N-Type Doping Method of an Organic Semiconductor and Its Application

Abstract

The present application discloses an n-type doping method for an organic semiconductor and its application. The doping method includes mixing a transition metal catalyst, an n-type organic semiconductor, and an anion dopant solution on a substrate for reaction to prepare a doped organic semiconductor. Among them, the preparation method of the anion dopant solution includes mixing an ammonium hydroxide-based anion, an amide solvent, and a molecular sieve, reacting at room temperature for 8 to 24 hours, filtering to obtain the clear liquid, and obtaining the anion dopant solution. The doping reaction between the transition metal catalyst, the n-type organic semiconductor, and the anion dopant solution is very rapid. The n-type doping method for the organic semiconductor has excellent doping efficiency, and the conductivity of the prepared doped organic semiconductor is effectively improved.

Description

Technical Field

[0001] The present application relates to the doping of organic semiconductors, and particularly to an n-type doping method and application of an organic semiconductor. Background Art

[0002] Organic semiconductors (OSCs) have a wide range of application scenarios in organic electronic devices such as thin-film transistors, light-emitting diodes, solar cells, and thermoelectrics. Chemical doping is a key method for controlling the carrier concentration and transport in organic semiconductors, and the performance of devices can be effectively improved by chemically doping organic semiconductors. Although researchers have made great efforts in the doping processes of p-type (hole) and n-type (electron) organic semiconductors, due to the limited stability and low doping efficiency of n-type dopants, the requirements are still not met.

[0003] Currently, n-type dopants mainly include precursor-type organic hydrides (such as benzimidazole derivatives), dimers of organic radicals (such as organometallic sandwich-type compounds with nineteen electrons), and n-type dopants with monovalent and polyvalent anions (such as OH - , F - and Ox 2- ); on the one hand, some studies have shown that molecular dopants combined with group X / XI transition metal nanoparticles or their complexes as catalysts can reduce the bond energy dissociation barrier of the hydride precursor of n-type dopants (such as N-DBMI), promoting the n-type doping reaction of organic semiconductors, but the selection of molecular dopants that can be used with transition metals is limited, restricting the application window of the catalytic doping method; on the other hand, simple anion dopants have strong reducing ability, but due to the lack of dissociable chemical bonds, they are not suitable for efficient catalytic doping methods.

[0004] Therefore, there is an urgent need to develop a new, universal, and highly efficient n-type catalytic doping strategy for anions to meet the application requirements of n-type doping of organic semiconductors in organic electronic devices. Summary of the Invention

[0005] Therefore, the technical problem to be solved by the present application is to overcome the above defects in the prior art. The purpose is to provide an n-type doping method for an organic semiconductor, by preparing a new anion dopant solution to enhance the doping reaction between it and the n-type organic semiconductor and the transition metal catalyst, so that the n-type doping method of the organic semiconductor has excellent doping efficiency, and the conductivity of the doped organic semiconductor prepared is effectively improved.

[0006] In the first aspect of the present application, a method for n-doping an organic semiconductor is provided, in which a transition metal catalyst, an N-type organic semiconductor, and an anion dopant solution are mixed and reacted on a substrate to prepare a doped organic semiconductor; wherein, the preparation method of the anion dopant solution includes:

[0007] Mixing a raw material including an ammonium hydroxide anion and an amide solvent with a molecular sieve, reacting at room temperature for 8 to 24 hours, filtering to obtain the clear liquid, and preparing the anion dopant solution;

[0008] The ammonium hydroxide anion includes a compound having the structure shown in Formula I,

[0009] Formula I,

[0010] In the formula, R 11 , R 12 , R 13 , R 14 each independently includes at least one of a substituted or unsubstituted C 1-12 alkyl group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted benzyl group, and R 11 , R 12 , R 13 , R 14 are not all methyl at the same time;

[0011] The amide solvent includes a compound having the structure shown in Formula II,

[0012] Formula II,

[0013] In the formula, R 15 , R 16 each independently includes at least one of hydrogen, a substituted or unsubstituted C 1-4 alkyl group, and a substituted or unsubstituted phenyl group, and R 17 includes at least one of hydrogen, a substituted or unsubstituted C 1-4 alkyl group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted amino group.

[0014] It is found that the doping reaction between the anion dopant solution prepared in the present application, the N-type organic semiconductor, and the transition metal catalyst is very rapid. The n-doping method of this organic semiconductor has a high doping efficiency, and the conductivity of the prepared doped organic semiconductor is effectively improved.

[0015] In any embodiment, the molar ratio of the ammonium hydroxide anion to the amide solvent is 1:(2 to 30), optionally 1:(3 to 20), and more preferably 1:(5 to 10).

[0016] In any embodiment, the molar ratio of the ammonium hydroxide-based anion to the mass of the molecular sieve is 1 mol:(40 - 200) g, preferably 1 mol:(50 - 150) g, and more preferably 1 mol:(70 - 100) g.

[0017] In any embodiment, the transition metal catalyst includes transition metal nanoparticles, and the n-type doping method of the organic semiconductor includes the following steps:

[0018] The transition metal nanoparticles are formed on the substrate by thermal evaporation deposition, and then a mixture including the n-type organic semiconductor and the anion dopant solution is coated on the substrate having the transition metal nanoparticles formed on its surface, and heated at 60 - 150 °C for 5 - 360 s to obtain the doped organic semiconductor.

[0019] In any embodiment, the transition metal catalyst includes transition metal complexes, and the n-type doping method of the organic semiconductor includes the following steps:

[0020] A mixture including the transition metal complexes, the n-type organic semiconductor, and the anion dopant solution is coated on the substrate, and heated at 60 - 150 °C for 5 - 360 s to obtain the doped organic semiconductor.

[0021] In any embodiment, the molar ratio of the anion dopant solution to the n-type organic semiconductor is (1 - 10):1, optionally (1 - 5):1, and more preferably (2 - 3):1.

[0022] In any embodiment, the molar ratio of the anion dopant solution to the transition metal catalyst is (1000 - 20):1, optionally (500 - 50):1, and more preferably (200 - 100):1.

[0023] In the second aspect of the present application, there is provided an application of the n-type doping method of the organic semiconductor provided in the first aspect of the present application in the preparation of organic optoelectronic devices.

[0024] Compared with the prior art, the present application has the following beneficial effects:

[0025] The present application provides an n-type doping method of an organic semiconductor. By using an anion dopant solution prepared by an ammonium hydroxide-based anion and an amide solvent under the action of a molecular sieve, the doping reaction between it and the n-type organic semiconductor and the transition metal catalyst is enhanced, so that the n-type doping method of the organic semiconductor has excellent doping efficiency, and the conductivity of the prepared doped organic semiconductor is effectively improved.

