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ORGANIC SINGLE-CRYSTALLINE HETEROJUNCTION COMPOSITE FILM, PREPARATION METHOD THEREOF AND METHOD OF USING THE SAME

20220173340 · 2022-06-02

    Inventors

    Cpc classification

    International classification

    Abstract

    An organic single-crystalline heterojunction composite film is provided. The organic single-crystalline heterojunction composite film comprises at least one organic single-crystalline efficiently coupled unit. The organic single-crystalline efficiently coupled unit constructed by two organic single-crystalline thin films laminated together, with highly efficient lamination. The organic single-crystalline heterojunction composite film of the present disclosure has multiple advantages, such as highly ordered molecular arrangement, few defects, long exciton diffusion length, and excellent charge carrier transportation in the single-crystalline layer, moreover, integration of optoelectronic function and flexibility could be realized. The preparation method of organic single-crystalline heterojunction composite film is also provided. High-quality organic single-crystalline heterojunction composite film has a wide range of applications in the fields of sensors, photodetectors, solar cells, displays, memory devices, complementary circuits, and so on.

    Claims

    1. An organic single-crystalline heterojunction composite film, wherein the organic single-crystalline heterojunction composite film comprises M organic materials, and M is a positive integer greater than or equal to 2; the organic single-crystalline heterojunction composite film comprises a laminated structure, wherein the laminated structure refers to the organic single-crystalline heterojunction composite film is composed of N layers of organic single-crystalline thin films stacked in sequence, and N is a positive integer greater than or equal to 2; the organic single-crystalline thin film is composed of the organic single crystal array; the organic single-crystalline heterojunction composite film comprises at least one organic single-crystalline efficiently coupled unit; the organic single-crystalline efficiently coupled unit is composed of an organic single-crystalline thin film M.sub.T and an organic single-crystalline thin film M.sub.B, and the organic single-crystalline efficiently coupled unit has highly efficient lamination; M.sub.T and M.sub.B are laminated together; materials constituting M.sub.T and M.sub.B are different; the highly efficient lamination of the organic single-crystalline efficiently coupled unit refers that a lamination area ratio R is ≥50%; the lamination area ratio R=A.sub.total/A.sub.large, wherein A.sub.total refers to a lamination area between the two organic single-crystalline thin films which constitute the organic single-crystalline efficiently coupled unit, and A.sub.large refers to an area of the larger one in the two thin films.

    2. The organic single-crystalline heterojunction composite film of claim 1, wherein a detection method of the lamination area ratio R comprises randomly selecting m adjacent crystals in the organic single-crystalline film M.sub.L in the organic single-crystalline efficiently coupled unit; wherein M.sub.L is the larger one in the two layers, R=A.sub.total/A.sub.large, A.sub.large is the total area of the m crystals, A.sub.large−A.sub.large1+A.sub.large2+ . . . +A.sub.largem, where A.sub.large1, A.sub.large2, . . . A.sub.largem represent the area of the 1, 2, . . . , m crystal, respectively; A.sub.large is the total lamination area of the m crystals, A.sub.total=A.sub.total1+A.sub.total2+ . . . +A.sub.totalm, where A.sub.total1, A.sub.total2, A.sub.totalm represent the lamination area of the 1, 2, . . . , m crystal, respectively; m is a positive integer greater than or equal to 7.

    3. The organic single-crystalline heterojunction composite film of claim 1, wherein at least one organic single-crystalline thin film has a two-dimensional high coverage in the organic single-crystalline efficiently coupled unit; the two-dimensional high coverage refers that a vertical coverage R.sub.V of the organic single-crystalline thin film is ≥80% in a direction V, and a lateral coverage R.sub.H is >70% in a direction H; the direction V is the crystal growth direction while the direction H is vertical to the crystal growth direction.

    4. The organic single-crystalline heterojunction composite film of claim 3, wherein R.sub.V=(l.sub.1+l.sub.2+ . . . +l.sub.n)/nL, where l.sub.1, l.sub.2, . . . , l.sub.n represent the length of the 1, 2, . . . , n crystals in the direction V, respectively; and L is the length of the substrate in the direction V; R.sub.H=(w.sub.1+w.sub.2+ . . . +w.sub.n)/W, where w.sub.1, w.sub.2, . . . , w.sub.n represent the width of the 1, 2, . . . , n crystals in the direction H, respectively; W is the width of a substrate in the direction H, and n is a positive integer greater than or equal to 7.

    5. The organic single-crystalline heterojunction composite film of claim 1, wherein at least one organic single-crystalline thin film in the organic single-crystalline efficiently coupled unit is selected from organic semiconductor molecules; other layers of organic single-crystalline thin films are selected from any one or more of organic semiconductor molecules, organic molecules with optoelectric properties, and organic molecules with ferroelectric properties; other layers include one or more layers.

    6. The organic single-crystalline heterojunction composite film of claim 5, wherein the organic semiconductor molecules are selected from any one or more of linear acenes and linear acene derivatives, linear heteroacenes and linear heteroacene derivatives, benzothiophene and benzothiophene derivatives, perylene and perylene derivatives, perylene diimides and perylene diimides derivatives, fullerene and fullerene derivatives, naphthalene diimides and naphthalene diimides derivatives.

    7. The organic single-crystalline heterojunction composite film of claim 1, wherein the organic single-crystalline efficiently coupled unit has a lamination coupling; the lamination coupling means that a lamination between the organic single-crystalline thin film M.sub.T and the organic single-crystalline thin film M.sub.B is well-aligned/uniformly orientated.

    8. The organic single-crystalline heterojunction composite film of claim 7, wherein the well-aligned/uniformly orientated lamination means that a degree of laminated orientation F.sub.L≥0.625.

    9. The organic single-crystalline heterojunction composite film of claim 7, wherein a detection method of the laminated orientation degree F.sub.L comprises: in the organic single-crystalline efficiently coupled unit, randomly selecting n crystals as samples in the M.sub.T and M.sub.B respectively, and n is a positive integer greater than or equal to 7; taking the crystal growth direction as the reference direction, and taking the angle between the direction of the longest dimension c.sub.T of the crystal C.sub.T in the M.sub.T and the reference direction as the orientation angle A.sub.T, A.sub.T is the average orientation angle of the n crystals in M.sub.T; taking the angle between the direction of the longest dimension c.sub.B of the crystal C.sub.B in the M.sub.B and the reference direction as the orientation angle A.sub.B, Ā.sub.B is the average orientation angle of the n crystals M.sub.B; the laminated orientation degree F.sub.L=0.5*(3*cos.sup.2Ā−1), where Ā=(Ā.sub.T−Ā.sub.B).

    10. A preparation method of the organic single-crystalline efficiently coupled unit, wherein an organic single-crystalline efficiently coupled unit is obtained by a laminating coupled growth method; the laminating coupled growth method refer to synergistic growth realized by M.sub.T and M.sub.B to acquire the organic single-crystalline efficiently coupled unit along a crystal growth direction; the organic single-crystalline efficiently coupled unit is composed of M.sub.T and M.sub.B with highly efficient lamination; M.sub.T and M.sub.B are laminated together, and the materials constituting the M.sub.T and M.sub.B are different; the highly efficient lamination of the organic single-crystalline efficiently coupled unit refers that the lamination area ratio R is ≥50%; R=A.sub.total/A.sub.large, A.sub.total refers to the area between the two organic single-crystalline thin films in the organic single-crystalline efficiently coupled unit, and the A.sub.large refers to the larger organic single-crystalline thin film in the two layers.

    11. The preparation method of the organic single-crystalline efficiently coupled unit of claim 10, wherein the laminating coupled growth method refers to applying shearing to a mixed solution for obtaining an organic single-crystalline efficiently coupled unit; the shearing refers to use a shearing tool to shear the mixed solution along a constant direction at a constant shearing speed and shearing temperature; the mixed solution refers to a solution in which two or more solutes are simultaneously dissolved; one of the solutes is selected from organic semiconductor molecules; the two or more solutes have a common solvent; the common solvent refers to a solvent in which the two or more solutes are simultaneously dissolved; the common solvent includes one or more solvents; a solubility (S) of the two or more solutes in a common solvent is ≥0.05 wt % (S≥0.05 wt %); there is no mutual reaction and co-crystal formation between different solutes; the two or more solutes realizes horizontal phase separation (unequal velocity phase separation) and/or vertical phase separation (different interface phase separation) during the crystal growth process; the horizontal phase separation means that the crystal growth rate between different solutes is not completely equal; the vertical phase separation means that the growth interface between different solutes is not completely the same; the growth interface refers to the interface that initiates the nucleation and growth of crystals in the growing process; the growth interface is selected from air-liquid interface and solid-liquid interface.

    12. The preparation method of the organic single-crystalline efficiently coupled unit of claim 11, wherein type of the growth interface is determined by observing whether the morphology of the organic single-crystalline thin film show a significant change after crossing the obstacles; the obstacles refer to the nanowires deposited on the substrate; a detection method for determining the type of the growth interface is: randomly selecting 2p+1 crystals that cross the obstacles along the crystal growth direction, and p is a positive integer greater than or equal to 1, |Ao|≤45°, Ao represents the included angle between the obstacle which meet the selected crystal aforementioned and the direction perpendicular to the crystal growth direction; the difference between the average thickness of the obstacles (h.sub.o) and the average thickness of the crystals (h) is less than or equal to 20 nm, that is, |h.sub.o−h.sub.o≤20 nm; if there is no significant morphology change for p+1 crystals after crossing the obstacles, the growth interface is considered as the air-liquid interface; if the morphology of p+1 crystals changes significantly after crossing the obstacles, the growth interface is the solid-liquid interface.

