Organic semiconductor N-type doping method catalyzed by COD (Chemical Oxygen Demand)-based organic metal complex based on solution method and application of organic semiconductor N-type doping method

Abstract

The invention relates to the field of chemical doping, and particularly discloses a COD-based organic metal complex catalyzed organic semiconductor N-type doping method based on a solution method and application thereof. The method comprises the following steps: mixing and reacting a COD-based organic metal complex, an N-type organic semiconductor and an N-type dopant on a substrate to obtain a doped organic semiconductor. According to the organic semiconductor N-type doping method, a COD-based organic metal complex is used as a soluble catalyst, chloride ions in the COD-based organic metal complex are uncoupled to generate an active substance in situ, breakage of a C-H bond in an N-type doping agent is promoted, H ions generated due to breakage of the C-H bond in the N-type doping agent are combined with the active substance, and the doping efficiency of the N-type doping agent is improved. The organic semiconductor N-type doping method has the advantages that electron transfer in an N-type doping agent is promoted, the N-type doping agent is coordinated with an N-type organic semiconductor, N-type doping of the organic semiconductor is achieved, N-type doping efficiency is remarkably improved, the problem that a traditional vapor deposition method is incompatible with printed electronic products is solved, and the organic semiconductor N-type doping method is widely applicable to preparation of electronic printed products.

Description

Technical Field

[0001] The present application relates to the technical field of chemical doping, and in particular to a solution-based COD-based organic metal complex-catalyzed organic semiconductor N-type doping method and application thereof. Background Art

[0002] Organic semiconductors (OSCs) have a wide range of applications in organic electronic devices such as thin-film transistors, light-emitting diodes, solar cells, and thermoelectrics. Chemical doping is a key method to control carrier concentration and transport in organic semiconductors. Chemical doping of organic semiconductors can effectively improve device performance. Although researchers have made great efforts in the doping process of both P-type (hole) organic semiconductors and N-type (electron) organic semiconductors, the limited stability of N-type dopants and low doping efficiency still cannot meet the needs.

[0003] In the prior art, the X / XI group transition metal nanoparticles deposited by vapor phase are used as catalysts to reduce the bond energy barrier of the hydride precursor of the N-type dopant (such as N-DBMI), thereby promoting the N-type doping reaction of the organic semiconductor. However, this method is based on the vapor phase deposition method to carry out N-type doping of the organic semiconductor, which is incompatible with the preparation method of the low temperature solution method for electronic printed products. In the patent with the publication number CN112993161A, gold nanoparticles with alkylthiol solubilizing groups (f-AuNPs) on the surface are used as catalysts to promote the N-type doping of the organic semiconductor. Although this method can use soluble catalysts, its doping efficiency is low, and it depends on the fine design and synthesis of nanoparticles (NPs), which limits its general applicability.

[0004] Therefore, there is an urgent need to develop a low-cost, simple and universally applicable solution-based organic semiconductor N-type doping strategy to meet the application of organic semiconductor N-type doping in electronic printed products. Summary of the invention

[0005] In view of the above-mentioned deficiencies in the prior art, the purpose of the present application is to provide an organic semiconductor N-type doping method based on COD-based organic metal complexes and its application, aiming to solve the problems of low applicability and low doping efficiency of the existing methods.

[0006] The technical solution of this application is as follows:

[0007] In a first aspect of the present application, a method for N-type doping of an organic semiconductor based on a COD-based organic metal complex is provided, comprising the steps of: mixing and reacting a COD-based organic metal complex, an N-type organic semiconductor and an N-type dopant on a substrate to obtain a doped N-type organic semiconductor.

[0008] Preferably, the organic semiconductor includes at least one of PO12, PDCNBse-DPP, and N2200, and its structure is shown in Formula I:

[0009]

[0010] Among them, R1 is R2 is 2-octyldodecyl, R3 is 2-ethylhexyl, and n1, n2, and n3 are independently selected from integers of 5 to 40.