[0026] Moreover, compared with the limitations in the selection of molecular dopants, the raw materials for preparing the anion dopant solution are more widely sourced. A variety of anion dopant solutions can be used in combination with transition metal catalysts to effectively improve the doping efficiency of subsequent N-type organic semiconductors. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings required for the description of the specific embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present application. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0028] Figure 1 It is a UV-Vis-NIR spectral test chart of the organic semiconductors doped with anions in Example 1 and Comparative Example 8 of the present application and doped with a molecular dopant in Comparative Example 7;

[0029] Figure 2 In a), it is a UV-Vis-NIR spectral test chart of the organic semiconductors doped with anions in Examples 2 to 4 and Comparative Examples 1 to 2 of the present application;

[0030] Figure 2 In b), it is a UV-Vis-NIR spectral test chart of the organic semiconductors doped with anions in Examples 5 to 7 and Comparative Example 6 of the present application;

[0031] Figure 2 In c), it is a UV-Vis-NIR spectral test chart of the organic semiconductors doped with anions in Examples 8 to 10 of the present application;

[0032] Figure 3 It is a UV-Vis-NIR spectral test chart of the organic semiconductors doped with anions in Examples 11 to 13 and Comparative Examples 3 to 5 of the present application;

[0033] Figure 4 It is a UV-Vis-NIR spectral test chart of the organic semiconductors doped with anions in Examples 14 to 15 of the present application;

[0034] Figure 5 In a), it is a UV-Vis-NIR spectral test chart of the organic semiconductors doped with anions in Example 16 and Comparative Example 9 of the present application;

[0035] Figure 5 In b), it is a UV-Vis-NIR spectral test chart of the organic semiconductors doped with anions in Example 17 and Comparative Example 10 of the present application;

[0036] Figure 5c) in this is the UV-Vis-NIR spectral test chart of the anion-doped organic semiconductors in Example 18 and Comparative Example 11 of this application;

[0037] Figure 5 d) in this is the UV-Vis-NIR spectral test chart of the anion-doped organic semiconductors in Example 19 and Comparative Example 12 of this application;

[0038] Figure 6 a) in this is the UV-Vis-NIR spectral test chart of the anion-doped organic semiconductors in Examples 20 - 21 of this application;

[0039] Figure 6 b) in this is the UV-Vis-NIR spectral test chart of the anion-doped organic semiconductors in Examples 22 - 23 of this application;

[0040] Figure 7 is the UV-Vis-NIR spectral test chart of the anion-doped organic semiconductors in Examples 24 - 25 of this application;

[0041] Figure 8 is the UV-Vis-NIR spectral test chart of the anion-doped organic semiconductors in Examples 26 - 28 of this application;

[0042] Figure 9 is the UV-Vis-NIR spectral test chart of the anion-doped organic semiconductors in Examples 29 - 30 of this application. Detailed implementation manners

[0043] Hereinafter, the implementation manners of the n-type doping method and its application of the organic semiconductors of this application specifically disclosed will be described in detail with appropriate reference to the accompanying drawings. However, there may be cases where unnecessary detailed descriptions are omitted. For example, there are cases where detailed descriptions of well-known matters are omitted and repeated descriptions of actually identical structures are omitted. This is to avoid the following description from becoming unnecessarily lengthy and to facilitate the understanding of those skilled in the art. In addition, the accompanying drawings and the following description are provided for those skilled in the art to fully understand this application and are not intended to limit the subject matter recited in the claims. Any product that is the same as or similar to this application obtained by anyone under the inspiration of this application or by combining the features of this application with those of other prior arts falls within the protection scope of this application.

[0044] The "range" disclosed in this application is defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, and the selected lower limit and upper limit define the boundaries of a particular range. The ranges defined in this way can include or exclude the end values and can be combined arbitrarily, that is, any lower limit can be combined with any upper limit to form a range. For example, the numerical range "a - b" represents an abbreviated representation of any real number combination between a and b, where a and b are both real numbers. For example, the numerical range "0 - 7" means that all real numbers between "0 - 7" have been fully listed herein, and "0 - 7" is only an abbreviated representation of these numerical combinations. Additionally, when stating that a certain parameter is an integer ≥ 3, it is equivalent to disclosing that the parameter is, for example, the integers 3, 4, 5, 6, 7, 8, 9, 10, 11, etc.

[0045] If there is no special instruction, all embodiments and optional embodiments of this application can be combined with each other to form a new technical solution.

[0046] If there is no special instruction, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0047] If there is no special instruction, all steps of this application can be carried out sequentially or randomly, preferably sequentially. For example, the method includes steps (1) and (2), which means that the method can include steps (1) and (2) carried out sequentially, or can also include steps (2) and (1) carried out sequentially. For example, when it is mentioned that the method may further include step (3), it means that step (3) can be added to the method in any order. For example, the method can include steps (1), (2), and (3), or can also include steps (1), (3), and (2), or can also include steps (3), (1), and (2), etc.

[0048] If there is no special instruction, the "including" and "comprising" mentioned in this application mean open-ended, and can also be closed-ended. For example, the "including" and "comprising" can mean that other components not listed can also be included or comprised, or can also only include or comprise the listed components.

[0049] If there is no special instruction, in this application, the term "or" is inclusive. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, any of the following conditions satisfies the condition "A or B": A is true (or exists) and B is false (or does not exist); A is false (or does not exist) while B is true (or exists); or both A and B are true (or exist).

[0050] This application proposes an n-type doping method for organic semiconductors, in which a transition metal catalyst, an N-type organic semiconductor, and an anion dopant solution are mixed and reacted on a substrate to prepare the doped organic semiconductor; wherein, the preparation method of the anion dopant solution includes:

[0051] Mix ammonium hydroxide anions, amide solvents, and molecular sieves, react at room temperature for 8 to 24 hours, filter to obtain the clear liquid, and prepare the anion dopant solution;

[0052] The ammonium hydroxide anions include compounds with the structure shown in Formula I,

[0053] Formula I,

[0054] In the formula, R 11 , R 12 , R 13 , R 14 each independently includes at least one of substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted phenyl, and substituted or unsubstituted benzyl, and R 11 , R 12 , R 13 , R 14 are not simultaneously methyl;

[0055] The amide solvents include compounds with the structure shown in Formula II,

[0056] Formula II,

[0057] In the formula, R 15 , R 16 each independently includes at least one of hydrogen, substituted or unsubstituted C 1-4 alkyl, and substituted or unsubstituted phenyl, and R 17 includes at least one of hydrogen, substituted or unsubstituted C 1-4 alkyl, substituted or unsubstituted phenyl, and substituted or unsubstituted amino.

[0058] In this article, the term "transition metal catalyst" refers to Group X and Group XI transition metals with catalytic activity.

[0059] In this article, the term "N-type organic semiconductor" refers to an acceptor-type organic semiconductor material (compound) with the property of easily accepting electrons, specifically an organic compound with a large electron affinity when two organic compounds are brought into contact. Therefore, as an acceptor-type organic semiconductor, any organic compound with electron-accepting properties can be used.

[0060] In this article, the term "room temperature" is 20 to 25 °C.

[0061] As used herein, the term "substituted or unsubstituted" means that at least one hydrogen of a substituent is replaced with deuterium, halogen, cyano, C 1-2 alkyl, C 3-30 cycloalkyl, C 6-30 aryl, C 2-30 heteroaryl or a combination thereof.

