CN114479020B - Polymer semiconductor photoresist with side chain containing azido group, and preparation method and application thereof - Google Patents
Polymer semiconductor photoresist with side chain containing azido group, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an organic polymer semiconductor photoresist with an azide group-containing side chain, a preparation method and application thereof, and realizes patterning of an organic semiconductor device by utilizing 365nm ultraviolet light to efficiently crosslink. The structural formula of the semiconductor photoresist is shown in the formula I, wherein Ar is any one of aryl, heteroaryl, aryl containing substituent groups and heteroaryl containing substituent groups, and the bonding mode in the group is at least one of single bond, double bond and triple bond; the heteroaryl is selected from any one of monocyclic heteroaryl, bicyclic heteroaryl and tricyclic heteroaryl, and a heteroatom in the heteroaryl is selected from at least one of oxygen, sulfur and selenium; the preparation method is to obtain the polymer through carbon-carbon coupling reaction. Efficient patterning of organic semiconductor devices is achieved.
Description
Technical Field
The invention belongs to the field of organic semiconductor materials, and particularly relates to a polymer semiconductor photoresist with an azide group-containing side chain, a preparation method thereof and application thereof in an organic photoelectric device.
Background
The conjugated polymer has photoelectric properties comparable with those of the traditional inorganic semiconductor material, and has unique mechanical flexibility, and has great application prospect in flexible electronic devices (Science, 2017,355,59). However, there are still limitations to the true use of organic semiconducting polymers in flexible circuits, such as the inability to mass pattern process by conventional photolithographic processes, and their solubility also limits the non-orthogonal solvent integration of the multilayer materials. Therefore, development of new methods for polymer semiconductor photolithographic processing is one of the requisite ways to realize organic flexible electronic devices.
The azide group is a photosensitive active group, a high-reactivity nitrene intermediate can be rapidly generated under the irradiation of ultraviolet light, the nitrene can undergo an insertion reaction with an adjacent C-H bond, and meanwhile, nitrogen (Nat. Mat.,2010,9,152) is released, so that chemical crosslinking is realized. The ultraviolet light of the reaction is controllable, and no byproduct remains, so that the ultraviolet light is widely applied to the fields of biology, chemistry and the like.
In recent years, organic semiconductor material patterning research using azide groups has been receiving increasing attention, but most of the semiconductor lithography patterning reported at present mainly involves binary or multicomponent physical blending (Nature, 2018,555,83; nature. Commun.,2020,11,1520), while the mobility of the patterned device is low. Currently, semiconductor type photoresist with carrier transport and patterning functions is still very lacking. The conjugated polymer integrating the functions of the semiconductor and the photoresist is expected to obtain a patterning device with high mobility, can improve the patterning precision, and has important research significance and practical value for developing an organic semiconductor integrated circuit.
Disclosure of Invention
The invention aims to provide a polymer semiconductor photoresist with a side chain containing an azide group, and a preparation method and application thereof; according to the invention, the azide group is introduced into the conjugated polymer side chain, so that the patterning of the ultraviolet light high-efficiency cross-linked organic semiconductor device is realized.
The polymer with the side chain containing the azide group has the structural formula shown in the following formula I:
in the formula I, R 1 、R 2 Are each independently selected from any one of C1-C50 linear or branched alkyl, C1-C50 alkoxy, C7-C50 aralkyl heteroaryl, and C5-C50 heteroalkyl;
the number average molecular weight of the polymer in the formula I is 5000-500000; further 20000-50000, in particular 28kDa.
