CN117946071A - Single-molecule self-assembled hole transport material, synthesis method and photoelectric device - Google Patents
Single-molecule self-assembled hole transport material, synthesis method and photoelectric device Download PDFInfo
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Abstract
The invention provides a single-molecule self-assembled hole transport material, which is a carbazole derivative taking pyridine dicarboxyl as an anchoring group and has a chemical general formula shown in the following formulaThe invention also relates to a synthesis method of the single-molecule self-assembled hole transport material and a photoelectric device prepared by using the synthesized material as the hole transport material. The single-molecule self-assembled hole transport material provided by the invention has good hole transport performance and strong interface passivation capability, and is suitable for large-scale preparation.
Description
Technical Field
The invention belongs to the technical field of organic semiconductors, and particularly relates to a self-assembled hole transport material containing carbazole derivatives, a synthesis method and application thereof in perovskite batteries and perovskite quantum dot light-emitting diodes.
Background
An organic semiconductor is a carbon-based material which combines photoelectric properties with a simple manufacturing process, and can be adjusted in energy level, performance, etc. by changing chemical structure. Organic semiconductors have been successfully used in the fabrication of light emitting diodes (now widely used in cell phone displays and televisions), solar cells, transistors and sensors. The organic hole transport material is taken as an important component of the novel photoelectric device, plays a role in collecting and transporting holes and blocking electrons in the device, and plays a vital role in photoelectric conversion efficiency and stability of the device.
In recent years, single-molecule self-assembled (SAM) hole transport materials have evolved into research hotspots in organic hole transport due to low raw material cost, easy purification, definite molecular structure, capability of being processed by using a green alcohol solvent, strong binding force with an ITO substrate and proper energy level. SAM materials firmly anchor the material to the substrate surface by chemical interaction of the acid of the anchor group (typically phosphoric acid, acetic acid, boric acid, etc.) with the ITO surface. The other end of the SAM material is typically a hole transporting group (typically carbazole or triphenylamine) that serves to transport holes in the device. Thus, self-assembled hole transport materials play a key role in photovoltaic devices, and the preparation of hole transport layers using small organic molecules containing anchoring groups has been demonstrated to have excellent charge selectivity (energy environ. Sci.,2019,12,230-237). However, the organic micromolecular hole transport materials with anchoring groups developed at present have the problems of poor stability, poor device performance and the like, and influence the application and market popularization of the self-assembled hole transport materials in photoelectric devices.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a self-assembled single-molecule (SAM) hole transport material which has good hole transport performance and strong interface passivation capability and is suitable for large-area preparation.
In order to achieve the above purpose, the invention provides a single molecule self-assembled hole transport material, which is a carbazole derivative taking pyridine dicarboxyl as an anchoring group, and has a chemical general formula shown in the following formula I:
Wherein R 1-R2 is independently selected from any one or two of benzofluorene, benzothiophene, benzofuran, indole, and R l-R2 can be at different substitution positions or different numbers of substitutions; l represents a single bond, phenylene, pyridylene, methylene, ethylene, propylene, butylene, preferably methylene.
Further, formula I includes, but is not limited to, any one of the following compounds 1 to 16:
the synthesis method of the single-molecule self-assembled hole transport material comprises the following steps:
(a) Firstly, chloridizing 4-hydroxypyridine-2, 6-dicarboxylic acid and phosphorus oxychloride, concentrating a reaction solution, directly dripping the reaction solution into a solution of Dichloromethane (DCM) mixed with Tertiary Butyl Alcohol (TBA) and 4-Dimethylaminopyridine (DMAP) for esterification reaction, and preparing an intermediate 1:
(b) Step of preparing intermediate 2 by catalytic coupling reaction of intermediate 1 and pinacol biborate in a mixed solution of potassium acetate and Tetrahydrofuran (THF) with tris (dibenzylideneacetone) palladium and 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl:
(c) A step of preparing intermediate 3 by catalytic coupling reaction of palladium acetate and X-phos in a mixed solution of potassium phosphate and tetrahydrofuran of intermediate 2 and bromoarene:
(d) Intermediate 3 is hydrolyzed in tetrahydrofuran solution of hydrochloric acid to give the final product.
