CN107573489B - Polymer semiconductor containing bispyridazole derivative receptor and preparation method and application thereof - Google Patents
Polymer semiconductor containing bispyridazole derivative receptor and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of polymer semiconductor materials, and discloses a polymer semiconductor containing a bispyridazole derivative receptor, and a preparation method and application thereof. The structure of the polymer semiconductor is shown as a formula (I). The preparation method comprises the following steps: (1) 2-tributyltin-4-alkylthiophene reacts with dibromo-benzobisoxazole derivative to prepare an intermediate a; (2) reacting the compound a with dibutyl tin b to obtain a compound c; (3) reacting the compound c with N-bromosuccinimide to obtain M1; (4) m1 and (E) -bis 1,2- (tri-n-butylstannyl) ethylene are subjected to palladium-catalyzed coupling reaction to obtain a final product. The synthesis route of the invention is simple and efficient, the raw materials are easy to obtain, the cost is low, the universality is high, the repeatability is good, the field effect transistor prepared by taking the polymer semiconductor of the invention as an active layer obtains outstanding bipolar transmission characteristics, and the market prospect is wide.
Description
Technical Field
The invention belongs to the field of polymer semiconductor materials, and relates to a polymer semiconductor containing a bispyridyl diazole derivative receptor, and a preparation method and application thereof.
Background
The bipolar polymer semiconductor material can simplify the preparation process of a bipolar logic complementary circuit and reduce the construction cost, but the material faces the challenges of low mobility, unbalanced carrier transmission, scarce construction units and the like. At present, the high-mobility bipolar polymer semiconductor material is mainly constructed by pyrrolopyrroledione and isoindigo derivative units, and only a few polymer semiconductor materials have hole and electron mobilities of more than 4.0cm at the same time2/V s (J.Am.chem.Soc.,2013,135,9540; chem.Mater.,2014,26, 696; adv.Mater.,2015,27, 4963). Therefore, exploring new design strategies, seeking new building blocks, remains one of the effective ways to address these challenges.
The pyridadiazole derivative is an electron acceptor unit which is rich in heteroatoms, strong in electron affinity and good in coplanarity, and is widely used for developing p-type organic small molecules and polymer semiconductor materials (J.Am.chem.Soc.,2013,135,2298; J.Am.chem.Soc.,2012,134,20609). However, no electron-transporting type pyridine diazole derivative-based polymer semiconductor material has been reported. Therefore, the development of novel electron-transporting type pyridine diazole derivative polymer semiconductor materials and the research of the performance of thin film field effect transistor devices thereof have important significance.
Disclosure of Invention
The invention aims to provide a polymer semiconductor material containing a bispyridazole derivative receptor, and a preparation method and application thereof. The invention aims to provide a compound, a polymer and a polymer semiconductor material, wherein the polymer semiconductor material has high mobility; the invention also provides a polymer field effect transistor with the polymer semiconductor.
A polymer semiconductor containing a bispyridazole derivative receptor is a polymer with a molecular structure general formula shown in a formula (I):
in the formula (I), R is any one of straight-chain alkyl with 6-16 total carbon atoms or branched-chain alkyl with 8-30 total carbon atoms;
ar is the following three cases: absent, a carbon-carbon double bond or a carbon-carbon triple bond;
x is oxygen atom, sulfur atom, selenium atom or tellurium atom;
n is an integer of 10 to 300.
In the formula (I), n is an integer of 10 to 300, preferably an integer of 50 to 150, and more preferably 100.
The straight-chain alkyl group having 6 to 16 carbon atoms in total may specifically be, but is not limited to, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl or n-hexadecyl; wherein the branched alkyl group having 8 to 30 carbon atoms in total may be, but not limited to, 2-ethylhexyl group, 2-butylhexyl group, 2-hexyloctyl group, 4-hexyldecyl group, 3-hexylundecyl group, 2-octyldecyl group, 2-octyldodecyl group, 3-octyltridecyl group, 2-decyldodecyl group, 2-decyltetradecyl group, 3-decylpentadecyl group, 2-dodecylhexadecyl group, 4-octyltetradecyl group, 4-decylhexadecyl group, 4-hexyldecyl group, 4-octyldodecyl group, 4-decyltetradecyl group or 4-dodecylhexadecyl group;
more preferably, the polymer semiconductor shown in the formula (I) is specifically polymer PBPTV or PBPT2V shown as follows:
in the PBPTV and PBPT2V, n is defined as in formula (I). n may specifically be an integer of 10 to 300, more specifically an integer of 50 to 150, and most specifically 100.