[0011] Preferably, the COD-based organometallic complex comprises at least one of Pd(COD)Cl2, Pt(COD)Cl2, [Rh(COD)Cl]2, and [Ir(COD)Cl]2, and its structure is shown in Formula II:

[0012]

[0013] Preferably, the N-type dopant includes at least one of N-DMBI-H and TAM, and its structure is shown in Formula III:

[0014]

[0015] Preferably, the method comprises the steps of: (a) spin coating a mixed solution of an N-type organic semiconductor and a COD-based organic metal complex on a substrate, then spin coating an N-type dopant solution on the substrate, and then annealing to obtain a doped N-type organic semiconductor; or

[0016] (b) An N-type organic semiconductor solution is spin-coated on a substrate, and then a mixed solution of a COD-based organic metal complex and an N-type dopant is spin-coated on the substrate, followed by annealing to obtain an N-type organic semiconductor.

[0017] Preferably, in the mixed solution of the N-type organic semiconductor and the COD-based organic metal complex, the molar percentage of the COD-based organic metal complex is 0.5-10 mol %; the solvent of the N-type dopant solution includes n-butyl acetate, and the concentration of the N-type dopant is 1-5 mg / mL.

[0018] Preferably, in the mixed solution of the COD-based organic metal complex and the N-type dopant, the molar ratio of the COD-based organic metal complex is 0.5-10 mol%; the solvent of the N-type organic semiconductor solution includes at least one of hexafluoroisopropanol, o-dichlorobenzene, and chlorobenzene, and the concentration of the N-type organic semiconductor is 3-5 mg / mL.

[0019] Preferably, the spin coating speed is 800-1500 rpm, and the spin coating method includes at least one of central spin coating and eccentric spin coating; the annealing temperature is 100-120° C., and the time is 5-15 s.

[0020] In a second aspect of the present application, there is provided a doped N-type organic semiconductor prepared by the N-type doping method of an organic semiconductor catalyzed by a COD-based organic metal complex based on a solution method according to the first aspect of the present application.

[0021] The third aspect of the present application provides a use of the doped N-type organic semiconductor according to the second aspect of the present application in the preparation of printed electronic products.

[0022] Compared with the existing technology, this application has the following advantages:

[0023] The present invention discloses a method for N-type doping of an organic semiconductor catalyzed by a COD-based organic metal complex based on a solution method. A ternary system of an organic semiconductor, a dopant, and a catalyst is formed by introducing a COD-based organic metal complex as a catalyst. During the doping reaction, the chloride ions in the COD-based organic metal complex are decoupled to generate active substances in situ, thereby promoting the breaking of the CH bond of the N-type dopant. The H ions generated by the breaking of the CH bond combine with the active substances, thereby promoting the electron transfer in the N-type dopant and coordinating with the N-type organic semiconductor to achieve N-type doping of the organic semiconductor.

[0024] (1) The method of the present application has high doping efficiency, so that the N-type semiconductor carries more electrons, thereby significantly improving the conductivity of the N-type organic semiconductor; (2) Compared with the prior art, the method of the present application does not rely on the fine design and synthesis of nanoparticles and has universal applicability; (3) In the method of the present application, the COD-based organic metal complex is a soluble catalyst. As a solution-based N-type doping method for organic semiconductors, this method can be widely used in the production and manufacturing of printed electronic devices. Since electronic printed products are usually processed using a low-temperature solution method, the method of the present application overcomes the problem of incompatibility between traditional vapor deposition methods and printed electronic products. (4) The method of the present application constitutes a ternary system of organic semiconductors, dopants, and catalysts, opening up a new research direction for the research and application of N-type doping of organic semiconductors. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for describing the embodiments are briefly introduced below.

[0026] Figure 1 A schematic diagram of a doping reaction provided in an embodiment of the present application;

[0027] Figure 2A schematic flow chart of a method for N-type doping of an organic semiconductor catalyzed by a COD-based organic metal complex based on a solution method provided in an embodiment of the present application;

[0028] Figure 3 The conductivity test graph of the doped N-type organic semiconductor prepared by the N-type doping method of organic semiconductor catalyzed by COD-based organic metal complex based on the solution method provided in the embodiment of the present application is as follows:

[0029] a is the chemical structure of the organic semiconductor PO12; b is the conductivity test of the doped N-type organic semiconductor prepared by two different methods; c is the conductivity test of the doped N-type organic semiconductor prepared by four different COD-based organometallic complexes. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical solutions and advantages of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the drawings and embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments. Based on the embodiments of the present application, all other embodiments obtained by ordinary technicians in this field without making creative work belong to the protection scope of the present application. In the absence of conflict, the following embodiments and features in the embodiments can be combined with each other.

