CN106299138A - With the synthesis of phosphate group material and the preparation of self-assembled film on oxide surface thereof - Google Patents

With the synthesis of phosphate group material and the preparation of self-assembled film on oxide surface thereof Download PDF

Info

Publication number
CN106299138A
CN106299138A CN201610652000.9A CN201610652000A CN106299138A CN 106299138 A CN106299138 A CN 106299138A CN 201610652000 A CN201610652000 A CN 201610652000A CN 106299138 A CN106299138 A CN 106299138A
Authority
CN
China
Prior art keywords
phosphoric acid
pyrene
self
oxide surface
inorganic oxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610652000.9A
Other languages
Chinese (zh)
Inventor
高德青
伍华瑞
郑朝月
黄维
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Tech University
Original Assignee
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN201610652000.9A priority Critical patent/CN106299138A/en
Publication of CN106299138A publication Critical patent/CN106299138A/en
Pending legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C1/00—Apparatus in which liquid or other fluent material is applied to the surface of the work by contact with a member carrying the liquid or other fluent material, e.g. a porous member loaded with a liquid to be applied as a coating
    • B05C1/02—Apparatus in which liquid or other fluent material is applied to the surface of the work by contact with a member carrying the liquid or other fluent material, e.g. a porous member loaded with a liquid to be applied as a coating for applying liquid or other fluent material to separate articles
    • B05C1/025—Apparatus in which liquid or other fluent material is applied to the surface of the work by contact with a member carrying the liquid or other fluent material, e.g. a porous member loaded with a liquid to be applied as a coating for applying liquid or other fluent material to separate articles to flat rectangular articles, e.g. flat sheets
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having a potential-jump barrier or a surface barrier
    • H10K10/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/80—Constructional details
    • H10K30/865—Intermediate layers comprising a mixture of materials of the adjoining active layers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

In organic electronic device develops, how to improve the performance of device, be the research emphasis in this field.In the factor affecting device performance, the interfacial characteristics between inorganic oxide layer and organic semiconductor layer is the most crucial.The modifying interface material that level-density parameter, the compatibility are good is used to modify the interface of inorganic oxide layer, it is possible to be effectively improved transmittability and the carrier density of interface carrier, thus improve device efficiency.The present invention synthesizes a class phosphoric acid material, is chemically bonded to oxide surface (ITO, Al with phosphate group2O3, perovskite, TiO2Deng) on, it is prepared for the self-assembled film of the pyrene unit that end group is macrocyclic structure；This monomolecular film improves contacting of organic semiconductor and inorganic oxide layer, reduce metal-oxide surface can, reach the effect that device performance improves.