Further, in the step (a), the molar ratio of the 4-hydroxypyridine-2, 6-dicarboxylic acid, phosphorus oxychloride, tertiary butanol and 4-dimethylaminopyridine is 1:2-3:2-3:0.05-0.1; the esterification reaction temperature is 100-150 ℃, and the esterification reaction time is 12-24 h.
Further, in the step (b), the molar ratio of the intermediate 1, the bisboronic acid pinacol ester, the potassium acetate, the tris (dibenzylideneacetone) palladium and the 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl is 1:1-1.5:1-3:0.02-0.03:0.04-0.06; the coupling reaction temperature is 50-60 ℃, and the coupling reaction time is 8-12 h.
Further, in the step (c), the molar ratio of the intermediate 2, the bromoarene, the potassium phosphate, the palladium acetate and the 2-dicyclohexyl phosphorus-2 ',4',6' -triisopropyl biphenyl is 1:1-1.5:1-3:0.02-0.03:0.04-0.06; the coupling reaction temperature is 50-60 ℃, and the coupling reaction time is 12-24 h.
Further, in the step (d), the pH of the reaction solution is 2-3; the reaction temperature is room temperature and the reaction time is 3-8 h.
Another object of the present invention is the use of an optoelectronic device comprising at least a transparent conductive glass substrate, a hole transport layer, a light absorbing layer, an electron transport layer and an electrode layer; or comprises a transparent conductive glass substrate, a hole transport layer, a light-emitting layer, an electron transport layer and an electrode layer in sequence; wherein the hole transport layer is the single-molecule self-assembled hole transport material shown in the general formula I. Alternatively, the organic hole transport layer is obtained by dissolving a single-molecule self-assembled hole transport material shown in a general formula I in solvents such as alcohols, tetrahydrofuran, anisole and the like to prepare a solution with the concentration of 1-10 mg/mL, and then coating the solution on a transparent conductive glass substrate.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the single-molecule self-assembled hole transport material provided by the invention, the pyridine dicarboxyl in the structure is used as an anchoring group, so that on one hand, the stability of the organic hole transport material is greatly improved, and the stability comprises chemical stability, device thermal stability, redox stability and the like which are in action with conductive glass; on the other hand, the work function of the conductive glass can be adjusted to be matched with the energy level of the active layer material, so that the interface carrier injection or extraction efficiency is improved; in the third aspect, structural defects of an interface can be passivated, the service life of carriers in an active layer is prolonged, and the open-circuit voltage and the filling factor of the photoelectric device are improved.
(2) According to the single-molecule self-assembled hole transport material provided by the invention, the carbazole derivative is introduced into the structure, so that the hole affinity of molecules is further improved, and the carbazole derivative is used as a hole transport material, thereby being beneficial to the transfer of carriers and further improving the hole transport performance of the material.
Drawings
FIG. 1 is a schematic view of an optoelectronic device according to the present invention;
FIG. 2 is a J/V plot of a perovskite cell prepared using Compound 1 provided by the present invention as a hole transport material;
FIG. 3 is a J/V plot of a perovskite cell prepared using Compound 2 provided by the present invention as a hole transport material;
FIG. 4 is a J/V plot of a perovskite cell prepared using Compound 3 provided by the present invention as a hole transport material;
FIG. 5 is a graph showing the maximum External Quantum Efficiency (EQE) as a function of voltage (V) for a perovskite light emitting diode prepared using Compound 1 provided by the present invention as a hole transport material;
FIG. 6 is a graph showing the maximum External Quantum Efficiency (EQE) as a function of voltage (V) for a perovskite light emitting diode fabricated using Compound 2 provided by the present invention as a hole transport material;
Fig. 7 is a graph showing the maximum External Quantum Efficiency (EQE) of a perovskite light emitting diode prepared using the compound 3 provided by the present invention as a hole transport material as a function of voltage (V).
