CN111116646A - Self-assembly interface material - Google Patents
Self-assembly interface material Download PDFInfo
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- CN111116646A CN111116646A CN201911209517.0A CN201911209517A CN111116646A CN 111116646 A CN111116646 A CN 111116646A CN 201911209517 A CN201911209517 A CN 201911209517A CN 111116646 A CN111116646 A CN 111116646A
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/3804—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se) not used, see subgroups
- C07F9/3882—Arylalkanephosphonic acids
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4056—Esters of arylalkanephosphonic acids
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
- C07F9/40—Esters thereof
- C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4075—Esters with hydroxyalkyl compounds
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- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/60—Organic compounds having low molecular weight
- H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
- H10K85/622—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing four rings, e.g. pyrene
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Abstract
In the development of organic electronic devices, how to improve the performance of the devices is the focus of research in this field. Among the factors affecting the device performance, the interfacial characteristics between inorganic materials and organic materials are very critical. The interface modification material with energy level matching and good compatibility is used for surface modification of the inorganic material, so that the organic/inorganic surface energy and compatibility can be effectively improved, and the transmission capability of interface carriers is improved. The invention prepares a pyrene material with different end groups and bonding groups as phosphate groups, and bonds the pyrene material to inorganic materials (ITO and Al) by a self-assembly method2O3Perovskite, TiO2Etc.) on the surface, a monolayer of pyrene material is formed; the interface structure can improve the organic material and inorganic materialContact and reduction of surface energy, and has great application in the field of organic electronic devices.
Description
Technical Field
The performance of organic electronic devices, including organic storage, organic thin film transistors, organic solar cells, etc., is affected by many factors, among which the interface between organic and inorganic layers is one of the important factors. The invention utilizes the chemical self-assembly process to carry out the treatment on the surface of the inorganic functional layer (ITO and Al)2O3Perovskite, TiO2Etc.) to modify surface properties for use in organic electronic devices.
Background
The organic material replaces the traditional semiconductor material to prepare the organic electronic device, and has huge potential application in the new fields of curved surface display, radio frequency identification, optical detection and the like.
In the organic electronic device structure, there are many factors that affect the device performance, wherein the interface characteristics between the inorganic oxide layer and the organic semiconductor layer determine the carrier transport ability and carrier density. The interface of the inorganic oxide layer is modified by using the interface modification material with energy level matching and good compatibility, so that the organic semiconductor material deposited on the interface can be promoted to be orderly arranged, few defects and large crystal grains, and meanwhile, the contact between the oxide layer and the organic layer can be adjusted, so that good carrier transmission is obtained, and finally, a high-efficiency organic electronic device is obtained.
The bonding groups commonly used for surface modification are mercapto (-SH), amino (-NH)2) Carboxyl group (-COOH), etc., in contrast to phosphoric acid group (-PO (OH)2) Has the characteristics of oxidation resistance and stability. In the preparation of organic electronic devices, organic interface materials can be used for improving the surface energy of inorganic materials, improving organic/inorganic interface contact and promoting the transmission of carriers. The invention uses phosphate group (-PO (OH) as bonding group with different terminal groups2) The pyrene material is self-assembled on the surface of an inorganic material (ITO, Al)2O3、TiO2Perovskite, etc.) to improve the surface properties of the organic electronic device.
Disclosure of Invention
The invention is characterized in that a series of phosphate groups (-PO (OH) with different end groups and bonding groups are synthesized2) The pyrene material is used for interface modification of inorganic materials.
(a) Synthesizing a series of pyrene phosphoric acid compounds;
wherein, R = hydrogen atom, alkyl, carbonyl, aldehyde group, carboxyl, amino, halogen atom (F, Cl, Br, I); n = 2-14.
(b) Pretreating the surface of the oxide;
(c) and forming a self-assembled film of pyrene phosphoric acid material on the surface of the treated inorganic matter.
The present invention also features the application of the synthesized phosphoric acid material in preparing one monomolecular film on the surface of inorganic material through chemical bonding.
Drawings
The above and other features and advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
FIG. 1.4- (1-pyrenyl) -butyl phosphate NMR hydrogen spectrum;
FIG. 2 is a schematic view of a self-assembly process;
FIG. 3 is a schematic diagram of a water contact angle of a blank silicon wafer (left graph) and a water contact angle of a phosphoric acid material 4- (1-pyrenyl) -butyl phosphoric acid self-assembled monolayer film (right graph);
FIG. 4 XPS schematic of P2P;
detailed description of the preferred embodiments
The following detailed description of the preferred embodiments of the invention is provided to enable those skilled in the art to more readily understand the advantages and features of the invention. The chemical synthesis of the material is illustrated below by taking the example of n = 2 in structural formula 1.
Example 1:
(1) and (3) synthesizing a self-assembly material 4- (1-pyrenyl) -butyl phosphoric acid.
