.

[0035] In order to grow an organic single-crystal film on a rough surface, by rationally selecting the substrate and modifying the gas-liquid interface to form nuclei, it is possible to allow crystals to grow over the obstacles at the bottom into continuous single crystals. Furthermore, since organic single crystals have flexibility, the single crystal grown at the gas-liquid interface can partially adapt to the undulations of the bottom surface, and the gap between the single crystal and the fibers on the bottom surface can be continuously filled along with the volatilization of the solution, so that close adhesion between the two can be achieved. Since the polymer fibers on the substrate are arranged in a predetermined direction, the shrinkage of droplets along the vertical orientation direction is hindered to a certain extent, so that a relatively continuous organic single crystal is usually obtained in the orientation direction parallel to the polymer of the bottom layer. The substrate is a glass plate, a silicon wafer, a metal oxide (AlO XThe substrate may be a rigid substrate such as ITO or FTO, or a flexible substrate such as polyimide (PI), polyethylene terephthalate (PET), or mica sheet. The substrate is not dissolved or corroded by the solvent used in the manufacturing process and may subsequently be modified to better grow single crystals on the oriented polymer. The modifying material for the substrate is a film material consisting of one or more of the following: silane group-containing self-assembling molecules, phosphate group-containing self-assembling molecules, or thiol group-containing self-assembling molecules. More preferably, modification with BCB and modification with c-PMMA are used.

[0036] Regarding the modification of the substrate with c-PMMA, specifically, PMMA is heated and dissolved with n-butyl acetate at 90°C to prepare a 25 mg / mL solution, which is then cooled to prepare it for use. 1,6-bis(trichlorosilyl)hexane (20 μL of the crosslinking agent is added to the PMMA-n-butyl acetate solution) is added as a crosslinking agent to prepare it for use. The substrate is placed on a spin coater, a vacuum pump is used to adsorb the substrate, the solution is dropped onto the substrate surface to completely cover it, and the substrate is spin-coated at a rotation speed of 4000 rpm for 30 seconds. After that, it is heat-treated in a nitrogen atmosphere at 100°C for 1 hour to crosslink it.

[0037] Regarding the substrate modification with BCB, specifically, the substrate is plasma-treated at 10% power for 120 seconds and then transferred to a glove box under a nitrogen atmosphere. The BCB precursor stock solution is diluted with trimethylbenzene (volume ratio 1:30) and thoroughly mixed, then filtered through a 220 nm pore size filter to prepare for use. The plasma-hydrolyzed substrate is placed in a spin coater, and the mecitrylene solution of the BCB precursor is dropped onto the substrate surface until it is completely covered. After spin-coating at a rotation speed of 4000 rpm for 30 seconds, the substrate is heat-treated in a nitrogen atmosphere at 123°C, 185°C, and 247°C in that order for 30 minutes to crosslink it.

[0038] Furthermore, in step S2, an organic single crystal is grown on the oriented polymer by a solution method.

[0039] Furthermore, the step of growing organic single crystals using the aforementioned solution method specifically involves: First, step S201 involves dissolving an organic semiconductor in a solvent to produce an organic semiconductor solution. The method includes step S202, which involves growing an organic single crystal on an oriented polymer by either a droplet-fixed crystallization method and its modification, or a meniscus coating method.

[0040] Furthermore, the step of producing a single crystal by the droplet-fixed crystallization method is, specifically, The process includes step S202, in which a substrate on which an oriented polymer has been produced is placed in a container, preferably on a cover glass, then the cover glass is placed in a petri dish, one drop of droplet fixative is placed in the center of the substrate on which the oriented polymer has been produced, the entire container is preheated and placed in this preheated temperature environment, then an organic semiconductor solution is dropped onto the droplet fixative, the container is quickly sealed to prevent the container from shaking during sealing in order to prevent the droplet from shifting position, and an organic single crystal is obtained once the evaporation of the solvent in the droplet is complete.

[0041] The specific procedure is as follows: In a cleanroom, place the substrate on which the oriented polymer has been manufactured onto a coverslip, place the coverslip in a petri dish, and place one drop of the fixative in the center of the substrate. Place the entire setup on a hot stage and preheat for 5-10 minutes until the temperature is equilibrium. Under these preheating conditions, 15-25 μL of a solution containing dissolved organic semiconductor is drawn in using a pipette and dropped onto the droplet fixative, and the petri dish is quickly covered. To prevent the droplet from shifting position, ensure that the petri dish is not shaken when sealed. After 5-30 minutes, when the solvent in the droplet has completely evaporated, an organic low-molecular-weight single crystal is obtained.

[0042] Furthermore, the droplet fixing material is a silicon wafer, a needle, or a metal rod.

[0043] Furthermore, the silicon wafer size is 3 x 3 mm. 2 That is the case.

[0044] Furthermore, a substrate on which a deformed-morphologically oriented polymer has been produced by the droplet-immobilized crystallization method is placed in a container, the substrate is tilted 0.1 to 5°, the entire container is preheated, an organic semiconductor solution is dropped onto the droplet-immobilized material under this preheated temperature environment, the container is quickly sealed, and an organic single crystal is obtained once the evaporation of the solvent in the droplet is complete.

[0045] Furthermore, the step of growing an organic single crystal by the meniscus coating method specifically involves adjusting the distance between the coating tool and the substrate on which the oriented polymer has been fabricated to 100-150 μm, preheating the substrate on which the oriented polymer has been fabricated for 10 minutes, injecting an organic semiconductor solution into the gap between the coating tool and the substrate, then moving the coating tool parallel to the substrate at a constant speed to shear the organic semiconductor solution, and after coating is completed, aspirating the excess organic semiconductor solution to prevent the grown crystal from dissolving by reflow, or The method includes immersing a substrate on which an oriented polymer has been fabricated in an organic semiconductor solution, lifting the substrate, forming a meniscus between the lifted substrate and the organic semiconductor solution, and completely separating the substrate from the organic semiconductor solution.

[0046] Furthermore, the application tool may be a scraper, blade, smooth rod, coil rod, brush, or bead.

[0047] Furthermore, the movement speed of the coating tool is 10 to 800 μm / s.

[0048] In step S201, the solvent for dissolving the organic semiconductor is selected considering the volatilization rate at a predetermined temperature, the solubility in the organic semiconductor, and the solubility in the oriented polymer organic semiconductor dispersed on the substrate. Preferably, the solubility of the organic semiconductor in the solvent is greater than 0.2 mg / mL, and the solvent does not dissolve the oriented polymer at the operating temperature.

[0049] Furthermore, the solvent is one or a mixture of n-hexane, n-heptane, metaxylene, and 4-methyl-2-pentanone.

[0050] The concentration of the organic semiconductor solution is 0.1 to 0.8 mg / mL, preferably 0.2 to 0.6 mg / mL. When organic semiconductors are dissolved in different solvents, the preheating temperature of the substrate differs. For example, with n-hexane, the preheating temperature is 20-28°C; with n-heptane, it is 36-40°C; and with metaxylene and paraxylene, it is 40-50°C. In the case of n-hexane, the preheating temperature can be as low as 4-6°C, but after that, it is no longer necessary to seal the petri dish with a sealing membrane. Most preferably, Tips-pentacene is a 0.4 mg / mL n-hexane solution with a preheating temperature of 25°C. Tips-TAP is a 0.3 mg / mL n-hexane solution with a preheating temperature of 25°C.

[0051] The present invention further provides a photoelectric device comprising the above-described organic single-crystal composite orientation polymer film, or an organic single-crystal composite orientation polymer film manufactured by the above-described method for manufacturing the organic single-crystal composite orientation polymer film.

[0052] Preferably, the photoelectric device is selected from a solar cell, a photodetector, a light-emitting diode, or a light-emitting field-effect transistor.

[0053] Preferably, the photodetector is a photomistor and a photosensitive field-effect transistor.

[0054] Preferably, the optoelectronic device further includes electrodes and a transport layer as required by the actual device configuration. The electrodes and transport layer may be manufactured in advance on a substrate, and then a composite film may be manufactured on the transport layer. Alternatively, the composite film may be manufactured directly on the substrate, and then the electrodes and transport layer may be manufactured on the composite film.