Specifically, the R 1 、R 2 Can be 2-decyl tetradecyl;
in the formula I, 0:1< x:y is less than or equal to 1:0; specifically, in the polymer, x and y are 1:0;
ar is selected from any one of aryl, heteroaryl, aryl containing substituent groups and heteroaryl containing substituent groups, and the bonding mode inside the groups is selected from at least one of single bonds, double bonds and triple bonds;
wherein, one of aryl or heteroaryl (phenyl, thienyl, thiazolyl, pyridyl, quinolinyl, furyl, pyrrolyl, imidazolyl, naphthyl and pyrenyl) or a combined fragment formed by connecting one or more of single bond, double bond, triple bond, oxygen, sulfur, silicon or nitrogen between the above units; the heteroatom in the heteroalkyl is at least one of oxygen, sulfur and selenium, and the heteroatom substitution number is 1-10; the heteroaryl is selected from any one of monocyclic heteroaryl, bicyclic heteroaryl and tricyclic heteroaryl, and a heteroatom in the heteroaryl is selected from at least one of oxygen, sulfur and selenium; the substituent is any one of C1-C50 alkyl, C1-C50 alkylthio, C1-C50 alkylcarbonyl, acyloxy, nitrile group and C1-C50 alkoxy, and the number of the substituent is an integer of 1-4.
For example, ar may be selected from any one of the following structural formulas a to u:
in Ar, R is selected from any one of hydrogen, C1-C50 alkyl and C1-C50 alkoxy; most preferred is any one of thienyl, bithiothienyl and bithiothienyl.
In the invention, the Ar is a group shown in the specification
Indicated at the position of the connection of formula I.
The invention also provides a preparation method of the polymer shown in the formula I.
The preparation method of the polymer shown in the formula I provided by the invention comprises the following steps: in the presence of an inert atmosphere and a catalyst, carrying out carbon-carbon coupling reaction on the compound shown in the formula II, the compound shown in the formula III and the compound shown in the formula IV in an organic solvent, and obtaining the polymer shown in the formula I after the carbon-carbon coupling reaction is finished;
in the formula II, III, IV, R 1 、R 2 And Ar is the same as in formula I, Y is a trialkyltin group or a borate group.
In the present invention, the trialkyltin group may be a trimethyltin group or a tributyltin group, and the borate group may be a 1,3, 2-dioxaborane-2-yl group or a 4, 5-tetramethyl-1, 2, 3-dioxapentaborane-2-yl group.
In the preparation method, the gas in the inert atmosphere is nitrogen;
the catalyst consists of a palladium catalyst and a phosphine ligand, wherein the palladium catalyst is selected from at least one of tetra (triphenylphosphine) palladium, tri (tri-p-methylphenyl phosphine) palladium, tri (dibenzylideneacetone) dipalladium and bis (1, 4-biphenylphosphine) butylpalladium dichloride, and can be specifically tri (dibenzylideneacetone) dipalladium; the phosphine ligand is selected from at least one of triphenylphosphine, o-trimethylphenylphosphine, tri (2-furyl) phosphine and 2- (di-tert-butyl phosphorus) biphenyl, and can be specifically o-trimethylphenylphosphine;
in the above preparation method, the molar ratio of the compound represented by formula ii, the compound represented by formula III, the compound represented by formula IV, the palladium catalyst and the phosphine ligand may be 1:0 to 20:0 to 20:0.01 to 0.03:0.03 to 0.12 (specifically, 1:0:1:0.03:0.12); the reaction temperature of the carbon-carbon coupling reaction can be 90-110 ℃, preferably 100 ℃, and the reaction time is 1-3 h, preferably 3h;
the organic solvent is at least one selected from toluene, N-dimethylformamide and chlorobenzene.
In the above preparation method, the trialkyltin reagent (compound shown in formula IV) is selected from trimethylphenyltin and/or tributylphenyltin;
in the preparation method, the coupling reaction further comprises the following steps: dropping the system after the coupling reaction into methanol, and filtering to obtain a solid; sequentially extracting the solid with acetone and n-hexane, and taking the solid after cable extraction; finally, extracting the solid obtained after the cable extraction by using chloroform, dripping chloroform dissolved with the target product into methanol, and carrying out suction filtration to obtain the solid, namely the polymer shown in the formula I.