[0031] It should be noted that if there are descriptions involving "first", "second", etc. in the implementation of this application, the descriptions of "first", "second", etc. are only used for descriptive purposes and cannot be understood as indicating or suggesting their relative importance and implicitly indicating the number of technical features indicated. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In addition, the technical solutions between the various embodiments can be combined with each other, but they must be based on the fact that ordinary technicians in the field can implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be deemed that such combination of technical solutions does not exist and is not within the scope of protection required by this application.

[0032] Chemical doping is a key method to control carrier concentration and transport in organic semiconductors (OSCs), which can improve the performance of thin-film transistors, light-emitting diodes, printed electronic devices, etc. In the process of N-type doping of organic semiconductors, there are problems of limited stability of dopants and low doping efficiency. In the prior art, the strategy designed to overcome the stability problem is to use air-stable precursor dopants, which can be doped into the main semiconductor to activate N-type organic semiconductor doping through CH bond or CC bond cleavage reactions. However, this method has poor doping efficiency due to the high activation energy required for bond cleavage. In addition, in order to meet the requirements of the doping rate, this method usually requires an annealing temperature of 120 to 150 ° C and an annealing time of more than 2 hours, which poses a huge obstacle to the commercial development of OSCs and their implementation on low-cost polymer substrates.

[0033] As a solution, researchers have found that vapor deposition of Group X / XI transition metal nanoparticles can effectively reduce the bond cleavage barrier of the hydride precursor of the N-type dopant (N-DMBI) and promote the N-type doping reaction of organic semiconductors. However, this vapor deposition method is incompatible with printed electronics, is too expensive, and hinders the fine control of catalyst particle size and loading, making it impossible to control the doping reaction.

[0034] Furthermore, in the patent with publication number CN112993161A, gold nanoparticles with alkylthiol solubilizing groups (f-AuNPs) on the surface are used as catalysts for N-type doping of organic semiconductors. The catalyst is a soluble catalyst, and its activity is activated after mild thermal activation. Although this method is compatible with printed electronic products, it relies on the fine design and synthesis of new nanoparticles, and the doping efficiency is not high, which limits its general applicability.

[0035] Based on this, the first aspect of the embodiment of the present application provides an organic semiconductor N-type doping method based on a COD-based organic metal complex, comprising the steps of: mixing and reacting a COD-based organic metal complex, an N-type organic semiconductor and an N-type dopant on a substrate to obtain a doped N-type organic semiconductor. Wherein, COD is 1,5-cyclooctadiene.

[0036] During the reaction, the chloride ions in the COD-based organometallic complex are decoupled to generate active substances in situ, so that the H ions generated by the breakage of the CH bond in the N-type dopant are combined with the active substances, thereby promoting the electron transfer in the N-type dopant and coordinating with the N-type organic semiconductor to achieve N-type doping of the organic semiconductor. The COD-based organometallic complex is a soluble catalyst, and it can be activated by a short treatment at a temperature of 120°C, which can meet the needs of the production and preparation of printed electronic products. The doped N-type organic semiconductor device prepared by the above method is low-cost and has universal applicability.

[0037] In some embodiments, the N-type organic semiconductor includes at least one of PO12, PDCNBSe-DPP, and N2200, and its structure is shown in Formula I:

[0038]

[0039] Among them, R1 is R2 is 2-octyldodecyl, R3 is 2-ethylhexyl, and n1, n2, and n3 are independently selected from integers of 5 to 40. For example, n1 can be 5, 10, 15, 20, 25, 30, 35 or 40, n2 can be 5, 10, 15, 20, 25, 30, 35 or 40, and n3 can be 5, 10, 15, 20, 25, 30, 35 or 40, but are not limited to the above-mentioned values, and other values ​​listed within the above-mentioned numerical range are also applicable.