    13. The preparation method of the organic single-crystalline efficiently coupled unit of claim 10, comprising: (1) preparing the mixed solution with two or more solutes that is capable of achieving horizontal phase separation and/or vertical phase separation, dissolving two or more solutes with a common solvent to control the two or more solutes to realize laminating coupled growth in the mixed solution; (2) regulating an ambient temperature and an ambient humidity of the growth environment to obtain a stable growth environment; during the crystal growth process, the deviation of the ambient temperature is ≤±2° C., and the deviation of the ambient humidity is ≤±3%; (3) adjusting a distance between the shearing tool and the substrate to obtain a solution storage space, and the solution storage space is the space formed between the substrate and the lower surface of the shearing tool; the distance is 50 μm to 300 μm; a deviation of the distance between the substrate and a lower surface of the shearing tool is ≤10 μm; the lower surface of the shearing tool is basically parallel to the substrate; (4) filling the mixed solution prepared in step (1) into the solution storage space in step (3), and keeping the solution still for 1 s to 30 s after filling; (5) using a shearing tool to shear the mixed solution along a constant direction at a constant shearing speed and shearing temperature, in order to obtain the organic single-crystalline efficiently coupled unit; each layer of the organic single-crystalline efficiently coupled unit is an organic single-crystalline thin film; the constant shearing temperature refers to the deviation of the shearing temperature is ≤±1° C. during the shearing process; the shearing temperature is 0° C. to 200° C.; the shearing speed is 10 μm/s to 2000 μm/s.

    14. The preparation method of the organic single-crystalline efficiently coupled unit according to claim 11, wherein the solute is any one or more selected from the group consisting of organic semiconductor molecules, photoelectric functional organic molecules, and ferroelectric functional organic molecules.

    15. The preparation method of the organic single-crystalline efficiently coupled unit of claim 14, wherein the organic semiconductor is any one or more selected from the group consisting of linear acenes and linear acenes derivatives, linear heteroacenes and linear heteroacene derivatives, benzothiophene and benzothiophene derivatives, perylene and perylene derivatives, fullerene and fullerene derivatives, cyanide or halogen substituted compounds.

    16. A preparation method of the organic single-crystalline heterojunction composite film, wherein the preparation method comprises steps in the preparation method of the organic single-crystalline efficiently coupled unit according to claim 11.

    17. The preparation method of the organic single-crystalline heterojunction composite film of claim 16, comprising: laminating single or multiple layers organic single-crystalline thin film fabricated by other methods onto the one or more fabricated organic single-crystalline efficiently coupled unit.

    18. The preparation method of the organic single-crystalline heterojunction composite film of claim 17, wherein the other methods are any one or more selected from the group consisting of casting method, solution shearing method, spin coating method, printing method, vapor phase deposition, and mechanical transfer method

    19. The preparation method of the organic single-crystalline heterojunction composite film of claim 16, comprising a post-treatment step; the post-treatment step refers to the post-treatment of the entire organic single-crystalline heterojunction composite films, and/or post-treatment of the organic single-crystalline efficiently coupled units, and/or post-treatment of each layer/multiple layers of organic single-crystalline thin films; the post-treatment is selected from any one or more of annealing, vacuum treatment, solvent annealing treatment, or surface treatment; the surface treatment is selected from any one or more of ultraviolet ozone treatment, plasma treatment, infrared light treatment, or laser etching.

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0073] FIG. 1 is the schematic diagram of an organic single-crystalline heterojunction composite film and the organic single-crystalline efficiently coupled unit.

    [0074] FIGS. 2A-2E are the schematic diagrams of the morphology of the organic single-crystalline heterojunction composite film; wherein FIG. 2A-FIG. 2C are schematic diagrams of the lamination area of organic single-crystalline heterojunction composite films with different morphologies, respectively; FIG. 2A and FIG. 2D are laminated organic single-crystalline heterojunction composite films with uniform orientation; FIG. 2B are organic single-crystalline heterojunction composite film with independently dispersed morphology; FIGS. 2C and 2E are organic single-crystalline heterojunction composite films grown in the staggered mode.

    [0075] FIGS. 3A-3F are schematic diagrams of different laminating methods between the two organic single crystals in the organic single-crystalline heterojunction composite film, wherein FIG. 3A is cross-stacked, FIG. 3B is bilayer, FIG. 3C is lateral-stacked, FIG. 3D is axial-stacked, FIG. 3E is core-shell stacked, and FIG. 3F is branched.

    [0076] FIGS. 4A-4I are different laminating methods between the three organic single crystals in the organic single-crystalline heterojunction composite film, respectively, and different colors represent different types of organic single crystals.

    [0077] FIG. 5 is a schematic diagram of the organic single-crystalline thin film of the present disclosure, l.sub.1, l.sub.2, . . . , 1.sub.n represent the length of the 1, 2, . . . , n crystals along the crystal growth direction, respectively, w.sub.1, w.sub.2, . . . , w.sub.n represent the width of the 1, 2, . . . , n crystals in the direction perpendicular to the crystal growth direction, respectively; L is the length of the substrate, W is the width of the substrate.

    [0078] FIG. 6A is a schematic diagram of the orientation angle between two layers of organic single crystals in the organic single-crystalline heterojunction composite film of the present disclosure, where A.sub.L is the laminated orientation angle; FIG. 6B is a schematic diagram of the included angle between the obstacle and the direction perpendicular to the crystal growth direction in the detection method for growth interface provided by the present disclosure, where Ao is the included angle.

    [0079] FIG. 7 is an optical microscopic image of organic single-crystalline thin film grown at the air-liquid interface.

    [0080] FIG. 8 is an optical microscopic image of organic single-crystalline thin film grown at the solid-liquid interface.

    [0081] FIG. 9 is a schematic diagram of the effect of the integrated array of optoelectronic devices of the present disclosure.

    [0082] FIGS. 10A-10B are the optical microscopic image and the schematic diagram of the organic single-crystalline heterojunction composite film of Example 1, respectively.

    [0083] FIGS. 11A-11B are the optical microscopic image and the polarized optical microscopic image of the organic single-crystalline heterojunction composite film of Example 1, respectively.

    [0084] FIG. 12 is a scanning electron micrograph of the organic single-crystalline heterojunction composite film of Example 1.

    [0085] FIG. 13 is the typical transfer curve for hole and electron transport under the working voltage of V.sub.D=−120V, V.sub.G=−120V in the ambipolar organic single-crystalline field-effect transistor, which is based on the organic single-crystalline heterojunction composite film of Example 1.

    [0086] FIG. 14 is a polarized optical microscopic image of the organic heterojunction film of Comparative Example 3.

    [0087] FIG. 15 is an optical microscopic image of the organic heterojunction film of Comparative Example 7.

    [0088] FIG. 16 is an optical microscopic image of the organic heterojunction film of Comparative Example 10.

    [0089] FIG. 17 is a schematic diagram of the evolution from the organic single-crystalline heterojunction composite film of the present disclosure to the optoelectronic device to the integrated array of optoelectronic devices.

    [0090] FIGS. 18A-18B are the optical microscopic image in the prior art that presents the morphology of the organic single-crystalline heterojunction, FIG. 18A is equivalent to FIG. 2a of H. Li, C. Fan, and W. Fu, Angewandte Chemie International Edition, 54, 956 (2015), and FIG. 18B is equivalent to FIG. 5e of H. Li and H. Li, Journal of the American Chemical Society, 141, 25 (2019).

    DETAILED DESCRIPTION OF THE EMBODIMENTS

    [0091] The present disclosure is further described below with reference to the drawings and embodiments. It should be noted that the following embodiments are used to illustrate the present disclosure but not to limit the scope of the present disclosure. In addition, it should be understood that after reading the teachings of the present disclosure, those skilled in the art can make various changes or modifications to the present disclosure, and these equivalent forms also fall within the scope defined by the appended claims of this application.

    [0092] The terms “upper”, “lower”, “left”, “right”, “vertical”, “parallel”, “inner”, “outer”, “before”, “after”, etc. indicate that the orientation or positional relationship is based on the orientation or positional relationship shown in the attached figures, and is only for the convenience of describing the present disclosure and simplifying the description, rather than indicating or implying that the pointed device or element must have a specific orientation or a specific/positional relationship orientation. The orientation or positional relationship shown in the figures are only for the convenience of describing the present disclosure and simplifying the description, rather than indicating or implying that the devices or elements referred to must have a specific position, or be constructed/operated in a specific direction/position, therefore, it cannot be understood as a limitation of the present disclosure.