Detailed Description
In order to further illustrate the technical means and effects adopted by the invention to achieve the preset purpose, the chemical general formula shown in the formula I is taken as an example, wherein L is preferably phenylene, and the specific implementation, structure, characteristics and effects according to the invention are described in detail with reference to the accompanying drawings and the preferred embodiments of the invention.
[ Example 1]
Synthesis of Compound 1
(1) Synthesis of intermediate 1:
SM1 (48 g,1.0 eq) was weighed into a 500mL three-necked flask, 200mL POCl 3 was added, the apparatus was connected to a tail gas treatment apparatus, the acidic tail gas was absorbed by aqueous NaOH solution, the temperature was raised to 100 ℃, the mixture was refluxed and stirred for about 10 hours, and the reaction was stopped; unscrewing the remaining POCl 3; tert-butanol (40 mL), DMAP (10 g), 20mL of ultra-dry DCM, and 10mL of pyridine were added to a 500mL flask and stirred well; diluting the concentrated solution in the last step with 50mL of ultra-dry DCM, transferring the diluted concentrated solution into a constant-pressure dropping funnel, and slowly dropping the diluted concentrated solution into a flask; after stirring for about 12 hours, the reaction solution was concentrated and separated by column chromatography to give 42.68g of a white solid product in a yield 57.6％.1H NMR(400MHz,DMSO-d6)δ7.38(s,2H),0.86(s,18H).HRMS(ESI,m/z):[M+H]+calculated for C15H21ClNO4,314.1159,found 314.1168.
(2) Synthesis of intermediate 2:
Intermediate 1 (5.0 g,1.0 eq), pinacol biborate (4.87 g,1.2 eq), potassium acetate (4.69 g,3.0 eq), pd 2(dba)3 (0.15 g), X-phos (0.30 g) were weighed into 50mL of ultra dry THF, stirred at 60 ℃ under argon; stirring for about 10 hours, and finishing the reaction; filtering the reaction solution, desalting, concentrating the reaction solution until about 10mL remains, stirring for about 30min, and separating out a large amount of products; suction filtration, washing with petroleum ether and drying to obtain white solid product 6.59g, yield 65.4％.1H NMR(400MHz,DMSO-d6)δ7.38(s,2H),0.86(s,30H).HRMS(ESI,m/z):[M+H]+calculated for C21H32BNO6,405.2323,found405.2349.
(3) Synthesis of intermediate 3:
SM3 (0.30 g,1 eq), intermediate 2 (0.33 g,1.2 eq), pd (OAc) 2 (0.05 g), X-phos (0.10 g) were weighed into a 50mL three-necked flask, THF (20 mL) and water (5 mL) were added and the temperature was raised to 50 ℃; stirring overnight, spin drying followed by column chromatography (PE: ea=7:1) to give a yellow product; oven drying to give 0.36g, yield 82.7％.1H NMR(400MHz,Chloroform-d)δ8.19–8.13(m,3H),7.81(s,1H),7.76–7.70(m,2H),7.62(dd,J＝7.4,1.6Hz,1H),7.60–7.51(m,4H),7.51–7.40(m,3H),7.35(td,J＝7.5,1.5Hz,1H),7.29(td,J＝7.5,1.5Hz,1H),1.56(s,18H).HRMS(ESI,m/z):[M+H]+calculated for C42H40N2O4,636.7920,found636.7957.