[0062] Studies have found that anion dopants have higher stability, but simple anions are not suitable for catalytic doping because they cannot undergo the covalent bond cleavage step required for catalytic doping. In this application, an anion dopant solution is prepared by specific ammonium hydroxide anions and amide solvents in the presence of molecular sieves, and then mixed and reacted with a transition metal catalyst and an N-type organic semiconductor on a substrate. The doping reaction is rapid, has a high doping efficiency, and the conductivity of the doped organic semiconductor prepared is effectively improved.

[0063] This application finds that the anion dopant solution needs to be prepared by specific ammonium hydroxide anions and amide solvents under the action of molecular sieves. If the R 11 , R 12 , R 13 , R 14 chain lengths in the ammonium hydroxide anions are too long or too short on average, the doping efficiency between the anion dopant solution and the N-type organic semiconductor will be greatly reduced. This is because when R 11 , R 12 , R 13 , R 14 in the ammonium hydroxide anion (tetramethylammonium hydroxide) are all methyl groups, the binding force inside the ammonium hydroxide anion is strong, and the anion cannot be separated to play a role. When the R 11 , R 12 , R 13 , R 14 chain lengths are too long, it will cause the molecular structure of the ammonium hydroxide anion to be too large, affecting the contact between the anion dopant solution and the N-type organic semiconductor, and thus affecting its doping effect.

[0064] In some embodiments, the reaction time in the method for preparing the anion dopant solution can be selected from 8 h, 10 h, 12 h, 14 h, 15 h, 16 h, 18 h, 20 h, 22 h, 24 h, or a value within the range formed by any two of the above.

[0065] In some embodiments, the N-type organic semiconductors include PDTzTI, PBTzI, PDTzTIT-2F, PDTzTIT, N2200, PBTI, f-BTI2TEGFT, NDI-EH, PDI-C 6 C 7At least one of them has a structure as shown in Formula III:

[0066]

[0067] Formula III

[0068] In the formula, R 1 includes 2-hexyldecyl, R 2 includes 2-octyldodecyl, R 3 includes , R 4 includes 2-ethylhexyl, R 5 includes 2-heptylhexyl, n1, n2, n3, n4, n5, n6, n7, n8 are each independently selected from integers from 5 to 40.

[0069] In some embodiments, the transition metal catalyst includes at least one of transition metal nanoparticles and transition metal complexes.

[0070] In some embodiments, the transition metal nanoparticles include at least one of nano Pt particles, nano Au particles, nano Pd particles, nano Ag particles, nano Cu particles, and nano Ni particles.

[0071] In some embodiments, the transition metal complex includes Pd 2 (dba) 3 , Pd(dba) 2 , Pd(OAc) 2 , Pd(acac) 2 at least one of them.

[0072] In some embodiments, the ammonium hydroxide anions include at least one of tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, ethyltrimethylammonium hydroxide, tributylmethylammonium hydroxide, methyltriethylammonium hydroxide, diethyldimethylammonium hydroxide, benzyltriethylammonium hydroxide, benzyltrimethylammonium hydroxide, triethylphenylammonium hydroxide, tetradecylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexyltributylammonium hydroxide, and N,N,N-(triethyl)-N-dodecylammonium hydroxide.

[0073] In some embodiments, the amide solvents include at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutyramide, N-methylformamide, N,N-diethylformamide, N,N-dipropylformamide, N,N-dibutylformamide, N,N-diphenylformamide, tetramethylurea, trimethylurea, and dimethylurea.

[0074] When the anion dopant solution prepared from the above-mentioned ammonium hydroxide anions and amide solvents is used in combination with a transition metal catalyst, the doping efficiency of the subsequent N-type organic semiconductor can be effectively improved, which has universality.

[0075] In some embodiments, the molecular sieve includes at least one of A-type molecular sieve, X-type molecular sieve, Y-type molecular sieve, SBA molecular sieve, MCM-type molecular sieve, ZSM-type molecular sieve, SAPO molecular sieve, ALPO-type molecular sieve, and ITQ molecular sieve.

[0076] In some embodiments, the A-type molecular sieve includes at least one of 3A molecular sieve, 4A molecular sieve, and 5A molecular sieve.

[0077] In some embodiments, the X-type molecular sieve includes at least one of 10X molecular sieve and 13X molecular sieve.

[0078] In some embodiments, the Y-type molecular sieve includes at least one of HY molecular sieve, NaY molecular sieve, USY molecular sieve, and RY molecular sieve.

[0079] In some embodiments, the SBA molecular sieve includes at least one of SBA-15 molecular sieve and SBA-16 molecular sieve.

[0080] In some embodiments, the MCM-type molecular sieve includes at least one of MCM-22 molecular sieve, MCM-41 molecular sieve, and MCM-48 molecular sieve.

[0081] In some embodiments, the SAPO molecular sieve includes at least one of SAPO-5 molecular sieve, SAPO-11 molecular sieve, SAPO-20 molecular sieve, SAPO-34 molecular sieve, SAPO-44 molecular sieve, and SAPO-47 molecular sieve.

[0082] In some embodiments, the ZSM-type molecular sieve includes at least one of ZSM-5 molecular sieve, ZSM-11 molecular sieve, ZSM-12 molecular sieve, ZSM-22 molecular sieve, ZSM-23 molecular sieve, ZSM-35 molecular sieve, and ZSM-48 molecular sieve.

[0083] In some embodiments, the ALPO-type molecular sieve includes at least one of ALPO-4, ALPO-15, and ALPO-18.

[0084] In some embodiments, the ITQ molecular sieve includes at least one of ITQ-24, ITQ-40, or ITQ-55.

[0085] In some embodiments, the molar ratio of ammonium hydroxide anions to amide solvents is 1:(2 - 30). In some embodiments, the molar ratio of ammonium hydroxide anions to amide solvents can be selected from 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29, 1:30 or a ratio within the range formed by any two of the above ratios.

[0086] In some embodiments, the molar ratio of ammonium hydroxide anions to the mass of molecular sieve is 1 mol:(40 - 200) g. In some embodiments, the molar ratio of ammonium hydroxide anions to the mass of molecular sieve can be selected from 1 mol:40 g, 1 mol:50 g, 1 mol:60 g, 1 mol:70 g, 1 mol:80 g, 1 mol:90 g, 1 mol:100 g, 1 mol:110 g, 1 mol:120 g, 1 mol:130 g, 1 mol:140 g, 1 mol:150 g, 1 mol:160 g, 1 mol:170 g, 1 mol:180 g, 1 mol:190 g, 1 mol:200 g or a ratio within the range formed by any two of the above ratios.

[0087] In some embodiments, the transition metal catalyst includes transition metal nanoparticles, and the n-type doping method of the organic semiconductor includes the following steps:

[0088] Form transition metal nanoparticles on the substrate by thermal evaporation deposition, and then coat a mixture including an n-type organic semiconductor and an anion dopant solution on the substrate including transition metal nanoparticles, and heat at 60 - 150 °C for 5 - 360 s to obtain the doped organic semiconductor.

[0089] In some embodiments, the heating temperature can be selected from 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C or a value within the range formed by any two of the above values, and the heating time can be selected from 5 s, 10 s, 20 s, 40 s, 50 s, 60 s, 80 s, 100 s, 120 s, 140 s, 150 s, 160 s, 180 s, 200 s, 220 s, 240 s, 250 s, 260 s, 280 s, 300 s, 320 s, 340 s, 350 s, 360 s or a value within the range formed by any two of the above values.