[0040] In some embodiments, the COD-based organometallic complex includes at least one of Pd(COD)Cl2, Pt(COD)Cl2, [Rh(COD)Cl]2, and [Ir(COD)Cl]2, and its structure is shown in Formula II:

[0041]

[0042]

[0043] In some embodiments, the N-type dopant includes at least one of N-DMBI-H and TAM, and its structure is shown in Formula III:

[0044]

[0045] Taking Pd(COD)Cl2 (COD-based organometallic complex), N-DMBI-H (N-type dopant) and PO12 (N-type organic semiconductor) as examples, the reaction process is as follows: Figure 1 As shown. The chloride ions in Pd(COD)Cl2 are decoupled to generate the active species Pd(COD)Cl in situ + , Pd(COD)Cl+ Promote the cleavage of the CH bond in N-DMBI-H. The H ions generated by the CH bond cleavage react with Pd(COD)Cl + Combined, the electrons in the N-type dopant are transferred and coordinated with the N-type organic semiconductor to complete the doping of the N-type organic semiconductor PO12.

[0046] In some embodiments, the method for N-type doping of an organic semiconductor based on a COD-based organometallic complex comprises the steps of:

[0047] S101. Use acetone and isopropanol as solvents to ultrasonically clean the borosilicate substrate (25 minutes each), then dry it with N2 gas flow, and then treat it with ultraviolet ozone for 20 minutes; in a glove box filled with N2, use a vapor deposition template to thermally evaporate a 30nm gold electrode with a length of 100μm and a width of 2000μm (O2, H2O<0.1ppm) to obtain a substrate.

[0048] S102. In a glove box filled with N2, spin-coat a mixed solution of an N-type organic semiconductor and a COD-based organometallic complex on the substrate prepared in S1 at a speed of 800 to 1500 rpm, then spin-coat an N-type dopant solution at a speed of 800 to 1500 rpm, and then anneal at 100 to 120°C for 5 to 15 seconds to obtain a doped N-type organic semiconductor.

[0049] Among them, the spin coating speed can be 800rpm, 900rpm, 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm or 1500rpm, etc., the annealing temperature can be 100°C, 105°C, 110°C, 115°C or 120°C, etc., and the annealing time can be 5s, 7s, 9s, 10s, 12s, 13s or 15s, etc., but are not limited to the values ​​listed above, and other values ​​not listed within the above numerical range are also applicable.

[0050] In some embodiments, in the mixed solution of the N-type organic semiconductor and the COD-based organic metal complex, the molar percentage of the COD-based organic metal complex is 0.5-10 mol%, for example, the molar ratio of the COD-based organic metal complex is 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol% or 10 mol%, etc. The solvent of the N-type dopant solution includes n-butyl acetate, and the concentration of the dopant is 1-5 mg / mL, for example, the concentration of the N-type organic semiconductor is 1 mg / mL, 2 mg / mL, 3 mg / mL, 4 mg / mL or 5 mg / mL, etc., but is not limited to the above-listed values, and other values ​​not listed within the above numerical range are also applicable.

[0051] In some embodiments, the spin coating method includes at least one of center spin coating and eccentric spin coating.

[0052] In some embodiments, see Figure 2 , the organic semiconductor N-type doping method based on COD-based organic metal complex may include the steps of:

[0053] S201. Use acetone and isopropanol as solvents to ultrasonically clean the borosilicate substrate (25 minutes each), then dry it with N2 gas flow, and then treat it with ultraviolet ozone for 20 minutes; in a glove box filled with N2, use a vapor deposition template to thermally evaporate a 30nm gold electrode with a length of 100μm and a width of 2000μm (O2, H2O<0.1ppm) to obtain a substrate.

[0054] S202. In a glove box filled with N2, spin-coat an N-type organic semiconductor solution on the substrate prepared in S1 at a speed of 800-1500 rpm, then spin-coat a mixed solution of a COD-based organic metal complex and an N-type dopant at a speed of 800-1500 rpm, and then anneal at 100-120°C for 5-15s to obtain a doped N-type organic semiconductor.