As a general inventive concept, the present invention also provides a method for preparing the above-mentioned polymer semiconductor containing the bispyridazole derivative acceptor, the method comprising the steps of:
(1) reacting 2-tributyltin-4-alkylthiophene with a dibromo-benzodiazole derivative to obtain an intermediate a, wherein the structural formula of the 2-tributyltin-4-alkylthiophene is as follows:
wherein R is any one of linear alkyl with 6-16 carbon atoms in total or branched alkyl with 8-30 carbon atoms in total;
the structural formula of the dibromo-benzodiazole derivative is as follows:
wherein X is an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom;
the structural formula of the intermediate a is as follows:
wherein R is any one of linear alkyl with 6-16 carbon atoms in total or branched alkyl with 8-30 carbon atoms in total;
(2) under the protection of nitrogen, carrying out palladium catalytic coupling reaction on the intermediate compound a and the compound b to obtain a compound c; the structural formula of the compound b is as follows:
wherein Ar is a carbon-carbon single bond, double bond or triple bond;
the intermediate compound c has a structural formula:
wherein R is any one of linear alkyl with 6-16 carbon atoms in total or branched alkyl with 8-30 carbon atoms in total; ar is a carbon-carbon single bond, double bond or triple bond; x is oxygen atom, sulfur atom, selenium atom or tellurium atom;
(3) under the protection of nitrogen, performing electrophilic reaction on the intermediate compound c and N-bromosuccinimide to obtain a monomer compound of a formula M1, wherein the structural formula is as follows:
wherein R is any one of linear alkyl with 6-16 carbon atoms in total or branched alkyl with 8-30 carbon atoms in total; ar is a carbon-carbon single bond, double bond or triple bond; x is oxygen atom, sulfur atom, selenium atom or tellurium atom;
(4) under the protection of inert gas, a monomer shown as a formula M1 and a monomer shown as (E) -bis 1,2- (tri-n-butylstannyl) ethylene are placed in a solvent for palladium-catalyzed coupling polymerization reaction, and after the reaction is finished, a polymer shown as a formula (I) is obtained, so that the polymer semiconductor containing the bipyridine diazole derivative receptor is obtained.
Preferably, in the preparation method of the polymer semiconductor material containing the bispyridazole derivative acceptor, the specific operation of the step (1) is as follows: under the protection of nitrogen, adding 2-tributyltin-4-alkylthiophene, dibromo-benzodiazole derivatives (purchased commercially), bis (triphenylphosphine) palladium dichloride catalyst and toluene solvent into a three-necked bottle, refluxing, stirring, reacting for 1-10 hours, cooling to room temperature, extracting with dichloromethane, drying an organic phase with magnesium sulfate, spin-drying the solvent to obtain a crude product, and purifying with a silica gel chromatographic column to obtain an oily liquid a; wherein the molar ratio of the fed reaction raw materials is as follows: 2-tributyltin-4-alkylthiophene: bis (triphenylphosphine) palladium dichloride ═ 1: 1-2: 0.01-0.1, preferably in a ratio of 1: 1.2: 0.05.
preferably, in the preparation method of the polymer semiconductor material containing the bispyridazole derivative acceptor, the specific operation of the step (2) is as follows: under the protection of nitrogen, adding an intermediate compound a, a compound b, a tetrakis (triphenylphosphine) palladium catalyst and a toluene solvent into a three-necked flask, refluxing, stirring, reacting for 10-72 hours, cooling to room temperature, extracting with dichloromethane, drying an organic phase with anhydrous magnesium sulfate, spin-drying the solvent to obtain a crude product, and purifying with a silica gel chromatographic column to obtain a red oily liquid c; wherein the molar ratio of the raw materials for reaction is that the compound b: intermediate compound a: tetrakis (triphenylphosphine) palladium ═ 1: 2.0-6.0: 0.01-0.1. wherein, the reaction time is preferably 24 hours, and the feeding proportion is preferably 1: 3: 0.05.
preferably, in the preparation method of the polymer semiconductor material containing the bispyridazole derivative acceptor, the specific operation of the step (3) is as follows: under the protection of nitrogen, adding trichloromethane and a compound c into a three-neck flask, placing the three-neck flask in an ice bath, slowly adding N-bromosuccinimide into a reaction flask in batches, stirring the mixture at room temperature for reaction for 5 to 24 hours, extracting the mixture by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, spin-drying the solvent to obtain a crude product, and purifying the crude product by using a silica gel chromatographic column to obtain a target product M1; wherein the molar ratio of the raw materials for reaction is that the compound c: n-bromosuccinimide ═ 1: 2.0-3.0. wherein, the reaction time is preferably 8 hours, and the feeding proportion is preferably 1: 2.5.