The invention also protects the compound shown in the formula II:
in the formula II, R 1 Selected from any one of C1-C50 straight-chain or branched alkyl, C1-C50 alkoxy, C7-C50 aralkyl and C5-C50 heteroalkyl. For example R 1 Can be selected from C1-C50 linear or branched alkyl.
The invention also provides a preparation method of the compound shown in the formula II, which comprises the following steps:
the compound shown in the formula V and N 3 Nucleophilic substitution reaction is carried out on the radical compound in a solvent to obtain a compound shown in a formula II;
in the formula V, A is selected from halogen atom or p-methoxy benzene sulfonyl chloride, for example, any one of F, cl, br, I and p-methoxy benzene sulfonyl chloride can be selected.
In the above preparation method, the compound represented by formula V and the N-containing compound 3 N in radical compounds 3 The molar ratio of the groups is 1:2-50, preferably 1:4; the N-containing 3 The radical compound may in particular be sodium azide.
The reaction temperature of the nucleophilic substitution reaction is room temperature, specifically 25 ℃, and the reaction time is 2-7 h, specifically 4h;
the solvent is DMF.
The invention also provides application of the polymer shown in the formula I.
The invention provides the application of the polymer containing the azide groups in at least one of the following (1) - (4): (1) Organic polymer semiconductor photoresist which can be used as a single component; (2) Crosslinking other polymer semiconductors as a general-purpose crosslinking agent; (3) implementing organic semiconductor patterning; (4) use in the manufacture of an organic optoelectronic device. The polymer comprises a non-conjugated polymer and a conjugated polymer (such as copolymer PDPP4T, the structural formula of which is shown as b in figure 7).
In the above application, the organic optoelectronic device includes at least one of an organic field effect transistor, an organic digital circuit, an organic solar cell, an organic thermoelectric, and an organic light emitting diode.
Compared with the prior art, the invention has the following advantages:
1. the raw materials used in the synthesis are convenient and easy to obtain, and the industrial production is easy.
2. The polymer has excellent carrier transmission performance and dissolution property, and is beneficial to solution processing of devices.
3. The polymer can realize the self semiconductor patterning by a simple photoetching technology, and is easy to construct an organic semiconductor large-scale integrated circuit.
4. The polymer can be subjected to efficient crosslinking reaction with other P-type conjugated polymers.
Drawings
FIG. 1 shows a process for the preparation of a compound of formula II according to example 1 of the present invention;
FIG. 2 is a flow chart showing the preparation of the polymer of formula I in example 2 of the present invention;
FIG. 3 shows a compound of formula II in example 1 of the present invention 1 H-NMR chart;
FIG. 4 shows a compound of formula II in example 1 of the present invention 13 C-NMR chart;
FIG. 5 is a polymer of formula I in example 2 of the present invention 1 H-NMR chart;
FIG. 6 shows a polymer of formula I in example 2 of the present invention 13 C-NMR chart;
FIG. 7 shows PDPP4T and F, respectively 4 BDOPV-2T polymer formula;
FIG. 8 is a PDPP4T-N according to example 2 of the invention 3 The polymer realizes a patterning legend;
FIG. 9 is a PDPP4T-N according to example 2 of the invention 3 A polymer cross-linked field effect transistor device structure;
FIG. 10 is a PDPP4T-N according to example 2 of the invention 3 Representative transfer curves for polymer cross-linked field effect transistor devices;
FIG. 11 shows a PDPP4T-N according to example 2 of the invention 3 The polymer is used as an additional component to crosslink the PDPP4T polymer to realize a representative transfer curve of the field effect transistor device;
FIG. 12 is a PDPP4T-N according to example 2 of the invention 3 And (3) an inverter circuit diagram and an output voltage curve prepared by polymer crosslinking.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The raw materials, reagents, and the like are commercially available from public sources unless otherwise specified.