Description

Synthesizing and self-assembled film on oxide surface with phosphate group material Preparation
Technical field
Organic electronic device includes organic electro luminescent, OTFT, organic solar batteries etc., research work Person finds in the device of preparation high efficiency, high stability is studied, and determines that in the various factors of device performance, organic layer is with inorganic Interface between Ceng plays conclusive effect.The present invention utilizes chemical self-assembly process to oxide surface (ITO, Al2O3, calcium Titanium ore, TiO2Deng) carry out surface modification, change the character of oxide surface, for the preparation of high-performance organic electronic device.
Background technology
In organic electronic device evolution, organic material is utilized to replace conventional semiconductor material to prepare organic electronic device It it is a dramatic change of modern electronics industry development；Utilize organic electronic device prepared by organic material in curved-surface display, nothing The frontiers such as line RF identification, light detection have huge potential application.
Nineteen nineties Tsumura A et al. reports thin film transistor (TFT) based on polythiophene, illustrates organic The huge advantage that material is prepared at transistor.In organic electronic device structures, the factor affecting device performance is a lot, Qi Zhongwu Interfacial characteristics between machine oxide skin(coating) and organic semiconductor layer determines transmittability and the carrier density of carrier.Use The interface of inorganic oxide layer modified by the modifying interface material that level-density parameter, the compatibility are good, can promote to deposit superincumbent organic Semi-conducting material arrangement is in order, defect is few, crystal grain is big (D.Knipp, R.A.Street andA.R. Appl.Phys.Lett.2003 93 347), contact between adjustable oxide skin(coating) and organic layer simultaneously thus obtain good Carrier transport (Danqing Liu, Zikai He, Yaorong Su, Ying Diao, Stefan C.B.Mannsfeld, Zhenan Bao, Jianbin Xu, and Qian Miao, Adv.Mater.2014,26,7190), final acquisition is high efficiency Organic electronic device.
There are sulfydryl (-SH), amido (-NH in the functional group being typically used as modifying on surface2), carboxyl (-COOH) etc., compare it Under, phosphate group (-PO (OH)2) there is the feature of non-oxidizability, stability.In prepared by organic electronic device, end group is big The self-assembled film of aromatic ring structure can reduce the surface energy of inorganic oxide, improves and deposits superincumbent organic semiconducting materials Interracial contact.The present invention is pyrene unit with end group, is linked to phosphate group (-PO (OH) by alkyl chain2) thus form a class New boundary material, to oxide surface (ITO, Al2O3、TiO2, perovskite etc.) modify, to obtain high performance electronics Device.
Summary of the invention
The invention is characterized in that and synthesize the phosphoric acid material that a series of end groups are pyrene unit.
According to an aspect of the present invention, it is provided that a kind of in the method forming monolayer self-assembled film, step includes:
A () synthesizes a series of pyrene phosphate cpd (structural formula 1)；
Structural formula 1
B () carries out pretreatment to oxide surface；
C () forms the self-assembled film of pyrene phosphoric acid material on the oxide surface processed.
Another feature of the present invention is to utilize the phosphoric acid material of synthesis, prepares one layer by being chemically bound in oxide surface The application of monomolecular film.
Accompanying drawing explanation
Above and other feature and the advantage of the present invention will be more clearly understood that in conjunction with drawings described below and detailed description, its In:
Fig. 1 self assembly schematic flow sheet；
Fig. 2 bare silicon wafer water contact angle (left figure) and phosphoric acid material 4-(1-pyrenyl)-butyl phosphoric acid self assembled monolayer Film water contact angle schematic diagram (right figure)；
The XPS schematic diagram of Fig. 3 P 2P；
Fig. 4 4-(1-pyrenyl)-butyl phosphoric acid hydrogen nuclear magnetic resonance spectrogram.
The detailed description of preferred embodiment
Below the preferred embodiments of the present invention are described in detail so that advantages and features of the invention can be easier to by Skilled artisan understands that.The chemosynthesis of illustrative material as a example by n=2 in structural formula 1 below.
Embodiment 1:
(1) synthesis of self-assembled material 4-(1-pyrenyl)-butyl phosphoric acid.
The preparation of 1-bromine pyrene:
In 50ml flask, by pyrene (2g, 10mmol) add, add dichloromethane 20ml, by NBS (1.87g, 10.5mmol) it is added thereto, lucifuge stirring 12h；Extracting with dichloromethane, organic moiety is dried with anhydrous magnesium sulfate, Doing eluant with petroleum ether and carry out post separation, obtain product, productivity is 95%.1H NMR(300MHz；CDCl3): δ 6.66 (2H, S), 3.77 (6H, m), 3.48 (2H, t), 1.65 (2H, m), 1.19 (9H, t), 0.56 (2H, t).
The preparation of 1-(the bromo-butyl of 4-) pyrene:
In 250ml flask, by 0.01mol 1-bromine pyrene material dissolution in the THF of 100ml, it is cooled to-50 DEG C, then will N-BuLi instills wherein, stirs ten minutes；The THF of 6-8ml is instilled wherein, until lithium salts precipitates, reaction stirring one hour； Reaction temperature is raised to-10 DEG C, then by the 1 of 0.288mmol, 6-dibromo-hexane is added thereto, and is stirred at room temperature two hours；Reaction knot Shu Houyong chloroform extracts, and washes (3 × 100ml), and anhydrous magnesium sulfate is dried organic facies, organic facies is filtered and is evaporated, and post separates, To product, productivity is 78%.1H NMR(300MHz；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).
The preparation of 4-(1-pyrenyl)-butyl phosphoric acid diethylester:
1-(the bromo-butyl of 4-) pyrene (800mg, 2.37mmol) and NSC 5284 (500mg, 3mmol) are joined In 10ml Shrek pipe, reaction is heated to 150 °, and reflux 12h；After having reacted, rotary evaporation removes unnecessary tricresyl phosphite second Ester, post separates (ethyl acetate: petroleum ether=2: 1) and obtains product, and productivity is 90%.1H NMR(300MHz；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).
The preparation of 4-(1-pyrenyl)-butyl phosphoric acid:
In 25ml flask, 4-(1-pyrenyl)-butyl phosphoric acid diethylester (1mmol) is dissolved in the dichloromethane of 15ml In, then bromotrimethylsilane (52mg, 3.44mmol) is added, stirring at normal temperature 24h；After having reacted, methylene chloride is steamed Dry, add methanol 40ml, 12h is stirred at room temperature；After having reacted, solvent methanol is evaporated, product recrystallized from acetonitrile, collects Product is white solid, and productivity is 95%.1H NMR(300MHz；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). (see Fig. 4)
(2) self-assembled film prepares (Fig. 1)
a.Al2O3The preparation of precursor liquid: 4.5g ANN aluminium nitrate nonahydrate is dissolved in the ethanol solution of 20ml, stirring at normal temperature 12h
B. silicon chip neutral detergent washed and use a large amount of ultra-pure water to clean, the most successively with acetone, ethanol, ultra-pure water Sonic oscillation 10min also uses N2Dry up
C. by cleaned Si/SiO2Substrate Plasma irradiates 10min
D. silicon chip, 4000r/min, 40s spin coating Al are taken out2O3Precursor liquid, 350 DEG C of annealing 30min
E. the slice, thin piece prepared is put into the THF solution (10 of 4-(1-pyrenyl)-butyl phosphoric acid-3M) in, room temperature self assembly 48h, then sample is taken out, 120 DEG C of annealing 0.5h, to prepare unimolecular layer membrane
(3) sign of material
A. water contact angle
By contact angle determination, systematically characterize surface and modify the SiO caused2The change of surface wettability.In Fig. 2 SiO2The contact angle on surface is 49.77 °, and the surface contact angle of 4-(1-pyrenyl)-butyl phosphoric acid self-assembled film is 73.4 °, due to The end group of 4-(1-pyrenyl)-butyl phosphoric acid is hydrophobic pyrene unit, and the increase of water contact angle demonstrates the success of self assembly molecule.
B.X-X-ray photoelectron spectroscopy X (XP5)
Fig. 3 is the XPS schematic diagram of P 2p, and combining in figure can be P contained by 4-(1-pyrenyl)-butyl phosphoric acid for the peak of 132ev The characteristic peak positions of element, this shows that 4-(1-pyrenyl)-butyl phosphoric acid is in oxide surface self assembly success.

