Application of C-H sigma bond compound as photo-activated n-type dopant in semiconductor material

Abstract

The invention discloses application of a C-H sigma bond compound as a light-activated n-type dopant in semiconductors, and belongs to the field of semiconductor functional materials and the field of organic electronics. As a high-stability, photo-activatable and efficient n-type dopant, the C-H sigma bond compound can realize efficient doping of semiconductor materials such as small organic molecule semiconductors, conjugated polymer semiconductors, carbon nanotubes, two-dimensional semiconductors and the like. Meanwhile, the n-type dopant can be compatible with a high-precision ultraviolet exposure technology, and regioselective doping of a semiconductor material is achieved. When the C-H sigma bond compound is used as an n-type dopant to be applied to electronic devices based on semiconductor materials, such as thin film transistors, thermoelectric devices, solar cells and light-emitting diodes, the bulk phase and interface defects of the semiconductor materials can be eliminated, the carrier concentration of the materials can be regulated and controlled, the electrical performance of small-size devices can be remarkably improved, and the performance of the devices can be improved. Therefore, miniaturization and integration of the device are realized.

Description

Technical Field

[0001] This invention relates to the application of C-H σ bond compounds as n-type dopants in high-efficiency, regionally controllable doping of semiconductor materials, belonging to the fields of semiconductor functional materials and organic electronics. Background Technology

[0002] Since the invention of semiconductor material purification technology, transistors, and integrated circuits, semiconductor materials and related technologies have triggered tremendous social changes with unprecedented breadth and depth. Driven by new demands represented by artificial intelligence and high-performance computing, improving the performance of semiconductor devices remains a focus of current research. In addition to optimizing and developing novel high-performance semiconductor materials, doping semiconductor materials to control their carrier types and concentrations has become a major way to improve the performance of semiconductor devices and fabricate complex electronic devices (Noh, YYet.al, Doping: A Key Enabler for Organic Transistors, Adv. Mater. 2018, 30, 180-1830).

[0003] Doping involves adding substances with redox activity or the ability to introduce new energy levels (i.e., dopants) to semiconductor materials to controllably generate additional charge carriers (holes or electrons), thereby altering the carrier type and adjusting the carrier concentration (Leo, K. et al., Doped Organic Transistors, Chem. Rev. 2016, 116, 13714). Dopants are essential for achieving doping, and developing novel, efficient dopants and applicable doping methods remains a hot research topic. n-type molecular dopants are essentially a class of molecular or ionic compounds with reducing capabilities that can undergo redox reactions with semiconductor materials, generating negatively charged and mobile charge carriers (polarons, bipolarons, or free radical anions, etc.) in semiconductor materials (Duan, L. et al., Efficient n-Dopants and Their Roles in Organic Electronics, Adv. Optical Mater. 2018, 1800536). For an ideal n-type dopant, it is generally required to meet the following conditions: (1) It has a strong reduction ability so that it can dop semiconductor materials with n-type doping and have high doping efficiency; (2) It is stable in air so as to facilitate preparation and storage; (3) It has mild operating conditions and simple and diverse processing methods to meet the needs of vacuum evaporation, solution processing and other requirements; (4) It can achieve regional controllable doping in semiconductor materials and accurately control the doping degree and doping region.

[0004] The strong reducing power of n-type dopants ensures their high doping efficiency, but it also leads to poor air stability. Therefore, their design and synthesis are quite challenging. Developing n-type dopants that combine air stability and strong doping ability is key to achieving efficient n-type doping. Currently, four types of n-type dopants have been developed: low-ionization-energy compounds, organic salts, organic hydrogen donors, and organic radical dimers, as shown in the table below. However, air-stable, and especially solution-stable, n-type dopants are still lacking. For example, the most commonly used n-type dopants, N-DMBI and (RuCp*mes)2, lose their n-type doping ability due to slow oxidation in solution (Barlow, S. et al., n-Doping of Organic Electronic Materials using Air-Stable Organometallics, Adv. Mater. 2012, 24, 699; Müllen, K. et al., n-Type Doping of Organic Semiconductors: Immobilization via Covalent Anchoring, Chem. Mater. 2019, 31, 4213; Ito, A. et al., A Dendritic Oligoarylamine-substituted Benzimidazole Derivative as AUseful n-Type Dopant, J. Mater. Chem. C, 2018, 6, 6429).

[0005]

[0006] In addition, precise control of the doping region of semiconductor materials can significantly improve the device performance of semiconductor materials (Moulé, A.Jet.al, Controlling Molecular Doping in Organic Semiconductors. Adv. Mater. 2017, 1703063). Currently, region-doped semiconductor materials have the following representative applications: (1) for manufacturing interconnects and electrodes in complex circuits (Lee, CWet.al, A Soluble Polyaniline Substituted with T-BOC: Conducting Patterns and Doping, Macromolecules 2004, 37, 4070); (2) for preparing pn junctions for functional electronic devices, such as diodes, thermoelectric devices, photodetectors, etc. (Chen, Y.et.al, Selective Doping of a Single Ambipolar Organic Semiconductor to Obtain p-and n-Type Semiconductors, Matter 2022, 5, 2882; Yu, Z.-D.et.al, High n-type and p-type conductivities and power factors achieved in a single conjugated polymer, Sci. Adv. 2023, 9, eadf3495); (3) for improving the device performance of field-effect transistors (FETs). Selective doping of the channel and contact regions of a FET can fill energy traps, modulate carrier polarity, reduce the injection barrier, and eliminate short-channel effects, further reducing the threshold voltage and improving device mobility and stability. This is crucial for the miniaturization and integration of FETs (Xu, Y. et.al, Doping: A Key Enabler for Organic Transistors, Adv. Mater. 2018, 30, 180-1830; Lüssem, B. et.al, Doped Organic Transistors Operating in the Inversion and Depletion Regime, Nat. Commun. 2013, 4, 2775).

[0007] Most dopants, due to their inherent doping ability, undergo rapid and uncontrollable doping reactions upon contact with semiconductor materials. Therefore, when processing dopants and semiconductor materials through methods such as spin coating or co-evaporation of mixed solutions, only a uniform doped system can usually be obtained (Zhao, W. et al., Chemical Doping of Organic Semiconductors for Thermoelectric Applications, Chem. Soc. Rev. 2020, 49, 7210). To achieve region-selective doping, methods such as inkjet printing, screen printing, thermal evaporation, or drop coating are often used to deposit dopants at specific locations on a pre-prepared semiconductor layer (Takeya, J. et.al, High-Speed ​​Organic Single-Crystal Transistor Responding to Very High Frequency Band, Adv. Funct. Mater. 2020, 30, 1909501; Noh, Y. et.al, Control of Ambipolar and Unipolar Transport in Organic Transistors by Selective Inkjet-Printed Chemical Doping for High Performance Complementary Circuits, Adv. Funct. Mater. 2014, 24, 6252). Currently, most n-type dopants suffer from poor air and thermal stability. Furthermore, solutions formulated with these dopants generally exhibit low viscosity and high fluidity. Consequently, these processing methods often suffer from poor versatility, complex operation, and low doping precision (>30 μm) (Menard, E. et al., Micro-and Nanopatterning Techniques for Organic Electronic and Optoelectronic Systems, Chem. Rev. 2007, 107, 1117). Achieving high-precision, region-selective doping of semiconductor materials solely through optimizing processing and doping methods is currently difficult. However, combining rational dopant molecule design with feasible doping methods holds promise for breakthroughs in addressing this issue. Summary of the Invention

[0008] To address the current limitations of n-type dopants, particularly those possessing both air stability and strong doping capability, and the difficulty in achieving regioselective doping using them, this invention aims to develop a class of n-type dopant systems with high stability, strong doping capability, and controllable doping properties, and to provide a doping method based on such dopants that can achieve regioselective doping with high precision.