Example 1:
synthesis of Compound of formula II (in formula II, R 1 Is 2-decyl tetradecyl, N 3 The groups being located at the ends of alkyl side chains
The specific reaction steps are as follows:
the chemical reaction flow chart is shown in figure 1. Compound 1 (0.96 mmol) was dissolved in 30mL DMF and compound 2NaN was added 3 (3.83 mmol), at room temperature for 7 hours,the reaction was stopped. Multiple extractions were performed with large amounts of water and dichloromethane. The organic phase was removed by rotary evaporation and separated by column chromatography on silica gel to give product 3 (0.48 mmol, yield: 49.9%); the structure validation data are as follows: 1 H NMR(400MHz,CDCl 3 ) δ=8.63 (d, j=4.4 hz, 2H), 7.22 (d, j=4.0 hz, 2H), 3.92 (d, j=8.0 hz, 4H), 3.25 (t, j=6.8 hz, 4H), 1.88 (m, 2H), 1.60-1.55 (m, 4H), 1.30-1.21 (m, 76H), 0.88 (t, 6H); HR-MS calculated as C 62 H 101 Br 2 N 8 O 2 S 2 (M + ) 1211.5850, mass spectrum peak 1211.5858.
Example 2:
synthesis of Polymer of formula I (wherein R 1 And R is R 2 Is 2-octyl dodecyl, N 3 The radical being located at R 1 Alkyl backbone ends; ar is a bithiophene substituent; when x: y=1:0, the polymer is defined as PDPP4T-N 3 )：
Chemical reaction scheme As shown in FIG. 2, the product 3 (0.050 mmol) and 5,5 '-bis (trimethylstannyl) -2,2' -bithiophene 4 (0.050 mmol) obtained in example 1 of the present invention were dissolved in anhydrous toluene, nitrogen was blown for 10min, 1.48. Mu. Mol of tris (dibenzylideneacetone) dipalladium catalyst and 5.93. Mu. Mol of ligand o-trimethylphenylphosphine were added, reacted at 100℃for 3 hours under nitrogen protection, cooled to room temperature, the reaction system was poured into 100mL of methanol, and solids were precipitated and filtered. The resulting solid was passed through a Soxhlet extractor with methanol, n-hexane and acetone to remove the catalyst, unreacted starting materials and oligomers in sequence, and finally the target product was extracted with chloroform. Pouring the chloroform solution dissolved with the target product into 200mL of methanol to separate out solid, and performing suction filtration to obtain a final product PDPP4T-N 3 The molecular weight Mn is 2.8kDa. (56.5 mg, yield 94%); the structure validation data are as follows: 1 H NMR(500MHz,1,1,2,2-tetrachloroethane-d 2 ,373k):δ＝8.75(s,2H),7.24-6.98(m,7H),3.95(m,4H),3.13(t,4H),1.91(s,2H),1.48-1.18(m,70H),0.81-0.78(t,6H). 13 C NMR(100MHz,solid)：δ= 160.79,141.20,136.94,128.93,124.22,108.69,45.73,39.09,32.84,30.69,23.59,14.89. Elemental analysis: calculated value C 70 H 104 N 8 O 2 S 4 C,69.03; h,8.61; n,9.20; s,10.53; actual value C,68.59; h,8.47; n,8.86; s,10.41.
Example 3:
the specific steps for patterning based on the polymers of formula I of the present invention are: the PDPP4T-N prepared in example 2 of the invention 3 The polymer (structural formula shown in FIG. 5) was dissolved in chloroform solution at room temperature, wherein PDPP4T-N 3 Is 3 mg/ml. The solution was then spin coated onto a silicon wafer by a spin coater at 3000 rpm with a film thickness of about 20 nm. The mask was then covered on the film and irradiated with 365nm uv LED lamp for 400 seconds at a power of 85 milliwatts per square centimeter. Then soaking the film after illumination in chloroform for 30 seconds, taking out, leaching twice with 5 ml of isopropanol, and drying the silicon wafer with nitrogen to realize patterning, wherein a patterning diagram is shown in fig. 8.
