N-type doping method of organic semiconductor and application of n-type doping method

Abstract

The invention discloses an n-type doping method of an organic semiconductor and application of the n-type doping method. The doping method comprises the steps that a transition metal catalyst, an N-type organic semiconductor and an anion dopant solution are mixed and react on a substrate, a doped organic semiconductor is prepared, a preparation method of the anion dopant solution comprises the steps that ammonium hydroxide anions, an amide solvent and a molecular sieve are mixed and react for 8-24 h at the normal temperature, filtering is conducted, clear liquid is taken, and the doped organic semiconductor is prepared. The anionic dopant solution is obtained. The doping reaction among the transition metal catalyst, the N-type organic semiconductor and the anionic dopant solution is very rapid, 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.

Description

Technical Field

[0001] The present application relates to doping of organic semiconductors, and in particular to an n-type doping method of organic semiconductors and applications 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] At present, N-type dopants mainly include precursor-type organic hydrides (such as benzimidazole derivatives), dimers of organic free radicals (such as organometallic sandwich compounds with 19 electrons), and dimers with monovalent and polyvalent anions (such as OH - , F - and Ox 2- ) as N-type dopants; on the one hand, 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 the N-type dopant (such as N-DBMI) and promote the n-type doping reaction of organic semiconductors, but the selection of molecular dopants that can be used in combination with transition metals is limited, which limits the application window of the catalytic doping method; on the other hand, simple anion dopants have strong reducing ability, but because they do not have dissociable chemical bonds, they are not suitable for high-efficiency catalytic doping methods.

[0004] Therefore, there is an urgent need to develop a new, universal, and highly efficient organic semiconductor n-type catalytic doping strategy suitable for anions to meet the application requirements of organic semiconductor n-type doping 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-mentioned defects in the prior art, and its purpose is to provide an n-type doping method for an organic semiconductor, by preparing a new anion dopant solution and improving the doping reaction between it and an N-type organic semiconductor and a transition metal catalyst, so that the n-type doping method for an organic semiconductor has excellent doping efficiency, and the conductivity of the prepared doped organic semiconductor is effectively improved.

[0006] In a first aspect of the present application, a method for n-type doping of an organic semiconductor is provided, wherein 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 method for preparing the anion dopant solution comprises:

[0007] 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;

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

[0009] Formula I,

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

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

[0012] Formula II,

[0013] In the formula, R 15 , R 16 , R 17 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 Each independently includes 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.

[0014] The study found that the doping reaction between the anion dopant solution prepared in the present application and the N-type organic semiconductor and the transition metal catalyst is very rapid, the n-type doping method of the 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:(2-30), optionally 1:(3-20), and more preferably 1:(5-10).

[0016] In any embodiment, the molar ratio of the ammonium hydroxide 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 comprises transition metal nanoparticles, and the n-type doping method of the organic semiconductor comprises 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 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.

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

[0020] 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.

[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] The second aspect of the present application provides the application of the n-type doping method of the organic semiconductor provided in the first aspect of the present application in the preparation of an organic photoelectric device.

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

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

[0026] Moreover, compared with the limited selection of molecular dopants, the raw materials for the preparation of the anion dopant solution are from a wider range of sources, and a variety of anion dopant solutions can be used in conjunction 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 implementation methods of the present application or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0028] Figure 1 It is a UV-Vis-NIR spectrum test chart of the organic semiconductor 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 a) is a UV-Vis-NIR spectrum test chart of the organic semiconductor doped with anions in Examples 2 to 4 and Comparative Examples 1 to 2 of the present application;

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

[0031] Figure 2 c) is a UV-Vis-NIR spectrum test chart of the anion-doped organic semiconductor in Examples 8 to 10 of the present application;

[0032] Figure 3 It is a UV-Vis-NIR spectrum test chart of the organic semiconductor 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 spectrum test chart of the organic semiconductor doped with anions in Examples 14 and 15 of the present application;

