CN106335874A - Pi-conjugated organic semiconductor molecular self-assembly structure and preparation method thereof - Google Patents
Pi-conjugated organic semiconductor molecular self-assembly structure and preparation method thereof Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title abstract description 27
- 238000005232 molecular self-assembly Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000007787 solid Substances 0.000 claims abstract description 10
- 239000002120 nanofilm Substances 0.000 claims abstract description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 27
- 239000012528 membrane Substances 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910002804 graphite Inorganic materials 0.000 claims description 14
- 239000010439 graphite Substances 0.000 claims description 14
- -1 1- octyl group Chemical group 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 11
- 150000001470 diamides Chemical class 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 125000005605 benzo group Chemical group 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 150000003949 imides Chemical class 0.000 claims description 5
- 239000002390 adhesive tape Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 206010008190 Cerebrovascular accident Diseases 0.000 claims 1
- 208000006011 Stroke Diseases 0.000 claims 1
- 239000006185 dispersion Substances 0.000 claims 1
- 239000002356 single layer Substances 0.000 abstract description 6
- 238000001338 self-assembly Methods 0.000 abstract description 5
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000005669 field effect Effects 0.000 abstract description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
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- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
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- 238000010992 reflux Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
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- 230000005611 electricity Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 150000002460 imidazoles Chemical class 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000000197 pyrolysis Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
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- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- CDKDZKXSXLNROY-UHFFFAOYSA-N octylbenzene Chemical compound CCCCCCCCC1=CC=CC=C1 CDKDZKXSXLNROY-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002094 self assembled monolayer Substances 0.000 description 1
- 239000013545 self-assembled monolayer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
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- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
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- Chemical & Material Sciences (AREA)
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- Physics & Mathematics (AREA)
- Composite Materials (AREA)
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- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Thin Film Transistor (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention provides two types of disc-shaped polycyclic aromatic hydrocarbon n-type organic semiconductor molecules having different symmetries, which are formed through an action between CDI or BPMI and a base along the lowest energy direction on the surface of the base, wherein a molecular film gradually reaches thermodynamic stability through changes of internal situation to form a two-dimensional structure of a high-density arrangement. By taking advantage of the self-assembly method of the disc-shaped polycyclic aromatic hydrocarbon organic molecules on a solid surface, a highly ordered semiconductor single-layer film is obtained, and the method is of great significance in the electronic transmission of such aspects as further adjusting and optimizing a field effect transistor, a diode, a light emitting diode, a solar cell and the like.
Description
Technical field
The present invention relates to the plate-like polycyclic aromatic hydrocarbon N-shaped organic semiconductor macromole of symmetric and unsymmetric is in highly directional pyrolysis stone
The preparation method of black (hopg) thin film, is prepared for cutting particularly to the symmetry by changing two kinds of molecules of bpmi and cdi respectively
So different high density and poroid unimolecular layer membrane self-assembled structures.
Background technology
The side such as molecule organic semiconductor thin film scene effect transistor, diode, light emitting diode, solaode (sc)
There is important application in face, therefore its preparation method causes widely concern.Molecule organic semiconductor thin film has many advantages: such as organic
Thing is easily obtained, and can effectively reduce the cost of device preparation；Organic film can prepare on a large scale it is adaptable to broad area device
Production；The preparation technology of organic electronic device more simple it is not necessary to strict external condition and harsh purity requirement；Become
The species of membrane technology is more, such as vacuum evaporation technology；Organic compound wide variety, some molecule organic semiconductors both can be led
Electricity, can light again, be easy to light and be electrically integrated；The transistor made with organic polymer, its electric property can be by organic
Molecular structure carries out suitable modification (connecting or clip suitable atom and group on strand) and is improved.