[0055] Among them, the spin coating speed can be 800rpm, 900rpm, 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm or 1500rpm, etc., the annealing temperature can be 100°C, 105°C, 110°C, 115°C or 120°C, etc., and the annealing time can be 5s, 7s, 9s, 10s, 12s, 13s or 15s, etc., but are not limited to the values ​​listed above, and other values ​​not listed within the above numerical range are also applicable.

[0056] In some embodiments, in the mixed solution of the COD-based organic metal complex and the N-type dopant, the molar ratio of the COD-based organic metal complex is 0.5-10 mol%, for example, the molar ratio of the COD-based organic metal complex is 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 4 mol%, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol% or 10 mol%, etc. The solvent of the N-type organic semiconductor solution includes at least one of hexafluoroisopropanol, o-dichlorobenzene, and chlorobenzene, and the concentration of the N-type organic semiconductor is 3-5 mg / mL, for example, the concentration of the N-type organic semiconductor is 3 mg / mL, 3.5 mg / mL, 4 mg / mL, 4.5 mg / mL or 5 mg / mL, etc., but is not limited to the above-listed values, and other values ​​not listed in the above numerical range are also applicable.

[0057] In some embodiments, the spin coating method includes at least one of center spin coating and eccentric spin coating.

[0058] According to a second aspect of the embodiments of the present application, a doped N-type organic semiconductor prepared by the above method is provided.

[0059] The third aspect of the embodiments of the present application provides an application of the above-mentioned doped N-type organic semiconductor in the preparation of printed electronic products. The printed electronic products include printed circuits or electronic components. In some embodiments, the prepared doped N-type organic semiconductor is used to prepare a diode, which is used in a printed circuit board.

[0060] The following is further described by means of specific examples.

[0061] PO12 and PDCNBSe-DPP were synthesized in the laboratory, N2200 was purchased from Flexterra Crop., Pd(COD)Cl2, Pt(COD)Cl2, [Rh(COD)Cl]2, [Ir(COD)Cl]2, N-DMBI-H, and TAM were purchased from Sigma-Aldrich, and other chemicals and reagents not otherwise specified were obtained from commercial sources. All chemicals and solvents were used directly without further purification.

[0062] Example 1

[0063] This embodiment provides a method for N-type doping of an organic semiconductor of a COD-based organic metal complex, and the specific steps are as follows:

[0064] The borosilicate substrate was ultrasonically cleaned using acetone and isopropanol as solvents (25 minutes each), dried with N2 gas flow, and then treated with ultraviolet ozone for 20 minutes; a 30nm gold electrode with a length of 100μm and a width of 2000μm was thermally evaporated (O2, H2O<0.1ppm) using an evaporation template in a glove box filled with N2 to obtain a substrate.

[0065] In a glove box filled with N2, an N-type organic semiconductor solution (hexafluoroisopropanol solution containing 3 mg / mL PO12) was spin-coated on the prepared substrate at a speed of 1500 rpm for 60 s, followed by a COD-based organic metal complex (Pd(COD)Cl2, 0.5 mol%) and an N-type dopant butyl acetate mixed solution (N-DMBI-H, 5 mg / mL) at a speed of 1500 rpm for 30 s, followed by annealing at 120°C for 10 s to obtain a doped N-type organic semiconductor.

[0066] Embodiments 2 to 4

[0067] Embodiments 2 to 4 respectively provide a method for N-type doping of an organic semiconductor using a COD-based organic metal complex. In the specific steps, the COD-based organic metal complex is replaced by Pt(COD)Cl2, [Rh(COD)Cl]2, and [Ir(COD)Cl]2, respectively, and the rest is consistent with Embodiment 1.

[0068] Example 5

[0069] This embodiment provides a method for N-type doping of an organic semiconductor with a COD-based organic metal complex. In the specific steps, the central spin coating is replaced by eccentric spin coating, and the rest is consistent with the first embodiment.

[0070] Embodiments 6 to 8

[0071] Examples 6 to 8 respectively provide a method for N-type doping of an organic semiconductor with a COD-based organometallic complex, in which the concentration of PO12 is replaced with 4 mg / mL, 4.5 mg / mL and 5, respectively, and the rest is consistent with Example 1.