[0009] To achieve the above objectives, this invention designs a series of C-H σ-bond-based compounds as photoactivated n-type dopants. These compounds themselves do not possess doping ability (referred to herein as inactive photoactivable dopants, iPADs), but can undergo electrocyclization reactions under photoactivation to generate organic negative hydrogen dopants with strong n-type doping ability (referred to herein as photoactivated dopants, PADs), which are used for n-type doping of semiconductor materials. After doping, PADs are transformed into more stable dopant ions (referred to herein as photoactivated dopant ions, PADs). + This makes the doping reaction irreversible. This type of dopant has the following advantages: (1) The dopant itself does not react with water or oxygen at room temperature and has excellent air stability; (2) It can exhibit the properties of photoactivated doping and can achieve precise control of the doping degree and doping region by controlling the dopant ratio, exposure dose, and exposure site.

[0010] In a first aspect of the invention, a C-H σ-bond-based compound of formula I is provided as a photoactivated n-type dopant:

[0011]

[0012] In Formula I, R and R′ represent the same or different substituents on the double bond, and R and R′ are independent of each other or connected to form a ring; Ar represents a nitrogen-containing five-membered aromatic heterocycle, a six-membered aromatic heterocycle and its fused ring structure, and Ar′ represents a five-membered aromatic ring, a six-membered aromatic ring and its fused ring structure. Ar and Ar′ may have one or more substituents selected from halogen atoms, cyano, amino, nitro, alkyl, alkoxy, cyano or halogen-substituted alkyl or alkoxy, as well as aromatic substituents such as thiophene, furanyl, selenene, phenyl, pyridinyl, etc.

[0013] In order for C-H σ-bond compounds (iPADs) that do not inherently possess n-type doping capability to generate substances with strong doping capability (i.e., reduction capability) after photoactivation, they must possess the following structural characteristics:

[0014] (1) Contains hexadene and its derivatives capable of undergoing electrocyclization reactions; (2) The atom at position 1 of the Ar group shown in Formula I is sp 2Hybridized nitrogen atom; (3) The atom at position 6 in the Ar′ group shown in formula I is sp 2 A hybrid carbon atom with one hydrogen atom substituent. For example... Figure 1 As shown, after UV activation, these compounds undergo an electrocyclization reaction, and the nitrogen atom at position 1 of the Ar group forms an N-C σ bond with the carbon atom at position 6 of the Ar′ group, thereby generating the corresponding active dopant (PAD). To restore the aromaticity of the PAD, it tends to undergo a hydride transfer reaction with acceptor molecules (such as n-type semiconductor materials). This aromatic stabilization enables the PAD to have a strong hydride-donating ability, thus exhibiting n-type doping capability. iPAD, however, cannot efficiently dope common semiconductor materials in the n-type manner due to its lack of hydride-donating ability and lower HOMO energy level.

[0015] Based on the above design principles, R and R′ are preferably hydrogen atoms, halogen atoms, alkyl groups, alkoxy groups, nitro groups, cyano groups, or halogen-substituted alkyl or alkoxy groups. When R and R′ are halogen atoms, fluorine atoms are more preferably used. When R and R′ are alkyl groups, they can be straight-chain alkyl groups, such as methyl, ethyl, n-propyl, n-butyl, etc.; they can also be branched alkyl groups, such as isopropyl, tert-butyl, etc.; and they can also be cycloalkyl groups, such as cyclohexyl, adamantyl, etc.

[0016] The aforementioned straight-chain alkyl and branched alkyl groups are preferably C1-C12 straight-chain or branched alkyl groups, more preferably C1-C6 straight-chain or branched alkyl groups; the aforementioned cycloalkyl groups are preferably C3-C12 cycloalkyl groups. The aforementioned alkoxy groups are preferably C1-C12 alkoxy groups, more preferably C1-C6 alkoxy groups.

[0017] R and R′ can connect to each other to form a ring Ar″, forming a compound as shown in Formula II:

[0018]

[0019] Wherein, Ar″ is a cyclic structure composed of substituted or unsubstituted C4-C8 cyclic alkenes, five-membered aromatic rings, or six-membered aromatic rings, and the substituents thereon can be halogen atoms, cyano, amino, nitro, alkyl, alkoxy, cyano or halogen-substituted alkyl or alkoxy, or aromatic substituents such as thiophene, furanyl, selenophene, phenyl, pyridyl, etc.

[0020] In Formula II, Ar″ is a cyclic structure containing carbon-carbon double bonds, preferably a five-membered or six-membered ring containing carbon-nitrogen double bonds. When Ar″ is a five-membered ring containing carbon-carbon double bonds, it is further preferably composed of cyclopentene, furanone, pyrrolidone, thiophene, selenene, furan, pyrrole, thiazole, oxazole, imidazole, selenazole, etc. When Ar″ is a six-membered ring containing carbon-carbon double bonds, it is further preferably composed of cyclohexene, benzene, pyridine, pyrazine, etc.

[0021]

[0022] Wherein, X is preferably a nitrogen atom substituted with S, Se, O, or an alkyl group; R 1 R 2 R 3 R 4 R 5 R 6 R 7 and R 8 Each of the following is preferably composed of hydrogen, chlorine, bromine, and fluorine atoms, cyano, amino, nitro, C1-C12 alkyl or alkoxy groups, cyano or halogen-substituted C1-C12 alkyl or alkoxy groups, thiophene, furanyl, selenophene, phenyl, pyridyl, or other aromatic substituents, and R in the ortho position. 1 R 2 R 3 R 4 R 5 R 6 R 7 and R 8 It can also form fused ring structures such as thiophene, furan, selenene, benzene, and pyridine.