[0090] In this text, the "mixture including an N-type organic semiconductor and an anion dopant solution" may either not contain a solvent other than the anion dopant solution, and the N-type organic semiconductor is soluble in the anion dopant solution for subsequent coating; or it may contain a solvent that can dissolve the N-type organic semiconductor, and the solution formed by the N-type organic semiconductor and the solvent is miscible with the anion dopant solution for subsequent coating.

[0091] It can be understood that the transition metal nanoparticles formed on the substrate have excellent catalytic activity, which can effectively improve the efficiency of the doping reaction between the subsequent N-type organic semiconductor and the anion dopant solution. The n-type doping method of the organic semiconductor in this application has a rapid reaction and can greatly save time costs.

[0092] In some embodiments, the transition metal catalyst includes transition metal nanoparticles, and the n-type doping method of the organic semiconductor includes the following steps:

[0093] Form transition metal nanoparticles on the substrate by thermal evaporation deposition, and then coat a solution containing an N-type organic semiconductor on the substrate with the surface formed with transition metal nanoparticles to obtain an organic semiconductor thin film;

[0094] Then coat the anion dopant solution on the organic semiconductor thin film and heat it at 60~150 °C for 5~360 s to obtain the doped organic semiconductor.

[0095] In this text, the "solution containing an N-type organic semiconductor" refers to dissolving the N-type organic semiconductor in a solvent for subsequent coating.

[0096] In some embodiments, the heating temperature can be selected as 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, 150 °C, or a value within the range formed by any two of the above values, and the heating time can be selected as 5 s, 10 s, 20 s, 40 s, 50 s, 60 s, 80 s, 100 s, 120 s, 140 s, 150 s, 160 s, 180 s, 200 s, 220 s, 240 s, 250 s, 260 s, 280 s, 300 s, 320 s, 340 s, 350 s, 360 s, or a value within the range formed by any two of the above values.

[0097] In some embodiments, the transition metal catalyst includes transition metal complexes, and the n-type doping method of the organic semiconductor includes the following steps:

[0098] Coat a mixture including a transition metal complex, an N-type organic semiconductor, and an anion dopant solution on the substrate and heat it at 60~150 °C for 5~360 s to obtain the doped organic semiconductor.

[0099] In this text, the "mixture including a transition metal complex, an N-type organic semiconductor, and an anion dopant solution" may either not contain solvents other than the anion dopant solution, with the N-type organic semiconductor and the transition metal complex being soluble in the anion dopant solution for subsequent coating; or it may contain a solvent capable of dissolving the N-type organic semiconductor and the transition metal complex, and the solution formed by the N-type organic semiconductor, the transition metal complex, and the solvent is miscible with the anion dopant solution for subsequent coating.

[0100] In some embodiments, the heating temperature can be selected as 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or a value within the range formed by any two of the above values, and the heating time can be selected as 5 s, 10 s, 20 s, 40 s, 50 s, 60 s, 80 s, 100 s, 120 s, 140 s, 150 s, 160 s, 180 s, 200 s, 220 s, 240 s, 250 s, 260 s, 280 s, 300 s, 320 s, 340 s, 350 s, 360 s, or a value within the range formed by any two of the above values.

[0101] In some embodiments, the transition metal catalyst includes a transition metal complex, and the method for n-type doping of an organic semiconductor includes the following steps:

[0102] Coat a solution including an N-type organic semiconductor on the substrate to obtain an organic semiconductor thin film;

[0103] Then coat a mixture including a transition metal complex and an anion dopant solvent on the organic semiconductor thin film, and heat at 60 - 150°C for 5 - 360 s to obtain the doped organic semiconductor.

[0104] In this text, the "solution containing an N-type organic semiconductor" refers to dissolving the N-type organic semiconductor in a solvent for subsequent coating.

[0105] In this text, the "mixture including a transition metal complex and an anion dopant solvent" may either not contain solvents other than the anion dopant solution, with the transition metal complex being soluble in the anion dopant solution for subsequent coating; or it may contain a solvent capable of dissolving the transition metal complex, and the solution formed by the transition metal complex and the solvent is miscible with the anion dopant solution for subsequent coating.

[0106] In some embodiments, the heating temperature can be selected from 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or a value within a range formed by any two of the above values, and the heating time can be selected from 5s, 10s, 20s, 40s, 50s, 60s, 80s, 100s, 120s, 140s, 150s, 160s, 180s, 200s, 220s, 240s, 250s, 260s, 280s, 300s, 320s, 340s, 350s, 360s, or a value within a range formed by any two of the above values.

[0107] In some embodiments, the molar ratio of the anionic dopant solution to the N-type organic semiconductor is (1~10):1. In some embodiments, the molar ratio of the anionic dopant solution to the N-type organic semiconductor can be selected from 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, or a ratio within a range formed by any two of the above ratios.

[0108] In some embodiments, the molar ratio of the anionic dopant solution to the transition metal catalyst is (1000~20):1. In some embodiments, the molar ratio of the anionic dopant solution to the transition metal catalyst can be selected from 1000:1, 900:1, 800:1, 700:1, 600:1, 500:1, 400:1, 300:1, 200:1, 100:1, 90:1, 80:1, 70:1, 60:1, 50:1, 40:1, 30:1, 20:1, or a ratio within a range formed by any two of the above ratios.

[0109] In some embodiments, the particle size of the transition metal nanoparticles is 1~10 nm, the nominal thickness of the transition metal nanoparticles is 0.1~1.5 nm, and the particle density of the transition metal nanoparticles is 0.8×10 12 ~3×10 12 cm -2 . In some embodiments, the particle size of the transition metal nanoparticles can be selected from 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, or a value within a range formed by any two of the above values, the nominal thickness of the transition metal nanoparticles can be selected from 0.1 nm, 0.2 nm, 0.4 nm, 0.5 nm, 0.6 nm, 0.8 nm, 1 nm, 1.2 nm, 1.4 nm, 1.5 nm, or a value within a range formed by any two of the above values, and the particle density of the transition metal nanoparticles can be selected from 0.8×10 12 cm -2 、1×10 12 cm -2, 1.2×10 12 cm -2 , 1.4×10 12 cm -2 , 1.5×10 12 cm -2 , 1.6×10 12 cm -2 , 1.8×10 12 cm -2 , 2×10 12 cm -2 , 2.2×10 12 cm -2 , 2.4×10 12 cm -2 , 2.5×10 12 cm -2 , 2.6×10 12 cm -2 , 2.8×10 12 cm -2 , 3×10 12 cm -2 , or a value within the range formed by any two of the above values.

[0110] In this article, the particle size, nominal thickness, and particle density of the transition metal nanoparticles can be measured using any known testing method. By way of example, the particle size and particle density of the transition metal nanoparticles can be calibrated by transmission electron microscopy (TEM), and the nominal thickness of the transition metal nanoparticles is the measurement data given by the crystal oscillator inside the evaporation machine.