preferably, in the preparation method of the polymer semiconductor material containing the bispyridazole derivative acceptor, the specific operation of the step (4) is as follows: adding M1, (E) -bis 1,2- (tri-n-butylstannyl) ethylene, a solvent and a palladium catalyst into a three-necked flask under the protection of nitrogen, carrying out reflux stirring reaction at the temperature of 100 ℃ and 150 ℃ for 10-72 hours, cooling to room temperature, settling reaction liquid in methanol, carrying out suction filtration, collecting a blue-brown solid, purifying a target polymer by using a Soxhlet extractor, and spin-drying the solvent to obtain a black solid with golden gloss; wherein the molar ratio of the raw materials for reaction is that a compound M1: (E) -bis 1,2- (tri-n-butylstannyl) ethylene: palladium catalyst 1: 1.0-1.5: 0.01-0.1. among them, the preferable reaction temperature is 120 ℃; the preferred reaction time is 48 hours; the preferable feeding ratio is 1: 1: 0.05. the palladium catalyst is at least one of tetrakis (triphenylphosphine) palladium, palladium acetate, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium, preferably bis (triphenylphosphine) palladium dichloride; the solvent is selected from at least one of toluene, xylene, methylnaphthalene, chlorobenzene, dichlorobenzene, dichloronaphthalene, trichlorobenzene, chloronaphthalene and tetrahydrofuran, and chlorobenzene is preferred.
The present invention also provides, as a general inventive concept, an application of any one of the polymer semiconductor materials containing the bipyridine diazole derivative acceptor shown in the formula (I) above in the preparation of a thin film FET device. In addition, the thin film FET device using the polymer containing the bipyridine diazole derivative acceptor shown in the formula (I) as an organic semiconductor active layer also belongs to the protection scope of the invention.
The invention designs a series of polymer semiconductor materials containing bispyridyl diazole derivative receptors by utilizing an isotactic double-receptor strategy, aiming at obtaining the electron transmission characteristic. The main design idea is as follows: 1) compared with a single electron acceptor, the double electron acceptor can enhance the electric lack density of the polymer repeating unit and improve the electron affinity of a molecular chain; 2) the relative position of pyridine nitrogen is controlled by chemical method, and the polymer molecular skeleton with regular region can be constructed, so that the assembling capacity and current carrier between polymer molecular chains can be improvedMobility; 3) the large pi conjugated skeleton rich in hetero atoms is constructed, so that the pi-pi interaction between molecular chains can be enhanced, and the carrier mobility is improved. The research shows that: in the air, the top gate FET device taking the bipyridine diazole derivative acceptor-based polymer semiconductor material as the organic semiconductor active layer shows ultra-high bipolar charge transport characteristics, and the highest hole and electron mobility of the top gate FET device are respectively 6.87cm2/V s and 8.49cm2and/V s, the polymer semiconductor material has wide market prospect in organic electronic devices such as bipolar inverters, logic circuits, bipolar field effect light-emitting diodes and the like.
The invention has the advantages that:
1. the synthesis method has the advantages of strong universality, short and efficient synthesis route, low development cost, high synthesis yield, easily available reaction raw materials and the like, can be popularized and applied to the amplified synthesis and production in the industry, and can also be popularized and applied to the synthesis of other various polymer semiconductors containing the bipyridine diazole derivative receptor.
2. The main chain of the polymer molecule has a large pi conjugated skeleton rich in hetero atoms, so that the pi-pi interaction between molecular chains can be enhanced, and the carrier mobility is improved.
3. The polymer semiconductor material contains double electron acceptor units with strong electron withdrawing capacity, can enhance the electron-deficient density of polymer repeating units, improves the electron affinity of molecular chains, and obtains high electron mobility.
4. The invention adopts a chemical method to accurately control the relative position of pyridine nitrogen, and can construct a polymer molecular skeleton with regular regions, thereby improving the assembling capacity among polymer molecular chains and the carrier mobility.
5. The bipyridine diazole derivative acceptor-based polymer semiconductor disclosed by the invention is used in a thin film FET device, and shows excellent bipolar charge transport characteristics, and the highest hole mobility and the highest electron mobility of the bipyridine diazole derivative acceptor-based polymer semiconductor are respectively 6.87cm2/V s and 8.49cm2and/V s. Meanwhile, the FET device shows excellent stability in a high-humidity air environment, and the polymer semiconductor is fully displayedThe material has wide market prospect in organic electronic devices such as bipolar reversers, logic circuits, bipolar field effect light-emitting diodes and the like.
Drawings
FIG. 1 shows the absorption spectra of PBPTV polymer containing bispyridazole derivative acceptor prepared in example 1 of the present invention in chlorobenzene solution and quartz plate.
FIG. 2 shows the absorption spectra of the polymer PBPT2V containing bispyridazole derivative acceptor prepared in example 2 of the present invention on chlorobenzene solution and quartz plate.
Fig. 3 is a schematic structural diagram of an FET device in which a polymer PBPTV or PBPT2V containing a bispyridiazole derivative acceptor prepared in an embodiment of the present invention is an organic active semiconductor layer.
Fig. 4 is a graph of output characteristics of a FET device in which PBPTV, which is a polymer containing a bispyridazole derivative acceptor prepared in example 1 of the present invention, is an organic active semiconductor layer.