(4) Synthesis of Compound 1:
Intermediate 3 (0.30 g,0.47 mmol) was weighed, 20mL THF,10mL water was added, concentrated hydrochloric acid was added dropwise, pH was adjusted to 2, and the mixture was stirred for 12h to hydrolyze the ester, spotted on a plate, and the hydrolysis was completed; when the reaction solution was concentrated to about 10mL of water remained, a precipitate was formed; after suction filtration, repeatedly washing the product with water; oven drying to obtain 0.18g of product with yield 75.1％.1H NMR(400MHz,Chloroform-d)δ8.15(dd,J＝7.4,1.5Hz,1H),8.15(s,2H),7.83(s,1H),7.80–7.74(m,2H),7.63(dd,J＝7.4,1.6Hz,1H),7.61–7.53(m,4H),7.48(s,1H),7.49–7.40(m,2H),7.35(td,J＝7.5,1.6Hz,1H),7.29(td,J＝7.5,1.5Hz,1H),1.55(s,6H).HRMS(ESI,m/z):[M+H]+calculated for C34H24N2O4,524.5760,found 524.5718.
[ Example 2]
Synthesis of Compound 2
Synthesis of Compound 2 and the procedure for the synthesis of Compound 1 were similar to each other to give 161mg of the product in a yield 78.1％.1H NMR(400MHz,Chloroform-d)δ8.24(s,1H),8.11(s,1H),8.09–8.03(m,1H),8.06–7.98(m,1H),7.83–7.77(m,2H),7.66–7.57(m,3H),7.54(dd,J＝7.5,1.6Hz,1H),7.47(td,J＝7.4,1.5Hz,1H),7.37(td,J＝7.4,1.6Hz,1H),7.34–7.24(m,3H).HRMS(ESI,m/z):[M+H]+calculated for C31H18N2O5,498.4940,found 498.4989.
[ Example 3]
Synthesis of Compound 3:
Synthesis of Compound 3 and the synthetic procedure for Compound 1 were similar to each other to give 141mg of the product in a yield 73.6％.1H NMR(400MHz,Chloroform-d)δ8.37–8.31(m,1H),8.14(s,2H),8.11–8.06(m,1H),7.92(s,1H),7.80–7.73(m,3H),7.69(dd,J＝7.6,1.5Hz,1H),7.66–7.60(m,1H),7.59–7.53(m,2H),7.45(td,J＝7.5,1.5Hz,1H),7.37–7.25(m,3H).HRMS(ESI,m/z):[M+H]+calculated for C31H18N2O4S,514.5550,found 514.5581.
[ Example 4]
The preparation method of the perovskite battery comprises the following steps:
S1, cleaning an IT0 conductive glass substrate (purified water, ethanol and acetone are sequentially subjected to ultrasonic treatment for 30 min);
S2, preparation of a Hole Transport Layer (HTL): dissolving the compound in ethanol, tetrahydrofuran or anisole solvent, spin-coating on ITO, and annealing at 120deg.C for 20min;
S3, preparing a perovskite film (perovskite layer): the solubility of the perovskite precursor solution is 1.2M, and the perovskite film is prepared by an antisolvent one-step method. Spin coating is divided into two stages, wherein the speed of the first stage is 1000rpm s -1, spin coating is 10s, and the acceleration is 800rpm s -2; the second stage is that 5000rpm s -1 is coated for 30s, the acceleration is 2000rpm s -2, 400 microliters of ethyl acetate is used as an antisolvent to be dripped in the center of the perovskite film 20s before the second stage is finished, and finally the perovskite film is obtained after heating at 100 ℃ for 30 min;
S4, preparing an Electron Transport Layer (ETL) and a hole blocking layer: PCBM solution was prepared using chlorobenzene at a concentration of 20mg mL -1, spin-coated in a two-step procedure (800 rmp s -1,10s;4000rmp s-1, 30 s), and annealed at 80℃for 10min.
S5, preparing a hole blocking layer: finally, preparing a hole blocking layer (ITO) by dripping an isopropanol solution of 120 uLBCP;
S6, preparing a back electrode: the negative electrode was formed by vapor deposition of 100nm silver using a vacuum vapor deposition apparatus (< 5×10 -4 Pa).