[0111] In some embodiments, the thickness of the doped organic semiconductor is 20 nm to 500 nm. In some embodiments, the thickness of the doped organic semiconductor can be selected as 20 nm, 50 nm, 100 nm, 120 nm, 150 nm, 200 nm, 220 nm, 250 nm, 300 nm, 320 nm, 350 nm, 400 nm, 420 nm, 450 nm, 500 nm, or a value within the range formed by any two of the above values.

[0112] This application presents the application of the n-type doping method of the organic semiconductor in some embodiments in the preparation of organic optoelectronic devices.

[0113] Examples

[0114] The following embodiments are for a better further understanding of the present application, and are not limited to the described best mode. They do not constitute a limitation to the content and protection scope of the present application. For those not specifying specific experimental steps or conditions in the embodiments, operations or conditions of conventional experimental steps described in the literature in this field can be followed. For reagents or instruments without indicating the manufacturer, they are all conventional reagent products that can be obtained through commercial purchase.

[0115] In the following examples and comparative examples, the sources of PDTzTI, PDTzTIT-2F, PDTzTIT, PBTzI, and PBTI refer to the references Shi et al., Adv. Mater. 2018, 30, 1705745; Shi et al., Chem. Mater. 2018, 30, 7988 - 8001;

[0116] The source of f-BTI2TEG-FT refers to the invention patent - An n-type doping method of an organic semiconductor and its application (Application No.: 202110163646.1, Application Date: February 5, 2021);

[0117] NDI-EH, PDI-C6C7, and N-DMBI-H are all purchased from Sigma-Aldrich; N2200 is purchased from FlexterraCorp.

[0118] I. Preparation Method

[0119] Example 1

[0120] Preparation of the anion dopant solution: In a 30 ml glass sample bottle, 10 g of 1M tetrabutylammonium hydroxide methanol solution (purchased from Sigma-Aldrich), 4.3 g of anhydrous N,N-dimethylformamide solvent are mixed, and then 2 g of 3A molecular sieve (purchased from Alfa-Aesar) is added. After stirring evenly, the reaction is carried out at 20 - 25 °C for 10 h, and then the solid is removed by filtration to obtain the anion dopant solution; among them, the molar ratio of tetrabutylammonium hydroxide to N,N-dimethylformamide is 1:10, and the molar ratio of tetrabutylammonium hydroxide to the mass of 3A molecular sieve is: 0.012 mol:2 g.

[0121] n-type doping of the organic semiconductor:

[0122] First, using a vacuum thermal evaporation machine at a rate of 0.1 Å / s, gold is evaporated and deposited on the cleaned glass substrate to form transition metal nanoparticles Au (the Angstrom Nexdep evaporation machine shows that the nominal thickness of the transition metal nanoparticles Au is 0.1 nm, and the particle size of the transition metal nanoparticles Au is 1.4 nm);

[0123] Then the N-type organic semiconductor PDI-C 6 C 7 Dissolve in anhydrous chloroform solvent (concentration 10 mg / mL), take 1 mL of PDI-C 6 C 7 solution and anion dopant solution (anion dopant solution and PDI-C 6 C 7 PDI-C in solution 6 C 7 The molar ratio is 2:1) and mixed, stirred evenly; then PDI-C 6 C 7 The mixed solution of the solution and the anion dopant solution is spin-coated on a glass substrate with transition metal nanoparticles Au deposited on the surface at a rotation speed of 1500 rpm, and then heated at 120° C. for 10 seconds to complete the catalytic doping reaction to obtain a doped organic semiconductor.

[0124] Embodiment 2~4

[0125] The anion dopant solution and the n-type doping of the organic semiconductor in Examples 2 to 4 are similar to the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the raw material ammonium hydroxide anions for preparing the anion dopant solution in Example 1 are adjusted to tributylmethylammonium hydroxide, tetraoctylammonium hydroxide, and benzyltrimethylammonium hydroxide, respectively, as shown in Tables 1 and 2.

[0126] Embodiment 5~7

[0127] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Examples 5 to 7 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the raw material amide solvent for preparing the anion dopant solution in Example 1 is adjusted to N-methylformamide, N,N-diphenylformamide, and tetramethylurea, respectively, as shown in Tables 1 and 2.

[0128] Embodiments 8 to 10

[0129] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Examples 8 to 10 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the raw material molecular sieves for preparing the anion dopant solution in Example 1 are adjusted to MCM-22 molecular sieve, SAPO-5 molecular sieve, and ZSM-5 molecular sieve, respectively, as shown in Tables 1 and 2.

[0130] Embodiments 11 to 13

[0131] The preparation methods of the anion dopant solutions and the n-type doping of the organic semiconductors in Examples 11 to 13 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the molar ratios of the ammonium hydroxide-based anion tetrabutylammonium hydroxide to the amide solvent N,N-dimethylformamide for preparing the anion dopant solution in Example 1 are adjusted to 1:2, 1:5, and 1:30, respectively. See Tables 1 and 2 for details.

[0132] Examples 14 to 15

[0133] The preparation methods of the anion dopant solutions and the n-type doping of the organic semiconductors in Examples 14 to 15 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the molar ratio of the ammonium hydroxide-based anion tetrabutylammonium hydroxide to the mass of 3A molecular sieve for preparing the anion dopant solution in Example 1 is adjusted to 0.012 mol:0.5 g and 0.012 mol:2.5 g, respectively. See Tables 1 and 2 for details.

[0134] Examples 16 to 19

[0135] The preparation methods of the anion dopant solutions and the n-type doping of the organic semiconductors in Examples 16 to 19 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the raw material N-type organic semiconductors for the n-type doping method of the organic semiconductor in Example 1 are adjusted to NDI-EH, N2200, PDTzTI, and f-BTI2TEG-FT, respectively. See Tables 1 and 2 for details.

[0136] Examples 20 to 21

[0137] The preparation methods of the anion dopant solutions and the n-type doping of the organic semiconductors in Examples 20 to 21 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the raw material transition metal catalysts for the n-type doping method of the organic semiconductor in Example 1 are adjusted to transition metal nanoparticles Pt and transition metal nanoparticles Cu, respectively. See Tables 1 and 2 for details.

[0138] Example 22

[0139] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Example 22 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the raw material transition metal catalyst for the n-type doping method of the organic semiconductor in Example 1 is adjusted to Pd 2 (dba) 3 , and the n-type doping of the organic semiconductor is as follows:

[0140] First, the N-type organic semiconductor PDI-C 6C 7 Dissolve it in anhydrous chloroform solvent (concentration 10 mg / mL), and then Pd 2 (dba) 3 Dissolve it in anhydrous chloroform solvent, and then the PDI-C 6 C 7 solution, the anion dopant solution and the Pd 2 (dba) 3 solution are mixed and stirred evenly. In the anion dopant solution and the PDI-C 6 C 7 solution, the molar ratio of PDI-C 6 C 7 , Pd 2 (dba) 3 is 100:50:1; subsequently, the PDI-C 6 C 7 solution, the Pd 2 (dba) 3 solution and the mixed solution of the anion dopant solution are spin-coated on a glass substrate at a rotation speed of 1500 rpm, and then heated at 120 °C for 10 s to complete the catalytic doping reaction, obtaining the doped organic semiconductor.