[0023] In Formulas I and II, the Ar group is a cyclic structure containing a carbon-nitrogen double bond, preferably a five-membered or six-membered ring containing a carbon-nitrogen double bond. When Ar is a five-membered ring containing a carbon-nitrogen double bond, it is preferably a pyrrole, indole, thiazole, selenazole, oxazole, imidazole, 1,2,4-thiadiazole, 1,2,4-selenazole, 1,2,4-oxadiazole, 1,2,4-triazole, 1,3,4-thiadiazole, 1,3,4-selenazole, 1,3,4-oxadiazole, 1,3,4-triazole, isothiazole, isoselenazole, isoxazole, pyrazole, etc. When Ar is preferably a six-membered ring containing a carbon-nitrogen double bond, it is preferably a pyridine, pyrimidine, pyridazine, etc.

[0024]

[0025] Wherein, X is preferably a nitrogen atom substituted with S, Se, O, or an alkyl group; R 1 R 2 R 3 and R 4 Preferably, the substituent is hydrogen, chlorine, bromine, or fluorine; cyano; amino; nitro; C1-C12 alkyl or alkoxy; cyano or halogen-substituted C1-C12 alkyl or alkoxy; thiophene, furanyl, selenophene, phenyl, pyridyl, or other aromatic substituents; and R in the ortho position. 1 R 2 R 3 and R 4 It can also form fused ring structures such as thiophene, furan, selenene, benzene, and pyridine.

[0026] In Formulas I and II, the Ar′ group is a cyclic structure containing a carbon-carbon double bond, preferably a five-membered or six-membered ring containing a carbon-carbon double bond. When Ar′ is a five-membered ring containing a carbon-carbon double bond, it is preferably a cyclopentadienyl group, thiophene, selenophene, furan, pyrrole, thiazole, selenazole, oxazole, imidazole, isothiazole, isoselenazole, isoxazole, pyrazole, 1,2,3-thiadiazole, 1,2,3-selendiazole, 1,2,3-oxadiazole, 1,2,3-triazole, etc. When Ar′ is a six-membered ring containing a carbon-carbon double bond, it is preferably a benzene group, pyridine, pyrazine, pyridazine, etc.

[0027]

[0028] X is preferably a nitrogen atom substituted with S, Se, O, or an alkyl group. R 1 R 2 R 3 and R 4 Preferably, the substituent is hydrogen, chlorine, bromine, or fluorine; cyano; amino; nitro; C1-C12 alkyl or alkoxy; cyano or halogen-substituted C1-C12 alkyl or alkoxy; thiophene, furanyl, selenophene, phenyl, pyridyl, or other aromatic substituents; and R in the ortho position. 1 R 2 R 3 and R 4 It can also form fused ring structures such as thiophene, furan, selenene, benzene, and pyridine.

[0029] The aforementioned C-H σ-bond compounds (iPAD) can be used as photoactivated n-type dopants for efficient, regio-controllable doping of organic semiconductors. Because iPAD lacks hydride anion donation capability and possesses a low HOMO energy level, it exhibits good water and oxygen stability, which has been experimentally verified (Example 8). Figure 1 and Figure 2 As shown, the unactivated dopant (iPAD) itself does not have doping ability, but undergoes a 6π electrocyclization reaction under light to form an activated dopant (PAD). After photoactivation, the generated PAD has a strong hydride anion donating ability, achieving efficient n-doping of semiconductor materials. Its doping ability has been experimentally verified (Examples 9 to 10).

[0030] The aforementioned C-H σ-bond compounds can serve as photoactivated n-type dopants for semiconductor materials such as conjugated polymer semiconductors, organic small molecule semiconductors, carbon nanotubes, and two-dimensional semiconductors, and are applicable to, but are not limited to, the following organic small molecule and polymer semiconductor materials:

[0031]

[0032]

[0033] Where n is a positive integer representing the degree of aggregation, with a preferred value range of 5 to 200; X 1 X 2 and X 3 Preferably, H, F, Cl, Br, or CN; Z 1 and Z 2 Preferred sp 2 Hybridized C or N.

[0034] R a and R b The preferred independent group is one of the following:

[0035]

[0036] Ar 1 Preferably, one of the following groups:

[0037]

[0038] Ar 2 and Ar 3 Preferably, one of the following groups:

[0039]

[0040] In polymer P7, the substituent is preferably Z. 1 =Z 2 =N,R 1 =R 2 =4-Tetradecyloctadecyl, Ar 1 =Difluorothiophene, then the preferred polymer P7 structure is as follows:

[0041]

[0042] C-H σ-bond compounds are mixed with this polymer (named PzDPP-2FT, with the degree of polymerization n preferably ranging from 10 to 100) in solution, and then spin-coated or drop-coated to form a film. With increasing exposure dose, the conductivity of PzDPP-2FT increases from 10... - 9 S cm -1 Improved to 8.4S cm -1 This demonstrates that C-H σ bond compounds can be used in photoactivated doped semiconductor materials (Example 12).

[0043] The preferred substituent in polymer P4 is R. 1 =R 2 =4-Octadectodecyltecosyl, Ar 1 =Thiophene, then the preferred polymer P4 structure is as follows:

[0044]

[0045] C-H σ-bond compounds are mixed with this polymer (named TBDOPV-T, with the degree of polymerization n preferably ranging from 10 to 100) to form a film. As the exposure dose increases, the conductivity of TBDOPV-T increases from 10... -7 S cm -1 Upgraded to 31Scm -1 The thermoelectric properties of TBDOPV-T were tested under different exposure doses, ranging from -85 to -145 μV K. -1 The Seebeck coefficient, and 9–23 μV m -1 K -2 The improved power factor, increased conductivity, and negative Seebeck coefficient all demonstrate that C-H σ-bond compounds can effectively n-dopate semiconductor materials, controlling the doping level and carrier concentration (Example 13).

[0046] The preferred substituent in polymer P6 is X. 1 =F,X 2 =H,Z 1 =C,R 1 =R 2 =4-Octadectodecyltecosyl, Ar 1 =Ethylene, then the preferred polymer P6 structure is as follows:

[0047]

[0048] C-H σ-bond compounds are mixed with this polymer (named FBDPPV, with the degree of polymerization n preferably ranging from 10 to 100) to form a film. As the exposure dose increases, the conductivity of FBDPPV increases from 10... -7 S cm -1 Upgraded to 2S cm -1 A FET was fabricated using a mixed thin film of a C-H σ-bond compound and the polymer as the active layer. A masking method was employed to selectively photo-activate the dopant in the channel region, achieving region-selective doping of the device's channel area. With increasing exposure dose (3×10⁻⁶), the dopant concentration increased. 11 cm -2 The interface defects were eliminated, and the migration rate increased from 0.4 cm. 2 V -1 s -1 Lift 0.7m 2 V -1 s -1 The threshold voltage decreased from 11V to -5V, demonstrating that C-H σ-bond compounds can effectively eliminate carrier traps in semiconductor materials and improve the device performance of FETs (Example 14).