Claims (4)

1. a class end group is the phosphoric acid material self assembly in inorganic oxide surface of big conjugate ring pyrene unit.
Phosphoric acid material monolayer the most according to claim 1, it is characterised in that the intermolecular strong interaction of pyrene helps In the ordered arrangement of self assembly, reduce the surface energy at interface simultaneously, improve and deposit contacting of superincumbent organic material.
Phosphoric acid material monolayer the most according to claim 1, it is characterised in that the number of pyrene molecular side chain carbon atom is Any one in 4-18.
4. it is characterized in that oxide substrate is TiO according to the pyrene monolayer described in claims 1 and 22、Al2O3、ITO、 Any one in perovskite.
CN201610652000.9A 2016-08-04 2016-08-04 With the synthesis of phosphate group material and the preparation of self-assembled film on oxide surface thereof Pending CN106299138A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610652000.9A CN106299138A (en) 2016-08-04 2016-08-04 With the synthesis of phosphate group material and the preparation of self-assembled film on oxide surface thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610652000.9A CN106299138A (en) 2016-08-04 2016-08-04 With the synthesis of phosphate group material and the preparation of self-assembled film on oxide surface thereof

Publications (1)

Publication Number Publication Date
CN106299138A true CN106299138A (en) 2017-01-04

Family

ID=57667919

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610652000.9A Pending CN106299138A (en) 2016-08-04 2016-08-04 With the synthesis of phosphate group material and the preparation of self-assembled film on oxide surface thereof

Country Status (1)

Country Link
CN (1) CN106299138A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109920915A (en) * 2019-03-08 2019-06-21 武汉理工大学 A kind of stabilization, efficient perovskite semiconductor thin-film solar cell and preparation method thereof
CN110649165A (en) * 2019-04-04 2020-01-03 原秀玲 Perovskite battery with tetraphenylbiphenyldiamine derivative as hole transport material
CN111116646A (en) * 2019-12-01 2020-05-08 苏州和颂生化科技有限公司 Self-assembly interface material
CN111490161A (en) * 2020-04-24 2020-08-04 电子科技大学 Organic thin field effect transistor and preparation method thereof
CN111710785A (en) * 2020-06-18 2020-09-25 浙江浙能技术研究院有限公司 Non-pinhole large-area controllable perovskite growth film forming process