[0055] Preferably, the method for manufacturing the electrode is vacuum deposition, sputtering, or subsequent transfer.

[0056] Preferably, the electrode material is one or a combination of gold, aluminum, silver, and titanium.

[0057] Preferably, the method for manufacturing the transport layer is spin coating, vacuum deposition, sputtering, or subsequent transfer.

[0058] Preferably, the material of the transport layer is selected from ZnO, TiO2, and MoO3.

[0059] The present invention further provides for the use of the above-described organic single-crystal composite orientation polymer film, the organic single-crystal composite orientation polymer film produced by the above-described method, and the above-described photoelectric device in one or more of the fields of organic photovoltaic power generation, organic photodetection, organic displays, transportation and logistics, mining and metallurgy, environment, medical devices, explosion-proof detection, food, water treatment, pharmaceuticals, and biotechnology.

[0060] By employing the above-described technical solutions, the present invention offers the following advantages and positive effects compared to the prior art.

[0061] This invention overcomes technical biases and realizes the production of heterojunction composite films of organic single crystals and oriented polymers. The oriented polymer is composed of organic polymer fibers oriented in one direction, and together with the organic semiconductor single crystal, ensures long-range order throughout the heterojunction, which is advantageous for high-speed carrier transport and long-range diffusion of excitons. The organic semiconductor single crystal tightly encases the polymer fibers and embeds the fibers within the organic single crystal, forming a large heterojunction interface area, expanding the distribution range of the built-in electric field, and promoting the dissociation of photogenerated excitons. This invention combines the advantages of long-range order and bulk heterojunctions, significantly improving photophysical properties compared to existing manufacturing methods. The long-range order of organic semiconductor single crystals and oriented polymer organic semiconductors ensures long-range diffusion of excitons and efficient carrier transport, allowing excitons to move sufficiently to the heterojunction interface, efficiently taking up and collecting carriers after dissociation, and reducing losses due to defect trapping. Meanwhile, the large-area contact of the bulk heterojunction efficiently dissociates excitons, reduces energy loss due to recombination, and increases the utilization rate of incident light energy. As a result, the last long-range ordered bulk heterojunction structure exhibits remarkable fluorescence quenching and the lowest fluorescence lifetime, and is expected to be applied to the design of devices related to high-performance photoelectric conversion.

[0062] To manufacture an oriented polymer film, the present invention confines the solvent crystals to the polymer solute in a thin two-dimensional space by the repulsive force of the solvent crystals against the polymer solute during oriented crystallization, and further achieves one-dimensional orientation through the flow field during crystallization. To ensure a firm bond between the organic single crystal and the oriented polymer fibers, the present invention controls the film thickness, concentration, and solidification rate of the organic polymer solution during the production of the oriented polymer, thereby controlling the undulation of the polymer fibers and facilitating the growth of the organic single crystal on the polymer fibers. Furthermore, by utilizing appropriate substrate modification to control the position influencing the nucleation of the organic semiconductor, and by utilizing the flexibility of the film-like single crystal to follow the undulation of the underlying polymer fibers, and by selecting an appropriate concentration of the organic semiconductor solution, crystal growth temperature, solvent, and its evaporation rate, the organic semiconductor solution is completely evaporated, and then the organic single crystal is grown firmly attached to the underlying oriented polymer fibers.

[0063] Furthermore, since the present invention is manufactured based on a solution process, it is easy to operate, has a wide range of applications, offers design flexibility in its material system, does not require special or complex equipment, and can be expected to be mass-produced. [Brief explanation of the drawing]

[0064] [Figure 1]There are two cases when growing organic single crystals on oriented polymer fibers. (a) The organic single crystal of the present invention firmly encloses and embeds the polymer fiber, forming a bulk heterojunction. (b) The area in contact with the polymer fiber of the organic single crystal is small, and while the single crystal itself maintains a flat crystal plane, it is supported only by a few undulating points on the fiber. (c) is a height diagram of the AFM of the bonding surface between the organic single crystal and the oriented polymer fiber in Example 6, which corresponds to case (a). (d) is an SEM image of the contact surface with the bottom-oriented P3HT fiber of a C60 single crystal obtained by uniformly forming nuclei in a droplet using the poor solvent diffusion method, and it can be seen that the surface is almost flat except for a slight growth step, which corresponds to case (b). [Figure 2] These are three cases for determining the long-range order of a sample under orthogonal polarization using a polarizing microscope. (a) and (b) are organic single crystals formed in Example 1 that show synchronized brightness changes and possess long-range order. (c) and (d) are unoriented P3HT fiber films formed in Comparative Example 7 that are not bright and lack long-range order. (e) and (f) are organic polycrystalline materials formed in Comparative Example 1 that are always bright and lack long-range order. [Figure 3] Selective field electron diffraction is used to determine whether a system has long-range order. (a) In Example 1, two sets of single-crystal diffraction spots are shown for Tips-pentacene and P3HT, indicating that the system has long-range order. (b) In Example 6, two sets of single-crystal diffraction spots are shown for Tips-TAP and P3HT, indicating that the system has long-range order. (c) In Comparative Example 8, Tips-pentacene shows multiple sets of diffraction spots, and P3HT shows a diffraction ring, indicating that the system has short-range order. [Figure 4] This is a plan view of an apparatus used to obtain oriented polymer fibers by spatial restriction and oriented crystallization. [Figure 5]The images are optical microscope topography of the composite films obtained in the examples and comparative examples of the present invention, where (a) is Example 1, (b) is Comparative Example 1, (c) is Comparative Example 2, (d) is Comparative Example 3, (e) is Comparative Example 4, (f) is Comparative Example 5, (g) is Comparative Example 6, (h) is Comparative Example 6, and (i) is Comparative Example 8. [Figure 6] The obtained P3HT limited-field electron diffraction patterns are shown as follows: (a) is an oriented P3HT film obtained in Example 1 by spatially limited and oriented crystallization using 1,3,5-trichlorobenzene as the solvent, and (b) is a disordered P3HT film produced in Comparative Example 8 using spin coating. [Figure 7] Example 1 shows a two-dimensional GIWAXS figure (100) obtained by irradiating P3HT, which was obtained by spatial restriction and orientation crystallization, with X-rays incident in the orientation direction. The crystal plane diffraction intensity of this figure is plotted against the orientation φ. [Figure 8] These are SEM images of the organic single crystal of Example 1, where (a) is the bonding surface with the polymer fiber, (b) is the top surface of the organic single crystal, and (c) is the bonding portion between the side surface of the organic single crystal and the polymer fiber. [Figure 9] This shows a comparison of the steady-state fluorescence characteristics of a photoelectric device with those of an oriented P3HT fiber, where (a) is Example 1 and (b) is Example 6. [Figure 10] This invention relates to transient fluorescence testing of photoelectric devices and their data fitting, wherein (a) the photoelectric devices are based on Example 1, Comparative Example 7, and Comparative Example 8, and (b) the photoelectric devices are based on Example 6, Comparative Example 9, and Comparative Example 10. [Figure 11] This is an optical microscope image of Example 2 under orthogonal polarization. [Figure 12] This is an optical microscope image of Example 3 under orthogonal polarization. [Figure 13] This is an optical microscope image of Example 4 under orthogonal polarization. [Figure 14] This is an optical microscope image of Example 5 under orthogonal polarization. [Figure 15] This is an optical microscope image of Example 6 under orthogonal polarization. [Figure 16] This is an optical microscope image of Example 7 under orthogonal polarization. [Figure 17] This is an optical microscope image of Example 8 under orthogonal polarization. [Figure 18] This is an optical microscope image of Example 9 under orthogonal polarization. [Figure 19] This is an optical microscope image of Example 10 under orthogonal polarization. [Figure 20] This is an optical microscope image of Example 11 under orthogonal polarization. [Figure 21] This is an optical microscope image of Example 12 under orthogonal polarization. [Figure 22] This is an optical microscope image of Example 13 under orthogonal polarization. [Figure 23] This is an optical microscope image of Comparative Example 7 under orthogonal polarization. [Modes for carrying out the invention]

[0065] The organic single-crystal composite oriented polymer film proposed in this invention, its manufacturing method, the photoelectric device therefor, and its use will be described in more detail below, along with the accompanying drawings and specific examples. The advantages and features of this invention will become clearer based on the following description.