[0049] The preferred substituent in polymer P6 is X. 1 =X 2 =F,Z 1 =C,R 1 =R 2 =4-Octadectodecyltecosyl, Ar 1 =Dithiophene, then the preferred polymer P6 structure is as follows:

[0050]

[0051] C-H σ-bond compounds are mixed with this polymer (named F4BDOPV-2T, with the degree of polymerization n preferably ranging from 10 to 100) to form a film. As the exposure dose increases, the conductivity of F4BDOPV-2T increases from 10... -6 S cm -1 Upgraded to 1Scm -1 A FET was fabricated using a mixed film of a C-H σ-bond compound and the polymer as the active layer. A laser-direct writing method was employed to selectively photoactivate the dopant in the contact region, achieving region-selective doping of the device's contact area. With increasing exposure dose, the mobility increased from 0.7 cm⁻¹. 2 V -1 s -1 Lift 1.1m 2 V -1 s -1 The threshold voltage decreased from 37V to 28V, and the contact resistance decreased from 10KΩ·cm to 1.5KΩ·cm, demonstrating that C-H σ bond compounds can effectively reduce the contact resistance of FETs and improve FET device performance (Example 16).

[0052] The above experiments demonstrate that C-H σ bond compounds can be used as n-dopers to achieve n-doping of commonly used organic small molecules, polymer semiconductors, carbon nanotubes, and two-dimensional semiconductor materials. They can be applied to optoelectronic functional devices such as field-effect transistors, solar cells, light-emitting diodes, and thermoelectric devices. They can eliminate bulk and interface defects in semiconductor materials, regulate the carrier concentration of materials, and significantly improve the electrical performance of small-sized devices, thereby realizing the miniaturization and integration of devices.

[0053] In a second aspect of the invention, a method for high-precision region-selective doping of semiconductor materials based on such photoactivated n-type dopants is provided.

[0054] Specific doping methods are as follows: Figure 2 As shown:

[0055] (1) Photoactive dopants (iPADs) are directly mixed with semiconductor materials or deposited onto the substrate by spin coating, drop coating or vapor deposition.

[0056] (2) Laser direct-write lithography or mask method can be used to activate specific regions in dopant-semiconductor material mixed films with high precision using ultraviolet light, so that the doping reaction only occurs in the photoactivated region, achieving high-precision selective doping. At the same time, controlling the exposure dose and dopant content can effectively control the degree of doping reaction, and realize the control of the degree of doping (specifically reflected in the carrier concentration and material energy level).

[0057] (3) Depositing organic encapsulating materials (such as CYTOP, PI, epoxy resin, etc.) or inorganic encapsulating materials (such as silicon oxide, etc.) by spin coating, vapor deposition, etc. can enhance the stability of the doped system. Attached Figure Description

[0058] Figure 1 This demonstrates the photoactivated doping mechanism of the C-H σ-bond compounds of the present invention. The unactivated dopant (iPAD) itself does not have doping ability. Under light irradiation, it undergoes a 6π electrocyclization reaction to form an activated dopant (PAD). After the PAD donates hydride ions, the molecule will regain its aromaticity. This aromatic stabilization enables the PAD to have a strong hydride ion donating ability, thus enabling efficient n-doping of semiconductor materials.

[0059] Figure 2 This paper demonstrates a high-precision region-selective doping process based on C-H σ-bond compounds. Photoactivated dopants (iPADs) are directly mixed with semiconductor materials to prepare thin films. Then, specific areas of the blended thin films are activated by ultraviolet light using laser direct writing or mask exposure methods, thereby achieving high-precision region-selective doping of semiconductor materials.

[0060] Figure 3 The solution stability of iPAD-1, a representative photoactivated n-type dopant based on C-H σ-bond compounds, is shown, where a represents iPAD-1 after 5 days of exposure to air. 1 b) is the H-NMR spectrum; b) is the N-DMBI after being placed in air for 5 days. 1 H-NMR nuclear magnetic resonance spectrum.

[0061] Figure 4 The images show the solution absorption spectra of iPAD-1, a representative photoactivated n-type dopant based on C-H σ-bond compounds, and FBDPPV, a representative polymer. In the image, a represents the absorption spectrum of a mixed solution of FBDPPV / 100 mol% iPAD-1 under different exposure doses, and b represents the absorption spectrum of the mixed solution of FBDPPV / 100 mol% iPAD-1 after photoactivation (365 nm, 0.6 J cm⁻¹). -2 The absorption spectra of thermally activated (annealed at 140℃ for 10 min) and thermally activated (annealed at 140℃ for 10 min).

[0062] Figure 5Grazing-incidence X-ray (GIWAXS) characterization of hybrid films of iPAD-1 and iPAD-2, representative photoactivated n-type dopants based on C-H σ-bond compounds, and FBDPPV, a representative polymer. From top to bottom: FBDPPV / 100 mol% iPAD-2 hybrid films after photoactivation (365 nm, 1.2 J cm⁻¹). -2 1D GIWAXS data for FBDPPV / 100mol% iPAD-2 hybrid films without photoactivation; 1D GIWAXS data for FBDPPV / 100mol% iPAD-1 hybrid films after photoactivation (365nm, 1.2J cm⁻¹). -2 1D GIWAXS data of FBDPPV / 100mol%iPAD-1 hybrid film without photoactivation; 1D GIWAXS data of FBDPPV intrinsic film; where (010) is the diffraction peak attributed to polymer π-π stacking, and (100) and (200) are the diffraction peaks attributed to polymer layered phase stacking. a is the out-of-plane diffraction signal; b is the in-plane diffraction signal. Due to the limited detection range of the CCD camera, Nearby data is missing.

[0063] Figure 6 Figure a is a schematic diagram of the four-probe conductivity testing method used to measure the conductivity of the doped organic semiconductor thin film in this invention; Figure b is a schematic diagram of the Seebeck coefficient testing method used to measure the Seebeck coefficient of the doped organic semiconductor thin film in this invention.

[0064] Figure 7 Method a of fabricating a channel-doped FET device according to the present invention includes: mixing an organic semiconductor and a C-H σ-bond compound in a certain proportion; spin-coating the mixed solution onto a glass substrate with patterned source and drain electrodes; then spin-coating a dielectric layer CYTOP; and finally evaporating a gate electrode to complete the device fabrication. Using the source and drain electrode mask of the device itself, the channel region is selectively exposed to ultraviolet light to achieve selective doping of the channel region. Method b of fabricating a contact-doped FET device according to the present invention includes: mixing an organic semiconductor and a C-H σ-bond compound in a certain proportion; spin-coating the mixed solution onto a glass substrate with patterned source and drain electrodes; then spin-coating a dielectric layer CYTOP with weak ultraviolet absorption; after exposing the device contact area to different doses of ultraviolet light using laser direct writing technology, the gate electrode is evaporated to complete the device fabrication.