    [0093] As shown in FIG. 1, the present disclosure provides an organic single-crystalline heterojunction composite film, which comprises M organic materials, and M is a positive integer greater than or equal to 2; the organic single-crystalline heterojunction composite film comprises a laminated structure (laminated construction/configuration/structure), and the laminated structure refers to the organic single-crystalline heterojunction composite film is composed of N layers of organic single-crystalline thin films stacked in sequence, and N is a positive integer greater than or equal to 2; the organic single-crystalline thin film is composed of the organic single crystal array, which is displayed in FIG. 2A, FIG. 2D, FIG. 5, FIGS. 10A-10B and FIGS. 11A-11B, and the organic single crystal array is composed of multiple crystals within single-crystalline state; the organic single-crystalline heterojunction composite film comprises at least one organic single-crystalline efficiently coupled unit; the organic single-crystalline efficiently coupled unit is composed of an organic single-crystalline thin film M.sub.T and an organic single-crystalline thin film M.sub.B, M.sub.T and M.sub.B are composed of different materials, additionally M.sub.T is located in the upper layer, and the M.sub.B is located in the lower layer. The organic single-crystalline efficiently coupled unit has highly efficient lamination, as shown in FIG. 2A, FIG. 2D, FIG. 3B, FIGS. 10A-10B, FIGS. 11A-11B and FIG. 12. A large lamination area ratio and intimate contact between the bilayer organic single-crystalline thin films could be observed in the above-mentioned optical microscopic images, polarized optical microscopic images, scanning electron microscopic images and schematic diagrams, moreover, high-quality organic single-crystalline heterojunction interfaces are formed.

    [0094] As shown in FIG. 9, the optoelectronic device proposed by the present disclosure can also be integrated in one or more dimensions to obtain an integrated array of optoelectronic devices. The integrated array of optoelectronic devices can be widely used in detectors, inverters, oscillators, backplane for light-emitting diode displays and so on.

    [0095] The organic single-crystalline thin films can be detected by instruments that could analyze fine structures, such as optical microscope with crossed polarizers, atomic force microscope, scanning electron microscope, transmission electron microscope, laser confocal Raman spectrometer, single-crystal diffractometer, and so on. The type of materials in the organic single-crystalline thin film can be detected by instruments that can analyze the composition of elements, such as scanning electron microscope, transmission electron microscope, laser confocal Raman spectrometer, X-ray diffractometer, infrared spectrometer and so on. The structure and morphology of organic single-crystalline heterojunction composite film and organic single-crystalline efficiently coupled unit can be inspected by optical microscope, atomic force microscope, scanning electron microscope, transmission electron microscope, and so on. The related performance of semiconductor devices can be tested by instruments that can analyze the electrical/optoelectrical performance, such as semiconductor parameter analyzer, Hall effect testing instrument, scanning probe microscope, ferroelectric analyzer, quantum efficiency measurement system, transient spectrometer, solar cell I-V tester, optoelectronic detection system, micro-fluorescence spectrometer, spectrum analyzer, conductance measurement system and so on.

    [0096] In order to characterize the morphology of organic single-crystalline efficiently coupled unit, an optical microscope was used for observation. To characterize the quality of the organic single-crystalline efficiently coupled unit provided by the present disclosure, field-effect transistors were prepared based on the organic single-crystalline heterojunction composite film containing organic single-crystalline efficiently coupled unit aforementioned, and the field-effect behaviors were tested with a semiconductor parameter analyzer.

    Example 1

    [0097] An organic single-crystalline heterojunction composite film based on 2,8-difluoro-5,11-bis[2-(triethylsilyl)ethynyl]-anthradithiophene (diF-TES-ADT) and 6,13-bis(triisopropylsilylethynyl)-5,7,12,14-tetraazapentacene (TIPS-TAP), a preparation method for organic field-effect devices based on the composite film, the following steps are included: [0098] (1) providing a heavily doped p-type Si/SiO.sub.2 substrate, wherein the thickness of silicon dioxide insulating layer is 300 nm, then spin-coating the crosslinked polystyrene (c-PS) on the substrate as modification layer; [0099] (2) growing p-type semiconductor molecule diF-TES-ADT and n-type semiconductor molecule TIPS-TAP on a substrate with pre-deposited Ag nanowires (with a diameter about 40 nm) respectively, and observing the morphology change of the organic single-crystalline thin film crossing the electrodes under an optical microscope to determine the growth interface of diF-TES-ADT and TIPS-TAP respectively, dynamic growth process of diF-TES-ADT and TIPS-TAP through the optical microscope to determine their growth rate respectively; [0100] (3) preparing a mixed solution (with total solute mass fraction of 1 wt %) using diF-TES-ADT and TIPS-TAP (1:1) in mesitylene, and stirring the solution on a hot stage at 50° C. for fully dissolving; [0101] (4) regulating the ambient temperature and ambient humidity of the growth environment at 20±1° C. and 50±3%, respectively; [0102] (5) adjusting the gap distance between the shearing tool and the substrate prepared in step (1) to 200±5 μm to form the solution storage space; [0103] (6) filling the mixed solution prepared in step (3) into the solution storage space prepared in step (5), and resting it for 5 seconds after the filling is completed; [0104] (7) using a shearing tool to shear the mixed solution slowly and uniformly in a constant direction at a shearing speed of 400±5 μm/s under a temperature of 60° C. to obtain the bilayer organic single-crystalline heterojunction composite film; [0105] (8) depositing the electrodes of Au by thermal evaporation under a high vacuum to obtain field-effect transistors based the organic single-crystalline heterojunction composite film obtained by step (7).

    [0106] The substrate can be selected from commonly used organic semiconductor device substrates. Further, the substrate can be a hard substrate, such as a silicon substrate (Si/SiO.sub.2), a metal oxide substrate (AlO.sub.x) and so on. And the substrate also could be a flexible polymer substrate, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI) and so on. The modification layer on the substrate can be selected from organic polymers or small molecule modification layers that will not be dissolved or corroded by the mixed solution. Preferably, the polymer can be selected from any one or more of polymethyl methacrylate (PMMA) and its cross-linked product (c-PMMA), polyvinyl alcohol (PVA) and its cross-linked product (c-PVA), polyvinyl acetate (PVAc) and its cross-linked product (c-PVAc), polyimide (PI), polyvinylidene fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene) (P(VDF-HFP)), poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)), polystyrene (PS) and its cross-linked products (c-PS), poly-α-methylstyrene (PαMS), polyvinylphenol (PVP) and its cross-linked products (c-PVP), parylene, divinyltetramethyldisiloxane-bis(benzocyclobutene) (BCB), perfluoro (1-butenyl vinyl ether) polymer (CYTOP), and cyanoethylpullulane (CYEP), if the polymers selected are more than two types, the modification layer could be prepared by two/more layers mixing/stacking together.

    [0107] Use optical microscope and atomic force microscope to extract the fine structure and morphology information to characterize the structure and morphology of the obtained organic single-crystalline semiconductor thin films, and the electrical performance of field-effect transistors is characterized by semiconductor parameter analyzer which is capable of detecting the comprehensive electrical properties of various semiconductor devices and materials.

    Example 2

    [0108] An organic single-crystalline heterojunction composite film based on 2,8-difluoro-5,11-bis[2-(triethylsilyl)ethynyl]-anthradithiophene (diF-TES-ADT) and 6,13-bis(triisopropylsilylethynyl)-5,7,12,14-tetraazapentacene (TIPS-TAP), a preparation method for organic field-effect devices based on the composite film.

    [0109] For the preparation method of the field-effect transistor device of the Example 2, referring to the Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure, morphology and performance characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3. The related device performance is shown in Table 4.

    Example 3

    [0110] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film.

    [0111] For the preparation method of the field-effect transistor device of the Example 3, referring to the Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure, morphology and performance characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3. The related device performance is shown in Table 4.

    Example 4

    [0112] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film.

    [0113] For the preparation method of the field-effect transistor device of the Example 4, referring to the Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure, morphology and performance characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3. The related device performance is shown in Table 4.

    Example 5

    [0114] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film.

    [0115] For the preparation method of the field-effect transistor device of the Example 5, referring to the Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure, morphology and performance characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3. The related device performance is shown in Table 4.

    Example 6

    [0116] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film.

    [0117] For the preparation method of the field-effect transistor device of the Example 6, referring to the Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure, morphology and performance characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3. The related device performance is shown in Table 4.

    Example 7

    [0118] An organic single-crystalline heterojunction composite film based on 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-PEN) and 2,7-dioctyl[1]benzothieno[3,2-b]benzothiophene (C.sub.8-BTBT) with a preparation method for the composite film.

    [0119] For the preparation method of the composite film of the Example 7, referring to the step (1-7) in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3.

    Example 8

    [0120] An organic single-crystalline heterojunction composite film based on TIPS-PEN and C.sub.8-BTBT with a preparation method for the composite film.

    [0121] For the preparation method of the composite film of the Example 8, referring to the step (1-7) in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3.

    Example 9

    [0122] An organic single-crystalline heterojunction composite film based on Perylene and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film.

    [0123] For the preparation method of the field-effect transistor device of the Example 9, referring to the Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure, morphology and performance characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3. The related device performance is shown in Table 4.

    Example 10

    [0124] An organic single-crystalline heterojunction composite film based on Perylene and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film.