Fig. 5 is a graph showing transfer characteristics of a FET device in which PBPTV, a polymer containing a bispyridazole derivative acceptor, prepared in example 1 of the present invention, is an organic active semiconductor layer.
Fig. 6 is a graph of output characteristics of an FET device using the polymer PBPT2V containing the bispyridazole derivative acceptor prepared in example 2 of the present invention as an organic active semiconductor layer.
Fig. 7 is a graph showing the transfer characteristics of an FET device using the polymer PBPT2V containing the bispyridazole derivative acceptor prepared in example 2 of the present invention as an organic active semiconductor layer.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified. The reaction substrates 4, 7-dibromo- [1,2,5] thiadiazolo [3,4-c ] pyridine and (E) -bis 1,2- (tri-n-butylstannyl) ethylene used in the following examples were all commercially available, and the remaining reaction solvents and catalysts used were all commercially available.
Detailed description of the preferred embodiment 1
The invention relates to a polymer semiconductor containing a bispyridyl diazole derivative receptor, in particular to a polymer semiconductor material with a chemical structure of PBPTV, and the synthetic route of the polymer semiconductor material is as follows:
(1) synthesis of an intermediate of formula a: under nitrogen protection, tributyl- [4- (2-decyltetradecyl) thiophen-2-yl ] stannane (5.8g,8.2mmol), 4, 7-dibromo- [1,2,5] thiadiazolo [3,4-c ] pyridine (2.0g,6.8mmol), bis (triphenylphosphine) palladium dichloride (0.24g,0.34mmol), and 70mL of toluene solvent were added to a three-necked flask. After refluxing for 4 hours, it was cooled to room temperature. Extracting with dichloromethane, drying the organic phase with magnesium sulfate, and spin-drying the solvent to obtain a crude product. Then purifying by a silica gel chromatographic column to obtain the target product 7-bromo-4- (4- (2-decyltetradecyl) thiophene-2-yl) - [1,2,5] thiazole [3,4-c ] pyridine with the yield equal to 85%.
The structural characterization data is as follows,
1H NMR(400MHz,CDCl3),δ(ppm):8.66(s,1H),8.53(s,1H),7.24(s,1H),2.65–2.64(d,2H),1.70(br,1H),1.30–1.24(m,40H),0.89-0.85(m,6H)；MALDI-TOF-MS:m/z＝636.19(M+).
as can be seen from the above, the compound has a correct structure and is the shown compound 7-bromo-4- (4- (2-decyltetradecyl) thiophen-2-yl) - [1,2,5] thiazole [3,4-c ] pyridine.
(2) Synthesis of an intermediate of formula c: under nitrogen protection, compound b (n-hexabutylditin) (0.33g,0.54mmol), compound a (1.03g,1.62mmol), tetrakis (triphenylphosphine) palladium catalyst (0.03g, 0.03mmol), and toluene solvent were added to a three-necked flask. After 24 hours of reflux, cool to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. Purifying by silica gel chromatographic column to obtain the target product 4, 4' -bis (4- (2-decyltetradecyl) thiophene-2-yl) -bis [1,2,5] thiazole [3,4-c ] pyridine with yield of 60%.
The structural characterization data is as follows,
1H NMR(400MHz,CDCl3),δ(ppm):9.44(s,2H),8.63(s,2H),7.25(s,2H),2.69-2.67(d,4H),1.74(br,2H),1.33–1.25(m,80H),0.87-0.85(t,12H)；MALDI-TOF-MS:m/z＝1110.39(M+).
as is clear from the above, the compound has a correct structure and is 4, 4' -bis (4- (2-decyltetradecyl) thiophen-2-yl) -bis [1,2,5] thiazolo [3,4-c ] pyridine.
(3) Synthesis of monomer of formula M1: under nitrogen, 20mL of chloroform and compound c (0.35g,0.3mmol) were added to a three-necked flask. It was placed in an ice bath and 4mL of N, N' -Dimethylformamide (DMF) in N-bromosuccinimide (NBS, 0.14g,0.8mmol) was added slowly to the reaction by syringe. After the dropwise addition, stirring at room temperature for 8 hours, extracting by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. Purifying by silica gel chromatographic column to obtain the target product 4,4 '-bis (5-bromo-4- (2-decyltetradecyl) thiophen-2-yl) -7, 7' -di [1,2,5] thiazole [3,4-c ] pyridine with yield equal to 90%.
The structural characterization data is as follows,
1H NMR(400MHz,CDCl3),δ(ppm):9.42(s,2H),8.44(s,2H),2.63–2.61(d,4H),1.80(br,2H),1.34–1.24(m,80H),0.88–0.85(t,12H)；MALDI-TOF-MS:m/z＝1267.11(M+).
as can be seen from the above, this compound has a correct structure and is 4,4 '-bis (5-bromo-4- (2-decyltetradecyl) thiophen-2-yl) -7, 7' -bis [1,2,5] thiazolo [3,4-c ] pyridine, which is a comonomer compound represented by formula M1 used in example 1.