[0066] The present invention provides an organic single-crystal composite oriented polymer film comprising an organic single crystal and an oriented polymer, wherein the oriented polymer consists of multiple polymer fibers of different lengths grown in one direction, as shown in Figure 1(a), and the organic single crystal tightly encloses the polymer fibers, forming effective contact over a large area. This tight enclosure means that the organic single crystal grows following the surface irregularities of the polymer fibers, while the opposite concept is that "the low molecular weight single crystal grows without following the surface irregularities of the oriented polymer fibers," characterized in that the surface in contact with the fibers of the low molecular weight single crystal is a straight convex surface with no depressions (see Figure 1(b)).

[0067] The aforementioned tight wrapping can be confirmed by observing topography with a scanning electron microscope (SEM) and measuring height with an atomic force microscope (AFM). As shown in Figure 1, when a large area of ​​effective contact is formed between the upper organic single crystal and the lower oriented polymer, the undulations of the lower polymer fibers cause height undulations on the surface of the upper organic single crystal, and depressions are formed on the lower surface of the organic single crystal due to contact with the polymer fibers. Therefore, it is possible to determine whether or not there are undulations on the upper surface of the upper organic single crystal by directly observing with SEM and AFM, and whether or not there is tight adhesion by mixing polyvinyl alcohol (PVA) into a 10% mass fraction aqueous solution, spin-coating it onto a composite film at a rotation speed of 2000 rpm for 30 s, drying it, peeling it off to expose the bonding surface between the upper organic single crystal and the polymer fibers, and observing whether or not there is a depression on this bonding surface. It is also possible to observe with SEM whether the side of the organic single crystal has a curved shape and is tightly bonded to the lower polymer fibers.

[0068] Furthermore, the aforementioned tight enveloping can be characterized by measuring the depth of the recess at the bonding surface between the organic single crystal and the polymer fibers using AFM. The recess refers to a situation where, within a narrow width range (usually 100 nm or less), the sample height is lower than the edge position in a width range where the edge sample heights on both sides are approximately the same. Since the length of the polymer fibers at the bottom is large, the recess is considered to be of a similar length. Because the polymer fibers are embedded inside the organic single crystal, a recess is created on its underside, and the difference in height between the lowest position of this recess and the edge position of the recess becomes the recess depth. If the polymer fibers are not embedded in the organic single crystal, the bottom surface of the organic single crystal is flat or only has growth steps, and there is no recess, i.e., the recess depth is 0 nm. Therefore, by randomly selecting 10 recesses on the underside of the organic single crystal and measuring the average value of their depths, the degree of adhesion between the organic single crystal and the oriented polymer can be reflected. Preferably, if the recess depth d is 5 nm or more, it is considered that the single crystal and the oriented fibers are tightly bonded.

[0069] Long-range order can be rudimentarily determined using a polarizing microscope. Specifically, the sample is placed on a sample stage, magnified to an appropriate magnification (tens or hundreds of times), and the microscope is operated in transmitted or reflected light mode. If the sample substrate is opaque, the microscope operates in reflected light mode. When the polarization angles of the microscope's polarizers are orthogonal, rotating the sample stage reveals, for example, a consistent alternating light-dark change in the entire field of view of both the organic single crystal and the oriented polymer, suggesting that both possess long-range order. If there is no brightness when rotating the sample stage under orthogonal polarization, it suggests that both the organic single crystal and the oriented polymer are amorphous short-range ordered structures, after ruling out 1) the principal optical axis of the organic single crystal overlapping with the incident light direction, and 2) the possibility that the organic single crystal is cubic. Finally, if there is always brightness when rotating the sample stage under orthogonal polarization, but no consistent alternating light-dark change, it suggests that the low-molecular-weight crystals and oriented fibers are polycrystalline and not uniformly oriented. Schematic diagrams of these three cases are shown in Figure 2.

[0070] The principle by which an optical microscope equipped with orthogonal polarizers can be used to determine whether organic semiconductor crystals and oriented polymer fibers possess long-range order is as follows: When polarized incident light is incident on a birefringent crystal in the direction of the non-principal optical axis, birefringence occurs, and the original polarized light is separated into two beams of light with polarization directions perpendicular to each other, one of which coincides with the polarization direction of the incident light. When observed using a polarizer perpendicular to the polarization direction of the polarizer, the crystal exhibits a constant brightness in the field of view due to the birefringence phenomenon, and as the sample rotates on the stage, the brightness shows a uniform and consistent alternating change of light and dark. Therefore, by observing whether or not a consistent change in brightness is observed, the long-range order of the system can be determined.

[0071] Long-range order can also be confirmed by limited-field electron diffraction, and the detection method is as follows: The sample is cut to an appropriate size and placed on a bare copper mesh, and observed using a transmission electron microscope (TEM). The electron beam acceleration voltage is 200 kV, and the area irradiated by the limited-field electron diffraction is a circular region with a diameter of approximately 1 μm. To avoid damage from the electron beam, it is necessary to snap the diffraction pattern immediately after moving to an area not irradiated by the electron beam. If two sets of single-crystal diffraction patterns are obtained, and after calibration the diffraction patterns can be matched to the unit cell parameters of the organic single crystal and the oriented polymer, respectively, it is shown that the obtained structure has long-range order. If a diffraction ring or multiple sets (more than two) of diffraction patterns are obtained, and the two sets of diffraction patterns correspond to the same material, it is shown that the obtained structure does not have long-range order. A schematic diagram is shown in Figure 3.

[0072] The principle for determining whether organic semiconductor crystals and oriented polymer fibers possess long-range order using limited-field electron diffraction is as follows: When a material possesses long-range order, each lattice point in the material exhibits the same scattering behavior to the electron beam. Therefore, the electron beam is coherently enhanced only at specific locations, resulting in regularly arranged diffraction spots. On the other hand, when a material does not possess long-range order, each lattice point scatters in various directions to the electron beam, and the electron beam exhibits multiple sets of diffraction spots, diffraction rings, or diffusion rings. Therefore, by observing whether or not a set of diffraction spots appears by electron diffraction, it is possible to determine whether or not the system possesses long-range order.

[0073] The uniformity of the orientation of the oriented polymer in a given direction is represented by the degree of orientation. The degree of orientation Π is obtained by irradiating X-rays in the orientation direction using grazing-incidence wide-angle scattering (GIWAXS) imaging, selecting the (100) crystal plane diffraction spot intensity, plotting the azimuthal angle, and calculating from the fitted peak shape using Equation 1. TIFF0007917198000001.tif10170Here, H is the half-width of the diffraction peak, and the unit is degree (°).

[0074] Here, the organic semiconductor forming the organic single crystal is any one or more selected from linear benzo compounds and derivatives thereof, linear heterobenzo compounds and derivatives thereof, benzothiophene compounds and derivatives thereof, perylene and derivatives thereof, and fullerene and derivatives thereof. More preferably, the organic semiconductor is selected from 6,13-bis(triisopropylsilylethynyl)pentacene (Tips-pentacene), 6,13-bis(triisopropylsilylethynyl)-5,7,12,14-tetraazapentacene, 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene (C8-BTBT), fullerene C 60 and perylene.

[0075] The organic polymer forming the oriented polymer is selected from linear conjugated homopolymers, donor-acceptor alternating copolymers, and polymers formed by polymerizing organic semiconductors with a molecular weight of less than 10000. More preferably, the organic polymer is poly(3-hexylthiophene-2,5-diyl) (poly(3hexylthiophene2,5-diyl), P3HT), PM6, PY-IT, etc.