[0065] Figure 8The image shows an organic semiconductor thin film with a 5 μm × 5 μm conductive array prepared according to the present invention, wherein: a is an optical microscope image, b is a morphology image, and c is a current diagram. The preparation method is as follows: an organic semiconductor and a C-H σ bond compound are mixed in a certain proportion, the mixed solution is spin-coated onto a conductive gold substrate or silicon substrate, and then the mixed film is subjected to high-precision ultraviolet exposure using a laser direct writing method. Detailed Implementation

[0066] The present invention will now be described in detail with reference to the accompanying drawings and embodiments, but this does not limit the scope of the invention in any way.

[0067] Examples 1 to 7 describe the synthesis methods of representative C-H σ bond compounds in this invention.

[0068] Example 1

[0069]

[0070] Synthesis of Compound 2: 2-Phenylacetazole (1.10 g, 6.82 mmol) was added to a 100 mL round-bottom flask, followed by 15 mL of chloroform to completely dissolve it. N-Bromosuccinimide (1.40 g, 7.85 mmol) was added in portions to the reaction system, which was heated to 60 °C and reacted for 16 hours. After the reaction system cooled to room temperature, the reaction solution was washed with saturated brine, dried over anhydrous sodium sulfate, and then distilled under reduced pressure to remove all solvent. The residual solid was purified by column chromatography (chloroform:petroleum ether = 3:2) to give a white solid (1.60 g, yield: 98%). 1 H NMR (CDCl3, 400MHz, ppm): δ7.88-7.85 (m, 2H), 7.74 (s, 1H), 7.45 (t, 3H). 13 C NMR (CDCl3, 101MHz, ppm): δ169.6, 144.9, 133.1, 130.4, 129.1, 126.3, 108.6.

[0071] Example 2

[0072]

[0073] Synthesis of Compound 3: Under nitrogen protection, 20 mL of dry tetrahydrofuran was added to a two-necked round-bottom flask containing Compound 2 (0.8 g, 3.33 mmol), and the reaction system was cooled to -78 °C. Freshly prepared lithium diisopropylamino (5.00 mmol) was slowly added to the round-bottom flask, and stirring was continued for 1 hour. A few drops of water were then added to quench the reaction. After the reaction system returned to room temperature, the solvent was evaporated and the mixture was extracted with diethyl ether / water. The organic phase was dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove all solvent. The obtained solid was purified by column chromatography (chloroform:petroleum ether = 3:2) to give a white solid (0.73 g, yield: 91%). 1 HNMR (CDCl3, 400MHz, ppm): δ7.95-7.93 (m, 2H), 7.46-7.44 (m, 3H), 7.22 (s, 1H). 13 CNMR (CDCl3, 101MHz, ppm): δ169.1, 132.6, 130.7, 129.1, 126.4, 126.1, 116.5.

[0074] Example 3

[0075]

[0076] Synthesis of Compound 4: Compound 3 (1.20 g, 5.0 mmol), pinacol diboronate (1.52 g, 6.0 mmol), KOAc (0.74 g, 7.50 mmol), Pd2(dba)3 (137 mg, 0.15 mmol), and PCy3 (210 mg, 0.75 mmol) were added to a microwave-controlled reaction tube. The tube was sealed and the atmosphere was replaced with nitrogen. The reaction tube was placed in a microwave reactor and reacted at 170 °C for 3 hours. The reaction mixture was then filtered through a diatomaceous earth short column and distilled under reduced pressure to remove all solvent. The remaining liquid was distilled under reduced pressure to obtain crude compound 4, which was directly used in the next reaction step. 1 H NMR (CDCl3, 400MHz, ppm): δ8.05-8.02(m,2H),7.97(s,1H),7.46-7.40(m,3H),1.39(s,12H).

[0077] Example 4

[0078]

[0079] Synthesis of Compound 7: Compound 5 (623 mg, 3.50 mmol), Compound 6 (500 mg, 2.33 mmol), tripotassium phosphate trihydrate (932 mg, 3.50 mmol), and Pd(PPh3)4 (80.0 mg, 0.07 mmol) were added to a two-necked round-bottom flask. Under nitrogen protection, 45 mL of dimethyl ethylene glycol (DME) and 22 mL of water were added to the reaction system, and the mixture was reacted at 70 °C for 24 hours. After the reaction system returned to room temperature, the solvent was removed, and the mixture was extracted with ethyl acetate and water. The extracted organic phase was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The residual solid was purified by column chromatography to give a white solid (542 mg, yield: 87%). 1 H NMR (CDCl3, 400MHz, ppm): δ 8.98 (d, 1H), 8.14 (d, 2H), 7.93 (d, 2H), 7.58-7.41 (m, 4H). 13 C NMR (CDCl3, 101MHz, ppm): δ162.3,154.0,140.5,136.3,134.3,130.4,130.0,126.3,125.5,125.4,125.3,125.0,123.4,122.7,121.4.

[0080] Example 5

[0081]

[0082] Synthesis of Compound 8: Under nitrogen protection, 15 mL of anhydrous tetrahydrofuran was added to a two-necked flask pre-filled with Compound 7 (500 mg, 1.87 mmol), and the mixture was cooled to -78 °C. Then, 1.6 mol / L n-butyllithium was added dropwise to the reaction system. -1 After stirring for 1 hour, Br2 (0.11 mL, 2.24 mmol) was added. The reaction was continued for another hour, then 40 mL of Na2S2O3 aqueous solution was added to quench the reaction. The mixture was extracted with ethyl acetate, and the organic phase was dried over anhydrous sodium sulfate and distilled under reduced pressure to remove all solvent. The residual solid was purified by column chromatography to give a white solid (575 mg, yield: 89%). 1 H NMR (CDCl3, 400MHz, ppm): δ 8.66 (d, 1H), 8.21 (d, 1H), 8.00 (d, 1H), 7.77 (d, 1H), 7.57 (t, 1H), 7.46 (dt, 3H). 13C NMR (CDCl3, 101MHz, ppm): δ 159.9, 152.9, 139.5, 137.7, 135.0, 129.4, 126.4, 125.7, 125.6, 124.4, 123.6, 121.4, 121.3, 118.9.

[0083] Example 6

[0084]

[0085] Synthesis of compound iPAD-1: Compound 4 (309 mg, 0.74 mmol), compound 8 (170 mg, 0.49 mmol), tripotassium phosphate trihydrate (197 mg, 0.74 mmol), and Pd(PPh3)4 (17.0 mg, 0.015 mmol) were added to a two-necked round-bottom flask. Under nitrogen protection, 25 mL of dimethyl ethylene glycol (DME) and 17 mL of water were added to the system, and the reaction was carried out at 70 °C for 24 hours. After cooling to room temperature, the solvent was removed, and the mixture was extracted with ethyl acetate and water. The organic phase was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The resulting solid was purified by column chromatography to give a white solid (153 mg, yield: 73%). 1 HNMR (CDCl3, 400MHz, ppm): δ8.23(d,1H),7.98(d,1H),7.92(s,4H),7.62-7.57(m,1H),7.51(d,1H),7.46-7.39(m,5H),7.36(s,1H). 13 C NMR (CDCl3, 101MHz, ppm): δ167.5,162.1,153.5,148.3,139.9,139.3,138.8,136.4,133.0, 130.8,129.0,126.7,126.3,125.6,125.5,125.4,125.2,123.7,123.5,122.2,121.7,117.6.