    [0125] For the preparation method of the field-effect transistor device of the Example 10, referring to the Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure, morphology and performance characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3. The related device performance is shown in Table 4.

    Example 11

    [0126] An organic single-crystalline heterojunction composite film based on TIPS-PEN and 9,10-diphenylanthracene (9,10-DPA) with a preparation method for the composite film.

    [0127] For the preparation method of the composite film of the Example 11, referring to the step (1-7) in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3.

    Example 12

    [0128] An organic single-crystalline heterojunction composite film based on TIPS-PEN and 9,10-diphenylanthracene (9,10-DPA) with a preparation method for the composite film.

    [0129] For the preparation method of the composite film of the Example 12, referring to the step (1-7) in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3.

    Example 13

    [0130] An organic single-crystalline heterojunction composite film based on Tetracene and TIPS-TAP with a preparation method for the composite film.

    [0131] For the preparation method of the composite film of the Example 13, referring to the step (1-7) in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3.

    Example 14

    [0132] An organic single-crystalline heterojunction composite film based on Tetracene and TIPS-TAP with a preparation method for the composite film.

    [0133] For the preparation method of the composite film of the Example 14, referring to the step (1-7) in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3.

    Example 15

    [0134] An organic single-crystalline heterojunction composite film based on 2,6-diphenylbisthieno[3,2-b:2′,3′-d]thiophene (DP-DTT) and TIPS-TAP with a preparation method for the composite film.

    [0135] For the preparation method of the composite film of the Example 15, referring to the step (1-7) in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3.

    Example 16

    [0136] An organic single-crystalline heterojunction composite film based on Rubrene and Fullerene (C.sub.60) with a preparation method for the composite film.

    [0137] For the preparation method of the composite film of the Example 16, referring to the step (1-7) in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3.

    Example 17

    [0138] A multiple layer organic single-crystalline heterojunction composite film based on Rubrene, C.sub.60 and TIPS-PEN, the following steps are included: [0139] (1) providing a heavily doped p-type Si/SiO.sub.2 substrate, wherein the thickness of silicon dioxide insulating layer is 300 nm, then spin-coating the crosslinked polystyrene on the substrate as modification layer; [0140] (2) preparing a mixed solution (with total solute mass fraction of 0.2 wt %) using Rubrene and C.sub.60 in chlorobenzene, then preparing a 0.1 wt % TIPS-PEN solution in 4-methyl-2-pentanone separately, and stirring the two solutions on a hot stage at 50° C. for fully dissolving; [0141] (3) regulating the ambient temperature and ambient humidity of the growth environment at 20±1° C. and 50±3%, respectively; [0142] (4) adjusting the gap distance between the shearing tool and the substrate prepared in step (1) to 200±5 μm to form the solution storage space; [0143] (5) filling the mixed solution prepared in step (2) into the solution storage space prepared in step (4), and resting it for 5 seconds after the filling is completed; [0144] (6) using a shearing tool to shear the mixed solution slowly and uniformly in a constant direction at a linear velocity of 400±5 μm/s under a temperature of 60° C. to obtain the bilayer organic single-crystalline heterojunction composite film; [0145] (7) using a shearing tool to shear the TIPS-PEN solution slowly and uniformly on the bilayer composite film prepared in step (6) in a constant direction at a linear velocity of 200±1 μm/s under a temperature of 30° C. to obtain the triple layer organic single-crystalline heterojunction composite film.

    [0146] The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3.

    Comparative Example 1

    [0147] An organic single-crystalline heterojunction composite film based on Perylene and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film, the following steps are included: [0148] (1) providing a heavily doped p-type Si/SiO.sub.2 substrate, wherein the thickness of silicon dioxide insulating layer is 300 nm, then spin-coating the crosslinked polystyrene on the substrate as modification layer; [0149] (2) preparing a 0.5 wt % TIPS-TAP solution in mesitylene, and stirring the solution on a hot stage at 50° C. for fully dissolving; [0150] (3) regulating the ambient temperature and ambient humidity of the growth environment at 20±1° C. and 50±3%, respectively; [0151] (4) adjusting the gap distance between the shearing tool and the substrate prepared in step (1) to 200±5 μm to form the solution storage space; [0152] (5) filling the mixed solution prepared in step (2) into the solution storage space prepared in step (4), and resting it for 5 seconds after the filling is completed; [0153] (6) using a shearing tool to shear the TIPS-TAP solution slowly and uniformly in a constant direction at a linear velocity of 400±5 μm/s under a temperature of 60° C. to obtain the organic single-crystalline thin film; [0154] (7) depositing the polycrystalline perylene thin film via thermal evaporation on the TIPS-TAP single-crystalline thin film; [0155] (8) depositing the Au electrodes by thermal evaporation under a high vacuum to obtain field-effect transistors based the organic single-crystalline & polycrystalline heterojunction obtained by step (7).

    [0156] The performance characterization methods are the same as those in Example 1. The related device performance is shown in Table 4. The perylene thin film can be judged as an organic polycrystalline film by observing through an optical microscope.

    Comparative Example 2

    [0157] An organic single-crystalline heterojunction composite film based on Perylene and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film, the following steps are included: [0158] (1) providing a heavily doped p-type Si/SiO.sub.2 substrate, wherein the thickness of silicon dioxide insulating layer is 300 nm, then spin-coating the crosslinked polystyrene on the substrate as modification layer; [0159] (2) preparing a 0.5 wt % TIPS-TAP solution in toluene, and stirring the solution on a hot stage at 50° C. for fully dissolving; [0160] (3) regulating the ambient temperature and ambient humidity of the growth environment at 20±1° C. and 50±3%, respectively; [0161] (4) spin-coating the TIPS-TAP solution on the substrate to obtain the TIPS-TAP organic polycrystalline thin film; [0162] (5) depositing the polycrystalline perylene thin film via thermal evaporation on the TIPS-TAP polycrystalline thin film; [0163] (6) depositing the Au electrodes by thermal evaporation under a high vacuum to obtain field-effect transistors based the organic polycrystalline & polycrystalline heterojunction obtained by step (5).

    [0164] The performance characterization methods are the same as those in Example 1. The related device performance is shown in Table 4. Similarly, the perylene thin film and TIPS-TAP thin film can be judged as organic polycrystalline thin films by observing through an optical microscope.

    Comparative Example 3

    [0165] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film.

    [0166] For the preparation method of the composite film of the Comparative Example 3, referring to the steps in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1.

    Comparative Example 4

    [0167] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film, the following steps are included: [0168] (1) providing a heavily doped p-type Si/SiO.sub.2 substrate, wherein the thickness of silicon dioxide insulating layer is 300 nm, then spin-coat the crosslinked polystyrene on the substrate as modification layer; [0169] (2) preparing a mixed solution (with total solute mass fraction of 1 wt %) using diF-TES-ADT and TIPS-TAP (1:1) in 1-butanol, filter out the undissolved particles after 30 minutes of ultra-sonication; [0170] (3) regulating the ambient temperature and ambient humidity of the growth environment at 20±1° C. and 50±3%, respectively; [0171] (4) adjusting the gap distance between the shearing tool and the substrate prepared in step (1) to 200±5 μm to form the solution storage space; [0172] (5) filling the mixed solution prepared in step (2) into the solution storage space prepared in step (4), and resting it for 5 seconds after the filling is completed; [0173] (6) using a shearing tool to shear the mixed solution slowly and uniformly in a constant direction at a linear velocity of 400±5 μm/s under a temperature of 60° C. to obtain the bilayer organic single-crystalline heterojunction composite film; [0174] (7) depositing the Au electrodes by thermal evaporation under a high vacuum to obtain field-effect transistors based the organic single-crystalline heterojunction composite film obtained by step (6).

    [0175] The structure, morphology and performance characterization methods are the same as those in Example 1. The related device performance is shown in Table 4.

    Comparative Example 5

    [0176] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and TIPS-TAP with a preparation method for the composite film.

    [0177] For the preparation method of the composite film of the Comparative Example 5, referring to the step (1-7) in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3.

    Comparative Example 6

    [0178] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and TIPS-TAP with a preparation method for the composite film.

    [0179] For the preparation method of the composite film of the Comparative Example 6, referring to the step (1-7) in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3.

    Comparative Example 7

    [0180] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film.

    [0181] For the preparation method of the composite film of the Comparative Example 7, referring to the step (1-7) in Example 1, the formula and process parameters are shown in Table 1 and Table 2, respectively. The structure and morphology characterization methods are the same as those in Example 1. The morphological parameters of the obtained organic single-crystalline heterojunction are shown in Table 3. The related device performance is shown in Table 4.