At present, organic semiconducting materials and organic electronic device are due to having excellent performance, processing technology and cheap
Cost industry and business application in terms of there are huge potentiality.These applications depend primarily on heterogeneous interface nanoscale shape
Looks Structure and electronic structure, carrier transporting mechanism in the film and how effectively to pass through to control organic semiconductor layer
Pattern remains the difficult point of current research to construct high performance organic film.We are from organic conjugate small molecular semiconductor material
Set out and optimized by different molecular structures and control its membrane structure, thus improving carrier further in semiconductor layer
Transmission characteristic, provides new visual angle and approach for preparing high performance organic semiconductor thin-film device.
Traditional microelectronics industry, people are being devoted to improving manufacture method thus producing finer device always
Part, but theoretic dimension limit will soon be reached.Therefore, some emerging manufactured smaller szie microelectronic components
Replacement scheme receives more and more attention, including this method of so-called molecular self-assembling.The method is passed through to make
Atom and molecule carry out spontaneous arrangement and combination on constructed good surface, thus obtaining the electricity of less nanoscale
Subfunction device system.By this means, can easily realize to device shape, the essence of substrate surface structure and composition
Really control.Once the mechanism of this spontaneous cohesive process can completely be understood and grasped, this shape of self assembly just can be passed through
Formula makes the surface nano-structure of metal material, semi-conducting material and molecular material obtain more widely extending.Molecule is from group
The modeling, molecular device, Surface Engineering and the nanosecond science and technology field that are contained in biotechnology have had and have been widely applied very much.
In following decades, molecular self-assembling will produce tremendous influence in emerging technology areas as a kind of technological means.
Polycyclic aromatic hydrocarbon type organic bpmi and cdi, the Organic substance of pi-conjugated plate-like has good planes of molecules and very
Strong rigidity, such compound has a very strong chemical stability, heat stability, the designability of its molecular structure and excellent
Photoelectric property obtained extensive research.This kind of material typically dissolves in organic solution, and processed is convenient, and its supermolecule is certainly
It is assembled in complicated, the regular function nano material aspect of preparation structure and shows significant advantage, and be controlled material macroscopic view
A kind of effective method of property.As a kind of typical n-type organic semiconducting materials, it is to construct organic optoelectronic device such as
The important materials of active layer in field-effect transistor, light emitting diode and solaode.Therefore, Pi-conjugated systems supermolecule from
Assembling has become as the study hotspot of the Disciplinary Frontiers such as information, material, biology in recent years.
At present, the special nature based on nano material and its application in terms of device, regulates and controls semiconductor molecule nano junction
The importance of structure increasingly highlights.Because the small molecule of pi-conjugated organic multi-ring aromatic structure is easy to assemble, in conjunction with existing
Some technology, modulate our required microstructures to control organic semi-conductor photoelectric property, to improve organic sun
Can conversion, optical conductor, electroluminescent, organic-inorganic composite semiconductor material, the efficiency of organic photoelectric molecular device have important
Meaning.
Content of the invention
An object of the present invention is to provide a kind of two-dimentional solid matter monolayer of symmetrical cool diamides (cdi) molecule
Film nanostructured.
One of for reaching above-mentioned purpose, the present invention adopts the following technical scheme that:
A kind of two-dimentional solid matter unimolecular layer membrane nanostructured of symmetrical cool diamides (cdi) molecule, by cdi in substrate table
Face is formed along the direction (along<010>direction for example on hopg) of minimum energy with substrate effect, and molecular film passes through internal
Situation changes, and progressivelyes reach thermodynamic (al) stable, defines the two-dimensional structure of high-density array.Multiring structure is subject to highly directional pyrolysis
The lattice modulating action of graphite, constitutes in substrate surface and makes up type monolayer membrane structure.
An object of the present invention also resides in provides a kind of two dimension of asymmetrical benzo list acid imide (bpmi) molecule
Poroid chirality unimolecular layer membrane nanostructured, by bpmi substrate surface along minimum energy direction (for example on hopg along <
010 > direction) form with substrate effect, molecular film passes through internal situation change, progressivelyes reach thermodynamic (al) stable, is formed
The two-dimensional structure of poroid arrangement.Multiring structure is subject to the lattice modulating action of highly oriented pyrolytic graphite, constitutes more in substrate surface
Apotype single-layer membrane structure.