(4) Synthesis of Polymer PBPTV having the formula (I): to a 25mL three-necked flask, under nitrogen protection, the monomeric compound of formula M1, 4 '-bis (5-bromo-4- (2-decyltetradecyl) thiophen-2-yl) -7, 7' -bis [1,2,5] thiazolo [3,4-c ] pyridine (152mg,0.12mmol), (E) -bis 1,2- (tri-n-butylstannyl) ethylene (73mg,0.12mmol), bis (triphenylphosphine) palladium dichloride (4mg,0.006mmol), and chlorobenzene (5mL) were added in sequence, thawed under argon for three freeze-pump-deoxygenation cycles, and the reaction mixture was heated to 120 ℃ for 48 h. After cooling, 200mL of methanol was added, stirred at room temperature for 2h, and filtered. The obtained polymer was extracted by a Soxhlet extractor. Extracting with methanol, acetone and n-hexane to colorless, removing small molecules and catalyst, and extracting with chloroform to obtain final product with yield of 80%.
The structural characterization data of the resulting polymer are as follows:
molecular weight characterization data are as follows: the weight average molecular weight was 50.6kDa, the number average molecular weight was 22.7kDa, and the polymer molecular weight distribution index was 2.23.
Elemental analysis (%) calculation (C)68H106N6S4)nC, 71.90; h, 9.41; n, 7.40; detects C, 71.80; h, 9.38; and N, 7.46.
From the above, the product has a correct structure and is a polymer PBPTV shown in formula (I).
Specific example 2
The invention relates to a polymer semiconductor containing a bispyridyl diazole derivative receptor, in particular to a polymer semiconductor material with a chemical structure of PBPT2V, and the synthetic route is as follows:
(1) synthesis of an intermediate of formula a: synthesized according to the synthesis method described above in example 1.
(2) Synthesis of an intermediate of formula c: under nitrogen protection, compound b [ (E) -1, 2-bis (tributyltin-yl) ethylene ] (0.56g,0.92mmol), compound a (1.75g,2.76mmol), tetrakis (triphenylphosphine) palladium catalyst (0.053g, 0.046mmol) and toluene solvent were added to a three-necked flask. After 24 hours of reflux, cool to room temperature. Extracting with dichloromethane, drying the organic phase with anhydrous magnesium sulfate, and spin-drying the solvent to obtain a crude product. Purifying by silica gel chromatographic column to obtain the target product (E) -1, 2-bis (4-4- (2-decyltetradecyl) thiophene-2-yl) - [1,2,5] thiazole [3,4-c ] pyridine-7-yl) ethylene with yield of 80%.
The structural characterization data is as follows,
1H NMR(400MHz,CDCl3),δ(ppm):8.67(s,2H),8.57(s,2H),8.54(s,2H),7.22(s,2H),2.66-2.65(d,4H),1.72(br,2H),1.32–1.25(m,80H),0.89-0.85(t,12H)；MALDI-TOF-MS:m/z＝1136.51(M+).
as can be seen from the above, the compound has a correct structure and is an intermediate compound (E) -1, 2-bis (4-4- (2-decyltetradecyl) thiophen-2-yl) - [1,2,5] thiazolo [3,4-c ] pyridin-7-yl) ethylene.
(3) Synthesis of an intermediate of formula M1: under nitrogen, 20mL of chloroform and compound c (0.50g,0.44mmol) were added to a three-necked flask. It was placed in an ice bath and 4mL of N, N' -dimethylformamide dissolved with N-bromosuccinimide (0.20g,1.10mmol) was added slowly to the reaction by syringe. After the dropwise addition, the reaction is carried out for 8 hours at room temperature, dichloromethane is adopted for extraction, the organic phase is dried by anhydrous magnesium sulfate, and the solvent is dried in a spinning mode to obtain a crude product. Purifying by silica gel chromatographic column to obtain the target product (E) -1, 2-bis (4- (5-bromo-4- (2-decyltetradecyl) thiophene-2-yl) - [1,2,5] thiazole [3,4-c ] pyridine-7-yl) ethylene with yield of 88%.
The structural characterization data is as follows,
1H NMR(400MHz,CDCl3),δ(ppm):8.47(s,2H),8.30(s,2H),8.26(s,2H),2.54-2.52(d,4H),1.75(br,2H),1.31-1.24(m,80H),0.88-0.85(t,12H)；MALDI-TOF-MS:m/z＝1293.38(M+).
as can be seen from the above, the compound has a correct structure and is a comonomer compound (E) -1, 2-bis (4- (5-bromo-4- (2-decyltetradecyl) thiophen-2-yl) - [1,2,5] thiazolo [3,4-c ] pyridin-7-yl) ethylene represented by formula M1.