    Comparative Example 8

    [0182] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film, the following steps are included: [0183] (1) providing a heavily doped p-type Si/SiO.sub.2 substrate, wherein the thickness of silicon dioxide insulating layer is 300 nm, then spin-coat the crosslinked polystyrene on the substrate as modification layer; [0184] (2) preparing a 0.5 wt % diF-TES-ADT solution in toluene and 0.5 wt % TIPS-TAP solution in toluene solution separately; [0185] (3) regulating the ambient temperature and ambient humidity of the growth environment at 20±1° C. and 50±3%, respectively; [0186] (4) adjusting the gap distance between the shearing tool and the substrate prepared in step (1) to 200±5 μm to form the solution storage space; [0187] (5) filling the TIPS-TAP solution prepared in step (2) into the solution storage space prepared in step (4), and resting it for 5 seconds after the filling is completed; [0188] (6) using a shearing tool to shear the TIPS-TAP solution slowly and uniformly on the substrate prepared in step (1) in a constant direction at a linear velocity of 400±5 μm/s under a temperature of 60° C. to obtain the TIPS-TAP single-crystalline thin film; [0189] (7) filling the diF-TES-ADT solution prepared in step (2) into the solution storage space prepared in step (4), and resting it for 5 seconds after the filling is completed; [0190] (8) using a shearing tool to shear the diF-TES-ADT solution slowly and uniformly on a PDMS film in a constant direction at a linear velocity of 400±5 μm/s under a temperature of 60° C. to obtain the diF-TES-ADT single-crystalline thin film; [0191] (9) transferring the diF-TES-ADT single-crystalline thin film prepared on the PDMS film onto the TIPS-TAP single-crystalline thin film prepared in step (6); [0192] (10) depositing the Au electrodes by thermal evaporation under a high vacuum to obtain field-effect transistors based the organic single-crystalline heterojunction composite film obtained by step (9).

    [0193] The structure, morphology and performance characterization methods are the same as those in Example 1. The related device performance is shown in Table 4.

    Comparative Example 9

    [0194] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and C.sub.60, a preparation method for organic field-effect devices based on the composite film, the following steps are included: [0195] (1) providing a heavily doped p-type Si/SiO.sub.2 substrate, wherein the thickness of silicon dioxide insulating layer is 300 nm, then spin-coating the crosslinked polystyrene on the substrate as modification layer; [0196] (2) preparing a 0.1 wt % diF-TES-ADT solution in hexane and 0.5 wt % C.sub.60 solution in chlorobenzene solution separately; [0197] (3) regulating the ambient temperature and ambient humidity of the growth environment at 25±1° C. and 40±3%, respectively; [0198] (4) adjusting the gap distance between the shearing tool and the substrate prepared in step (1) to 200±5 μm to form the solution storage space; [0199] (5) filing the C.sub.60 solution prepared in step (2) into the solution storage space prepared in step (4), and resting it for 5 seconds after the filling is completed; [0200] (6) using a shearing tool to shear the C.sub.60 solution slowly and uniformly on the substrate prepared in step (1) in a constant direction at a linear velocity of 400±5 μm/s under a temperature of 80° C. to obtain the C.sub.60 single-crystalline thin film; [0201] (7) filling the diF-TES-ADT solution prepared in step (2) into the solution storage space prepared in step (4), and resting for 5 seconds after the filling is completed; [0202] (8) using a shearing tool to shear the diF-TES-ADT solution slowly and uniformly on the C.sub.60 single-crystalline thin film in a constant direction at a linear velocity of 200±5 μm/s under a temperature of 30° C. to obtain the organic single-crystalline heterojunction composite film; [0203] (9) depositing the Au electrodes by thermal evaporation under a high vacuum to obtain field-effect transistors based the organic single-crystalline heterojunction composite film obtained by step (8).

    [0204] The structure, morphology and performance characterization methods are the same as those in Example 1. The related device performance is shown in Table 4.

    Comparative Example 10

    [0205] An organic single-crystalline heterojunction composite film based on diF-TES-ADT and TIPS-TAP, a preparation method for organic field-effect devices based on the composite film, the following steps are included: [0206] (1) providing a heavily doped p-type Si/SiO.sub.2 substrate, wherein the thickness of silicon dioxide insulating layer is 300 nm, then spin-coating the crosslinked polystyrene on the substrate as modification layer; [0207] (2) preparing a mixed solution (with total solute mass fraction of 0.1 wt %) using diF-TES-ADT and TIPS-TAP (1:1) in toluene, filtering out the undissolved particles after 30 minutes of ultra-sonication; [0208] (3) using the droplet-pinned crystallization method (DPC) for crystallization, dropping the mixed solution on the substrate (on a hot stage of 40° C.) on which a fixed silicon wafer is placed, wherein a bilayer organic single-crystalline heterojunction is prepared after the solvent is completely evaporated; [0209] (4) depositing the Au electrodes by thermal evaporation under a high vacuum to obtain field-effect transistors based the organic single-crystalline heterojunction composite film obtained by step (3).

    [0210] The structure, morphology and performance characterization methods are the same as those in Example 1. The related device performance is shown in Table 4.

    [0211] The morphology of the organic single-crystalline semiconductor layers obtained in Examples 1-17 and Comparative Examples 1-10 were characterized by optical microscope (with crossed-polarizers) and atomic force microscope, and the performance of the related devices were tested by a semiconductor parameter analyzer. Optical microscopy is a simple and effective method for observing the morphology of organic single-crystalline thin films. Organic single crystals are anisotropic due to the highly ordered intrinsic structure with periodical molecular ordering. Under the orthogonal linearly polarized light of optical microscope, the object with anisotropy will exhibit the birefringence behavior. When the crystal growth direction is parallel or perpendicular to the polarization angle, the image can be used to determine whether the crystal axis in the field of view is highly oriented by observing whether uniform color and brightness changes occur. This method could be applied to confirm the single-crystallinity (A. Yamamura et al., Science Advances, 4, eaao5758, (2018)). In the polarized optical microscopic image, if the color or gray scale is non-uniform or the color changes, it indicates that the obtained crystal is not a single crystal. For example, as shown in FIG. 1(a) in the literature report (C. W. Sele et al., Advanced Materials, 21, 4926 (2009)), the non-uniform color/gray-scale and large density of grain boundaries were overserved, which indicated that the obtained organic film is polycrystalline. For another example, as shown in FIG. 2 (d-g) in the literature report (C. Kim et al., ACS Applied Materials Interfaces, 5, 3716, (2013)), the crystallites with nearly rounded shape were displayed in the obtained organic film, the brightness inside crystallites are quite different, showing the Maltese cross phenomenon, indicating that the crystallites are spherulites instead of single crystals. The crystals are single crystals if the color/gray-scale of the crystal is basically uniform. For instance, as shown in FIG. 11B, basically uniform color/gray-scale of each crystal is displayed in the bright area. In the same area, the color/gray-scale between different crystals is basically the same, indicating a typical organic single-crystalline thin film. It should be noted that the large-area bright and dark regions of the crystalline thin film in FIG. 11B do not mean the appearance of polycrystallinity, since the orientation of the molecular long axis in the crystals between different regions are slightly different (K. Sakamoto et al., Applied Physics Letter, 100, 123301, (2012)), the angular difference with the polarization axis of the polarizer results in bright and dark divisions. Through the scanning electron microscope, the structure of the bilayer or multilayer organic single-crystalline heterojunction composite film on the microscopic scale can be observed.