Example 4:
PDPP4T-N according to example 2 of the invention 3 The application of the self-patterning film of the polymer in the field effect transistor comprises the following specific steps: the PDPP4T-N prepared in example 2 of the invention 3 The polymer was dissolved in chloroform solution at room temperature, wherein PDPP4T-N 3 Is 3 milligrams per milliliter. Then the solution is processed on Si/SiO of the gold-containing electrode by a spin coater 2 Spin-coating on the substrate at 3000 rpm with a film thickness of about 20 nm (device structure shown in fig. 9). The mask was then covered on the film and irradiated with 365nm uv LED lamp for 400 seconds at a power of 85 milliwatts per square centimeter. And then soaking the illuminated film in chloroform for 30 seconds, taking out, leaching twice with 5 ml of isopropanol, and drying the silicon wafer with nitrogen to realize the patterning of the field effect transistor device. The mobility of the patterned device can reach 0.78cm 2 V -1 s -1 A representative transfer curve is shown in fig. 10.
Example 5:
PDPP4T-N according to example 2 of the invention 3 The application of the patterned P-type conjugated polymer film of the polymer in the field effect transistor comprises the following specific steps: the copolymer of pyrrolopyrrole dione and bithiophene, PDPP4T (formula shown in FIG. 7b, molecular weight 5.3 kDa) was reacted with PDPP4T-N 3 The solution was dissolved in chloroform at a mass ratio of 100:5 at room temperature, wherein the concentration of PDPP4T was 3 milligrams per milliliter. The blend solution was then spin coated onto a silicon wafer by a spin coater at 3000 rpm with a film thickness of about 20 nm. The mask was then covered on the film and irradiated with 365nm uv LED lamp for 400 seconds at a power of 85 milliwatts per square centimeter. And then soaking the film after illumination in chloroform for 30 seconds, taking out, leaching twice with 5 ml of isopropanol, and drying the silicon wafer with nitrogen to realize patterning. The mobility of the patterned device can reach 2.74cm 2 V -1 s -1 A representative transfer curve is shown in fig. 11.
Example 5:
PDPP4T-N based on the second embodiment of the invention 3 The specific steps of the conjugated polymer film patterning in the inverter are as follows: PDPP4T-N was prepared by the procedure described in example III 3 After patterning the polymer, spin coating a layer F 4 BDOPV-2T (FIG. 7 b) polymer, a simple logic gate was constructed: specific test conditions for inverter (FIG. 12) are V dd The range of input and output voltages is 0-50V, and the highest gain value is 68 (fig. 12) as shown in the test result, which proves that the cross-linking agent has potential application value in the aspect of organic digital circuits.
Claims (8)
1. A polymer of formula I:
in the formula I, R 1 Selected from C1-C50 linear or branched alkyl groups or C1-C50 alkoxy groups;
ar is a bithiophene substituent;
in the formula I, x and y=1:0;
the number average molecular weight of the polymer shown in the formula I is 5000-500000.
2. A process for preparing a polymer of formula I according to claim 1, comprising the steps of: in the presence of an inert atmosphere and a catalyst, carrying out carbon-carbon coupling reaction on the compound shown in the formula II and the compound shown in the formula IV in an organic solvent, and obtaining the polymer shown in the formula I after the carbon-carbon coupling reaction is finished;
in the formulas II and IV, R 1 And Ar is as defined in formula I, Y is a trialkyltin group or a borate group.
3. The preparation method according to claim 2, characterized in that: the gas of the inert atmosphere is nitrogen;
the catalyst consists of a palladium catalyst and a phosphine ligand, wherein the palladium catalyst is selected from at least one of tetra (triphenylphosphine) palladium, tri (tri-p-methylphenyl phosphine) palladium, tri (dibenzylideneacetone) dipalladium and bis (1, 4-diphenyl phosphine) butyl palladium dichloride; the phosphine ligand is selected from at least one of triphenylphosphine, o-triphenylphosphine, tri (2-furyl) phosphine and 2- (di-tert-butyl phosphorus) biphenyl;
the molar ratio of the compound shown in the formula II, the compound shown in the formula IV, the palladium catalyst and the phosphine ligand is 1:1:0.03:0.12;
the reaction temperature of the carbon-carbon coupling reaction can be 90-110 ℃ and the reaction time is 1-3 h;
the organic solvent is selected from at least one of toluene, N-dimethylformamide and chlorobenzene;
the trialkyltin reagent is selected from trimethylphenyl tin and/or tributylphenyl tin.