Preparation of 1-bromopyrene:
in a 50 ml flask, pyrene (2 g,10 mmol) was added, followed by addition of 20 ml of dichloromethane, and NBS (1.87 g,10.5 mmol) was added thereto, followed by stirring for 12 hours in the dark; the extraction was carried out with dichloromethane, the organic fraction was dried over anhydrous magnesium sulfate and then column separated with petroleum ether as eluent to give the product in 95% yield.1H NMR (300 MHz; CDCl3): δ6.66 (2H, s), 3.77 (6H, m), 3.48 (2H, t), 1.65 (2H, m), 1.19 (9H, t), 0.56(2H, t)。
Preparation of 1- (4-bromo-butyl) pyrene:
dissolving 0.01 mol of 1-bromopyrene raw material in 100 ml of THF (tetrahydrofuran) in a 250 ml flask, cooling to-50 ℃, dropping n-butyllithium into the solution, and stirring for ten minutes; dripping 6-8 ml of THF into the solution until lithium salt is precipitated, and stirring the solution for one hour; the reaction temperature was raised to-10 ℃ and 0.288 mmol of 1, 6-dibromohexane was added thereto, followed by stirring at room temperature for two hours; after the reaction was completed, the mixture was extracted with chloroform, washed with water (3X 100 ml), the organic phase was dried over anhydrous magnesium sulfate, the organic phase was filtered and evaporated to dryness, and column separation was carried out to obtain the product in a yield of 78%.1H NMR (300 MHz; CDCl3): δ 8.27 (1H, d), 8.18 (1H,d), 8.16 (1H, d), 8.12 (2H, d), 8.0 (3H, m), 3.47 (2H, t), 3.38 (2H, t), 2.03(4H, t), 1.55 (1H, s)。
Preparation of diethyl 4- (1-pyrenyl) -butylphosphate:
1- (4-bromo-butyl) pyrene (800 mg, 2.37 mmol) and triethyl phosphite (500 mg, 3 mmol) were added to a 10 ml schlenk tube, the reaction was heated to 150 ℃ and refluxed for 12 h; after completion of the reaction, the excess triethyl phosphite was removed by rotary evaporation and column separation (ethyl acetate: petroleum ether = 2: 1) gave the product in 90% yield.1H NMR (300 MHz; CDCl3):δ 8.25 (1H, d), 8.16 (2H, m), 8.11 (1H, s), 8.10 (1H, s), 8.02 (2H, m), 7.85(1H, d), 4.08 (4H, m), 3.37 (2H, t), 1.97 (2H, t), 1.82 (4H, d), 1.30 (6H,d)。
Preparation of 4- (1-pyrenyl) -butyl phosphoric acid:
in a 25 ml flask, 4- (1-pyrenyl) -butyl diethyl phosphate (1 mmol) was dissolved in 15 ml of dichloromethane, and trimethylbromosilane (52 mg, 3.44 mmol) was added thereto and stirred at room temperature for 24 hours; after the reaction is finished, evaporating the dichloromethane serving as a solvent to dryness, adding 40 ml of methanol, and stirring at room temperature for 12 hours; after the reaction is finishedThe solvent methanol was evaporated to dryness and the product recrystallized from acetonitrile and the product collected as a white solid with a yield of 95%.1H NMR (300 MHz; CDCl3) δ 8.36 (1H, d), 8.23(4H, m), 8.12 (1H, s), 8.05 (2H, m), 7.95 (1H, d), 3.34 (2H, t), 1.86 (2H, t), 1.63 (4H, s). (nuclear magnetism see FIG. 1)
(2) Self-assembled film preparation (FIG. 2)
a. Al2O3Preparing a precursor solution: 4.5 g of aluminum nitrate nonahydrate is dissolved in 20 ml of ethanol solution and stirred for 12 hours at normal temperature
b. Washing silicon wafer with neutral detergent, cleaning with large amount of ultrapure water, sequentially ultrasonically oscillating with acetone, ethanol and ultrapure water for 10 min, and treating with N2Blow-dry
c. Cleaning the cleaned Si/SiO2The substrate was irradiated with Plasma for 10 min
d. Taking out the silicon wafer, spin-coating Al at 4000 r/min for 40 s2O3Annealing the precursor solution at 350 ℃ for 30 min
e. Placing the prepared slices into a THF solution (10) of 4- (1-pyrenyl) -butyl phosphoric acid-3M), self-assembling for 48h at normal temperature, taking out the sample, and annealing at 120 ℃ for 0.5 h to prepare molecular layer film
(3) Characterization of materials
a. Water contact angle (fig. 3)
Surface modification induced SiO by contact angle determination is systematically characterized2A change in the wettability of the surface. SiO in FIG. 32The contact angle of the surface is 49.77 degrees, the contact angle of the surface of the 4- (1-pyrenyl) -butyl phosphate self-assembled membrane is 73.4 degrees, and the increase of the water contact angle proves the success of the self-assembled molecule because the terminal group of the 4- (1-pyrenyl) -butyl phosphate is a hydrophobic pyrene unit.
b. X-ray photoelectron Spectroscopy (XPS) (FIG. 4)
FIG. 4 is an XPS schematic of P2P, in which the peak with a binding energy of 132 eV is the characteristic peak position of the P element contained in 4- (1-pyrenyl) -butyl phosphate, which indicates that the self-assembly of 4- (1-pyrenyl) -butyl phosphate on the oxide surface is successful.
Claims (3)
1. A self-assembly interface material is characterized in that pyrene materials with different end groups and phosphate groups serving as bonding groups have a structural formula
Wherein, R = hydrogen atom, alkyl, carbonyl, aldehyde group, carboxyl, amino, halogen atom (F, Cl, Br, I); n = 2-14.
2. The pyrene material of claim 1, which is used to surface-modify an inorganic material, wherein a monomolecular layer is formed by self-assembly, and the strong interaction between pyrene units enhances the ordered arrangement between molecules, reduces the surface energy, and improves the interface contact between organic and inorganic materials.
3. The pyrene material according to claim 2 for surface modification of an inorganic material, wherein the inorganic material is TiO2、Al2O3ITO, perovskite.
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| CN106299138A (en) * | 2016-08-04 | 2017-01-04 | 南京工业大学 | With the synthesis of phosphate group material and the preparation of self-assembled film on oxide surface thereof |
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| CN106299138A (en) * | 2016-08-04 | 2017-01-04 | 南京工业大学 | With the synthesis of phosphate group material and the preparation of self-assembled film on oxide surface thereof |
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Application publication date: 20200508 |