[0034] Figure 5 a) is a UV-Vis-NIR spectrum test chart of the anion-doped organic semiconductor in Example 16 and Comparative Example 9 of the present application;

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

[0036] Figure 5c) is a UV-Vis-NIR spectrum test chart of the anion-doped organic semiconductor in Example 18 and Comparative Example 11 of the present application;

[0037] Figure 5 d) is a UV-Vis-NIR spectrum test chart of the anion-doped organic semiconductor in Example 19 and Comparative Example 12 of the present application;

[0038] Figure 6 a) is a UV-Vis-NIR spectrum test chart of the anion-doped organic semiconductor in Examples 20 to 21 of the present application;

[0039] Figure 6 b) is a UV-Vis-NIR spectrum test chart of the anion-doped organic semiconductor in Examples 22 to 23 of the present application;

[0040] Figure 7 It is a UV-Vis-NIR spectrum test chart of the organic semiconductor doped with anions in Examples 24 to 25 of the present application;

[0041] Figure 8 It is a UV-Vis-NIR spectrum test chart of the organic semiconductor doped with anions in Examples 26 to 28 of the present application;

[0042] Fig. 9 This is a UV-Vis-NIR spectrum test chart of the anion-doped organic semiconductor in Examples 29 to 30 of the present application. DETAILED DESCRIPTION

[0043] Hereinafter, the n-type doping method of the organic semiconductor of the present application and the implementation method of its application are specifically disclosed 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 and repeated descriptions of actually the same structure 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 drawings and the following description are provided for those skilled in the art to fully understand the present application and are not intended to limit the subject matter described in the claims. Any product that is identical or similar to the present application and is obtained by anyone under the inspiration of the present application or by combining the features of the present application with other prior arts shall fall within the scope of protection of the present application.

[0044] The "range" disclosed in the present application is defined in the form of a lower limit and an upper limit, and 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 range defined in this way can include or exclude end values, and can be arbitrarily combined, that is, any lower limit can be combined with any upper limit to form a range. For example, the numerical range "ab" 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 in this article, and "0-7" is just an abbreviated representation of these numerical combinations. In addition, when a certain parameter is expressed as an integer ≥3, it is equivalent to disclosing that the parameter is, for example, an integer of 3, 4, 5, 6, 7, 8, 9, 10, 11, etc.

[0045] If not otherwise specified, all embodiments and optional embodiments of the present application can be combined with each other to form a new technical solution.

[0046] Unless otherwise specified, all technical features and optional technical features of this application can be combined with each other to form a new technical solution.

[0047] Unless otherwise specified, all steps of the present application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (1) and (2), which means that the method may include steps (1) and (2) performed sequentially, or may include steps (2) and (1) performed sequentially. For example, mentioning that the method may also include step (3) means that step (3) may be added to the method in any order, for example, the method may include steps (1), (2) and (3), or may include steps (1), (3) and (2), or may include steps (3), (1) and (2, etc.

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

[0049] If not specifically stated, 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) and B is true (or exists); or both A and B are true (or exist).

[0050] The present application proposes a method for n-type doping of an organic semiconductor, wherein 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 method for preparing the anion dopant solution comprises:

[0051] The anion dopant solution is prepared by mixing ammonium hydroxide anions, amide solvents and molecular sieves, reacting at room temperature for 8 to 24 hours, and filtering the clear liquid to obtain the anion dopant solution;

[0052] The ammonium hydroxide anion includes a compound of the structure shown in Formula I,

[0053] Formula I,

[0054] In the formula, R 11 , R 12 , R 13 , R 14 Each independently includes substituted or unsubstituted C 1-12 At least one of an alkyl group, a substituted or unsubstituted phenyl group, and a substituted or unsubstituted benzyl group, and R 11 , R 12 , R 13 , R 14 Not methyl at the same time;

[0055] Amide solvents include compounds of the structure shown in Formula II,

[0056] Formula II,

[0057] In the formula, R 15 , R 16 , R 17 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 Each independently includes 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.

[0058] As used herein, the term "transition metal catalyst" refers to Group X and Group XI transition metals having catalytic activity.