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102145885A (en) * 2011-03-04 2011-08-10 南京师范大学 Method for preparing surface phosphorylated water-soluble carbon nanotube and prepared carbon nanotube
CN103396503A (en) * 2013-07-17 2013-11-20 浙江大学 New zwitter-ionic polymer containing multiple phosphonic acid end groups, preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102145885A (en) * 2011-03-04 2011-08-10 南京师范大学 Method for preparing surface phosphorylated water-soluble carbon nanotube and prepared carbon nanotube
CN103396503A (en) * 2013-07-17 2013-11-20 浙江大学 New zwitter-ionic polymer containing multiple phosphonic acid end groups, preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOHN H. TAPHOUSE ET AL.: "A Pyrenylpropyl Phosphonic Acid Surface Modifi er for Mitigating the Thermal Resistance of Carbon Nanotube Contacts", 《ADV. FUNCT. MATER.》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109920915A (en) * 2019-03-08 2019-06-21 武汉理工大学 A kind of stabilization, efficient perovskite semiconductor thin-film solar cell and preparation method thereof
CN109920915B (en) * 2019-03-08 2021-07-20 武汉理工大学 Stable and efficient perovskite semiconductor thin-film solar cell and preparation method thereof
CN110649165A (en) * 2019-04-04 2020-01-03 原秀玲 Perovskite battery with tetraphenylbiphenyldiamine derivative as hole transport material
CN111116646A (en) * 2019-12-01 2020-05-08 苏州和颂生化科技有限公司 Self-assembly interface material
CN111490161A (en) * 2020-04-24 2020-08-04 电子科技大学 Organic thin field effect transistor and preparation method thereof
CN111710785A (en) * 2020-06-18 2020-09-25 浙江浙能技术研究院有限公司 Non-pinhole large-area controllable perovskite growth film forming process
CN111710785B (en) * 2020-06-18 2022-08-16 浙江浙能技术研究院有限公司 Non-pinhole large-area controllable perovskite growth film forming process

Similar Documents

Publication Publication Date Title
CN106299138A (en) With the synthesis of phosphate group material and the preparation of self-assembled film on oxide surface thereof
CN102050428B (en) Method for arranging one-dimensional organic nano materials in orientating and patterning manner
CN112538085B (en) Molecular heterojunction and monomolecular field effect transistor
CN106103449A (en) Azepine nitrence analog and the purposes as semiconductor thereof
TWI469973B (en) Tetrathiafulvalene derivative, and organic film and organic transistor using the same
CN104302622A (en) Phenacene compounds for organic electronics
He et al. Molecular phase engineering of organic semiconductors based on a [1] benzothieno [3, 2-b][1] benzothiophene core
CN106495221B (en) A kind of preparation method of single layer molybdenum disulfide nano sheet
Xu et al. Crystal hierarchical supramolecular architectures from 1-D precursor single-crystal seeds
Niu et al. A facile approach for the fabrication of 3D flower-like Cu2S nanostructures on brass mesh with temperature-induced wetting transition for efficient oil-water separation
CN108503637A (en) A kind of novel N asymmetric acid imide molecules and its organic-inorganic composite body
Chen et al. Understanding the effect of antisolvent on processing window and efficiency for large-area flexible perovskite solar cells
CN110256456A (en) The organic nano material and its preparation method and application of thiophene spirane structure glycol racemic modification
CN104882540B (en) Planes of molecules is parallel to Si/SiO2The preparation method of the porphyrin monolayers on surface
Li et al. Single crystal ribbons and transistors of a solution processed sickle-like fused-ring thienoacene
CN104403129B (en) Double-component crosslinking agent and preparation method thereof, purposes
CN105399074B (en) A kind of graphene nanobelt and its synthetic method and application
CN101949026A (en) Method for preparing perylene polyimide derivative film
Kataeva et al. Charge-transfer complexes of linear acenes with a new acceptor perfluoroanthraquinone. The interplay of charge-transfer and F··· F interactions
CN108558933A (en) One kind has the exploitation and application of the aromatic amine material of charge storage
CN111116646A (en) Self-assembly interface material
JP5728777B2 (en) Organic compounds, organic semiconductor compounds, semiconductor elements, and solar cells
CN102295554A (en) Liquid crystal with high fullerene content and its preparation method
CN101838275B (en) Method for synthesizing 6-methyl-dibenzothienophridine
JP5578414B2 (en) Organic transistor using tetrathiafulvalene derivative and method for producing the same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20170104

RJ01 Rejection of invention patent application after publication