[0076] The organic single crystal composite oriented polymer film of the present invention further comprises a substrate on which the oriented polymer is aligned and grown in one direction. The substrate herein may be a substrate in a narrow sense. The substrate may be a hard substrate such as a glass plate, a silicon wafer, a metal oxide (AlO X , ITO, FTO)) or a flexible substrate such as polyimide (PI), polyethylene terephthalate (PET), mica sheet, etc. The substrate may be modified with silane group-containing self-assembled molecules, phosphate group-containing self-assembled molecules, or thiol group-containing self-assembled molecules. The substrate may also be a substrate in a broad sense, that is, when applied to a semiconductor device, the substrate herein includes an electrode and a transport layer, and polymer fibers can be oriented and grown on the transport layer.

[0077] The present invention further provides a method for producing an oriented polymer film in the above-mentioned organic single-crystal composite oriented polymer film, wherein an oriented organic polymer film is obtained on a substrate by spatial restriction and oriented crystallization.

[0078] When manufacturing an oriented polymer film using the aforementioned spatial restriction and orientation crystallization method, the apparatus shown in Figure 4 is employed, comprising a motor 1, a threaded rod 2, a ball nut 3, a jig 5, and a temperature gradient hot stage 4. The output shaft of the motor 1 is connected to the threaded rod 2, the threaded rod 2 is screwed into the ball nut 3, the jig 5 is used to drive the substrate, the temperature gradient hot stage 4 is positioned parallel to the threaded rod 2, the jig 5 is fixedly connected to the ball nut 3, and the jig 5 is placed on the temperature gradient hot stage 4. The motor 1 rotates the threaded rod 2, the ball nut 3 moves along the threaded rod 2, and the jig 5 moves on the temperature gradient hot stage 4. The movement speed of the jig 5 is equal to the movement speed of the substrate and equal to the solidification speed of the organic polymer. The temperature gradient hot stage 4 may be a Kofler melting point meter, the substrate is placed on the temperature gradient hot stage 4, and the size of the substrate preferably does not exceed the size of the hot stage, but is preferably a square with side lengths of 1 to 1.5 cm.

[0079] The method for producing an oriented polymer film using the apparatus shown in Figure 4 is as follows:

[0080] Preparation of organic polymer solution: Weigh the required mass of organic polymer and an organic solvent that is solid at room temperature, heat to melt the organic solvent, and prepare the organic polymer solution.

[0081] Subsequently, the substrate 6 is clamped with the jig 5, and after the temperature reaches equilibrium, a small amount of organic polymer solution is drawn in with a clean glass dropper and 2 to 4 drops are dropped onto the substrate. A clean glass plate modified with octadecyltrichlorosilane (OTS), which has been preheated on the hot stage to a temperature higher than the melting point of the organic solvent, is quickly placed over the solution droplets. The motor 1 is started and the jig 5, together with the substrate 6, is moved at a constant speed toward the low-temperature region on the temperature gradient hot stage 4 until the liquid film has completely solidified, thereby controlling the movement speed of the jig 5 on the temperature gradient hot stage. A movement speed of 5 to 800 μm / s is preferable. The temperature of the initial placement position of the substrate is above the melting point of the organic solvent used. Then, an object pre-cooled at a low temperature (e.g., a tweezers head, a needle head, etc.) is brought into contact with the low-temperature side surface of the hot stage of the glass plate, creating a gradient in which the temperature decreases vertically from the substrate to the glass plate placed on top of it. Under low-temperature induction, the organic solvent in the liquid film is nucleated and grown on the surface of the upper glass plate. Once the nucleation of the organic solvent is observed, the pre-cooled object used to induce nucleation is removed. By pressing the glass plate with a weight of m≧100g, the thickness of the liquid film sandwiched between the glass plate and the substrate can be reduced, thereby reducing the thickness of the resulting polymer film, enhancing the spatial limiting effect, and facilitating the formation of an oriented structure.

[0082] The jig is moved at a constant speed along with the substrate toward the low-temperature region of the temperature gradient hot stage. During the growth of solvent crystals, the organic polymer solute is constantly extruded and concentrated in a very thin area near the substrate surface. Simultaneously, orientational crystallization of the organic solvent occurs due to orientational movement on the temperature gradient hot stage, resulting in the polymer exhibiting a concentration decrease gradient from the low-temperature region to the high-temperature region of the temperature gradient hot stage. Therefore, due to the combined effect of the spatial limiting effect and the concentration gradient, the polymer gradually undergoes orientational crystallization from the high-temperature region to the low-temperature region in conjunction with the orientational crystallization of the organic solvent. When the liquid film completely solidifies, a polymer semiconductor film oriented in one direction is finally obtained.

[0083] After the liquid film has completely solidified, the glass plate is peeled off, and the solidified liquid film is left in an environment below the melting point of the organic solvent or in a vacuum to sublimate the organic solvent, or the solid organic solvent is removed with an orthogonal solvent to obtain an oriented polymer film on the substrate. The orthogonal solvent is a solvent that dissolves the solid organic solvent but does not dissolve the manufactured compound polymer.

[0084] Organic solvents used to dissolve organic polymers generally have good solubility for the corresponding organic polymer, are solid at room temperature, and can be easily removed by sublimation or orthogonal solvent dissolution. Preferably, they are chlorinated aromatic hydrocarbon solvents such as 1,3,5-trichlorobenzene, 1,2,3-trichlorobenzene, or 1,2,4,5-tetrachlorobenzene.

[0085] Low-temperature pre-cooling in articles is a relative concept; if the temperature is lower than the melting point of the organic solvent, and the difference between the two temperatures is 80°C or more, the article is considered to have been pre-cooled at a low temperature.

[0086] The present invention further provides a method for producing an organic single-crystal composite oriented polymer film, which involves first producing an oriented polymer according to the above-described spatial restriction and orientation crystallization method, and then growing an organic single crystal on the oriented polymer by a solution method.

[0087] The present invention will be specifically described using the characterization methods described above, with reference to specific examples and comparative examples. Example 1

[0088] A method for manufacturing a composite film structure of a Tips-pentacene-based organic single crystal semiconductor and oriented P3HT fibers includes the following steps. (1) P-type with a thickness of 575 μm and a silica insulating layer with a thickness of 300 nm <100> A silicon wafer is prepared, and a BCB-modified substrate is spin-coated onto the silicon substrate. (2) Prepare a 1,3,5-trichlorobenzene solution of 2 mg / mL P3HT and heat it at 90°C until completely dissolved. (3) Place the substrate manufactured in step (1) on the Kofler melting point meter (i.e., the temperature gradient hot stage in Figure 4), with the right side of the melting point meter being the low temperature region and the left side being the high temperature region, align the right edge of the substrate to approximately 63°C, and press the left side of the substrate tightly against the jig. Using a clean glass plate dropper, drop 2-3 drops of the solution prepared in step (2) onto the substrate, quickly cover it with an OTS-modified glass plate preheated to 80°C, and press a 100g weight preheated to 63°C onto it. (4) The servo motor is activated, and the substrate is moved to the low-temperature region at a constant speed of approximately 40 μm / s using a jig, allowing the 1,3,5-trichlorobenzene to slowly orient and solidify. (5) Once the liquid film has completely solidified, leave it to stand at approximately 50°C for about 3 minutes, then remove the substrate from the hot stage and peel off the OTS-modified glass plate placed on top of it. (6) The obtained substrate is left to stand at room temperature for 1 day to allow 1,3,5-trichlorobenzene to volatilize and obtain an oriented P3HT film. (7) The circuit board manufactured in step (6) is 24 x 24 mm 2 Place the substrate on a cover glass, then place a polyethylene plastic petri dish cover glass with a diameter of 35 mm and a height of 10 mm on top, and place a stainless steel embroidery needle on the substrate as a droplet holder. Preheat the entire setup on a 25°C hot stage for 10 minutes to equilibrium the temperature, and leave the petri dish on the hot stage throughout the entire growth of the organic single crystal. (8) Prepare an n-hexane solution of 0.4 mg / mL Tips-pentacene and sonicate it for 20 minutes to completely dissolve the solute. (9) Aspirate 20 μL of the solution prepared in step (8) using a pipette gun and gently drop it onto the needle on the substrate, ensuring that the droplet does not slide off the substrate. Then immediately close the lid of the petri dish to seal the petri dish with a sealing membrane. After standing for approximately 10 minutes, once the solvent has completely evaporated, open the petri dish, remove the droplet fixative, and obtain a Tips-pentacene single crystal array composite P3HT oriented fiber film on the substrate. To characterize the topography and structure of the organic single-crystal composite oriented polymer film, observations were made using an optical microscope, a scanning electron microscope, and an atomic force microscope. The resulting topography of the composite film is shown in Figure 5(a). From Figure 5(a), it was found that the organic semiconductor is covered on the oriented P3HT fibers as a band of crystals. Furthermore, the SEM topography of the bonding surface between the organic single crystal and the oriented polymer (Figure 8(a)), the topography of the surface of the organic single crystal (Figure 8(b)), and the junction between the side of the organic single crystal and the oriented polymer (Figure 8(c)) showed that the Tips-pentacene single crystal was firmly attached to the oriented P3HT fibers. To characterize the long-range order of the organic single-crystal composite-oriented polymer semiconductor film, observation was performed using a polarizing microscope and selected-field electron diffraction with a transmission electron microscope. As shown in the polarizing microscope images in Figures 2(a) and (b), synchronized brightness changes were observed under orthogonal polarization. As shown in Figure 3(a), the selected-field electron diffraction showed only one pair of Tips-pentacene single-crystal diffraction spots and P3HT diffraction spots, indicating that the film possesses overall long-range order. To characterize the photophysical properties of the organic single-crystal composite-oriented polymer semiconductor film, tests were performed using a fluorescence spectrometer. As shown in Figure 9(a), the composite film exhibited a clear fluorescence quench phenomenon. From Figure 10(a), the obtained fluorescence lifetime was found to be 10⁹ ps. As shown in Figure 6(a), the electron diffraction pattern of the obtained P3HT film exhibited diffraction spots similar to those of a single crystal, and the absence of prominent diffraction rings indicated good orientation in the thickness direction of the entire film. When X-rays were incident in the direction of this orientation and the crystal plane diffraction intensity against the azimuthal angle φ of the 2D GIWAXS image (100) was plotted, a P3HT oriented polymer with an orientation degree of 87% was obtained, as shown in Figure 7. Furthermore, from Figure 1(c), it was found that the basal depression depth of the obtained Tips-pentacene single crystal was 7.3 nm. Example 2