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

[0060] In this article, the term "normal temperature" is 20~25℃.

[0061] In this context, the term "substituted or unsubstituted" means that at least one hydrogen of the substituent is replaced by deuterium, halogen, cyano, C 1-24 Alkyl, C 3-30 Cycloalkyl, C 6-30 Aryl, C 2-30 heteroaryl or a combination thereof.

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

[0063] The present application found that the anion dopant solution needs to be prepared from specific ammonium hydroxide anions and amide solvents under the action of molecular sieves. If R in the ammonium hydroxide anions 11 , R 12 , R 13 , R 14 When the chain length is too long or too short, the doping efficiency between the anion dopant solution and the N-type organic semiconductor will be greatly reduced. This is because the R 11 , R 12 , R 13 , R 14 When all of them are methyl groups, the internal binding force of the ammonium hydroxide anion (tetramethylammonium hydroxide) is strong, and the anion cannot separate and play a role, while R 11 , R 12 , R 13 , R 14 Too long a chain length will result in an overly large molecular structure of the ammonium hydroxide anion, which will affect the contact between the anion dopant solution and the N-type organic semiconductor, and further affect its doping effect.

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

[0065] In some embodiments, the N-type organic semiconductor includes at least one of PDTzTI, PBTzI, PDTzTIT-2F, PDTzTIT, N2200, PBTI, f-BTI2TEGFT, NDI-EH, and PDI-C6C7, and its structure is shown in Formula III:

[0066]

[0067] Formula III,

[0068] 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.

[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 at least one of Pd2(dba)3, Pd(dba)2, Pd(OAc)2, and Pd(acac)2.

[0072] In some embodiments, 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, tetradecyltrihexylammonium hydroxide, and N,N,N-(triethyl)-N-dodecylammonium hydroxide.

[0073] In some embodiments, 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.

[0074] The anion dopant solution prepared from the above-mentioned ammonium hydroxide anions and amide solvents can be used in conjunction with a transition metal catalyst to effectively improve the doping efficiency of subsequent N-type organic semiconductors and has universal applicability.

[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 a SAPO-5 molecular sieve, a SAPO-11 molecular sieve, a SAPO-20 molecular sieve, a SAPO-34 molecular sieve, a SAPO-44 molecular sieve, and a SAPO-47 molecular sieve.

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

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

[0084] In some embodiments, the ITQ molecular sieve comprises 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 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 in a range consisting of any two of the above ratios.

[0086] In some embodiments, the mole ratio of ammonium hydroxide anions to the mass ratio of molecular sieves is 1 mol: (40-200) g. In some embodiments, the mole ratio of ammonium hydroxide anions to the mass ratio of molecular sieves can be selected as 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 in the range of any two of the above ratios.

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

[0088] Transition metal nanoparticles are formed on the substrate by thermal evaporation deposition, and then a mixture including an N-type organic semiconductor and an anion dopant solution is coated on the substrate including the transition metal nanoparticles, and heated at 60-150° C. for 5-360 seconds to obtain a doped organic semiconductor.

[0089] 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 in the range consisting of any two of the above values, and the heating time can be selected as 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 in the range consisting of any two of the above values.

[0090] Herein, "a mixture including an N-type organic semiconductor and an anion dopant solution" may contain no solvent other than the anion dopant solution, and the N-type organic semiconductor is soluble in the anion dopant solution for subsequent coating; or 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 subsequent doping reaction between the N-type organic semiconductor and the anion dopant solution. The n-type doping method of the organic semiconductor in this application reacts quickly and can greatly save time costs.

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

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

[0094] Then, the anion dopant solution is coated on the organic semiconductor film and heated at 60-150° C. for 5-360 s to obtain a doped organic semiconductor.

[0095] Herein, “a 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 in the range consisting of any two of the above values, and the heating time can be selected as 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 in the range consisting of any two of the above values.