(4) Synthesis of Polymer PBPT2V having the chemical formula (I): into a 25mL three-necked flask, the monomer compound represented by the formula M1 (E) -1, 2-bis (4- (5-bromo-4- (2-decyltetradecyl) thiophen-2-yl) - [1,2,5] thiazol [3,4-c ] pyridin-7-yl) ethylene (259mg,0.2mmol), (E) -bis 1,2- (tri-n-butylstannyl) ethylene (121mg,0.2mmol), bis (triphenylphosphine) palladium dichloride (7mg,0.01mmol), and chlorobenzene (5mL) were added in this order, deoxygenated by three freeze-pump-thaw cycles under argon, and the reaction mixture was heated to 120 ℃ for 48 h. After cooling, 200mL of methanol was added, stirred at room temperature for 2h, and filtered. The obtained polymer was extracted by a Soxhlet extractor. Extracting with methanol, acetone and n-hexane to colorless, removing small molecules and catalyst, and extracting with chloroform to obtain the final product with yield of 92%.
The structural characterization data of the resulting polymer are as follows:
molecular weight characterization data are as follows: the weight average molecular weight was 52.2kDa, the number average molecular weight was 20.9kDa, and the polymer molecular weight distribution index was 2.50.
Elemental analysis (%) calculation (C)70H108N6S4)nC, 72.36; h, 9.37; n, 7.23; detects C, 72.18; h, 9.28; and N, 7.21.
As can be seen from the above, the product has a correct structure and is the polymer PBPT2V shown in formula (I).
Determination of spectral properties and thin film field effect transistor properties of the polymers PBPTV and PBPT2V prepared in examples 1 and 2 above:
(1) absorption Spectrum Properties of polymers PBPTV and PBPT2V
FIG. 1 is a UV-VIS-NIR absorption spectrum of a thin film of polymer PBPTV on chlorobenzene solution and quartz slides. As can be seen from FIG. 1, the PBPTV polymer solution and the film both exhibit a wide absorption range, the absorption maximum absorption side band values of the film are all around 865nm, and the corresponding optical band gap is 1.43eV (the optical band gap is according to the formula E)g1240/λ calculation, where EgIs the optical band gap and lambda is the absorption maximum side band value of the film).
FIG. 2 shows UV-VIS-NIR absorption spectra of a thin film of polymer PBPT2V on chlorobenzene solution and a quartz slide. As can be seen from FIG. 2, the solutions and films of PBPT2V polymer each exhibited a wide absorption range, with the absorption maximum absorption side bands of the films being around 867nm, and the corresponding optical band gaps being 1.43eV (optical band gaps according to equation E)g1240/λ calculation, where EgIs the optical band gap and lambda is the absorption maximum side band value of the film).
(2) Performance measurement of thin film field effect transistors made of polymers PBPTV and PBPT2V
The invention adopts a top grid bottomContact (TGBC) device structure the semiconductor properties of the polymer thin film were studied, and a schematic diagram of the device structure is shown in fig. 3. The detailed device construction procedure was performed as described in literature (adv. mater.,2017,29, 1602410). A highly doped silicon wafer is used as a substrate, and silicon dioxide is used as an insulating layer (300 nm); gold (Au) source/drain electrode source and drain electrodes (gold/titanium, 30nm/5nm) were prepared by a photolithography process. The FET device had a channel width (W) of 1400 μm and a channel length (L) of 5 μm. The substrate is firstly treated by oxygen plasma for 5 minutes and then sequentially washed by acetone, deionized water and ethanol. Then, the SiO is treated with Octadecyltrichlorosilane (OTS) under vacuum2Modifying the surface of the insulating layer, and then modifying an OTS-modified substrate (OTS-Treated SiO)2Substrate) was placed in a vacuum oven at 60 ℃ for drying. In a nitrogen box, semiconductor active layers (Polymer Semiconductors) were prepared by spin-coating 8-15 mg/mL solutions of polymeric dichlorobenzene and film samples were annealed at 180 ℃ for 10min in the nitrogen box. The active layer is composed of the copolymer of the generic formula (I) obtained in example 1 or example 2 PBPTV and PBPT 2V. Subsequently, the film sample was subjected to annealing (180 ℃ C.) in a nitrogen atmosphere. Subsequently, a dielectric layer of polymethyl methacrylate (PMMA, about 1150nm) was prepared by spin coating an 80mg/mL solution of butyl methacrylate (PMMA) acetate using PMMA having a weight average molecular weight of 996kDa and a dielectric constant k of about 2.17. The entire device was then placed in a vacuum oven at 80 ℃ and baked for 30 minutes to remove the butyl acetate solvent. Finally, a layer of aluminum (Al) with the thickness of about 100nm is evaporated on the PMMA dielectric layer to be used as a gate electrode. The semiconductor characteristics of the FETs were measured in air using a Keithley 4200SCS semiconductor tester, with typical output and transfer curves as shown in fig. 4-7. Wherein, the hole and electron mobility of the saturation region can be calculated by the following equation: i isDS＝(W/2L)Ciμ(VG–VT)2(saturation region, V)DS＝VG–VT). Wherein, IDSIs the drain current, μ is the carrier mobility, VGIs the gate voltage, VTIs a threshold voltage, CiIs an insulator capacitor.