[0089] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 1, but the concentration of the P3HT solution is set to 5 mg / mL. The methods for topography and structural characterization are the same as in Example 1. As shown in Figure 11, the obtained composite film exhibited synchronous brightness and darkness under orthogonal polarization, and the depth of the depression at the bottom of the Tips-pentacene single crystal was 9.2 nm. Example 3

[0090] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 1, but when growing the Tips-pentacene single crystals, the hot stage is preheated in a glove box with a moisture content of less than 5 ppm at a preheating temperature of 5°C, and after dropping the Tips-pentacenene-hexane solution, the petri dish lid is simply placed over it; there is no need to seal it with a sealing film. The methods for topography and structural characterization are the same as in Example 1. As shown in Figure 12, the obtained composite film exhibited synchronous brightness and darkness under orthogonal polarization, and the depth of the depression on the bottom surface of the Tips-pentacene single crystal was 6.3 nm. Example 4

[0091] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 1, but when growing the Tips-pentacene single crystal, Tips-pentacene is dissolved in n-heptane at a concentration of 0.4 mg / mL, and the preheating temperature of the hot stage is set to 38°C. The methods for topography and structural characterization are the same as in Example 1. As shown in Figure 13, the obtained composite film exhibited synchronous brightness and darkness under orthogonal polarization, and the depth of the depression on the bottom surface of the Tips-pentacene single crystal was 5.5 nm. Example 5

[0092] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for manufacturing the organic single-crystal composite oriented polymer film in this embodiment is the same as in Example 1, but the substrate is a silicon wafer with a 300 nm thick silica insulating layer that does not require BCB modification. The methods for topography and structural characterization are the same as in Example 1. As shown in Figure 14, the obtained composite film exhibited synchronous brightness and darkness under orthogonal polarization, and the depression depth of the bottom surface of the Tips-pentacene single crystal was 5.3 nm. Example 6

[0093] A method for producing a composite film structure of Tips-TAP organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 1, except that the substrate is a silicon wafer with a 300 nm thick silica insulating layer modified with c-PMMA, and Tips-TAP is prepared in a 0.3 mg / mL n-hexane solution when growing the Tips-TAP single crystal. The methods for characterizing the topography, structure, and properties are the same as in Example 1. The topography of the obtained composite film is shown in Figure 5(g), and the orthogonal polarized microscope image of the obtained composite film is shown in Figure 15. From these figures, it was observed that the film showed synchronous brightness and darkness under orthogonal polarization, and the depth of the depression at the bottom of the Tips-TAP single crystal was 7.6 nm. The steady-state fluorescence showed a significant fluorescence quench, as shown in Figure 9(b). The fluorescence lifetime calculated from the transient fluorescence fitting curve in Figure 10(b) was 112 ps. Example 7

[0094] A method for producing a composite film structure of Tips-TAP organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 1, except that the substrate is a silicon wafer with a silica insulating layer modified with c-PMMA, and when growing the Tips-TAP single crystal, Tips-TAP is prepared in a 0.3 mg / mL metaxylene solution, and the hot stage preheating temperature is 45°C. The methods for characterizing the topography, structure, and properties are the same as in Example 1. As shown in Figure 16, the obtained composite film exhibited synchronous brightness and darkness under orthogonal polarization, and the depression depth of the bottom surface of the Tips-TAP single crystal was 6.9 nm. Example 8

[0095] A method for manufacturing a composite film structure of a Tips-pentacene-based organic single crystal semiconductor and oriented P3HT fibers includes the following steps. The method for producing the oriented polymer fibers in this embodiment refers to steps (1-6) of Example 1. Furthermore, organic single crystals are produced by bar-coating, or meniscus coating. (1) Prepare a Tips-pentacene n-heptane solution with a concentration of 0.5 mg / mL and dissolve it thoroughly using ultrasound. (2) Adjust the distance between the coating rod and the substrate coated with the oriented polymer to 200 ± 5 μm. (3) After preheating the substrate coated with the oriented polymer at 38°C for 10 minutes, drop 10 μL of the solution prepared in step (1) onto the coating rod, filling the gap between the coating rod and the substrate with the solution. (4) The coating rod is controlled to move at a constant speed in a constant direction at a speed of 400 ± 5 μm / s to coat the substrate with the solution. (5) By using dust-free paper to aspirate excess liquid between the coating rod and the substrate, an organic single crystal is produced on the oriented polymer. The methods for characterizing the topography, structure, and properties were the same as those in Example 1. The topography of the obtained composite film is shown in Figure 5(i), and as shown in Figure 17, the composite film exhibited synchronous brightness under orthogonal polarization, with a basal depression depth of 8.0 nm for the Tips-pentacene single crystal. Example 9

[0096] A method for producing a composite film structure of C8-BTBT-based organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 1, except that the organic semiconductor solution is a 0.6 mg / mL C8-BTBT 4-methyl-2-pentanone solution and the crystal growth temperature is 55°C. The methods for characterizing the topography, structure, and properties are the same as in Example 1. As shown in Figure 18, the obtained composite film exhibited synchronous brightness and darkness under orthogonal polarization, and the depression depth of the basal surface of the C8-BTBT single crystal was 7.4 nm. Example 10

[0097] A method for producing a composite film structure of perylene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 1, but the organic semiconductor solution is a 0.4 mg / mL perylene metaxylene solution, the crystal growth temperature is 35°C, and sealing with a sealing film is not performed. The methods for characterizing the topography, structure, and properties are the same as in Example 1. As shown in Figure 19, the obtained composite film exhibited synchronous brightness and darkness under orthogonal polarization, and the depression depth of the bottom surface of the perylene single crystal was 7.1 nm. Example 11