[0072] Embodiments 9 to 14

[0073] Examples 9 to 14 respectively provide a method for N-type doping of an organic semiconductor with a COD-based organic metal complex, wherein the molar percentage of Pd(COD)Cl2 is 1 mol%, 2 mol%, 5 mol%, 8 mol% and 10 mol%, and the rest is consistent with Example 1.

[0074] Embodiments 15 to 19

[0075] Examples 15 to 19 respectively provide a method for N-type doping of an organic semiconductor with a COD-based organic metal complex, wherein the molar percentage of Pt(COD)Cl2 is 1 mol%, 2 mol%, 5 mol%, 8 mol% and 10 mol%, and the rest is consistent with Example 1.

[0076] Embodiments 20 to 24

[0077] Embodiments 20 to 24 respectively provide a method for N-type doping of an organic semiconductor with a COD-based organic metal complex, wherein the molar percentage of [Rh(COD)Cl]2 is 1 mol%, 2 mol%, 5 mol%, 8 mol% and 10 mol%, and the rest is consistent with Embodiment 1.

[0078] Embodiments 25 to 29

[0079] Examples 25 to 29 respectively provide a method for N-type doping of an organic semiconductor with a COD-based organic metal complex, wherein the molar percentage of [Ir(COD)Cl]2 is 1 mol%, 2 mol%, 5 mol%, 8 mol% and 10 mol%, and the rest is consistent with Example 1.

[0080] Embodiment 30

[0081] This embodiment provides a method for N-type doping of an organic semiconductor of a COD-based organic metal complex, and the specific steps are as follows:

[0082] The borosilicate substrate was ultrasonically cleaned using acetone and isopropanol as solvents (25 minutes each), dried with N2 gas flow, and then treated with ultraviolet ozone for 20 minutes; a 30nm gold electrode with a length of 100μm and a width of 2000μm was thermally evaporated (O2, H2O<0.1ppm) using an evaporation template in a glove box filled with N2 to obtain a substrate.

[0083] In a glove box filled with N2, an N-type organic semiconductor solution (hexafluoroisopropanol solution containing 3 mg / mL PO12) and a COD-based organic metal complex (Pd(COD)Cl2, 0.5 mol%) were spin-coated on the prepared substrate at a speed of 1500 rpm for 60 s, and then an N-type dopant n-butyl acetate solution (N-DMBI-H, 5 mg / mL) was spin-coated at a speed of 1500 rpm for 30 s, followed by annealing at 120°C for 10 s to obtain a doped N-type organic semiconductor.

[0084] Examples 31 to 33

[0085] Examples 31 to 33 respectively provide a method for N-type doping of an organic semiconductor with a COD-based organic metal complex. In the specific steps, the molar percentage of Pd(COD)Cl2 is 2 mol%, 5 mol%, 8 mol% and 10 mol%, and the rest is consistent with Example 30.

[0086] Embodiments 34 to 36

[0087] Examples 34 to 36 respectively provide a method for N-type doping of an organic semiconductor with a COD-based organometallic complex, in which the concentration of N-DMBI-H is replaced with 1 mg / mL, 2 mg / mL and 4 mg / mL, and the rest is consistent with Example 30.

[0088] Embodiments 37-38

[0089] Examples 37 to 38 respectively provide a method for N-type doping of an organic semiconductor of a COD-based organometallic complex. In the specific steps, the organic semiconductor PO12 is replaced by N2200 (a chlorobenzene solution containing 5 mg / mL N2200) and PDCNBSe-DPP (an o-dichlorobenzene solution containing 4 mg / mL PDCNBSe-DPP), respectively, and the rest is consistent with Example 1.

[0090] Embodiments 39 to 40

[0091] Examples 39 to 40 respectively provide a method for N-type doping of an organic semiconductor of a COD-based organometallic complex, in which the organic semiconductor PO12 is replaced by N2200 (a chlorobenzene solution containing 5 mg / mL N2200) and PDCNBSe-DPP (an o-dichlorobenzene solution containing 4 mg / mL PDCNBSe-DPP), respectively, and the rest is consistent with Example 30.