In such scheme, constitute high-sequential the molecule cdi (cool diamides) of the self-assembled film structure of two dimension and
Bpmi (benzamide) planar arrangement all in hopg substrate, (includes semiconductor molecule by the active force between molecule
Between and molecule and solvent between) cooperative interaction and molecule and substrate between obtains.
The pi-conjugated molecule organic semiconductor self-assembled structures of two kinds of the present invention multi-ring plate-likes, have different symmetric N-shapeds
Molecule organic semiconductor cdi and bpmi constructs the order thin film structure of molecular level, and this kind of molecule has structure pi-conjugated greatly,
There is good photoelectric property, both two dimension self-assembled structures, to improving solaode conversion ratio, improve photoelectric device effect
Rate has important using value.
Preferably, described cdi and bpmi has a following molecular structure:
The synthetic route of described cdi and bpmi sees below formula i and ii respectively:
Cdi and bpmi can be by method below or method synthesis that is any known or finding in the future.
Cdi synthesizes:
Under the conditions of compound and maleic anhydride and tetrachloroquinone molal quantity identical, stirring oil bath is at 240 DEG C
Reacting by heating 10 minutes, reflux condensation mode, obtain compound 2.Compound 2 and lauryl amine reaction stirring oil bath are added at 240 DEG C
Thermal response 10 minutes, reflux condensation mode, and nitrogen, nitrogen '-dimethyl -1,3- Malondiamide (1.0g) mixes, then by imidazoles
(5.5g) it is added in mixture, at 180 DEG C, argon protection stirring reaction 4 hours, then pass through silica gel column chromatography purification, that is,
Can get the cool diamides (cdi) that purity is 95%.
Bpmi synthesizes:
Under the conditions of compound and maleic anhydride and tetrachloroquinone molal quantity identical, 240 DEG C of stirring oil bath adds
Thermal response 10 minutes, reflux condensation mode, obtain compound 2.By compound 2 (0.8g) and nitrogen, nitrogen '-dimethyl -1,3- Malondiamide
(1.0g) mixes, and then imidazoles (5.5g) is added in mixture, argon protection stirring reaction 4 hours at 180 DEG C, then
By silica gel column chromatography purification, that is, the orange-yellow benzo monoamides (bpmi) (95%) obtaining.
An object of the present invention also resides in the two-dimentional solid matter list providing symmetrical cool diamides molecule of the present invention
The two dimension poroid chirality unimolecular layer membrane nanostructured of molecule tunic nanostructured or asymmetrical benzo list acid imide molecule
Preparation method, comprise the steps:
(1) solution containing cdi or bpmi is prepared using the solvent that can dissolve cdi or bpmi；
(2) cleaning treatment substrate；
(3) solution containing cdi or bpmi configuring step (1) is added drop-wise in the fresh substrate of step (2), and solute is in base
Basal surface spreads, solution evaporation, and the unimolecular layer membrane that be can get cdi or bpmi of sequential 2 D after Thermodynamically stable is received
Rice structure.
Preferably, preparation is carried out at room temperature in step (1).
Preferably, solvent for use be 1- octyl group benzene, a kind in the long chain alkane class (the such as tetradecane) of c8-c20, preferably
1- octyl group benzene for purity >=99%.
Preferably, purity >=95% of cdi or bpmi.
Preferably, the concentration of the solution of cdi or bpmi is 10-4-10-6Mol/l, for example, 3 × 10-6mol/l、9×10- 6mol/l、15×10-6mol/l、30×10-6mol/l、50×10-6mol/l、75×10-6mol/l、90×10-6Mol/l etc..
Preferably, adopt ultrasonic disperse during preparation.
Preferably, power when ultrasonic is 100w, and the ultrasonic time is more than 10 minutes, preferably more than 20 minutes, with
Guarantee that semiconductor molecule can be homogeneously dispersed in solvent.
Preferably, substrate described in step (2) is highly oriented pyrolytic graphite (hopg), preferably surface atom level is smooth
Highly oriented pyrolytic graphite.