[0098] A method for producing a composite film structure of C8-BTBT-based organic single crystals and oriented PM6 fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 9, but the organic polymer solution is a 2 mg / mL PM6 1,3,5-trichlorobenzene solution and the organic semiconductor solution is a 0.6 mg / mL C8-BTBT n-hexane solution. The methods for characterizing the topography, structure, and properties are the same as in Example 1. The obtained oriented polymer film had an orientation degree of 89%, and as shown in Figure 20, the composite film exhibited synchronous brightness and darkness under orthogonal polarization, with a depression depth of 6.7 nm at the bottom of the C8-BTBT single crystal. Example 12

[0099] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented PY-IT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 1, except that the organic polymer solution is a 2 mg / mL PY-IT 1,2,4,5-tetrachlorobenzene solution. The methods for characterizing the topography, structure, and properties are the same as in Example 1. The obtained oriented polymer film had a degree of orientation of 78%, and as shown in Figure 21, the composite film exhibited synchronous brightness and darkness under orthogonal polarization, with a depression depth of 6.2 nm at the bottom of the Tips-pentacene single crystal. Example 13

[0100] C 60 A method for manufacturing a composite film structure of an organic single-crystal semiconductor and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 1, but the organic semiconductor solution is 0.4 mg / mL C 60 The solution is a metaxylene solution, and the crystal growth temperature is 30°C. The method for characterizing the topography, structure, and properties is the same as in Example 1. As shown in Figure 22, the obtained composite film exhibits synchronized brightness and darkness under orthogonal polarization, C 60 The depth of the depression at the base of the single crystal was 7.9 nm. Example 14

[0101] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for manufacturing the organic single-crystal composite orientation polymer film in this embodiment is the same as in Example 1, but the movement speed of the jig when manufacturing the orientation polymer film is set to 5 μm / s. Example 15

[0102] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this embodiment is the same as in Example 1, but the movement speed of the jig when producing the oriented polymer film is set to 300 μm / s. Example 16

[0103] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for manufacturing the organic single-crystal composite oriented polymer film in this embodiment is the same as in Example 1, but the movement speed of the jig when manufacturing the oriented polymer film is set to 800 μm / s. Example 17

[0104] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 1, but Tips-pentacene is prepared as a 0.2 mg / mL n-hexane solution. Example 18

[0105] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this example is the same as in Example 1, but Tips-pentacene is prepared as a 0.8 mg / mL n-hexane solution. Example 19

[0106] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this embodiment is the same as in Example 8, but the movement speed of the coating rod when producing the organic single-crystal film is set to 20 μm / s. Example 20

[0107] A method for producing a composite film structure of Tips-pentacene-based organic single crystals and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film in this embodiment, referring to Example 8, is as follows: the movement speed of the coating rod when producing the organic single-crystal film is 800 μm / s. Comparative Example 1

[0108] A method for producing a composite film structure of Tips-pentacene-based organic polycrystalline material and oriented P3HT fibers includes the following steps. The method for producing the organic polycrystalline composite oriented polymer semiconductor film of Comparative Example 1 is the same as in Example 1, but the concentration of the P3HT solution is 10 mg / mL, and the same organic solvent as in Example 1 is used for dissolution. As shown in Figure 5(b), the Tips-pentacene film was determined to be an organic polycrystalline film based on microscopic observation. Comparative Example 2

[0109] A method for manufacturing a composite film structure of a Tips-pentacene-based organic polycrystalline semiconductor and oriented P3HT fibers includes the following steps. The method for producing the organic polycrystalline composite oriented polymer semiconductor film of Comparative Example 2 is the same as in Example 1, but the preheating temperature of the hot stage when growing the Tips-pentacene organic polycrystals is set to 17°C. As shown in Figure 5(c), the Tips-pentacene film was determined to be an organic polycrystalline film based on microscopic observation. Comparative Example 3

[0110] A method for manufacturing a composite film structure of a Tips-pentacene-based organic polycrystalline semiconductor and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer semiconductor film in Comparative Example 2 is the same as in Example 1, but the concentration of the Tips-pentacene solution is 1 mg / mL. As shown in Figure 5(d), the Tips-pentacene film was determined to be an organic polycrystalline film based on microscopic observation. Comparative Example 4

[0111] A method for manufacturing a composite film structure of a Tips-pentacene-based organic polycrystalline semiconductor and oriented P3HT fibers includes the following steps. The method for producing the organic polycrystalline composite oriented polymer semiconductor film of Comparative Example 4 is the same as in Example 1, but the solvent used in the Tips-pentacene solution is cyclohexane. As shown in Figure 5(e), the Tips-pentacene film was determined to be a discontinuous organic polycrystalline film based on microscopic observation. Comparative Example 5

[0112] A method for manufacturing a composite film structure of a Tips-pentacene-based organic polycrystalline semiconductor and oriented P3HT fibers includes the following steps. The method for producing the organic polycrystalline composite oriented polymer semiconductor film of Comparative Example 5 is the same as in Example 1, but the movement speed of the jig when producing the P3HT oriented fibers is set to 1000 μm / s. As shown in Figure 5(f), the Tips-pentacene film was determined to be a discontinuous organic polycrystalline film based on microscopic observation. Comparative Example 6

[0113] A method for manufacturing a composite film structure of Tips-TAP-based organic single-crystal semiconductor and oriented P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer semiconductor film of Comparative Example 6 is the same as in Example 6, but the Tips-TAP solution is prepared using cyclohexane. As shown in Figure 5(h), the Tips-TAP film was observed under a microscope and determined to be a discontinuous organic polycrystalline film. Comparative Example 7

[0114] A method for manufacturing a composite film structure of a Tips-pentacene-based organic single crystal semiconductor and disordered P3HT fibers includes the following steps. The method for producing the organic single crystal in Comparative Example 7 is the same as in Example 1, but the method for producing the P3HT disordered film is as follows: The P3HT was completely dissolved by heating it to 60°C using a mixed solvent of o-dichlorobenzene and n-heptane in a volume ratio of 3:2, and then allowed to stand at room temperature for 1 day. This solution was then spin-coated onto a clean silicon wafer substrate at a rotation speed of 8000 rpm. Observation of the Tips-pentacene film with a polarizing microscope revealed synchronized brightness and darkness, and it was determined to be an organic single crystal film as shown in Figure 23. As shown in Figure 6(b), the non-orientation of P3HT could be determined by the diffraction ring shown in the limited-field electron diffraction pattern. Its transient fluorescence characteristics were characterized as shown in Figure 10(a), and the fluorescence lifetime was 150 ps. Comparative Example 8

[0115] A method for producing a blended film structure of Tips-pentacene-based organic polycrystalline material and P3HT includes the following steps. (1) P-type with a thickness of 575 μm and a silica insulating layer with a thickness of 300 nm <100> A silicon wafer is prepared, and a BCB-modified substrate is spin-coated onto the silicon substrate. (2) Prepare a chlorobenzene solution of P3HT and Tips-pentacene in a mass ratio of 1:7 to a concentration of 15 mg / mL, and heat to 60°C to completely dissolve. (3) BCB modified substrate in step (1) 1 × 1 cm 2 Cut to size and place on the spin coat. (4) The solution prepared in step (2) is dropped onto the substrate and spread evenly. Then, the spin coater is started and the film is spin-coated for 60 seconds at a rotation speed of 1000 rpm to obtain a blend film of Tips-pentacene organic semiconductor and P3HT. The blended film consisted of disordered P3HT and Tips-pentacene polycrystalline material. The method for characterizing its structure and properties was the same as in Example 1. The electron diffraction pattern shown in Figure 3(b) was a diffraction ring, indicating that the obtained film structure lacked long-range order. The transient fluorescence characteristics of the film were characterized as shown in Figure 10(a), with a fluorescence lifetime of 571 ps. Comparative Example 9

[0116] A method for producing a composite film structure of Tips-TAP organic single crystals and disordered P3HT fibers includes the following steps. The method for producing the organic single-crystal composite oriented polymer film of Comparative Example 9 is described in Comparative Example 7. Its transient fluorescence characteristics are characterized as shown in Figure 10(b), and its fluorescence lifetime was 154 ps. Comparative Example 10

[0117] A method for manufacturing a blend film structure of Tips-TAP-based organic semiconductor and P3HT includes the following steps. The method for producing the blend film of organic semiconductor and P3HT in Comparative Example 10 is the same as in Comparative Example 8. The spin-coated solution was a chlorobenzene solution prepared by mixing P3HT and Tips-TAP in a mass ratio of 1:7 to a total concentration of 15 mg / mL. Its transient fluorescence characteristics were characterized as shown in Figure 10(b), and the fluorescence lifetime was 240 ps. The manufacturing conditions for the samples in the above examples and comparative examples are summarized in the table below.