[0097] In some embodiments, the transition metal catalyst comprises a transition metal complex, and the method for n-type doping of an organic semiconductor comprises the following steps:

[0098] A mixture including a transition metal complex, an N-type organic semiconductor and an anion dopant solution is coated on a substrate and heated at 60-150° C. for 5-360 s to obtain a doped organic semiconductor.

[0099] In this article, "a mixture including a transition metal complex, an N-type organic semiconductor and an anion dopant solution" may not contain a solvent other than the anion dopant solution, and both the N-type organic semiconductor and the transition metal complex are 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 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 in the range consisting of any two of the above values, and the heating time can be selected as 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 in the range consisting of any two of the above values.

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

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

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

[0104] Herein, “a solution containing an N-type organic semiconductor” refers to dissolving the N-type organic semiconductor in a solvent for subsequent coating.

[0105] In this article, "a mixture including a transition metal complex and an anion dopant solvent" may not contain any solvent other than the anion dopant solution, and the transition metal complex is soluble in the anion dopant solution for subsequent coating; or it may contain a solvent that can dissolve 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 as 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, or a value in the range consisting of any two of the above values, and the heating time can be selected as 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 in the range consisting of any two of the above values.

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

[0108] In some embodiments, the molar ratio of the anion dopant solution to the transition metal catalyst is (1000~20):1. In some embodiments, the molar ratio of the anion dopant solution to the transition metal catalyst can be selected as 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 in the range consisting of 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 1 nm, 2 nm, 3 nm, 4 nm, 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, or a value in a range consisting of any two of the above values; the nominal thickness of the transition metal nanoparticles can be 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 in a range consisting of any two of the above values; the particle density of the transition metal nanoparticles can be 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 in the range consisting of 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 tested by any known test method. As an example, the particle size and particle density of the transition metal nanoparticles can be calibrated by a transmission electron microscope (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 in a range consisting of any two of the above values.

[0112] The present application proposes the application of an n-type doping method of an organic semiconductor in some embodiments in the preparation of an organic optoelectronic device.

[0113] Example

[0114] The following examples are provided for a better understanding of the present application, are not limited to the best mode of implementation, and do not limit the content and scope of the present application. If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be carried out. If the manufacturer of the reagents or instruments is not specified, they are all conventional reagent products that can be obtained commercially.

[0115] In the following examples and comparative examples, the sources of PDTzTI, PDTzTIT-2F, PDTzTIT, PBTzI, and PBTI refer to 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 number: 202110163646.1, application date: 2021-02-05);

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

[0118] 1. Preparation method

[0119] Example 1

[0120] Preparation of anion dopant solution: In a 30 ml glass sample bottle, 10 g of 1 M tetrabutylammonium hydroxide methanol solution (purchased from Sigma-Aldrich) and 4.3 g of anhydrous N,N-dimethylformamide solvent were mixed, and then 2 g of 3A molecular sieve (purchased from Alfa-Aesar) was added, stirred evenly, reacted at 20-25°C for 10 h, and then filtered to remove the solid to obtain anion dopant solution; wherein the molar ratio of tetrabutylammonium hydroxide to N,N-dimethylformamide is 1:10, and the mass ratio of the mole of tetrabutylammonium hydroxide to the mass of 3A molecular sieve is: 0.012 mol:2 g.

[0121] n-type doping of organic semiconductors:

[0122] First, a vacuum thermal evaporator was used to deposit gold on a cleaned glass substrate at a rate of 0.1Å / s to form transition metal nanoparticles Au (the Angstrom Nexdep evaporator showed that the nominal thickness of the transition metal nanoparticles Au was 0.1nm and the particle size of the transition metal nanoparticles Au was 1.4nm);

[0123] Then, the N-type organic semiconductor PDI-C6C7 was dissolved in anhydrous chloroform solvent (concentration 10 mg / mL), 1 mL of PDI-C6C7 solution was mixed with an anion dopant solution (the molar ratio of the anion dopant solution to PDI-C6C7 in the PDI-C6C7 solution was 2:1), and stirred evenly; then, the mixed solution of the PDI-C6C7 solution and the anion dopant solution was 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 10s 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] Embodiment 8-10

[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 anion dopant solutions and n-type doping of organic semiconductors in Examples 11 to 13 are similar to the anion dopant solution and n-type doping of organic semiconductors in Example 1, except that the molar ratio of the ammonium hydroxide anion tetrabutylammonium hydroxide and the amide solvent N,N-dimethylformamide used to prepare the anion dopant solution in Example 1 is adjusted to 1:2, 1:5, and 1:30, respectively, as shown in Tables 1 and 2.