[0086] Example 7

[0087]

[0088] Synthesis of compound iPAD-2: Compound 9 (500 mg, 3.14 mmol), compound 10 (560 mg, 3.45 mmol), sodium methoxide (167 mg, 3.14 mmol), and dimethyl sulfoxide (7 mL) were added to a 25 mL reaction flask. The reaction was carried out at room temperature for 24 hours, quenched with water, and the product was extracted with dichloromethane. After washing with saturated brine, the solvent was removed under reduced pressure, and the product was purified by silica gel column chromatography (evolving solvent: dichloromethane: petroleum ether = 1:1) to obtain an orange solid (351 mg, yield 37%). 1 H NMR (400MHz, CDCl3, ppm): δ8.10(d,J=8.0Hz,1H),8.01(d,J=16.4Hz,1H),7.91(d,J=8.0Hz,1H),7.78(s,1H),7.66(d,J=7.6Hz, 1H), 7.49 (t, J = 7.5Hz, 1H), 7.43 (d, J = 7.6Hz, 1H), 7.39–7.32 (m, 2H), 7.25 (m, J = 7.3Hz, 1H), 7.16 (d, J = 16.4Hz, 6H), 1.51 (s, 1H). 13 CNMR (101MHz, CDCl3, ppm) δ183.3,154.0,146.6,140.6,137.4,133.3,129.7,12 7.9,125.7,125.6,125.0,124.8,123.1,122.1,121.2,120.9,120.7,52.7,24.0.

[0089] Example 8: Solution stability of photoactivated n-type dopants based on C-H σ bond compounds

[0090] The solution stability of photoactivated n-type dopants based on C-H σ bond compounds is illustrated using compound iPAD-1 as an example.

[0091] Compounds iPAD-1 and N-DMBI were dissolved in approximately 0.5 mL of deuterated chloroform to prepare solutions of approximately 3 g / L. -1 The solution was analyzed using nuclear magnetic resonance (NMR) technology to monitor the proton NMR spectrum of the solution after it had been exposed to air for a period of time. 1 H NMR). For example Figure 3 As shown, after 5 days, most of N-DMBI was oxidized to N-DMBI. + However, it loses its n-type doping ability; while iPAD-1 exhibits excellent stability, with no significant change in its NMR signal, indicating that it has excellent solution stability.

[0092] Examples 9 to 10: Characterization of doping behavior of photoactivated n-type dopants based on C-H σ-bond compounds

[0093] The doping behavior of activated n-type dopants based on C-H σ bond compounds is illustrated using compound iPAD-1 as the dopant and polymer FBDPPV as the semiconductor material.

[0094] Example 9: Ultraviolet-Visible Absorption Spectroscopy

[0095] In this embodiment, UV-Vis absorption spectroscopy was used to characterize the photoactivated n-type doping behavior of C-H σ-bond compounds. The spectroscopic measurements were performed using a mixed solution of iPAD-1 and polymer FBDPPV (chlorobenzene as solvent, iPAD-1 ratio 100 mol%). Figure 4 As shown in Figure a. The mixed solution was treated with ultraviolet light (wavelength 365 nm, power 20 mW cm⁻¹). -2 Photoactivation was performed, and as the exposure dose increased, the absorption peaks at wavelengths of 980 nm and higher, belonging to the doped product (FBDPPV polarons), gradually increased, while the intensity of the characteristic absorption peaks at 600–800 nm, belonging to the undoped FBDPPV, gradually decreased, indicating that n-type doping occurred in the mixed system after photoactivation.

[0096] The experimental results demonstrate that the system containing this type of C-H σ bond compound can be photoactivated to initiate a doping reaction.

[0097] A mixed solution of FBDPPV and iPAD-1 was subjected to thermal activation treatment (annealing at 140℃ for 10 min). The spectrum of the mixed solution did not change. Figure 4 As shown in Figure b. In-situ illumination of the mixed solution immediately revealed the disappearance of the characteristic absorption peak of the undoped FBDPPV and the uplift of the FBDPPV polaron absorption peak, indicating the occurrence of the doping reaction.

[0098] The experimental results demonstrate that the system containing this type of C-H σ bond is photoactivated but thermally inert.

[0099] Example 10: Electron Paramagnetic Resonance Spectroscopy (ESR)

[0100] A mixed solution of FBDPPV and 100 mol% iPAD-1 was spin-coated onto a quartz substrate. The mixed film was then photoactivated (wavelength 365 nm, power 20 mW cm⁻¹). -2 n-type doping occurs, and the spin concentration of the doped system gradually increases with the increase of exposure dose. The ESR test results are shown in Table 1.

[0101] The experimental results show that when using this C-H σ bond compound to construct a photoactivated doping system, the doping degree of the system can be effectively controlled by adjusting the exposure dose.

[0102] Table 1

[0103] <![CDATA[Exposure dose (J cm -2 )]]> 0 0.4 0.8 1.2 <![CDATA[Spin concentration (cm -3 )]]> <![CDATA[- a ]]> <![CDATA[1.79×10 19 ]]> <![CDATA[3.71×10 19 ]]> <![CDATA[3.98×10 19 ]]>

[0104] a Unactivated FBDPPV / 100mol%iPAD-1 hybrid films showed no paramagnetic signal.

[0105] Example 11: The Influence of Photoactivated n-type Dopant Based on C-H σ-bond Compounds on the Solid-phase Microstructure of Organic Semiconductor Thin Films

[0106] The following example illustrates the use of C-H σ bond compounds iPAD-1 and iPAD-2 as photoactivated n-type dopants and polymer FBDPPV as a semiconductor material.

[0107] Since iPAD does not possess n-type doping capability, it does not undergo n-type doping when mixed with FBDPPV in solution. Furthermore, only weak interactions such as van der Waals forces exist between the two. Therefore, during the deposition of thin films from the FBDPPV / iPAD mixed solution using methods such as spin coating, the dopant iPAD has minimal impact on polymer accumulation in the crystalline region, and its GIWAXS signal remains essentially unchanged. Figure 5 As shown. Meanwhile, the incorporation of iPAD has almost no effect on the layered stacking distance and π–π stacking distance of FBDPPV; therefore, iPAD may be more concentrated in the amorphous regions. The hybrid film was photoactivated (wavelength 365 nm, exposure dose 1.2 J cm⁻¹). -2 After that, its GIWAXS signal remained unchanged, which indicates that the conversion process from unactivated dopant (iPAD) to photoactivated dopant (PAD) does not change the stacking structure of the polymer in the crystalline region.