[0141] Example 23

[0142] The preparation method of the anion dopant solution and the n-type doping of the organic semiconductor in Example 23 is similar to that of the anion dopant solution and the n-type doping of the organic semiconductor in Example 22, except that: the raw material transition metal catalyst in the n-type doping method of the organic semiconductor in Example 22 is adjusted to the transition metal complex Pd(acac) 2 , as shown in Table 1 and Table 2 specifically.

[0143] Examples 24 - 25

[0144] The preparation method of the anion dopant solution and the n-type doping of the organic semiconductor in Examples 24 - 25 is similar to that of the anion dopant solution and the n-type doping of the organic semiconductor in Example 22, except that: the molar ratios of the anion dopant solution and the transition metal complex Pd 2 (dba) 3 in the n-type doping method of the organic semiconductor in Example 22 are adjusted to 20:1 and 1000:1 respectively (achieved by adjusting the dosage of the transition metal complex Pd 2 (dba) 3 ), as shown in Table 1 and Table 2 specifically.

[0145] Examples 26 - 28

[0146] The preparation methods of the anion dopant solutions and the n-type doping of the organic semiconductors in Examples 26 to 28 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that: the anion dopant solution in the n-type doping method of the organic semiconductor in Example 1 is combined with PDI-C 6 C 7 in the solution, and the molar ratios of PDI-C 6 C 7 are adjusted to 1:1, 5:1, and 10:1 respectively (achieved by adjusting the dosage of the anion dopant solution). See Tables 1 and 2 for details.

[0147] Example 29

[0148] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Example 29 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that: the n-type doping method of the organic semiconductor in Example 1 is adjusted. The specific n-type doping method of the organic semiconductor is as follows:

[0149] First, using a vacuum thermal evaporation machine at a rate of 0.1 Å / s, gold is evaporated and deposited on the cleaned glass substrate to form transition metal nanoparticles Au (the Angstrom Nexdep evaporation machine shows that the nominal thickness of the transition metal nanoparticles Au is 0.1 nm, and the particle size of the transition metal nanoparticles Au is 1.4 nm);

[0150] Then, the N-type organic semiconductor PDI-C 6 C 7 is dissolved in anhydrous chloroform solvent (concentration 10 mg / mL). At 20 - 25 °C, 100 μL of the PDI-C 6 C 7 solution is spin-coated at a speed of 1500 rpm in the center on the cleaned glass substrate to obtain an organic semiconductor thin film;

[0151] Finally, the anion dopant solution (the molar ratio of the anion dopant solution to PDI-C 6 C 7 in the solution of PDI-C 6 C 7 is 2:1) is spin-coated on the organic semiconductor thin film at a rotation speed of 2000 rpm, and then heated at 120 °C for 10 s to complete the catalytic doping reaction, obtaining the doped organic semiconductor.

[0152] Example 30

[0153] The preparation method of the anion dopant solution and the n-type doping of the organic semiconductor in Example 30 is similar to that of the anion dopant solution and the n-type doping of the organic semiconductor in Example 22, except that the n-type doping method of the organic semiconductor in Example 22 is adjusted. The specific n-type doping method of the organic semiconductor is as follows:

[0154] First, dissolve the N-type organic semiconductor PDI-C 6 C 7 in anhydrous chloroform solvent (concentration 10 mg / mL). At 20 - 25 °C, take 100 μL of PDI-C 6 C 7 solution and spin-coat it onto the cleaned glass substrate at a speed of 1500 rpm to obtain an organic semiconductor thin film;

[0155] Then dissolve Pd 2 (dba) 3 in isobutyl acetate solvent. Mix the Pd 2 (dba) 3 solution with the anion dopant solution, where the molar ratio of the anion dopant solution to Pd 2 (dba) 3 is 100:1, and stir evenly; subsequently, spin-coat the mixed solution of the Pd 2 (dba) 3 solution and the anion dopant solution onto the organic semiconductor thin film at a rotation speed of 1500 rpm, and then heat it at 120 °C for 10 s to complete the catalytic doping reaction, obtaining the doped organic semiconductor.

[0156] Comparative Example

[0157] Comparative Example 1

[0158] The preparation method of the anion dopant solution and the n-type doping of the organic semiconductor in Comparative Example 1 is similar to that of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the ammonium hydroxide-based anion, the raw material for preparing the anion dopant solution in Example 1, is adjusted to tetramethylammonium hydroxide, as shown in Tables 1 and 2 specifically.

[0159] Comparative Example 2

[0160] The preparation method of the anion dopant solution and the n-type doping of the organic semiconductor in Comparative Example 2 is similar to that of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the ammonium hydroxide-based anion, the raw material for preparing the anion dopant solution in Example 1, is adjusted to octadecylammonium hydroxide, as shown in Tables 1 and 2 specifically.

[0161] Comparative Examples 3 - 5

[0162] The preparation methods of the anion dopant solutions and the n-type doping of the organic semiconductors in Comparative Examples 3 to 5 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Comparative Example 1, except that the molar ratios of ammonium hydroxide-based anion tetrabutylammonium hydroxide to amide solvent N,N-dimethylformamide for preparing the anion dopant solution in Comparative Example 1 are adjusted to 1:2, 1:5, and 1:10, respectively. See Tables 1 and 2 for details.

[0163] Comparative Example 6

[0164] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Comparative Example 6 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the raw material molecular sieve for preparing the anion dopant solution in Example 1 is not added. See Tables 1 and 2 for details.

[0165] Comparative Example 7

[0166] The preparation method of the n-type doping of the organic semiconductor in Comparative Example 7 is similar to that of the n-type doping of the organic semiconductor in Comparative Example 1, except that the anion doping solution is not introduced into the n-type doping of the organic semiconductor in Comparative Example 1, and the molecular dopant N-DMBI-H is added. The n-type doping method of the organic semiconductor is as follows:

[0167] First, use a vacuum thermal evaporation machine to deposit gold on the cleaned glass substrate at a rate of 0.1 Å / s to form transition metal nanoparticles Au (the Angstrom Nexdep evaporation machine shows that the nominal thickness of the transition metal nanoparticles Au is 0.1 nm and the particle size of the transition metal nanoparticles Au is 1.4 nm);

[0168] Then dissolve both N-type organic semiconductor PDI-C 6 C 7 and N-DMBI-H in anhydrous chloroform solvent (the molar ratio of PDI-C 6 C 7 to N-DMBI-H is 1:1), and stir evenly; subsequently, spin-coat the mixed solution of PDI-C 6 C 7 and N-DMBI-H on the glass substrate with deposited transition metal nanoparticles Au on the surface at a rotation speed of 1500 rpm, and then heat at 120 °C for 10 s to complete the catalytic doping reaction, obtaining the doped organic semiconductor.

[0169] Comparative Example 8

[0170] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Comparative Example 8 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that: the n-type doping of the organic semiconductor in Example 1 does not introduce a transition metal catalyst. See Tables 1 and 2 for details.

[0171] Comparative Example 9

[0172] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Comparative Example 9 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 16, except that: the n-type doping of the organic semiconductor in Example 16 does not introduce a transition metal catalyst. See Tables 1 and 2 for details.

[0173] Comparative Example 10

[0174] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Comparative Example 10 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 17, except that: the n-type doping of the organic semiconductor in Example 17 does not introduce a transition metal catalyst. See Tables 1 and 2 for details.