    [0212] FIG. 10 and FIG. 11 show the morphologies of the organic single-crystalline heterojunction composite film prepared in Example 1. In FIG. 10, a bilayer organic single-crystalline heterojunction composite film with uniform orientation can be seen. The FIG. 10A is the topography observed under an optical microscope at 100× magnification, the thinner strips represent diF-TES-ADT crystals, and the wider strips are TIPS-TAP crystals. The FIG. 10B is a schematic diagram of the morphology corresponding to FIG. 10A, the dark gray stripes in FIG. 10B represent TIPS-TAP crystals, and the light gray stripes represent diF-TES-ADT crystals. It can be clearly observed the uniform morphology in the bilayer organic single crystals, and the overall morphology including the crystal thickness is well controlled. The FIG. 11A shows a larger range (at 20× magnification) observation of diF-TES-ADT and TIPS-TAP bilayer organic single-crystalline heterojunction composite films under an optical microscope. The FIG. 11B is the corresponding polarized optical microscopic image of FIG. 11A, it can be seen that laminating coupled growth can be realized in the organic single-crystalline heterojunction composite film for achieving highly efficient lamination ratio, moreover, the two-dimensional high coverage and large-area continuous growth are achieved at the same time. The uniform color in the optical microscopic image once again proves the well-regulated crystal thickness. In addition, the birefringence behavior exhibited in the heterojunction composite film displayed in the polarized optical microscopic image in FIG. 11B indicates its single-crystalline nature, thereby, the obtained bilayer heterojunction composite film is proved as an organic single-crystalline heterojunction composite film. The morphology and sophisticated structure of organic single-crystalline thin film in the optical microscopic image could be analyzed via using software that can analyze image pixels (such as Image J software, Matlab, Photoshop, Adobe Illustrator, etc., the present disclosure takes Image J software as an example). For example, the lamination area ratio between diF-TES-ADT organic single-crystalline thin film and TIPS-TAP organic single-crystalline thin film can be calculated in the FIG. 10, seven adjacent crystals in TIPS-TAP organic single-crystalline thin film (which has a relatively larger area in the two organic single-crystalline thin film) are randomly selected for the calculation, and the selected area is shown in FIGS. 10A-10B. A.sub.large=1432.59 μm.sup.2+1384.30 μm.sup.2+1471.49 μm.sup.2+1561.36 μm.sup.2+1625.75 μm.sup.2+1191.15 μm.sup.2+1239.44 μm.sup.2=9906.0 8 μm.sup.2, A.sub.large is the total area of 7 TIPS-TAP crystals, A.sub.total=(901.41 μm.sup.2+692.15 μm.sup.2+949.70 μm.sup.2+885.30 μm.sup.2+997.99 μm.sup.2+820.92 μm.sup.2+7 88.72 μm.sup.2)=6036.19 μm.sup.2, A.sub.total is the sum of the lamination area between the 7 selected TIPS-TAP crystals and the 7 selected diF-TES-ADT crystals in diF-TES-ADT single-crystalline thin film (which has a relatively smaller area in the two organic single-crystalline thin film). Thereby, R=A.sub.total/A.sub.large=55.8% could be calculated. The requirement that the lamination area ratio needs to be greater than or equal to 50% could be achieved, which means that the highly efficient lamination of the organic single-crystalline efficiently coupled unit could be realized. Selecting 7 adjacent TIPS-TAP crystals for calculating the vertical coverage ratio of the organic single-crystalline thin film, R.sub.V=((87.73 μm+87.73 μm+87.73 μm+87.73 μm+87.73 μm+87.73 μm+87.73 μm)/7)/87.73 μm=100%, therefore, it can be considered that the high/full vertical coverage ratio is achieved in the direction V. The quite high horizontal coverage ratio is also obtained in the direction H, R.sub.H=(16.51 μm+15.96 μm+16.70 μm+16.70 μm+18.72 μm+13.39 μm+13.03 μm)/117.25 μm=94.68%, thus, the two-dimensional high coverage is ensured, moreover, it could be considered as realizing almost full coverage, which provides a large-area channel for charge carrier transport. For the degree of laminated orientation calculation, firstly, select 7 crystals in the diF-TES-ADT organic single-crystalline thin film and calculate the average orientation angle Ā.sub.T of the 7 crystals (the reference direction is the same as the direction V), Ā.sub.T=((−0.74°)+(−1.19°)+0.55°+1.70°+0.99°+0.45°+1.61°)/7=0.48°, then select 7 crystals in the TIPS-TAP organic single-crystalline thin film and calculate the average orientation angle Ā.sub.B of the 7 crystals (the reference direction is the same as the direction V), Ā.sub.B=(0.45°±0.82°±1.79°±2.87°±1.25°±1.79°+1.17°)/7=1.45°, the laminated orientation angle could be obtained, Ā=(Ā.sub.T−Ā.sub.B)=−0.97°, finally, the degree of laminated orientation could be calculated, F.sub.L=0.5*(3*cos.sup.2Ā−1)=0.999, the F.sub.L is very close to 1, which indicates that the almost completely parallel orientation is achieved. Therefore, the lamination coupling (that is, the well-aligned/uniformly orientated lamination) in the bilayer organic single-crystalline heterojunction composite film is verified, and the realization of synergistic growth for bilayer organic single crystals provides convenience for the subsequent preparation of devices and exhibition of high-performance electronic/optoelectronic behaviors. The diF-TES-ADT single-crystalline thin film is grown on top of the TIPS-TAP single-crystalline thin film, and the two organic single-crystalline thin films are combined by laminating (as shown in FIG. 3B). A single-crystalline heterojunction with a clear bilayer structure is formed, as shown in the scanning electron microscopic image shown in FIG. 12, the diF-TES-ADT single crystals are selectively grown on the upper surface of the TIPS-TAP single crystals, and the obtained bilayer single-crystalline heterojunction composite film is completely laminated, which is beneficial for the formation of a high-quality heterojunction interface and satisfying the requirements of an organic single-crystalline efficiently coupled unit. The FIG. 13 shows the transfer curve of hole and electron transport of a typical ambipolar organic field-effect transistor (V.sub.DS=−120V, .sub.VG=−120V) based on the organic single-crystalline heterojunction composite film prepared in Example 1, respectively. After calculation, both the hole and electron mobility in the saturation region exceeds 0.1 cm.sup.2V.sup.−1s.sup.−1, as shown in Table 3, a good ambipolar performance of charge carrier transport is achieved.

    [0213] In the process of laminating coupled growth, due to the different structures of the two organic molecules (for example, diF-TES-ADT comprises S atoms in the core and F atoms in the side chain, thus there are F-F and F-S interactions existed between the molecules), the different interaction between solutes and the substrate modification layer, the different interaction between solutes and the solvents, and the different crystallization rate of the two organic molecules (the different crystallization rate referring to the crystallization rate is not exactly the same) in the solution under the shearing force, therefore, there is the possibility of realizing horizontal phase separation and/or vertical phase separation at different interfaces, as the laminating coupled growth mode of the bilayer organic single-crystalline thin film shown in Table 1. For example, FIG. 7 and FIG. 8, the detection method for vertical phase separation is to observe whether the morphology changes when the crystal crossing the obstacles (nanowires). In FIG. 7, 7 crystals whose crystal growth direction crosses the silver nanowire obstacles are selected, through analysis by ImageJ software, we can observe the angles between the silver nanowire and the vertical crystal growth direction where the crystal meets the silver nanowire are both less than 45° (specifically, |A.sub.o| is 27.00°, 29.06°, 13.13°, 18.44°, 3.37°, 10.62°,23.20°), thus the requirements of obstacles are satisfied. The average thickness of silver nanowire h.sub.o is about 40±5 nm, and the average thickness of the crystal h.sub.o is about 25±3 nm, |h.sub.o−h|<20 nm, when the morphology of 7 crystals is basically unchanged before and after crossing the silver nanowires, the growth mode can be determined as having an air-liquid interface.

    [0214] The morphologies of the organic single-crystalline heterojunction composite films obtained in Examples 2-17 are similar to those in FIG. 10 and FIG. 11, the thickness, width, and gap of the crystals are only slightly changed, thus the detailed description will be omitted here. The organic field-effect transistors obtained in Examples 2-6 and Examples 9-10 all exhibited obvious ambipolar transport performance, and the obtained hole and electron mobility are shown in Table 4, respectively, which can be applied to electroluminescent devices and complementary integrated circuits.

    [0215] In order to illustrate that the organic single-crystalline heterojunction composite film provided by the present disclosure has a highly ordered heterojunction interface, Comparative Example 1 and Comparative Example 2 adopt two different types of organic semiconductor small molecules (p-type perylene and n-type TIPS-TAP), the organic single-crystalline & polycrystalline heterojunction was prepared by combining the solution and evaporation method. The polycrystalline thin film can be determined through the characterization of the optical microscope. Through the characterization, an organic single-crystalline & polycrystalline heterojunction is obtained in Comparative Example 1, and organic polycrystalline & polycrystalline heterojunction c is obtained Comparative Example 2. The performance of organic field-effect transistors prepared based on the two heterojunctions aforementioned (which are not single-crystalline state) is shown in Table 4. It can be observed that the hole and electron mobility has dropped by nearly an order of magnitude compared with heterojunction composite film containing two single-crystalline thin films (for example, organic single-crystalline heterojunction composite film in Example 1). In Comparative Example 1, the hole mobility is 0.007 cm.sup.2V.sup.−1s.sup.−1, and the electron mobility is 0.04 cm.sup.2V.sup.−1s.sup.−1, the hole and electron mobility in Comparative Example 2 are 0.008 cm.sup.2V.sup.−1s.sup.−1 and 0.02 cm.sup.2V.sup.−1s.sup.−1, respectively. Both examples well illustrated that the order of the heterojunction interface formed by organic single-crystalline & polycrystalline or organic polycrystalline & polycrystalline is greatly reduced, which affects the transport performance of the two types of charge carriers.

    [0216] In the mixed solution, the control of the growth rate and/or the difference in growth interface between different solutes is needed to obtain horizontal phase separation and/or vertical phase separation, the mutual interference of different solutes during nucleation crystal growth should be avoided, or else the morphology of the organic single-crystalline heterojunction composite film will be affected. In order to illustrate the importance of the control aforementioned, two solutes having the same growth interfaces (the air-liquid interface) and similar growth rates are used for comparison in Comparative Example 3. The morphology of the obtained heterojunction composite film is shown in FIG. 14, the quite uneven color/gray-scale of the crystals could be observed in the polarized optical microscopic image, indicating that the obtained organic film is polycrystalline, and it is even impossible to distinguish the respective morphologies of different types of organic films. If the horizontal phase separation or vertical phase separation is not existed when the different solutes are mixed in the same solution, serious interference to the nucleation growth of crystals will be caused, thus, it is impossible to obtain a single-crystalline thin film, furthermore, it is impossible to obtain an organic single-crystalline efficiently coupled unit with lamination coupling properties, which is harmful to the subsequent preparation of optoelectronic devices.

    [0217] In order to illustrate that the solutes need to be fully dissolved in the mixed solution, Comparative Example 4 choose 1-butanol as the solvent, which has a lower solubility for the selected solute molecules. Since the solubility of the two solutes in 1-butanol is not high enough, the solubility S is <0.05 wt % under stable conditions, ultimately, almost no corresponding organic single-crystalline heterojunction composite film is obtained on the substrate. This is because solvent evaporates very quickly, and solutes with insufficient solubility are easier to precipitate out, as a result, under the applied shearing force, the supply of raw materials in the solution storage space has been exhausted before the crystal grows, only some solid residues can be obtained on the substrate in the end.