[0132] Embodiment 14-15

[0133] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor 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 anion tetrabutylammonium hydroxide used to prepare the anion dopant solution in Example 1 to the mass ratio of the 3A molecular sieve is adjusted to 0.012 mol:0.5 g and 0.012 mol:2.5 g, respectively, as shown in Tables 1 and 2 for details.

[0134] Embodiments 16 to 19

[0135] The anion dopant solution and the n-type doping of the organic semiconductor in Examples 16 to 19 are similar to the preparation methods 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 semiconductor in the n-type doping method of the organic semiconductor in Example 1 is adjusted to NDI-EH, N2200, PDTzTI, and f-BTI2TEG-FT, respectively, as shown in Tables 1 and 2.

[0136] Embodiment 20-21

[0137] The anion dopant solution and the n-type doping of the organic semiconductor in Examples 20 to 21 are similar to the preparation methods 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 of the n-type doping method of the organic semiconductor in Example 1 is adjusted to transition metal nanoparticles Pt and transition metal nanoparticles Cu, as shown in Tables 1 and 2.

[0138] Embodiment 22

[0139] The anion dopant solution and the n-type doping of the organic semiconductor in Example 22 are similar to the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the raw material transition metal catalyst of the n-type doping method of the organic semiconductor in Example 1 is adjusted to Pd2(dba)3, and the n-type doping of the organic semiconductor is specifically as follows:

[0140] First, an N-type organic semiconductor PDI-C6C7 is dissolved in an anhydrous chloroform solvent (concentration 10 mg / mL), and then Pd2(dba)3 is dissolved in an anhydrous chloroform solvent. Then, the PDI-C6C7 solution, an anion dopant solution and a Pd2(dba)3 solution are mixed and stirred evenly, wherein the molar ratio of PDI-C6C7 and Pd2(dba)3 in the anion dopant solution and the PDI-C6C7 solution is 100:50:1; then, a mixed solution of the PDI-C6C7 solution, the Pd2(dba)3 solution and the anion dopant solution is spin-coated on a glass substrate 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.

[0141] Embodiment 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 of 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 Tables 1 and 2 for details.

[0143] Embodiment 24-25

[0144] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Examples 24 to 25 are similar to those 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 Pd2(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 amount of the transition metal complex Pd2(dba)3), as shown in Tables 1 and 2.

[0145] Embodiments 26 to 28

[0146] The anion dopant solution and the n-type doping of the organic semiconductor in Examples 26 to 28 are similar to the preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Example 1, except that the molar ratio of the anion dopant solution in the n-type doping method of the organic semiconductor in Example 1 to the PDI-C6C7 in the PDI-C6C7 solution is adjusted to 1:1, 5:1, and 10:1, respectively (achieved by adjusting the amount of the anion dopant solution), as shown in Tables 1 and 2.

[0147] Embodiment 29

[0148] The anion dopant solution and the n-type doping of the organic semiconductor in Example 29 are similar to 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, a vacuum thermal evaporator was used to deposit gold on a cleaned glass substrate at a rate of 0.1Å / s to form transition metal nanoparticles Au (the Angstrom Nexdep evaporator showed that the nominal thickness of the transition metal nanoparticles Au was 0.1nm and the particle size of the transition metal nanoparticles Au was 1.4nm);

[0150] Then, the N-type organic semiconductor PDI-C6C7 was dissolved in anhydrous chloroform solvent (concentration 10 mg / mL), and 100 μL of the PDI-C6C7 solution was spin-coated on the cleaned glass substrate at a speed of 1500 rpm at 20-25°C to obtain an organic semiconductor film;

[0151] Finally, the anion dopant solution (the molar ratio of the anion dopant solution to PDI-C6C7 in the PDI-C6C7 solution is 2:1) is spin-coated on the organic semiconductor film at a rotation speed of 2000 rpm, and then heated at 120°C for 10 seconds to complete the catalytic doping reaction to obtain a doped organic semiconductor.