[0092] Embodiment 41

[0093] This embodiment provides a method for N-type doping of an organic semiconductor using a COD-based organic metal complex. In the specific steps, the dopant is replaced with TAM, and the rest is consistent with Example 30.

[0094] Embodiments 42 to 43

[0095] Examples 42 to 43 respectively provide a method for N-type doping of an organic semiconductor of a COD-based organometallic complex. In the specific steps, the organic semiconductor PO12 is replaced by N2200 (a chlorobenzene solution containing 5 mg / mL N2200) and PDCNBSe-DPP (an o-dichlorobenzene solution containing 4 mg / mL PDCNBSe-DPP), respectively, and the rest is consistent with Example 42.

[0096] Comparative Example 1

[0097] This comparative example provides an organic semiconductor N-type doping method, and the specific steps are as follows:

[0098] A layer of gold nanoparticles (AuNP) with a nanometer thickness was evaporated on a borosilicate substrate, and then a PO12 solution (hexafluoroisopropanol solution containing 3 mg / mL PO12) was spin-coated on the center of the substrate at a speed of 1500 rpm for 60 seconds, and then an N-type dopant n-butyl acetate solution (N-DMBI-H, 5 mg / mL) was spin-coated on the center of the substrate at a speed of 1500 rpm for 30 seconds, and then annealed at 120°C for 10 seconds to obtain a doped N-type organic semiconductor.

[0099] Comparative Examples 2-3

[0100] Comparative Examples 2 to 3 respectively provide an organic semiconductor N-type doping method, in which PO12 is replaced by N2200 (chlorobenzene solution containing 5 mg / mL N2200) and PDCNBSe-DPP (o-dichlorobenzene solution containing 4 mg / mL PDCNBSe-DPP), respectively, and the rest is consistent with Comparative Example 1.

[0101] Comparative Example 4

[0102] This comparative example provides an organic semiconductor N-type doping method, in which AnNP is replaced by f-AuNP in the specific steps, and the rest is consistent with comparative example 1.

[0103] Comparative Examples 5-6

[0104] Comparative Examples 5 to 6 respectively provide an organic semiconductor N-type doping method, in which PO12 is replaced by N2200 (chlorobenzene solution containing 5 mg / mL N2200) and PDCNBSe-DPP (o-dichlorobenzene solution containing 4 mg / mL PDCNBSe-DPP), respectively, and the rest is consistent with Comparative Example 4.

[0105] Test Example 1

[0106] Conductivity test: The example group used vacuum-evaporated 30nm Au as the bottom contact electrode (two-probe form), and the comparative group used 30nm Al as the bottom contact electrode (two-probe form). The channel length (L) and width (W) were 100μm and 2mm, respectively. After sample preparation, the samples placed in the glove box were tested for I–V curves using the Keithley 4200SCS semiconductor characterization system, and then their conductivity was calculated according to the standard equation ζ=(1 / R)×(L / (W·h)), where R is the device resistance and h is the film thickness measured by the Tencor KLAD120 step profiler.

[0107] The conductivity of the doped N-type organic semiconductors prepared in Examples 1 to 4, 6 to 29, and Comparative Examples 1 and 4 was tested. The test results are as follows: Figure 3 shown. Figure 3 Figure a in the middle is the structural diagram of N-type organic semiconductor PO12. Figure 3 In the figure b, Seq-D represents the N-type organic semiconductor film prepared by the method of Example 1, and SeqD+C represents the doped N-type organic semiconductor film prepared by the method of Example 30. Figure 3It can be seen from b that the two different preparation methods in the present application can improve the conductivity of the doped N-type organic semiconductor. When the method of Example 1 is used, the conductivity is highest when the molar percentage of the COD-based organic metal complex is 5 mol%. When the preparation method of Example 30 is used, the conductivity is highest when the molar percentage of the COD-based organic metal complex is 8 mol%. On the other hand, the four different COD-based organic metal complexes all have the effect of improving the conductivity of the doped N-type organic semiconductor. Among them, under the conditions of the preparation method of Example 1, when the molar percentage of the COD-based organic metal complex is 2 mol%, the conductivity of the doped N-type organic semiconductor is significantly improved. When Pt(COD)Cl2 is used as the COD-based organic metal complex, the conductivity of the doped N-type organic semiconductor is improved best.