Perovskite battery performance test: the voltammetric characteristic curve (I-V) of the solar cell was recorded by a Keithley 2400 digital source meter, the light source was a xenon lamp (0 sram XBO 450) simulating AM 1.5 sunlight, the intensity was 1000W/m 2, and the temperature was 25℃after silicon cell correction. The incident photon conversion efficiency (Incidentphoton-to-electron covertion efficiency, IPCE), also known as external quantum efficiency (External quantum efficiency, EQE), was measured as oriel-74125, the light source as a 300W xenon lamp (ILC Technology, USA), and the modulation frequency was 2Hz. The J-V data of the test cells are shown in Table 1 and FIGS. 2-4.
Stability test of perovskite solar cell: the relative values of the photoelectric conversion efficiency to the original efficiency of the prepared perovskite solar cell device after being left for 240 hours under the conditions of a Relative Humidity (RH) of 85% and a temperature of 50 ℃ are shown in table 1.
TABLE 1
As can be seen from table 1 and fig. 2-4: (1) The pyridine carboxyl compound disclosed by the invention is applied to perovskite batteries as a hole transport material, the short circuit density of the batteries is more than 20mA/cm -2, the open circuit voltage is more than 1.00V, and the filler is more than 70%. The comparative 2PACz compound showed excellent light conversion efficiency. The method is mainly characterized in that the carbazole unit and the pyridine dicarboxylic are introduced, so that the energy level of the material is regulated to be more matched with the energy level of the active layer material, the interface carrier injection and extraction efficiency is improved, and the device efficiency is improved. In addition, the service life of carriers in the perovskite active layer is prolonged through the structural defect of the passivation interface, and the open-circuit voltage and the filling factor of the perovskite battery are improved. (2) As carbazole units and pyridine carboxyl groups are introduced, the chemisorption stability of the hole transport material can be improved, and as can be seen from Table 1, after the perovskite cell using the compound of the invention as the hole transport material is placed for 240 hours in a high-temperature and high-humidity state, the perovskite cell still has good photoelectric conversion efficiency, the comparison original value is higher than 80%, and the reference device is only 45%, so that the cell has good stability.
[ Example 5]
The preparation method of the perovskite light-emitting diode device comprises the following steps:
S1, an ITO anode is formed by scrubbing an ITO (indium tin oxide) glass substrate with the coating thickness of 150nm with ethanol, then washing with acetone twice, washing with ultrasonic waves for 20min, transferring to an isothermal table for drying after washing is finished, cooling after baking is finished, and transferring to UV-O 3 for treatment for 15min;
S2, preparation of a Hole Transport Layer (HTL): dissolving the compound in ethanol, tetrahydrofuran or anisole solvent, spin-coating on ITO, and annealing at 120deg.C for 20min;
S3, rotating the perovskite quantum dot on the transmission layer at 2000rpm/45S with the spin-coating parameter of 1000 acceleration, using a vacuum evaporation instrument to evaporate 45nm of TPBi as an electron transmission layer, and evaporating 100nm of Al as a back electrode on the electron injection layer in a vacuum way.
The prepared perovskite light-emitting device was subjected to I-V-L test, and the relevant performance parameters thereof were obtained as shown in Table 2.
TABLE 2
As can be seen from table 2 and fig. 5-7: (1) The pyridine carboxyl compound disclosed by the invention is used as a hole transport material to be applied to a perovskite light-emitting diode, the starting voltage is 2.6V, the light-emitting brightness is greater than 10000cd/m 2, and the external quantum efficiency is greater than 14%. Due to the introduction of the transmission unit and the pyridine carboxyl, the front-line orbit energy level of the material is regulated to be more matched with the energy level of the active layer material, and good interface carrier injection and extraction efficiency is shown. The test shows that the compound 1-compound 3 has wide application space in perovskite light-emitting diodes.