    [0218] In order to illustrate that the growth conditions of the organic single-crystalline heterojunction composite film preparation method provided by the present disclosure need to be strictly controlled, Comparative Examples 5-7 used the same materials, the same substrate modification layer, the same solvent and the same growth temperature as in Example 1. However, due to the growth conditions are not precisely controlled, such as the standing time is too long or too short, the distance between the shearing tool and the substrate is too large, the shearing speed is too fast or too slow, the ambient temperature is too high, or the ambient humidity is too high, the mismatch will be caused between the solute deposition rate, the solvent evaporation rate and the meniscus movement speed owing to the factors aforementioned, therefore, the stable growth environment cannot be provided for obtaining organic single-crystalline heterojunction composite film with ideal morphology. The morphology of the organic heterojunction composite film obtained in Comparative Example 7 is shown in the optical microscopic image of FIG. 15 (the morphologies of Comparative Examples 5 and 6 are similar to those of Comparative Example 7), a lot of randomly oriented, curved or discontinuous crystals are displayed (the degree of laminated orientation is 0.389), the coverage ratio (including horizontal and vertical direction) of the crystal is low (R.sub.V=76.41%, R.sub.H=54.90%), similarly, the lamination area ratio between the two layer of crystals is also quite low (R=23.55%). Attributed to the non-regular crystal morphology, the double-layer crystals obtained without controlling the growth conditions is difficult to be applied for preparing optoelectronic devices. Moreover, due to the uncertainty of the morphology, the obtained electronic/optoelectronic behaviors are unable to be corrected, thus the real performance cannot be reflected. The only device prepared in Comparative Example 7 is also showing a low performance (the p-type mobility is 0.0003 cm.sup.2V.sup.−1s.sup.−1, and the n-type mobility cannot be detected).

    [0219] In order to illustrate the advantages of the preparation method provided by the present disclosure in obtaining the well-control over the morphology of organic single-crystalline heterojunction composite films, Comparative Example 8 uses the mechanical transfer method to prepare the organic single-crystalline heterojunction composite film, the diF-TES-ADT film prepared on the PDMS is transferred onto the pre-formed TIPS-TAP film to fabricated the heterojunction composite film through the physical electrostatic adsorption. First of all, the difficulties in positioning caused by the manual operation leads to myriad challenges in realizing large-scale transferring, so the ratio of successful lamination of the heterojunction composite film is very low. Additionally, since the thickness of the diF-TES-ADT organic single-crystalline thin film is only about 20 nm, many cracks appear on the crystal surface due to stress during the mechanical transferring process, the quality of the crystal is severely damaged, and it is hard to control the degree of orientation of the lamination between the two layers of films, leading to the inconsistent laminated orientation between the final double-layer films. As a result, the lamination area between the double-layer films is reduced, and the ambipolar transport performance is seriously affected. The performance obtained is shown in Table 4, the device does not show p-type performance, only the electron mobility of 0.13 cm.sup.2V.sup.−1s.sup.−1 is obtained. Comparative Example 9 used a two-step orthogonal solvent method to grow two layers of organic single crystals. Since the already grown TIPS-TAP organic single-crystalline thin film has become the roadblock for the growth of the second layer organic single-crystalline thin film (diF-TES-ADT), leading to the disturbance to the orientation of diF-TES-ADT during growth. The crystals are prone to display bifurcation or bending morphology, moreover, part of the crystals will stop growing due to the hindrance of the growth front, result in the non-uniform morphology of the organic heterojunction film ultimately. On the other hand, when the second layer of diF-TES-ADT organic single-crystalline thin film is grown, the diF-TES-ADT solution is spread on the already grown TIPS-TAP organic single-crystalline thin film, causing damage to the crystal surface of the TIPS-TAP thin film. As a result, the quality of the organic heterojunction interface is degraded. As the performance of the organic field-effect transistor shown in Table 4, the greatly reduced mobilities (the hole mobility is 0.10 cm.sup.2V.sup.−1s.sup.−1, and the electron mobility is 0.003 cm.sup.2V.sup.−1s.sup.−1) prove that the crystal surface of the TIPS-TAP single-crystalline thin film has been damaged. Comparative Example 10 used the DPC method reported in H. Li et al., Advanced Materials, 24, 2588 (2012) to prepare an organic single-crystalline heterojunction composite film with a mixed solution, the same materials as in Example 1 are adopted. As shown in the optical microscopic image of FIG. 16, due to the lack of directional shearing, a suitable morphology cannot be obtained in the organic heterojunction composite film, and two types of organic crystals can barely be distinguished, which causing barriers for subsequent realization of electronic/optoelectronic behaviors. Because of the difficulty in distinguishing the morphology of heterojunction film, it is possible that the performance of one type of organic semiconductor molecules has not been reflected, therefore the ambipolar transport cannot be realized in the organic heterojunction. The performance of the obtained device is shown in Table 4, only the hole mobility of 0.06 cm.sup.2V.sup.−1s.sup.−1 is exhibited while the electron transport performance is not obtained.

    [0220] In summary, through Comparative Examples 1-10, it can be explained that only the method for preparing the organic single-crystalline heterojunction composite film provided by the present disclosure could be used to realize the laminating coupled growth of the organic single-crystalline efficiently coupled unit. Thereby, an organic single-crystalline heterojunction composite film is obtained with high quality heterojunction interface, highly efficient lamination, and at least one layer of organic single-crystalline thin film to achieve an ideal morphology with two-dimensional high coverage.

    [0221] Through Examples 1-17 and Comparative Examples 1-10, it can be illustrated that the following three conditions must be met in order to achieve the preparation of organic heterojunction composite films (possessing ideal material form, morphology and structure) and related optoelectronic devices: 1) In the organic heterojunction composite film, each component should be guaranteed in the single-crystalline form, and a high-quality heterojunction interface must be realized; 2) the two or more layers of organic single-crystalline thin films are grown through laminating coupled growth to achieve highly efficient lamination, that is, an organic single-crystalline heterojunction composite film with laminated structure which comprises a large lamination area ratio; 3) at least one organic single-crystalline thin film in the organic single-crystalline heterojunction composite film can achieve two-dimensional high coverage. If the first two conditions are met, a high-quality organic single-crystalline heterojunction composite film can be obtained, and the morphology and device performance have been greatly improved compared with the existing level. For an organic single-crystalline heterojunction composite film with an ideal morphology, the three prerequisites aforementioned need to synergistically work together to achieve the purpose of the present disclosure.

    TABLE-US-00001 TABLE 1 Formulations and process parameters A of Example 1-17 and Comparative Example 3-7 (substrate, modification layer, solutes and their respective ratio, solvent, shearing temperature and shearing velocity) modification shearing shearing No. substrate layer solutes and their respective ratio solvent temperature velocity Example 1 SiO.sub.2 c-PS diF-TES-ADT:TIPS-TAP = 1:1 Mesitylene 60° C. 400 ± 5 μm/s Example 2 SiO.sub.2 c-PS diF-TES-ADT:TIPS-TAP = 1:1 Mesitylene 80° C. 800 ± 5 μm/s Example 3 SiO.sub.2 c-PS diF-TES-ADT:TIPS-TAP = 1:1 Mesitylene 40° C. 200 ± 5 μm/s Example 4 SiO.sub.2 c-PS diF-TES-ADT:TIPS-TAP = 2:1 Mesitylene 60° C. 400 ± 5 μm/s Example 5 SiO.sub.2 c-PS diF-TES-ADT:TIPS-TAP = 1:2 Mesitylene 60° C. 400 ± 5 μm/s Example 6 SiO.sub.2 PMMA diF-TES-ADT:TIPS-TAP = 1:1 N-octane 40° C. 50 ± 1 μm/s Example 7 PEN c-PMMA TIPS-PEN:C.sub.8-BTBT = 1:1 Toluene: 30° C. 10 ± 1 μm/s CHCl.sub.3 = 1:1 Example 8 SiO.sub.2 c-PMMA TIPS-PEN:C.sub.8-BTBT = 1:1 CHCl.sub.3  0° C. 10 ± 1 μm/s Example 9 SiO.sub.2 OTS Perylene:TIPS-TAP = 1:1 Toluene 100° C.  2000 ± 20 μm/s Example 10 SiO.sub.2 PMMA & Perylene:TIPS-TAP = 1:2 Toluene: 50° C. 600 ± 5 μm/s P(VDF- Heptane = 1:1 TrFE- CFE) Example 11 SiO.sub.2 PVA TIPS-PEN:9,10-DPA = 1:1 Toluene 60° C. 400 ± 10 μm/s Example 12 SiO.sub.2 c-PVP TIPS-PEN:9,10-DPA = 1:1 Dodecane 80° C. 1000 ± 5 μm/s Example 13 AlO.sub.x ODPA Tetracene:TIPS-TAP = 1:1 M-xylene 60° C. 200 ± 1 μm/s Example 14 SiO.sub.2 PI Tetracene:TIPS-TAP = 1:1 M-xylene 80° C. 800 ± 10 μm/s Example 15 SiO.sub.2 PI TIPS-TAP:dp-dtt = 1:1 P-xylene 80° C. 800 ± 5 μm/s Example 16 SiO.sub.2 PI Rubrene:C.sub.60 = 1:1 1-chloro- 200° C.  20 ± 1 μm/s naphthalene Example 17 SiO.sub.2 PI Rubrene:C.sub.60 = 1:1 Chlorobenzene 60° C. 400 ± 5 μm/s Comparative SiO.sub.2 c-PS diF-TES-ADT:TIPS-PEN = 1:1 Mesitylene 60° C. 400 ± 5 μm/s Example 3 Comparative SiO.sub.2 c-PS diF-TES-ADT:TIPS-TAP = 1:1 1-butanol 60° C. 400 ± 5 μm/s Example 4 Comparative SiO.sub.2 c-PS diF-TES-ADT:TIPS-TAP = 1:1 Mesitylene 60° C. 5 ± 1 μm/s Example 5 Comparative SiO.sub.2 c-PS diF-TES-ADT:TIPS-TAP = 1:1 Mesitylene 60° C. 10000 ± 20 μm/s Example 6 Comparative SiO.sub.2 c-PS diF-TES-ADT:TIPS-TAP = 1:1 Mesitylene 60° C. 200 ± 5 μm/s Example 7 **The actual process parameters (including the shearing temperature and shearing velocity) are allowed to have a deviation of ±2% from the parameters listed in the table.