[0108] The conductivity of the doped N-type organic semiconductors prepared in Example 1, Example 30, Examples 37 to 43, and Comparative Examples 1 to 6 was tested. The test results are shown in Table 1.

[0109] Table 1. Conductivity of N-type organic semiconductors

[0110]

[0111] As can be seen from Table 1, the conductivity of the doped N-type organic semiconductor prepared by the organic semiconductor N-type doping method based on COD-based organic metal complexes of the present application is significantly improved compared with the methods of the prior art. Among them, the conductivity of the doped N-type organic semiconductor prepared by the Seq D+C method is higher. The conductivity using N-DMBI-H as the N-type dopant is better, which also shows that the doping efficiency of N-DMBI-H as an N-type dopant is higher.

[0112] In summary, the organic semiconductor N-type doping method of the COD-based organic metal complex of the present application has high doping efficiency, can significantly improve the conductivity of the doped N-type organic semiconductor, and overcome the problem that the traditional vapor deposition method is incompatible with printed electronic products.

[0113] It should be understood that the application of the present application is not limited to the above examples. For ordinary technicians in this field, improvements or changes can be made based on the above description. All these improvements and changes should fall within the scope of protection of the claims attached to this application.

Claims

1. A method for N-type doping of organic semiconductors catalyzed by COD-based organometallic complexes based on a solution method, characterized in that: The method comprises the steps of: mixing and reacting a COD-based organic metal complex, an N-type organic semiconductor and an N-type dopant on a substrate to obtain a doped N-type organic semiconductor; Among them, COD is 1,5-cyclooctadiene.

2. The method according to claim 1, characterized in that The N-type organic semiconductor includes at least one of PO12, PDCNBSe-DPP, and N2200, and its structure is shown in Formula I: Among them, R1 is R2 is 2-octyldodecyl, R3 is 2-ethylhexyl, and n1, n2, and n3 are independently selected from integers of 5 to 40.

3. The method according to claim 1, characterized in that The COD-based organic metal complex includes at least one of Pd(COD)Cl2, Pt(COD)Cl2, [Rh(COD)Cl]2, and [Ir(COD)Cl]2, and its structure is shown in Formula II:

4. The method according to claim 1, characterized in that: The N-type dopant includes at least one of N-DMBI-H and TAM, and its structure is shown in Formula II:

5. The method according to claim 1, characterized in that The method comprises the steps of: (a) spin coating a mixed solution of an N-type organic semiconductor and a COD-based organic metal complex on a substrate, and then spin coating an N-type dopant solution on the substrate, followed by annealing to obtain a doped N-type organic semiconductor; or (b) Spin coating an N-type organic semiconductor solution on a substrate, and then spin coating a mixed solution of a COD-based organic metal complex and an N-type dopant on the substrate, followed by annealing to obtain a doped N-type organic semiconductor.

6. The method according to claim 5, characterized in that In the mixed solution of the N-type organic semiconductor and the COD-based organic metal complex, the molar percentage of the COD-based organic metal complex is 0.5-10 mol %; The solvent of the N-type dopant solution includes n-butyl acetate, and the concentration of the N-type dopant is 1-5 mg / mL.

7. The method according to claim 5, characterized in that In the mixed solution of the COD-based organic metal complex and the N-type dopant, the molar ratio of the COD-based organic metal complex is 0.5 to 10 mol %; The solvent of the N-type organic semiconductor solution includes at least one of hexafluoroisopropanol, o-dichlorobenzene and chlorobenzene, and the concentration of the N-type organic semiconductor is 3-5 mg / mL.

8. The method according to claim 5, characterized in that The spin coating speed is 800-1500 rpm, and the spin coating method includes at least one of central spin coating and eccentric spin coating; The annealing temperature is 100-120° C., and the annealing time is 5-15 seconds.

9. A doped N-type organic semiconductor prepared by the solution-based COD-based organic metal complex-catalyzed N-type doping method of organic semiconductor according to any one of claims 1 to 8.

10. Use of the doped N-type organic semiconductor according to claim 9 in preparing printed electronic products.

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