[0108] The experimental results demonstrate that compounds containing C-H σ bonds have good compatibility with semiconductor materials, which ensures an effective carrier transport path in the doped thin film.

[0109] Examples 12 to 16 describe methods for fabricating devices and testing the electrical and thermoelectric properties of C-H σ-bond compound photoactivated doped organic semiconductor thin film materials.

[0110] Example 12: Test method for electrical conductivity

[0111] The following example illustrates the use of C-H σ bond compound iPAD-2 as a photoactivated n-type dopant and polymers PzDPP-2FT, TBDOPV-T, F4BDOPV-2T, and FBDPPV as semiconductor materials.

[0112] Gold electrodes were fabricated on Si / SiO2 or borosilicate glass substrates using photolithography and vacuum evaporation. The substrates with gold electrodes were then sequentially washed with acetone, industrial cleaning solution, water, and isopropanol, and dried in a vacuum oven at 80°C until ready for use. The polymer and iPAD-2 were dissolved separately in o-dichlorobenzene solvent to prepare 3g L... -1 The solutions were mixed in equal proportions and spin-coated to prepare a blend film. The blend film was then photoactivated (wavelength 365 nm, power 20 mW cm⁻¹). -2 The conductivity of the thin film was tested. The conductivity test employed a four-probe testing method (e.g., ...). Figure 6 As shown in Figure a), the test was performed using a Keithley 4200 semiconductor tester.

[0113] As shown in Table 2 below, the conductivity of the four semiconductor materials and the iPAD-2 hybrid film was significantly improved after ultraviolet exposure, indicating that the C-H σ bond compound can be used as a photoactivated dopant to dop semiconductor materials.

[0114] Table 2

[0115]

[0116] Example 13: Test Method for Thermoelectric Performance

[0117] The following example illustrates the use of iPAD-2, a C-H σ-bond compound, as a photoactivated n-type dopant, and TBDOPV-T, a polymer, as a semiconductor material.

[0118] The fabrication method for the devices used in Seebeck coefficient testing is the same as that used in conductivity testing. During testing, the two ends of the thin-film device substrate need to be placed at constant high and low temperatures to create a temperature gradient within the thin-film device (e.g., ...). Figure 6 (As shown in b). After measuring the thermoelectric potential across the thin-film device at different temperature differences, the Seebeck coefficient of the corresponding doped thin film can be calculated.

[0119] The relationships between the conductivity, Seebeck coefficient, and power factor of the iPAD-2 photoactivated doped TBDOPV-T thin film and the exposure dose are shown in Table 3 below. At 1.1 J / cm², -2 At the exposure dose, the conductivity of TBDOPV-T film reaches as high as 31 S cm⁻¹. -2 The power factor is as high as 21 μW / m. –1 K –2 .

[0120] The experimental results demonstrate that such C-H σ-bonded compounds can efficiently n-dopate semiconductor materials after photoactivation, thereby achieving excellent thermoelectric performance. Furthermore, this doping method exhibits regioselectivity, allowing for the selective fabrication of n-legs in thermoelectric devices, and holds potential application prospects in complex and integrated thermoelectric devices.

[0121] Table 3

[0122] <![CDATA[Exposure dose (J cm -2 )]]> 0.2 0.4 0.6 0.8 1.1 1.3 <![CDATA[Conductivity (S cm -1 )]]> 4.5 10.0 15.7 22.0 31.1 27.7 <![CDATA[Seebeck coefficient (μV K -1 )]]> -144.8 -120.4 -109.3 -98.1 -85.1 -87.6 <![CDATA[Power factor (μW m -1 K -2 )]]> 9.3 14.4 18.8 21.2 22.5 21.2

[0123] Example 14: Fabrication and Testing Methods of Channel-Doped Field-Effect Transistor Devices

[0124] The following example illustrates the use of iPAD-2, a C-H σ-bond compound, as a photoactivated n-type dopant, and FBDPPV, a polymer, as a semiconductor material.

[0125] Device fabrication process as follows Figure 7 As shown in Figure a, source and drain electrodes were fabricated on borosilicate glass substrate using photolithography and vacuum evaporation. The substrate with source and drain electrodes was sequentially washed with acetone, industrial cleaning solution, water, and isopropanol, and then dried in a vacuum oven at 80°C for later use. First, iPAD-2 and polymer in different proportions were mixed in a solution, and a mixed thin film was prepared by spin coating. Then, a dielectric layer (such as CYTOP) was spin-coated, and finally, the gate electrode was deposited to complete the FET device fabrication. Using the source and drain electrodes themselves as masks, a 365nm ultraviolet light source was used to expose the back of the device, performing region-selective n-type doping of the FET's channel region. This device fabrication process is simple, requiring only simple ultraviolet irradiation to achieve selective channel doping. The polymer mobility was measured using a Keithley 4200 semiconductor tester.

[0126] The test results are shown in Table 4. At a lower iPAD-2 concentration (0.01 mol%), channel doping had limited effect on device performance improvement, with only a decrease in the device threshold voltage from 9.8 V to 9.4 V and a decrease in device mobility from 0.45 cm⁻¹. 2 V -1 s -1 Increased to 0.49cm 2 V -1 s -1 Meanwhile, this low dopant concentration does not cause a significant increase in the device's off-state current, and the device's on / off ratio remains unchanged, ensuring effective gate control of the device current. Increasing the iPAD-2 concentration to 0.02 mol% and optimizing the exposure dose improved the mobility from 0.48 cm⁻¹. 2 V -1 s -1 Rise to 0.71cm 2 V -1 s-1 The threshold voltage decreased from 11V to 5V, demonstrating that this photoactivated channel doping method can effectively improve the device's electrical performance. Further increasing the iPAD-2 concentration to 0.03mol% and increasing the exposure dose further reduced the threshold voltage from 10V to -5V. 11 cm -2 The interfacial charge defects were eliminated.

[0127] The experimental results show that by adjusting the exposure dose and the molar ratio of photoactivated dopant, this C-H σ-bond compound can effectively eliminate carrier traps in the semiconductor in the channel and significantly improve the device performance of the FET.

[0128] Table 4

[0129]

[0130]

[0131] Example 15: Fabrication and Testing Methods of Channel-Doped Field-Effect Transistor Devices

[0132] The following example illustrates the use of C-H σ bond compound iPAD-2 as a photoactivated n-type dopant and polymer F4BDOPV-2T as a semiconductor material.

[0133] Device fabrication process as follows Figure 7 As shown in Figure b, source and drain electrodes were fabricated on a borosilicate glass substrate using photolithography and vacuum evaporation. The substrate with the source and drain electrodes was sequentially washed with acetone, industrial cleaning solution, water, and isopropanol, and then dried in a vacuum oven at 80°C for later use. First, a hybrid film of iPAD-2 and polymer was prepared on the substrate using spin coating. Then, a dielectric layer with weak UV absorption, CYTOP, was spin-coated. Different doses of UV exposure (wavelength 375nm) were applied to the device contact area using laser direct writing technology to achieve selective doping of the device contact area. Finally, the gate electrode was deposited to complete the device fabrication. The polymer mobility was measured using a Keithley 4200 semiconductor tester.