[0175] Comparative Example 11

[0176] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Comparative Example 11 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 18, except that: the n-type doping of the organic semiconductor in Example 18 does not introduce a transition metal catalyst. See Tables 1 and 2 for details.

[0177] Comparative Example 12

[0178] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Comparative Example 12 are similar to those of the anion dopant solution and the n-type doping of the organic semiconductor in Example 19, except that: the n-type doping of the organic semiconductor in Example 19 does not introduce a transition metal catalyst. See Tables 1 and 2 for details.

[0179] Table 1 Preparation Parameters of Anion Dopant Solution

[0180]

[0181]

[0182] Table 2 n-Type Doping Parameters of Organic Semiconductor

[0183]

[0184]

[0185] II. Test Methods

[0186] 1) Test of conductivity measurement

[0187] In the example group, 30 nm Au by vacuum evaporation was used as the bottom contact electrode (two-probe form), and in the comparative example group, 30 nm Al was used as the bottom contact electrode (two-probe form). The channel length (L) and width (W) were 100 μm and 2 mm respectively. After sample preparation, the I-V curve of the sample placed in the glove box was measured using a Keithley 4200-SCS semiconductor characterization system, and then its conductivity was calculated according to the standard equation σ = (1 / R) × (L / (W·h)), where R is the device resistance and h is the film thickness measured by a Tencor KLAD-120 profilometer.

[0188] 2) Test of UV-vis-NIR

[0189] The sample to be tested was placed in a sealed glass cuvette to avoid exposure to ambient air, and the absorption spectrum was collected on a Shimadzu UV-3600 UV-VIS-NIR spectrometer. The UV-vis-NIR spectral test diagrams of each example and comparative example are shown in Figures 1 - 9 .

[0190] Table 3 Performance parameters of each example and comparative example

[0191]

[0192] III. Analysis of test results of each example and comparative example

[0193] It can be seen from Examples 1 to 30 and Comparative Examples 1 to 12 that the anion dopant solution prepared from ammonium hydroxide anions and amide solvents under the action of molecular sieves can react rapidly with the N-type organic semiconductor under the action of a transition metal catalyst, and the doping efficiency is significantly improved; it can be seen from Examples 1 to 4, Examples 16 to 19, Comparative Examples 1 to 2, and Comparative Examples 8 to 12 that the conductivity of the doped organic semiconductor prepared from this anion dopant solution and the N-type organic semiconductor under the action of a transition metal catalyst has also been improved.

[0194] See Figure 1 , it can be seen from Example 1 and Comparative Example 8 that the organic semiconductor PDI-C 6 C 7 film shows a very obvious doping phenomenon in the presence of a transition metal Au nanoparticle catalyst, and a strong PDI-C 6 C 7 ˙ − radical absorption peak (600 nm - 1000 nm) appears in the UV-Vis-NIR test curve; in the absence of a catalyst, PDI-C6 C 7 The thin film cannot be doped; in addition, as can be seen from Example 1 and Comparative Example 7, the anion dopant solution and the organic hydride N-DMBI-H catalytically doped organic semiconductor PDI-C 6 C 7 thin films exhibit similar PDI-C 6 C 7 ˙ − free radical absorption peaks, and the organic semiconductor PDI-C after catalytic doping with the anion dopant solution 6 C 7 thin film has slightly higher UV peaks, indicating that the anion dopant solution in this application has the same catalytic doping behavior as N-DMBI-H and slightly better doping effect.

[0195] See Figure 1 and Figure 2 for a)~ Figure 2 for b). As can be seen from Examples 1 to 7 and Comparative Examples 1 to 2, the types of ammonium hydroxide anions and amide solvents used to prepare the anion dopant solution have an impact on its catalytic doping behavior. Among them, the cation of the ammonium hydroxide anion cannot be too large or too small. When the cation is too small, such as using tetramethylammonium hydroxide, the electrostatic attraction between the tetramethyl cation and the dopant anion may be too large, hindering the doping effect of the anion on the organic semiconductor. When the cation is too large, such as using octatetracontanylammonium hydroxide, the large volume of the dopant will hinder the diffusion process of the dopant in the organic semiconductor thin film, thus seriously affecting the doping behavior of the anion dopant solution; see Figure 1 and Figure 2 . As can be seen from Examples 1 to 10 and Comparative Example 6, the introduction of molecular sieve in the preparation of the anion dopant solution is very crucial. It is possible that the molecular sieve plays a role in absorbing the reaction products of ammonium hydroxide anions and amide solvents, which is beneficial to the improvement of the subsequent catalytic doping efficiency of the anion dopant solution.

[0196] See Figure 1 and Figure 3 . As can be seen from Example 1, Examples 11 to 13, and Comparative Examples 3 to 5, controlling the molar ratio of ammonium hydroxide anions to amide solvents to 1:(2~30) can achieve efficient doping of organic semiconductors.

[0197] See Figure 1 and Figure 4, as can be seen from Examples 14 to 15, controlling the molar ratio of ammonium hydroxide anions to the mass of the molecular sieve to be 1 mol:(40 - 200) g is beneficial for more molecular sieves to fully promote the reaction between ammonium hydroxide anions and amide solvents, and further beneficial for the subsequent anion dopant solution to exhibit stronger doping behavior in the organic semiconductor thin film.

[0198] See Figure 1 , Figure 5 a) - Figure 5 d) in. As can be seen from Examples 1, 16 - 19, and Comparative Examples 8 - 12, the catalytic doping behavior of this anion dopant solvent is universal for a variety of organic semiconductors. After the organic semiconductor thin film is catalytically doped by the anion dopant solution and the transition metal catalyst, the conductivity performance has been effectively improved. In particular, the conductivity of imide - type organic semiconductors shows a significant increase after catalytic doping.

[0199] See Figure 6 , as can be seen from Examples 21 - 23, the catalytic doping behavior of the anion dopant solution is universal for different transition metal catalysts (nanoparticle catalysts and organometallic complex catalysts).

[0200] See Figure 7 , as can be seen from Examples 24 - 25, the presence of a small amount of transition metal catalyst can effectively promote the occurrence of the catalytic doping reaction of the anion dopant solution.

[0201] See Figure 8 , as can be seen from Examples 26 - 28, controlling the molar ratio of the anion dopant solution to the organic semiconductor to be (1 - 10):1 can achieve efficient doping.

[0202] See Figure 9 , as can be seen from Examples 29 - 30, the doping of organic semiconductors can also be carried out by sequential catalytic doping, and the effect of sequential catalytic doping is equivalent to that of co - blending catalytic doping.

[0203] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application, and they should all be covered by the scope of the claims and the specification of the present application. In particular, as long as there is no structural conflict, the technical features mentioned in each embodiment can be combined in any way. The present application is not limited to the specific embodiments disclosed in the text, but includes all technical solutions that fall within the scope of the claims.