[0152] Embodiment 30

[0153] The anion dopant solution and the n-type doping of the organic semiconductor in Example 30 are similar to 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, the N-type organic semiconductor PDI-C6C7 was dissolved in anhydrous chloroform solvent (concentration 10 mg / mL), and 100 μL of the PDI-C6C7 solution was spin-coated on a cleaned glass substrate at a speed of 1500 rpm at 20-25°C to obtain an organic semiconductor film;

[0155] Then, Pd2(dba)3 is dissolved in isobutyl acetate solvent, and the Pd2(dba)3 solution is mixed with an anion dopant solution, wherein the molar ratio of the anion dopant solution to Pd2(dba)3 is 100:1, and stirred evenly; then, the mixed solution of the Pd2(dba)3 solution and the anion dopant solution is spin-coated on the organic semiconductor film at a rotation speed of 1500 rpm, and then heated at 120°C for 10s to complete the catalytic doping reaction to obtain a doped organic semiconductor.

[0156] Comparative Example

[0157] Comparative Example 1

[0158] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Comparative Example 1 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 ammonium hydroxide anion for preparing the anion dopant solution in Example 1 is adjusted to tetramethylammonium hydroxide, as shown in Tables 1 and 2 for details.

[0159] Comparative Example 2

[0160] The preparation methods of the anion dopant solution and the n-type doping of the organic semiconductor in Comparative Example 2 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 ammonium hydroxide anion for preparing the anion dopant solution in Example 1 is adjusted to tetraoctadecyl ammonium hydroxide, as shown in Tables 1 and 2 for details.

[0161] Comparative Examples 3~5

[0162] The preparation methods of the anion dopant solutions and n-type doping of organic semiconductors in Comparative Examples 3 to 5 are similar to those of the anion dopant solution and n-type doping of organic semiconductors in Comparative Example 1, except that the molar ratio of the ammonium hydroxide anion tetrabutylammonium hydroxide and the amide solvent N,N-dimethylformamide used to prepare the anion dopant solution in Comparative Example 1 is adjusted to 1:2, 1:5, and 1:10, respectively, as shown in Tables 1 and 2.

[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, as shown in 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 n-type doping of the organic semiconductor in Comparative Example 1 is not introduced into the anion doping solution, and the molecular dopant N-DMBI-H is added; the n-type doping method of the organic semiconductor is specifically as follows:

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

[0168] Then, the N-type organic semiconductors PDI-C6C7 and N-DMBI-H were dissolved in anhydrous chloroform solvent (the molar ratio of PDI-C6C7 to N-DMBI-H was 1:1) and stirred evenly; then, the mixed solution of PDI-C6C7 and N-DMBI-H was 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.

[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 no transition metal catalyst is introduced into the n-type doping of the organic semiconductor in Example 1, as shown in 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 no transition metal catalyst is introduced into the n-type doping of the organic semiconductor in Example 16, as shown in 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 no transition metal catalyst is introduced into the n-type doping of the organic semiconductor in Example 17, as shown in 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 no transition metal catalyst is introduced into the n-type doping of the organic semiconductor in Example 18, as shown in 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 no transition metal catalyst is introduced into the n-type doping of the organic semiconductor in Example 19, as shown in 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 semiconductors

[0183]

[0184]

[0185] 2. Test Method

[0186] 1) Conductivity test

[0187] The embodiment group used 30nm Au vacuum-evaporated 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 100um and 2mm, respectively. After sample preparation, the samples placed in the glove box were tested for IV curve using the Keithley 4200-SCS semiconductor characterization system, and then their 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 the Tencor KLAD-120 step profiler.