Fig. 4 is a graph of an output characteristic of a FET device using PBPTV, which is a polymer containing a bispyridazole derivative acceptor and prepared in example 1, as an organic active semiconductor layer, showing a good linear region and a saturation region, which indicates that the PBPTV-based FET device has a good field effect modulation performance.
Fig. 5 is a transfer characteristic curve of an FET device in which the polymer PBPTV containing the bispyridazole derivative acceptor prepared in example 1 is used as an organic active semiconductor layer, when a source-drain voltage is ± 100V. The device exhibits good bipolar device performance with hole and electron mobilities of 6.87 and 8.49cm, respectively2/V s。
Fig. 6 is an output characteristic curve of a FET device using the polymer PBPT2V containing the bispyridazole derivative acceptor prepared in example 2 as an organic active semiconductor layer, showing a good linear region and a saturation region, which indicates that the PBPT 2V-based FET device has a good field effect modulation performance.
Fig. 7 is a transfer characteristic curve of an FET device using the polymer PBPT2V containing the bispyridazole derivative acceptor prepared in example 2 as an organic active semiconductor layer, when the source-drain voltage is ± 100V. The device exhibits good bipolar device performance with hole and electron mobilities of 1.99 and 0.35cm, respectively2/V s。
Furthermore, the results of the study obtained confirm that: the bipyridine diazole derivative acceptor-based polymer semiconductor shown in the formula (I) is a bipolar conjugated polymer with excellent comprehensive performance; the ultrahigh hole and electron mobility depends on the fact that the polymer semiconductor material has a large coplanar framework, a strong heteroatom effect, an isotactic molecular chain framework and good solution processability. The preparation method provided by the invention has the advantages of simplicity, effectiveness, easily available raw materials, strong popularization and the like. By changing different solubilizing alkyl chains, heteroatom substitution and conjugated bridging units, a series of bipyridyl diazole derivative acceptor-based polymer semiconductor materials with excellent comprehensive performance can be prepared, which has very important significance for researching the internal relation between the structure and the performance of a bipolar polymer semiconductor and has guiding significance for developing high-performance bipolar polymer semiconductor materials in the future.
Claims (11)
1. A polymer semiconductor containing a bispyridazole derivative receptor is characterized in that: the polymer semiconductor has a molecular structure general formula shown in a formula (I);
in the formula (I), R is any one of straight-chain alkyl with 6-16 total carbon atoms or branched-chain alkyl with 8-30 total carbon atoms;
ar is the following three cases: absent, a carbon-carbon double bond or a carbon-carbon triple bond;
x is oxygen atom, sulfur atom, selenium atom or tellurium atom;
n is an integer of 10 to 300.
2. The bispyridazole derivative-acceptor-containing polymer semiconductor of claim 1, wherein: in the formula (I), n is an integer of 50-150.
3. The polymer semiconductor containing a bispyridazole derivative acceptor according to claim 1 or 2, characterized in that: the straight-chain alkyl group with the total number of carbon atoms of 6-16 is n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl or n-hexadecyl; the branched alkyl group having a total carbon number of 8 to 30 is 2-ethylhexyl, 2-butylhexyl, 2-hexyloctyl, 3-hexylundecyl, 2-octyldecyl, 2-octyldodecyl, 3-octyltridecyl, 2-decyldodecyl, 2-decyltetradecyl, 3-decylpentadecyl, 2-dodecylhexadecyl, 4-octyltetradecyl, 4-decylcetyl, 4-hexyldecyl, 4-octyldodecyl, 4-decyltetradecyl or 4-dodecylhexadecyl.
4. The polymer semiconductor containing the bispyridazole derivative acceptor according to claim 1 or 2, wherein the polymer semiconductor represented by formula (I) is specifically a polymer represented by PBPTV or PBPT2V as follows:
5. a method for preparing a polymer semiconductor containing a bispyridazole derivative acceptor according to any one of claims 1-3, characterized in that it comprises the following synthetic steps:
(1) reacting 2-tributyltin-4-alkylthiophene with a dibromo-benzodiazole derivative to obtain an intermediate a, wherein the structural formula of the 2-tributyltin-4-alkylthiophene is as follows:
wherein R is as defined in claims 1-3;
the structural formula of the dibromo-benzodiazole derivative is as follows:
wherein X is an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom;
the structural formula of the intermediate a is as follows:
wherein R is as defined in claims 1-3;
(2) under the protection of nitrogen, carrying out palladium catalytic coupling reaction on the intermediate compound a and the compound b to obtain an intermediate compound c; the structural formula of the compound b is as follows:
wherein Ar is as defined in claim 1;
the structural formula of the intermediate compound c is as follows:
wherein in the intermediate compound c, R, Ar and X are as defined in claims 1-3;
(3) under the protection of nitrogen, performing electrophilic reaction on the intermediate compound c and N-bromosuccinimide to obtain a monomer compound of a formula M1, wherein the structural formula is as follows:
(4) under the protection of inert gas, a monomer shown as a formula M1 and a monomer shown as (E) -bis 1,2- (tri-n-butylstannyl) ethylene are placed in a solvent for palladium-catalyzed coupling reaction, and after the reaction is finished, a polymer shown as a formula (I) is obtained, so that the polymer semiconductor containing the bipyridine diazole derivative receptor is obtained.