Claims

1. A method for n-type doping of an organic semiconductor, characterized in that: A transition metal catalyst, an N-type organic semiconductor and an anion dopant solution are mixed and reacted on a substrate to prepare a doped organic semiconductor; wherein the preparation method of the anion dopant solution comprises: The raw materials including ammonium hydroxide anions and amide solvents are mixed with molecular sieves, reacted at room temperature for 8 to 24 hours, and the clear liquid is filtered to obtain the anion dopant solution; The ammonium hydroxide anion includes a compound of the structure shown in Formula I, Formula I, In the formula, R 11 , R 12 , R 13 , R 14 Each independently includes substituted or unsubstituted C 1-12 alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted benzyl, and R 11 , R 12 , R 13 , R 14 Not methyl at the same time; The amide solvent includes a compound with a structure shown in Formula II, Formula II, In the formula, R 15 , R 16 Each independently includes hydrogen, substituted or unsubstituted C 1-4 At least one of an alkyl group, a substituted or unsubstituted phenyl group, R 17 including hydrogen, substituted or unsubstituted C 1-4 At least one of an alkyl group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted amino group; The N-type organic semiconductor includes at least one of PDTzTI, PBTzI, PDTzTIT-2F, PDTzTIT, N2200, PBTI, f-BTI2TEG-FT, NDI-EH, and PDI-C6C7, and its structure is shown in Formula III: Formula III, In the formula, R1 includes 2-hexyldecyl, R2 includes 2-octyldodecyl, and R3 includes , R4 includes 2-ethylhexyl, R5 includes 2-hexylheptyl, and n1, n2, n3, n4, n5, n6, n7, and n8 are each independently selected from an integer of 5-40.

2. The method for n-type doping of an organic semiconductor according to claim 1, characterized in that: The transition metal catalyst comprises at least one of transition metal nanoparticles and transition metal complexes, and the transition metal nanoparticles comprise at least one of nano-Pt particles, nano-Au particles, nano-Pd particles, nano-Ag particles, nano-Cu particles, and nano-Ni particles. The transition metal complex comprises at least one of Pd2(dba)3, Pd(dba)2, Pd(OAc)2, and Pd(acac)2; The ammonium hydroxide anion includes at least one of tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, ethyltrimethylammonium hydroxide, tributylmethylammonium hydroxide, methyltriethylammonium hydroxide, diethyldimethylammonium hydroxide, benzyltriethylammonium hydroxide, benzyltrimethylammonium hydroxide, triethylphenylammonium hydroxide, tetradecylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, tetrapentylammonium hydroxide, decyltrihexylammonium hydroxide and N,N,N-(triethyl)-N-dodecylammonium hydroxide; The amide solvent includes at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutyramide, N-methylformamide, N,N-diethylformamide, N,N-di-n-propylformamide, N,N-dibutylformamide, N,N-diphenylformamide, tetramethylurea, trimethylurea, and dimethylurea; The molecular sieve includes at least one of A-type molecular sieve, X-type molecular sieve, Y-type molecular sieve, SBA molecular sieve, MCM-type molecular sieve, ZSM-type molecular sieve, SAPO molecular sieve, ALPO-type molecular sieve and ITQ molecular sieve; the A-type molecular sieve includes at least one of 3A molecular sieve, 4A molecular sieve and 5A molecular sieve; the X-type molecular sieve includes at least one of 10X molecular sieve and 13X molecular sieve; the Y-type molecular sieve includes at least one of HY molecular sieve, NaY molecular sieve, USY molecular sieve and RY molecular sieve; the SBA molecular sieve includes at least one of SBA-15 molecular sieve and SBA-16 molecular sieve; the MCM-type molecular sieve includes MCM-22 molecular sieve, MCM-41 molecular sieve and MCM-48 molecular sieve. The SAPO molecular sieve comprises at least one of SAPO-5 molecular sieve, SAPO-11 molecular sieve, SAPO-20 molecular sieve, SAPO-34 molecular sieve, SAPO-44 molecular sieve and SAPO-47 molecular sieve; the ZSM molecular sieve comprises at least one of ZSM-5 molecular sieve, ZSM-11 molecular sieve, ZSM-12 molecular sieve, ZSM-22 molecular sieve, ZSM-23 molecular sieve, ZSM-35 molecular sieve and ZSM-48 molecular sieve; the ALPO molecular sieve comprises at least one of ALPO-4, ALPO-15 and ALPO-18; the ITQ molecular sieve comprises at least one of ITQ-24, ITQ-40 and ITQ-55.

3. The n-type doping method of an organic semiconductor according to claim 1, characterized in that: The molar ratio of the ammonium hydroxide anion to the amide solvent is 1:(2-30), and the molar ratio of the ammonium hydroxide anion to the mass of the molecular sieve is 1 mol:(40-200) g.

4. The n-type doping method of an organic semiconductor according to claim 1, characterized in that: The transition metal catalyst comprises transition metal nanoparticles, and the n-type doping method of the organic semiconductor comprises the following steps: The transition metal nanoparticles are formed on the substrate by thermal evaporation deposition, and then a mixture including the N-type organic semiconductor and the anion dopant solution is coated on the substrate with the transition metal nanoparticles formed on the surface, and heated at 60-150° C. for 5-360 seconds to obtain the doped organic semiconductor.

5. The method for n-type doping of an organic semiconductor according to claim 1, characterized in that: The transition metal catalyst comprises transition metal nanoparticles, and the n-type doping method of the organic semiconductor comprises the following steps: Forming the transition metal nanoparticles on the substrate by thermal evaporation deposition, and then coating the solution containing the N-type organic semiconductor on the substrate with the transition metal nanoparticles formed on the surface to obtain an organic semiconductor film; The anion dopant solution is then coated on the organic semiconductor film and heated at 60-150° C. for 5-360 seconds to obtain the doped organic semiconductor.

6. The method for n-type doping of an organic semiconductor according to claim 1, characterized in that: The transition metal catalyst comprises a transition metal complex, and the n-type doping method of the organic semiconductor comprises the following steps: A mixture including the transition metal complex, the N-type organic semiconductor and the anion dopant solution is coated on the substrate, and heated at 60-150° C. for 5-360 s to obtain the doped organic semiconductor.

7. The method for n-type doping of an organic semiconductor according to claim 1, characterized in that: The transition metal catalyst comprises a transition metal complex, and the n-type doping method of the organic semiconductor comprises the following steps: coating a solution comprising the N-type organic semiconductor on the substrate to obtain an organic semiconductor thin film; Then, a mixture including the transition metal complex and the anion dopant solvent is coated on the organic semiconductor film, and heated at 60-150° C. for 5-360 s to obtain the doped organic semiconductor.

8. The method for n-type doping of an organic semiconductor according to any one of claims 1 to 7, characterized in that: The molar ratio of the anion dopant solution to the N-type organic semiconductor is (1-10):1, and the molar ratio of the anion dopant solution to the transition metal catalyst is (1000-20):

1.

9. The n-type doping method of an organic semiconductor according to claim 4 or 5, characterized in that: The particle size of the transition metal nanoparticles is 1-10 nm, the nominal thickness of the transition metal nanoparticles is 0.1-1.5 nm, and the particle density of the transition metal nanoparticles is 0.8×10 12 ~3×10 12 cm -2 .

10. Use of the n-type doping method of an organic semiconductor according to any one of claims 1 to 9 in preparing an organic photoelectric device.

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