[0134] The test results are shown in Table 5. In the undoped state, the device with a longer channel (L = 20 μm, W = 400 μm) exhibited better device performance, with a mobility of 0.68 cm⁻¹. 2 V -1 s -1 The threshold voltage is 17V. After photo-activated doping, the device mobility increased to 1.06 cm⁻¹. 2 V -1 s -1This demonstrates that contact doping promotes efficient carrier injection. Furthermore, after illumination, the device's on / off ratio did not significantly decrease, ensuring effective gate control of the channel current. For devices with shorter channels (L = 5 μm, W = 200 μm), severe non-ideal behavior is exhibited in the undoped state, with a threshold voltage as high as 36 V and a mobility of only 0.68 cm⁻¹. 2 V -1 s -1 After contact doping, the device mobility increased to 1.07 cm⁻¹. 2 V -1 s -1 The threshold voltage drops to 28V, and the non-ideal behavior of the device disappears. The contact resistance of the device before and after photoactivation is measured at the device operating voltage (V). G The contact resistance (at 80V) decreased from 10KΩ·cm to 1.5KΩ·cm, proving that the photoactivated doping method can effectively reduce the contact resistance and significantly improve the device performance of the FET.

[0135] Table 5

[0136]

[0137] Example 16 describes the application of C-H σ-bond compounds in high-precision regional selective doping of semiconductor thin films.

[0138] The following example illustrates the use of C-H σ bond compound iPAD-2 as a photoactivated n-type dopant and polymer PzDPP-2FT as a semiconductor material.

[0139] A 5 μm × 5 μm conductive array was fabricated by UV exposure of a PzDPP-2FT / iPAD-1 blend film using laser direct writing. This conductive array was confirmed by conductive probe atomic force microscopy. Figure 8 As shown in Figure c, the current value in the doped region is significantly higher than that in the undoped region, and the spacing between the doped regions is 5 μm, consistent with the exposed pattern. Furthermore, since organic semiconductor materials undergo significant bleaching after doping, this 5 μm × 5 μm conductive array can be verified using an optical microscope, as shown below. Figure 8 As shown in Figure a.

[0140] These experiments demonstrate that the photo-activated doping method can achieve high-precision regional selective doping of semiconductor materials, with a doping precision of up to 5 μm.

Claims

1. The use of C-H σ-bond compounds as photoactivated n-type dopants in semiconductor materials, wherein the general structural formula of the C-H σ-bond compounds is shown in Formula I: In Formula I, R and R′ represent the same or different substituents on the double bond, and R and R′ are independent of each other or connected to form a ring; Ar represents a substituted or unsubstituted nitrogen-containing five-membered aromatic heterocycle, six-membered aromatic heterocycle or its fused ring structure, and Ar′ represents a substituted or unsubstituted five-membered aromatic ring, six-membered aromatic ring or its fused ring structure; the substituents on Ar and Ar′ are selected from halogen atoms, cyano, amino, nitro, alkyl, alkoxy, cyano-substituted alkyl or alkoxy, halogen-substituted alkyl or alkoxy, and aryl.

2. The use as described in claim 1, characterized in that, R and R′ are each independently selected from hydrogen atom, halogen atom, cyano, nitro, alkyl, alkoxy, cyano-substituted alkyl or alkoxy, halogen-substituted alkyl or alkoxy.

3. The use as described in claim 1, characterized in that, R and R′ are connected to form a loop, which forms loop Ar″, as shown in Equation II: Ar″ is a cyclic structure composed of substituted or unsubstituted C4-C8 cyclic alkenes, five-membered aromatic rings, or six-membered aromatic rings, and its substituents are selected from halogen atoms, cyano, amino, nitro, alkyl, alkoxy, cyano-substituted alkyl or alkoxy, halogen-substituted alkyl or alkoxy, and aryl.

4. The use as described in claim 3, characterized in that, The ring Ar″ shown in Formula II is selected from one of the following structures: Wherein, X is a nitrogen atom substituted with S, Se, O, or an alkyl group; R 1 R 2 R 3 R 4 R 5 R 6 R 7 and R 8 Selected from hydrogen, chlorine, bromine, fluorine, cyano, amino, nitro, C1-C12 alkyl or alkoxy, cyano or halogen-substituted C1-C12 alkyl or alkoxy, aryl, with R in the ortho position. 1 R 2 R 3 R 4 R 5 R 6 R 7 and R 8 They can be independent of each other or form a ring structure.

5. The use as described in claim 1, characterized in that, The Ar group shown in Formula I is selected from one of the following structures: Wherein, X is a nitrogen atom substituted with S, Se, O, or an alkyl group; R 1 R 2 R 3 and R 4 Selected from hydrogen, chlorine, bromine, fluorine, cyano, amino, nitro, C1-C12 alkyl or alkoxy, cyano or halogen-substituted C1-C12 alkyl or alkoxy, aryl, with R in the ortho position. 1 R 2 R 3 and R 4 They can be independent of each other or form a ring structure.

6. The use as described in claim 1, characterized in that, The Ar′ group shown in Formula I is selected from one of the following structures: Wherein, X is a nitrogen atom substituted with S, Se, O, or an alkyl group; R 1 R 2 R 3 and R 4 Selected from hydrogen, chlorine, bromine, fluorine, cyano, amino, nitro, C1-C12 alkyl or alkoxy, cyano or halogen-substituted C1-C12 alkyl or alkoxy, aryl, with R in the ortho position. 1 R 2 R 3 R 3 and R 4 They can be independent of each other or form a ring structure.

7. The use as described in claim 1, characterized in that, The semiconductor material is an organic small molecule semiconductor material, a conjugated polymer semiconductor material, a carbon nanotube, or a two-dimensional semiconductor material.

8. The use as described in claim 7, characterized in that, The semiconductor material is one of the following materials: Where n is a positive integer representing the degree of aggregation; X 1 X 2 and X 3 Each is selected from H, F, Cl, Br, and CN; Z 1 and Z 2 Each is independent as a sp 2 Hybridized C or N; R a and R b Independently selected from one of the following groups: Ar 1 Selected from one of the following groups: Ar 2 and Ar 3 Independently selected from one of the following groups:

9. The use as described in claim 8, characterized in that, The semiconductor material is one of the following conjugated polymers: F4BDOPV-2T, PzDPP-2FT, TBDOPV-T, or FBDPPV:

10. The use as described in claim 1, characterized in that, The C-H σ-bond compound shown in Formula I is mixed with a semiconductor material in solution and then processed into a blend film. High-precision regional selective doping of the semiconductor material is achieved by laser direct writing or mask exposure.

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