4. A method of preparation according to claim 2 or 3, characterized in that: the coupling reaction further comprises the following steps: dropping the system after the coupling reaction into methanol, and filtering to obtain a solid; sequentially extracting the solid with acetone and n-hexane, and taking the solid after cable extraction; finally, extracting the solid obtained after the cable extraction by using chloroform, dripping chloroform dissolved with the target product into methanol, and carrying out suction filtration to obtain the solid, namely the polymer shown in the formula I.
5. A method of preparation according to claim 2 or 3, characterized in that: the preparation method of the compound shown in the formula II comprises the following steps:
the compound shown in the formula V and N 3 Nucleophilic substitution reaction is carried out on the radical compound in a solvent to obtain a compound shown in a formula II;
6. the method of manufacturing according to claim 5, wherein: the compound of formula V and the N-containing compound 3 N in radical compounds 3 The mol ratio of the groups is 1:2-50; the N-containing 3 The radical compound is sodium azide;
the reaction temperature of the nucleophilic substitution reaction is room temperature, and the reaction time is 2-7 h;
the solvent is DMF.
7. Use of a polymer of formula I according to claim 1 in at least one of the following (1) - (4):
(1) Organic polymer semiconductor photoresists which can themselves be a single component; (2) Crosslinking other polymer semiconductors as a general-purpose crosslinking agent; (3) implementing organic semiconductor patterning; (4) use in the manufacture of an organic optoelectronic device.
8. The use according to claim 7, characterized in that:
the other polymer includes a non-conjugated polymer and a conjugated polymer;
the organic photoelectric device comprises at least one of an organic field effect transistor, an organic digital circuit, an organic solar cell, an organic laser and an organic light emitting diode.
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| JP2008095065A (en) * | 2006-09-12 | 2008-04-24 | Hitachi Chem Co Ltd | Production method of conjugate polymer, conjugate polymer synthesized by the production method, and organic electronics element and organic electroluminescent element using the conjugate polymer |
| CN111187399A (en) * | 2020-02-26 | 2020-05-22 | 中国科学院化学研究所 | Near-infrared light-controlled bistable field effect transistor polymer and preparation method and application thereof |
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| JPS6086543A (en) * | 1983-10-19 | 1985-05-16 | Hitachi Ltd | Formation of micropattern |
| US4571375A (en) * | 1983-10-24 | 1986-02-18 | Benedikt George M | Ring-opened polynorbornene negative photoresist with bisazide |
| KR100973799B1 (en) * | 2003-01-03 | 2010-08-03 | 삼성전자주식회사 | Photoresist composition for multi-micro nozzle head coater |
| GB0310858D0 (en) * | 2003-05-12 | 2003-06-18 | Univ Cambridge Tech | Polymer transistor |
| CN104725612B (en) * | 2015-03-24 | 2016-09-21 | 中国科学院化学研究所 | Conjugated polymer material of one class side chain hydrogen bonds group and preparation method and application |
| JP7123330B2 (en) * | 2016-08-10 | 2022-08-23 | 三星ディスプレイ株式會社 | PHOTORESIST COMPOSITION AND METHOD FOR FORMING METAL PATTERN USING THE SAME |
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| JP2008095065A (en) * | 2006-09-12 | 2008-04-24 | Hitachi Chem Co Ltd | Production method of conjugate polymer, conjugate polymer synthesized by the production method, and organic electronics element and organic electroluminescent element using the conjugate polymer |
| CN111187399A (en) * | 2020-02-26 | 2020-05-22 | 中国科学院化学研究所 | Near-infrared light-controlled bistable field effect transistor polymer and preparation method and application thereof |
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