6. The method for preparing a polymer semiconductor containing a bispyridazole derivative acceptor according to claim 5, wherein the method comprises the following steps: the specific operation of the step (1) is as follows: adding 2-tributyltin-4-alkylthiophene, dibromobenzodiazole derivatives, bis (triphenylphosphine) palladium dichloride catalyst and toluene solvent into a three-necked flask under the protection of nitrogen, refluxing, stirring, reacting for 1-10 hours, cooling to room temperature, extracting with dichloromethane, drying an organic phase with magnesium sulfate, spin-drying the solvent to obtain a crude product, and purifying with a silica gel chromatographic column to obtain an oily liquid a; wherein the molar ratio of the fed reaction raw materials is as follows: 2-tributyltin-4-alkylthiophene: bis (triphenylphosphine) palladium dichloride ═ 1: 1-2: 0.01-0.1.
7. the method for preparing a polymer semiconductor containing a bispyridazole derivative acceptor according to claim 5, wherein the method comprises the following steps: the specific operation of the step (2) is as follows: under the protection of nitrogen, adding an intermediate compound a, a compound b, a tetrakis (triphenylphosphine) palladium catalyst and a toluene solvent into a three-necked flask, refluxing, stirring, reacting for 10-72 hours, cooling to room temperature, extracting with dichloromethane, drying an organic phase with anhydrous magnesium sulfate, spin-drying the solvent to obtain a crude product, and purifying with a silica gel chromatographic column to obtain a red oily liquid c; wherein the molar ratio of the raw materials for reaction is that the compound b: intermediate compound a: tetrakis (triphenylphosphine) palladium ═ 1: 2.0-6.0: 0.01-0.1.
8. the method for preparing a polymer semiconductor containing a bispyridazole derivative acceptor according to claim 5, wherein the method comprises the following steps: the specific operation of the step (3) is as follows: under the protection of nitrogen, adding trichloromethane and a compound c into a three-neck flask, placing the three-neck flask in an ice bath, slowly adding N-bromosuccinimide into a reaction flask in batches, stirring the mixture at room temperature for reaction for 5 to 24 hours, extracting the mixture by using dichloromethane, drying an organic phase by using anhydrous magnesium sulfate, spin-drying the solvent to obtain a crude product, and purifying the crude product by using a silica gel chromatographic column to obtain a target product M1; wherein the molar ratio of the raw materials for reaction is that the compound c: n-bromosuccinimide ═ 1: 2.0-3.0.
9. the method for preparing a polymer semiconductor containing a bispyridazole derivative acceptor according to claim 5, wherein the method comprises the following steps: the specific operation of the step (4) is as follows: adding M1, (E) -bis 1,2- (tri-n-butylstannyl) ethylene, a solvent and a palladium catalyst into a three-necked flask under the protection of nitrogen, carrying out reflux stirring reaction at the temperature of 100 ℃ and 150 ℃ for 10-72 hours, cooling to room temperature, settling reaction liquid in methanol, carrying out suction filtration, collecting a blue-brown solid, purifying a target polymer by using a Soxhlet extractor, and spin-drying the solvent to obtain a black solid with golden gloss; wherein the molar ratio of the raw materials for reaction is that a compound M1: (E) -bis 1,2- (tri-n-butylstannyl) ethylene: palladium catalyst 1: 1.0-1.5: 0.01-0.1; the palladium catalyst is at least one of tetrakis (triphenylphosphine) palladium, palladium acetate, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium; the solvent is at least one selected from toluene, xylene, methylnaphthalene, chlorobenzene, dichlorobenzene, dichloronaphthalene, trichlorobenzene, chloronaphthalene and tetrahydrofuran.
10. Use of a polymer semiconductor comprising a bispyridazole derivative acceptor according to any one of claims 1-3 or a polymer semiconductor comprising a bispyridazole derivative acceptor prepared by a preparation method according to any one of claims 4-8 for the preparation of a polymer thin film FET device.
11. The use according to claim 10, wherein the use comprises the preparation of a polymer thin film FET device with the polymer semiconductor comprising the bispyridazole derivative acceptor as an organic semiconductor active layer.
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