    TABLE-US-00002 TABLE 2 Formulations and process parameters B of Example 1-17 and Comparative Example 3-7 (standing time, ambient temperature, ambient humidity, gap distance, the solubility of solute (S) and laminating coupled growth fashion between two layers of organic single-crystalline thin films) solubility laminating standing ambient ambient gap of solute coupled growth No. time temperature humidity distance (S) fashion Example 1 5 s 20 ± 1° C. 50 ± 3% 200 ± 5 μm S > 0.5 wt % Horizontal and Vertical phase separation Example 2 10 s 20 ± 1° C. 50 ± 3% 200 ± 5 μm S > 0.5 wt % Horizontal and Vertical phase separation Example 3 5 s 20 ± 1° C. 50 ± 3% 200 ± 5 μm S > 0.5 wt % Horizontal and Vertical phase separation Example 4 5 s 20 ± 1° C. 50 ± 3% 200 ± 5 μm S > 0.5 wt % Horizontal and Vertical phase separation Example 5 5 s 20 ± 1° C. 50 ± 3% 150 ± 5 μm S > 0.5 wt % Horizontal and Vertical phase separation Example 6 5 s 20 ± 1° C. 40 ± 2% 150 ± 5 μm S > 0.05 wt % Horizontal and Vertical phase separation Example 7 10 s 20 ± 1° C. 40 ± 2% 200 ± 5 μm S > 0.5 wt % Horizontal phase separation Example 8 10 s 20 ± 1° C. 40 ± 2% 200 ± 5 μm S > 0.5 wt % Horizontal phase separation Example 9 15 s 25 ± 1° C. 50 ± 3% 150 ± 5 μm S > 0.5 wt % Horizontal phase separation Example 10 2 s 25 ± 1° C. 50 ± 3% 150 ± 5 μm S > 0.5 wt % Horizontal phase separation Example 11 15 s 25 ± 1° C. 50 ± 3% 300 ± 5 μm S > 0.5 wt % Horizontal and Vertical phase separation Example 12 15 s 25 ± 1° C. 50 ± 3% 300 ± 5 μm S > 0.5 wt % Horizontal and Vertical phase separation Example 13 15 s 25 ± 1° C. 30 ± 1% 300 ± 5 μm S > 0.5 wt % Horizontal phase separation Example 14 10 s 25 ± 1° C. 30 ± 2% 300 ± 5 μm S > 0.5 wt % Horizontal phase separation Example 15 10 s 25 ± 1° C. 30 ± 2% 200 ± 5 μm S > 0.5 wt % Horizontal phase separation Example 16 5 s 25 ± 1° C. 30 ± 2% 200 ± 5 μm  S > 0.05 wt % Vertical phase separation Example 17 5 s 20 ± 1° C. 50 ± 3% 200 ± 5 μm  S > 0.05 wt % Vertical phase separation Comparative 10 s 25 ± 1° C. 50 ± 2% 200 ± 5 μm S > 0.5 wt % N/A Example 3 Comparative 10 s 25 ± 1° C. 50 ± 2% 200 ± 5 μm S > 0.5 wt % N/A Example 4 Comparative 60 s 30 ± 3° C. 50 ± 5% 50 ± 1 μm S > 0.5 wt % N/A Example 5 Comparative 0 s 40 ± 3° C. 70 ± 3% 200 ± 5 μm S > 0.5 wt % N/A Example 6 Comparative 60 s 25 ± 1° C. 70 ± 5% 800 ± 100 μm S > 0.5 wt % N/A Example 7 ** The actual process parameters (including standing time, ambient temperature, ambient humidity, gap distance, and solubility of solute (S)) are allowed to have a deviation of ±2% from the parameters listed in the table.

    TABLE-US-00003 TABLE 3 Morphology parameters of the organic single- crystalline heterojunction composite film of Examples 1-17 and Comparative Examples 5-7 degree of vertical horizontal lamination laminated coverage coverage area orientation ratio of ratio of No. ratio R F.sub.L M.sub.L (R.sub.V) M.sub.L (R.sub.H) Example 1 55.80% 0.999   100% 94.68% Example 2 51.37% 0.974   100% 90.37% Example 3 53.29% 0.989   100% 86.42% Example 4 65.01% 1   100% 90.03% Example 5   100% 0.942   100% 89.67% Example 6 55.03% 0.873 98.76% 85.48% Example 7 80.04% 0.725 89.37% 82.45% Example 8 91.22% 0.664 82.17% 71.31% Example 9 50.97% 0.631 84.62% 75.99% Example 10 57.20% 0.706 92.07% 73.65% Example 11 73.67% 0.980 95.33% 80.12% Example 12 65.05% 0.965 92.18% 84.49% Example 13 61.64% 0.878 99.76% 87.23% Example 14 73.54% 0.922   100% 89.56% Example 15 82.57% 0.839 83.95% 76.38% Example 16 52.95% 0.653 84.08% 77.97% Example 17 50.76% 0.741 89.32% 81.90% Comparative 25.83% 0.395 96.37% 67.49% Example 5 Comparative 43.20% 0.237 89.12% 42.73% Example 6 Comparative 23.55% 0.389 76.41% 54.90% Example 7 **Actually obtained crystal morphology parameters (including lamination area ratio R, degree of laminated orientation F.sub.L, vertical coverage ratio of M.sub.L (R.sub.V) and horizontal coverage ratio of M.sub.L (R.sub.H)) are allowed ±3% deviation from the tested parameters listed in the table.

    TABLE-US-00004 TABLE 4 Performance statistics of saturation region mobilities of the organic single-crystalline field-effect transistors at V.sub.DS = −120 V, V.sub.G = −120 V obtained in Examples 1-6, Example 9-10 and Comparative Examples 1-2, Comparative Examples 4, Comparative Examples 7-10. Hole mobility Electron mobility Example 1 0.13 cm.sup.2V.sup.−1s.sup.−1 0.20 cm.sup.2V.sup.−1s.sup.−1 Example 2 0.11 cm.sup.2V.sup.−1s.sup.−1 0.16 cm.sup.2V.sup.−1s.sup.−1 Example 3 0.08 cm.sup.2V.sup.−1s.sup.−1 0.18 cm.sup.2V.sup.−1s.sup.−1 Example 4 0.12 cm.sup.2V.sup.−1s.sup.−1 0.13 cm.sup.2V.sup.−1s.sup.−1 Example 5 0.14 cm.sup.2V.sup.−1s.sup.−1 0.16 cm.sup.2V.sup.−1s.sup.−1 Example 6 0.17 cm.sup.2V.sup.−1s.sup.−1 0.12 cm.sup.2V.sup.−1s.sup.−1 Example 9 0.09 cm.sup.2V.sup.−1s.sup.−1 0.25 cm.sup.2V.sup.−1s.sup.−1 Example 10 0.05 cm.sup.2V.sup.−1s.sup.−1 0.37 cm.sup.2V.sup.−1s.sup.−1 Comparative Example 1 0.007 cm.sup.2V.sup.−1s.sup.−1 0.04 cm.sup.2V.sup.−1s.sup.−1 Comparative Example 2 0.008 cm.sup.2V.sup.−1s.sup.−1 0.02 cm.sup.2V.sup.−1s.sup.−1 Comparative Example 4 0.05 cm.sup.2V.sup.−1s.sup.−1 0.08 cm.sup.2V.sup.−1s.sup.−1 Comparative Example 7 0.0003 cm.sup.2V.sup.−1s.sup.−1 N/A Comparative Example 8 N/A 0.13 cm.sup.2V.sup.−1s.sup.−1 Comparative Example 9 0.10 cm.sup.2V.sup.−1s.sup.−1 0.003 cm.sup.2V.sup.−1s.sup.−1 Comparative Example 10 0.06 cm.sup.2V.sup.−1s.sup.−1 N/A