Preferably, described cleaning is carried out by the method that adhesive tape is peeled off.
Preferably, in step (3), the amount of the 1- octyl group benzole soln containing cdi or bpmi of Deca is 0.5-15 μ l, preferably
For 1-5 μ l.
Preferably, the time of solution evaporation is more than 5 minutes, preferably 10-50 minute.
Preferably, the method for the present invention may include following steps:
1) prepare the 1- octyl group benzole soln containing cdi or bpmi under room temperature: cdi or bpmi (purity >=95%) is dissolved in 1-
Octyl group benzene (1-phenyloctane, c14h22, purity >=99%) in, obtaining concentration is 10-4-10-6Cdi and bpmi of mol/l
1- octyl group benzole soln；And with ultrasonic more than 20 minutes of Ultrasound Instrument (power be 100w), to guarantee that semiconductor molecule can be uniform
Ground is scattered in 1- octyl group benzene；
2) cleaning treatment substrate: select the smooth hopg of surface atom level, the method preparation through being peeled off with adhesive tape is clean
Smooth substrate；
3) preparing multi-ring pi-conjugated machine semiconductor molecule membrane structure: by step 1) 1- of cdi or bpmi for preparing is pungent
Base benzole soln Deca step 2) arrive ready totally smooth substrate surface, after volatilizing more than 5 minutes, solute is in substrate surface
Diffusion, solution evaporation, can get cdi the or bpmi unimolecular layer membrane nanostructured of sequential 2 D after Thermodynamically stable.
The method that the present invention utilizes the self assembly in the surface of solids for the multi-ring plate-like aromatic hydrocarbons organic molecule, obtains high-sequential
Semiconductor single thin film, its for further adjust and optimize field-effect transistor, diode, light emitting diode, solar energy
The electric transmission of the aspects such as battery has and its important meaning.
Brief description
Fig. 1 a is in the stm image (20nm × 20nm) of the monofilm nanostructured of high-density array for cdi membrane structure；
Fig. 1 b is high-resolution stm image (7nm × 7nm) of the single-layer membrane structure of high-density array of cdi membrane structure；
Fig. 2 a is in the stm image (16nm × 16nm) of the monofilm nanostructured of poroid arrangement for bpmi membrane structure；
Fig. 2 b is in high-resolution stm image (7nm × 7nm) of the single-layer membrane structure of poroid arrangement for bpmi membrane structure.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that described enforcement
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Hereinafter sequential 2 D monofilm nanostructured of cdi molecule of the present invention and preparation method thereof is carried out in detail
Bright:
Embodiment 1
In 1.5ml centrifuge tube, add cdi (about 0.5mg) in the 1- octyl group benzene of 1ml, ultrasonic disperse about 20
Minute makes molecule be completely dissolved, and dilutes ten times, drips solution (about 1 μ l) to clean hopg surface after being transferred to dropper
(the new hopg peeling off), because graphite and solution are all hydrophobic, solution diffuses to form film in uniform thickness in graphite surface,
Cdi Molecular Adsorption forms dimensional high-density arrangement monofilm nano thin-film structure on hopg surface.
It is fixed to dripping the hopg having above-mentioned solution on sample stage, then make the slow approximating spline of stm needle point (pt/ir, 80:20)
Product surface until be immersed in solid/liquid interfaces, but not in contact with to graphite surface, then with being entered with PSTM (stm)
Row measurement, obtains the stm image (with reference to Fig. 1 a, Fig. 1 b) of orderly cdi of arranging between solid/liquid interfaces.In order to needle point is reduced or avoided
Impact to the stm image of scanning, changes different needle points for several times and measures and compare, to obtain real view data.By scheming
1a and Fig. 1 b understands, cdi molecular self-assembling has become the close-packed configuration forming sequential 2 D arrangement.