[0118] The manufacturing conditions for the samples produced using the droplet-fixed crystallization method are as follows: TIFF0007917198000002.tif234170TIFF0007917198000003.tif235170TIFF0007917198000004.tif235170TIFF0007917198000005.tif234170

[0119] The manufacturing conditions for the sample produced by growing organic single crystals using the meniscus coating method are as follows: TIFF0007917198000006.tif146170

[0120] Examples 1-7 and Comparative Examples 1-6 investigated the effects of various manufacturing conditions on organic semiconductor crystallization. Organic semiconductor single crystals may grow by forming nuclei at the gas-liquid interface or at the solid-liquid interface, depending on the substrate modification layer. Therefore, it is necessary to select an appropriate substrate and modification layer. From Examples 1, 5, and 6, it is preferable that the substrate be modified with c-PMMA or BCB.

[0121] For a single crystal to grow across oriented polymer semiconductor fibers pre-dispersed on a substrate, it is necessary to form nuclei at the gas-liquid interface and grow the organic semiconductor single crystal. Furthermore, the polymer fibers on the substrate must not have excessive undulations, otherwise it will affect the progress of mass transfer during crystal growth. In addition, the undulation of the oriented polymer fibers increases with increasing polymer solution concentration, and fiber aggregation is severe during rapid solidification, resulting in relatively large undulations. Therefore, it is necessary to control the concentration of the organic polymer solution and the solidification rate. For Examples 1-2 and Comparative Example 1, it was found that the concentration of the organic polymer solution needed to be controlled to 2-5 mg / ml, and for Examples 1, 14-16, and Comparative Example 5, it was found that the solidification rate needed to be controlled to 5-800 μm / s. Under these conditions, organic semiconductor single crystals can be formed on oriented polymer fibers.

[0122] Furthermore, the concentration of the organic semiconductor solution, the crystal growth temperature, and the choice of solvent affect the nucleation rate and crystal growth rate of the organic semiconductor. If the nucleation rate is too high and the solvent volatilizes too quickly, crystal growth cannot keep up with the movement of the liquid film, increasing the tendency of the low-molecular-weight organic semiconductor to form polycrystalline structures. On the other hand, if the nucleation rate is too low and the solvent volatilizes too slowly, the low-molecular-weight organic semiconductor tends to undergo uniform nucleation within the solution, forming coarse crystals and resulting in poor contact with the underlying polymer fibers. Therefore, it is necessary to control the concentration of the organic semiconductor solution, the crystal growth temperature, and the solvent. Only when the solution concentration is 0.2 to 0.8 mg / ml (Examples 1, 6, 9, 11, 17 to 18, Comparative Example 3), the combined effect of the crystal growth temperature and the corresponding appropriate solvent (Examples 1, 3, 4, 6, 7, 9, Comparative Examples 2 to 4, 6) allows for the production of low-molecular-weight organic semiconductor single crystals that adhere tightly to oriented polymer fibers.

[0123] By characterizing the photophysical properties of photoelectric devices using fluorescence spectra, the ability of long-range ordering in photoelectric conversion can be determined. When incident light irradiates a sample, photogenerated excitons are generated in the sample. Some of these excitons can move to the heterojunction interface and dissociate into free carriers under the action of the built-in electric field, while other excitons recombine before moving to the heterojunction interface, emitting photons again and being detected by the detector. Therefore, in steady-state fluorescence, the fluorescence intensity of the composite system is detected as decaying, indicating that more photogenerated excitons are dissociating than in single-component systems, i.e., higher photoelectric conversion efficiency (see Figure 9). In transient fluorescence, it has been shown that the faster the fluorescence decay rate of the system, the faster the migration speed of photogenerated excitons, the higher the dissociation efficiency, i.e., the higher the photoresponsiveness and photoelectric conversion efficiency. The fluorescence decay rate is defined by the fluorescence lifetime τ and is obtained by exponential fitting to the transient fluorescence curve. TIFF0007917198000007.tif27170

[0124] Examples 1 and 6, and Comparative Examples 7-10 investigated the effect of different degrees of order in composite films on the photophysical properties of photoelectric devices. As shown in Figure 9, Examples 1 and 6 showed a clear fluorescence quenching phenomenon compared to single-oriented P3HT fibers, indicating the presence of an effective charge transfer process in the long-range ordered composite film. As shown in Figure 10, the fluorescence lifetime clearly tends to decrease with increasing long-range order in the composite film (fluorescence lifetime of Example 1: 109 ps, Comparative Example 7: 150 ps, ​​Comparative Example 8: 571 ps, Example 6: 112 ps, Comparative Example 9: 154 ps, Comparative Example 10: 240 ps), suggesting that improved long-range order increased exciton diffusion distance and carrier mobility, further improving the photoelectric conversion capability of the composite film, thereby enabling the manufacture of high-performance photoelectric devices.

[0125] Although embodiments of the present invention have been described in detail above with reference to the drawings, the present invention is not limited to the above embodiments. Even if various modifications are made to the present invention, these modifications shall be included within the scope of protection of the present invention as long as they fall within the scope of the claims of the present invention and the corresponding technology. [Explanation of Symbols]

[0126] 1- Motor, 2- Screw rod, 3- Ball nut, 4- Temperature gradient hot stage, 5- Jig, 6- Circuit board

Claims

1. It comprises an oriented polymer, which is a polymer fiber in which organic polymers are grown in a unidirectional arrangement, and an organic semiconductor single crystal that tightly encases the polymer fiber. The term "firmly encased" means that the organic semiconductor single crystal grows in close contact with the surface of the polymer fiber, the surface microtopography of the organic semiconductor single crystal is undulating, and there is a recess at the bonding surface between the organic semiconductor single crystal and the oriented polymer, with a recess depth of 5 nm or more. The organic semiconductor is one or more selected from linear benzo compounds and their derivatives, linear heterobenzo compounds and their derivatives, benzothiophene compounds and their derivatives, perylene and its derivatives, and fullerene and its derivatives. The organic semiconductor single crystal composite oriented polymer film is characterized in that the organic polymer is a linear conjugated homopolymer, a donor-acceptor alternating copolymer, or a polymer formed by polymerizing an organic semiconductor with a molecular weight of less than 10,000.

2. The aforementioned tight wrapping is detected by measuring the recess depth of the bonding surface between the organic semiconductor single crystal and the oriented polymer, wherein the recess depth is the difference in height between the lowest position of the recess and the edge position of the recess, and the average value of the depths is measured by randomly selecting 10 recesses on the bonding surface between the organic semiconductor single crystal and the oriented polymer, as described in claim 1.

3. The organic semiconductor single crystal composite orientation polymer film according to claim 1, characterized in that the organic semiconductor is 6,13-bis(triisopropylsilylethynyl)pentacene, 6,13-bis(triisopropylsilylethynyl)-5,7,12,14-tetraazapentacene, 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene, fullerene, or perylene.

4. The organic semiconductor single crystal composite orientation polymer film according to claim 1, characterized in that the organic polymer is poly(3-hexylthiophene-2,5-diyl), PM6, or PY-IT.

5. The organic semiconductor single crystal composite orientation polymer film according to claim 1, further comprising a substrate on which the polymer fibers are arranged and grown in one direction.

6. The organic semiconductor single crystal composite orientation polymer film according to claim 5, characterized in that the substrate is a glass plate, a silicon wafer, a metal oxide, polyimide, polyethylene terephthalate, or a mica sheet.

7. The organic semiconductor single crystal composite orientation polymer film according to claim 5, characterized in that the substrate is a substrate modified with a silane group-containing self-assembling molecule, a phosphate group-containing self-assembling molecule, or a thiol group-containing self-assembling molecule.