Claims (10)
1. A single molecule self-assembled hole transport material having the chemical formula shown in formula (I):
Wherein R 1-R2 is independently selected from any one or two of benzofluorene, benzothiophene, benzofuran, indole, and R l-R2 can be at different substitution positions or different numbers of substitutions;
L represents a single bond, phenylene, pyridylene, methylene, ethylene, propylene, butylene.
2. The single molecule self-assembled hole transporting material of claim 1, wherein L represents phenylene.
3. The single molecule self-assembled hole transporting material of claim 2, wherein formula (I) includes, but is not limited to, any one of the following compounds 1 to 16:
4. a synthetic method of a single-molecule self-assembled hole transport material comprises the following steps:
(a) The method comprises the steps of chloridizing 4-hydroxypyridine-2, 6-dicarboxylic acid and phosphorus oxychloride, concentrating the reaction solution, directly dripping the reaction solution into a dichloromethane mixed with tertiary butanol and 4-dimethylaminopyridine for esterification reaction, and preparing an intermediate 1:
(b) The step of preparing intermediate 2 by catalytic coupling reaction of tris (dibenzylideneacetone) palladium and 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl in a mixed solution of potassium acetate and tetrahydrofuran of intermediate 1 and pinacol biborate:
(c) A step of preparing intermediate 3 by catalytic coupling reaction of palladium acetate and X-phos in a mixed solution of potassium phosphate and tetrahydrofuran of intermediate 2 and bromoarene:
(d) Hydrolyzing the intermediate 3 in tetrahydrofuran solution of hydrochloric acid to obtain a final product;
In the above reaction formula, R 1-R2 is independently selected from any one or two of benzofluorene, benzothiophene, benzofuran and indole, and R l-R2 can be different substitution positions or different substitution numbers; l represents any one of phenylene, pyridylene, methylene, ethylene, propylene, and butylene.
5. The method of synthesizing a single molecule self-assembled hole transporting material according to claim 4, wherein in step (a), the molar ratio of 4-hydroxypyridine-2, 6-dicarboxylic acid, phosphorus oxychloride, t-butanol, and 4-dimethylaminopyridine is 1:2-3:2-3:0.05-0.1; the esterification reaction temperature is 100-150 ℃, and the esterification reaction time is 12-24 h.
6. The method for synthesizing the single-molecule self-assembled hole transport material according to claim 4, wherein in the step (b), the molar ratio of the intermediate 1 to the bisboronic acid pinacol ester to the potassium acetate to the tris (dibenzylideneacetone) palladium to the 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl is 1:1 to 1.5:1 to 3:0.02 to 0.03:0.04 to 0.06; the coupling reaction temperature is 50-60 ℃, and the coupling reaction time is 8-12 h.
7. The method of synthesizing a single molecule self-assembled hole transporting material according to claim 4, wherein in step (c), the molar ratio of intermediate 2, bromoarene, potassium phosphate, palladium acetate and 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl is 1:1-1.5:1-3:0.02-0.03:0.04-0.06; the coupling reaction temperature is 50-60 ℃, and the coupling reaction time is 12-24 h.
8. The method of synthesizing a single molecule self-assembled hole transporting material according to claim 4, wherein in step (d), the pH of the reaction solution is 2-3; the reaction temperature is room temperature and the reaction time is 3-8 h.
9. An optoelectronic device comprises a transparent conductive glass substrate, a hole transmission layer, a light absorption layer, an electron transmission layer and an electrode layer which are sequentially arranged; or comprises a transparent conductive glass substrate, a hole transport layer, a luminescent layer, an electron transport layer and an electrode layer which are sequentially arranged; the hole transport layer is obtained by dissolving a single-molecule self-assembled hole transport material represented by the general formula (I) according to any one of claims 1 to 3 in a solvent such as alcohols, tetrahydrofuran, anisole, etc., to prepare a solution having a concentration of 1 to 10mg/mL, and then coating the solution on a transparent conductive glass substrate.
10. The optoelectronic device of claim 9, wherein the optoelectronic device is a perovskite cell or a perovskite quantum dot light emitting diode.
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