[0188] 2) UV-vis-NIR testing

[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 spectrum test diagrams of each embodiment and comparative example are shown in Figure 1 to Figure 9 .

[0190] Table 3 Performance parameters of various embodiments and comparative examples

[0191]

[0192] III. Analysis of test results of various embodiments and comparative examples

[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 N-type organic semiconductors under the action of transition metal catalysts, 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 the anion dopant solution and N-type organic semiconductors under the action of transition metal catalysts is also improved.

[0194] See also Figure 1 As can be seen from Example 1 and Comparative Example 8, the organic semiconductor PDI-C6C7 film is very obviously doped in the presence of transition metal Au nanoparticle catalysts. A strong PDI-C6C7˙ - Radical absorption peak (600nm~1000nm); In the absence of catalyst, PDI-C6C7 film cannot be doped; In addition, it can be seen from Example 1 and Comparative Example 7 that the organic semiconductor PDI-C6C7 film doped with anion dopant solution and organic hydride N-DMBI-H catalyzed exhibits similar PDI-C6C7˙ - The free radical absorption peak, and the UV peak of the organic semiconductor PDI-C6C7 film after catalytic doping by the anion dopant solution is slightly higher, which indicates that the anion dopant solution in this application has the same catalytic doping behavior as N-DMBI-H, and the doping effect is slightly better.

[0195] See also Figure 1 , Figure 2 a)~ Figure 2 b), it can be seen from Examples 1 to 7 and Comparative Examples 1 to 2 that the types of ammonium hydroxide anions and amide solvents used to prepare the anion dopant solution have an effect on its catalytic doping behavior, wherein the cation of the ammonium hydroxide anion cannot be too large or too small. When the cation is too small, for example, when tetramethyl ammonium hydroxide is used, 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, for example, when tetraoctadecyl ammonium hydroxide is used, the volume of the dopant is too large, which will hinder the diffusion process of the dopant in the organic semiconductor film, thereby 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 sieves in the preparation of the anion dopant solution is very critical. The molecular sieves may play a role in absorbing the reaction products of ammonium hydroxide anions and amide solvents, which is beneficial to the subsequent catalytic doping efficiency of the anion dopant solution.

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

[0197] See also 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 molecular sieves to be 1 mol:(40 to 200) g is beneficial for more molecular sieves to fully promote the reaction between ammonium hydroxide anions and amide solvents, thereby facilitating the anion dopant solution to subsequently exhibit stronger doping behavior in the organic semiconductor film.

[0198] See also Figure 1 , Figure 5 a)~ Figure 5 d), it can be seen from Example 1, Examples 16 to 19, and Comparative Examples 8 to 12 that the catalytic doping behavior of the anion dopant solvent is universal for a variety of organic semiconductors, and the electrical conductivity of the organic semiconductor film is effectively improved after being catalytically doped with the anion dopant solution and the transition metal catalyst, especially the electrical conductivity of the imide organic semiconductor is greatly improved after catalytic doping.

[0199] See also Figure 6 As can be seen from Examples 20 to 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 also Figure 7 As can be seen from Examples 24 to 25, the presence of a small amount of transition metal catalyst can effectively promote the occurrence of the anion dopant solution-catalyzed doping reaction.

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

[0202] See also Fig. 9 As can be seen from Examples 29 to 30, the doping of organic semiconductors can also be performed by sequential catalytic doping, and the effect of sequential catalytic doping is comparable to that of 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 aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application, and they should all be included in the scope of the claims and specification of the present application. In particular, as long as there is no structural conflict, the various technical features mentioned in the various embodiments can be combined in any way. The present application is not limited to the specific embodiments disclosed herein, 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 , R 17 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 Each independently includes 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.

2. The method for n-type doping of an organic semiconductor according to claim 1, characterized in that: 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 to 40; The transition metal catalyst comprises at least one of transition metal nanoparticles and transition metal complexes. 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. 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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