8. The organic semiconductor single crystal composite orientation polymer film according to claim 5, characterized in that the substrate is a substrate modified with crosslinked polymethyl methacrylate or benzocyclobutene.

9. The organic semiconductor single crystal composite orientation polymer film according to claim 7, characterized in that the substrate is a substrate modified with crosslinked polymethyl methacrylate or benzocyclobutene.

10. First, step A1 involves dissolving an organic polymer, which is a linear conjugated homopolymer, a donor-acceptor alternating copolymer, or a polymer formed by polymerizing an organic semiconductor with a molecular weight of less than 10,000, in an organic solvent to produce an organic polymer solution. Step A2 of the spatially restricted and orientation crystallization method, The substrate is placed on a temperature gradient hot stage, and the temperature of the initial position of the substrate on the temperature gradient hot stage is set to be between the melting point and boiling point of the organic solvent. The organic polymer solution is dropped onto the substrate, and a preheated sheet-like member is placed over the solution droplets. Before moving the substrate, a pre-cooled article is brought into contact with the surface of the sheet-like member on the side of the temperature gradient hot stage that is closer to the low temperature region, thereby creating a gradient in which the temperature decreases vertically from the substrate to the sheet-like member, and the organic solvent in the liquid film is nucleated and grown on the surface of the sheet-like member under low-temperature induction, and when the nucleation of the organic solvent is observed, the pre-cooled article is removed. Next, step A2 includes moving the substrate towards a region with a lower temperature than the initial position on the temperature gradient hot stage while controlling the substrate's movement speed. Step S1 for manufacturing an oriented polymer film, By rationally selecting and modifying the substrate, single crystals are nucleated at the gas-liquid interface, the single crystals grown at the gas-liquid interface partially conform to the undulations of the bottom surface, and as the solution evaporates, the gaps between the single crystals and the fibers of the bottom surface are continuously filled, thereby achieving close contact between the two. Step S2 involves growing a single crystal of an organic semiconductor, which is one or more selected from linear benzo compounds and their derivatives, linear heterobenzo compounds and their derivatives, benzothiophene compounds and their derivatives, perylene and its derivatives, and fullerene and its derivatives, on an oriented polymer. A method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 1, characterized by including the above.

11. The method for producing an organic semiconductor single crystal composite oriented polymer film according to claim 10, characterized in that the concentration of the organic polymer solution is 0 to 5 mg / mL.

12. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 11, characterized in that the concentration of the organic polymer solution is 2 to 4 mg / mL.

13. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 10, characterized in that in step S2, an organic semiconductor single crystal is grown on the orientation polymer by a solution method.

14. The step of growing an organic semiconductor single crystal using the aforementioned solution method specifically involves: First, step S201 involves dissolving an organic semiconductor in a solvent to produce an organic semiconductor solution, A method for producing an organic semiconductor single crystal composite oriented polymer film according to claim 13, comprising step S202 of growing an organic semiconductor single crystal on an oriented polymer by either a droplet-fixed crystallization method and its modification, or a meniscus coating method.

15. The step of producing a single crystal by the aforementioned droplet-fixed crystallization method is, specifically, A method for producing an organic semiconductor single crystal composite oriented polymer film according to claim 14, characterized by comprising step S202, in which a substrate on which an oriented polymer has been produced is placed in a container, a droplet fixing object is placed in the center of the substrate on which the oriented polymer has been produced, the entire container is preheated, an organic semiconductor solution is dropped onto the droplet fixing object at this preheating temperature, and an organic semiconductor single crystal is obtained when the evaporation of the solvent in the droplet is complete.

16. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 15, characterized in that the droplet fixing material is a silicon wafer, a needle, or a metal rod.

17. A modified form of the droplet-fixed crystallization method is characterized in that a substrate on which an oriented polymer has been manufactured is placed in a container, the substrate is tilted by 0.1 to 5°, the entire container is preheated, an organic semiconductor solution is dropped onto the droplet-fixed material, the container is quickly sealed, and an organic semiconductor single crystal is obtained when the evaporation of the solvent in the droplet is completed under preheating temperature conditions. This is the method for producing an organic semiconductor single crystal composite oriented polymer film according to claim 14.

18. The step of growing an organic semiconductor single crystal by the meniscus coating method described above specifically includes: After adjusting the distance between the coating tool and the substrate on which the oriented polymer has been fabricated to 100-150 μm, the substrate on which the oriented polymer has been fabricated is preheated, and at this preheated temperature, the organic semiconductor solution is injected into the gap between the coating tool and the substrate. Then, the coating tool is moved parallel to the substrate at a constant speed to shear the organic semiconductor solution, and after coating is complete, the excess organic semiconductor solution is aspirated, or A method for producing an organic semiconductor single crystal composite oriented polymer film according to claim 14, characterized by comprising immersing a substrate on which an oriented polymer has been manufactured in an organic semiconductor solution, withdrawing the substrate, forming a meniscus between the withdrawn substrate and the organic semiconductor solution, and completely separating the substrate from the organic semiconductor solution.

19. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 18, characterized in that the coating tool is a scraper, a blade, a smooth rod, a coil rod, a brush, or beads.

20. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 18, characterized in that the movement speed of the coating tool is 10 to 800 μm / s.

21. The method for producing an organic semiconductor single crystal composite oriented polymer film according to claim 14, characterized in that, in step S201, the solubility of the organic semiconductor in the solvent is greater than 0.2 mg / mL, and the solvent does not dissolve the oriented polymer.

22. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 21, characterized in that, in step S201, the solvent is a mixture of one or more of n-hexane, n-heptane, metaxylene, and 4-methyl-2-pentanone.

23. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 14, characterized in that the concentration of the organic semiconductor solution is 0.1 to 0.8 mg / mL.

24. The method for producing an organic semiconductor single crystal composite oriented polymer film according to claim 10, characterized in that the surface of the sheet-like member that comes into contact with the organic polymer solution is modified with octadecyltrichlorosilane.

25. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 10, characterized in that the article pre-cooled at a low temperature is below the melting point of the organic solvent, and the difference between it and the melting point of the organic solvent is greater than 80°C.

26. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 10, characterized in that the sheet-like member is pressed using a weight m ≥ 100 g while the substrate is being moved.

27. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 10, characterized in that the moving speed of the substrate is 5 to 800 μm / s.

28. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 10, characterized in that the substrate is a glass plate, a silicon wafer, a metal oxide, polyimide, polyethylene terephthalate, or a mica sheet.

29. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 10, characterized in that the organic solvent has a melting point of less than 30°C, is easily heated, or can be easily removed by an orthogonal solvent dissolution method.

30. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 29, characterized in that the organic solvent is a chlorinated aromatic hydrocarbon solvent.

31. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 30, characterized in that the organic solvent is 1,3,5-trichlorobenzene, 1,2,3-trichlorobenzene, or 1,2,4,5-tetrachlorobenzene.

32. The method for producing an organic semiconductor single crystal composite oriented polymer film according to claim 10, characterized in that the organic polymer is a linear conjugated homopolymer, a donor-acceptor alternating copolymer, or a polymer formed by polymerizing an organic semiconductor with a molecular weight of less than 10,000.

33. The method for producing an organic semiconductor single crystal composite orientation polymer film according to claim 10, characterized in that the organic polymer is poly(3-hexylthiophene-2,5-diyl), PM6, or PY-IT.

34. A photoelectric device characterized by comprising an organic semiconductor single crystal composite orientation polymer film according to any one of claims 1 to 9.

35. Use of the organic semiconductor single crystal composite orientation polymer film according to any one of claims 1 to 9 in the fields of organic photovoltaic power generation, organic photodetection, organic displays, transportation and logistics, mining and metallurgy, environment, medical devices, explosion-proof detection, food, water treatment, pharmaceuticals, and biology.

36. Use of the photoelectric device according to claim 34 in the fields of organic photovoltaic power generation, organic photodetection, organic displays, transportation and logistics, mining and metallurgy, environment, medical devices, explosion-proof detection, food, water treatment, pharmaceuticals, and biology.

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