With reference to Fig. 1 a and 1b, the brighter petal-like part of in figure is cdi molecular bulk, cool because cool have pi-conjugated greatly
System, produces higher tunnel current, the parameter of measurement is 1.0 ± 0.1nm (theoretical value 1nm) in stm measurement, and image
The dark part of middle brightness is the amide moieties with alkyl chain, because its electric conductivity is poor, so its stm dark images.
From image 1a it is seen that, close-packed arrays between cdi molecule, formed rectangle cell configuration, unit cell dimension be a=
1.8 ± 1nm, b=1.2 ± 1nm, α=60 °, only comprise a cdi molecule in a unit cell.Mainly pass through model moral between molecule
Hua Li, molecule is mainly π-π effect with the effect of substrate, forms sequential 2 D nanostructured.Cdi Molecular Graphs picture is shown as carrying
There is the petal shape of two ears.Learnt by dft molecular simulation and Theoretical Calculation, the energy of each structure cell is(including the interaction interacting with structure cell and base inside structure cell).
By in 1b, we can find, the angle of structure cell arrangement is 60 °, consistent with 60 ° of graphite base, so molecule exists
Suprabasil row is equally induced by substrate, cdi molecule cool structure two ends, there are two dark sections, this is mainly
Molecule amide group change molecule electron cloud arrangement, in addition, in Fig. 1 b we it is found that the length of this molecule with
Distance between seat is very close, thus, it can be known that intermolecular do not have mutually tangling of alkyl chain, so this nanostructured is main
By controlling that π-π acts on.The orderly nanostructured of n-type semiconductor molecule can significantly improve the electronics of cdi unimolecular layer membrane
Mobility, makes opto-electronic device and solaode have higher efficiency, the therefore self-assembled structures of cdi molecule and cdi divides
The Thermodynamically stable self-assembled structures of son are significant.
Embodiment 2
In 1.5ml centrifuge tube, add bpmi (about 0.4mg) in the 1- octyl group benzene of 1ml, ultrasonic disperse about 20
Minute makes molecule be completely dissolved guarantees dispersed, ten times of dilution, drips solution (about 1 μ l) extremely after being then transferred to dropper
Clean smooth hopg surface, because graphite and solution are all hydrophobic, solution, after graphite surface divergent contour band is stable, will drip
The hopg having above-mentioned solution is fixed on sample stage, then makes stm needle point (pt/ir, 80:20) slowly approach sample surfaces until soaking
Enter to solid/liquid interfaces, but not in contact with to graphite surface, be scanned with PSTM (stm), obtain orderly bpmi
The stm image (with reference to Fig. 2 a, Fig. 2 b) of molecule.From Fig. 2 a and Fig. 2 b, bpmi forms sequential 2 D cavernous structure.
With reference to Fig. 2 a and 2b, the brighter part of in figure is bpmi molecular bulk, because pi-conjugated system is produced in stm measurement
The higher tunnel current of life, the length of measurement is 1.2 ± 0.1 (theoretical values 1.15nm), and the dark part of brightness in image
It is alkane side chain, because its electric conductivity is weaker, so its afterbody stm dark images.
From image 2a it is seen that, close-packed arrays between bpmi molecule, formed cavernous structure, unit cell dimension be a=1.9
± 0.1nm, b=2.20 ± 0.1nm, α=120 °, comprise two bpmi molecules in a unit cell, between molecule, pass through Van der Waals
Power, the active force between alkyl chain, and intermolecular hydrogen bond and molecule are orderly with the interaction formation two dimensional height of substrate
Nanostructured.Learnt by dft molecular simulation and Theoretical Calculation, the energy of each structure cell is -0.261,
(including the interaction interacting with structure cell and base inside structure cell).
By in Fig. 2 b, we it is found that molecule in bpmi in two kinds of different direction self assemblies arrangements, two kinds
The angle in direction is 120 °, and thus it could be speculated that this molecule is subject to, orthohexagonal graphite base induction is relatively strong, and molecule is right along one
Claim axle to define chiral structure, self-assembled structures image stabilization, be difficult to change in time.And the hole of thin film also carries enough
One c60Molecule, therefore this kind is organized the die-filling role serving as template in common assembling and is also had important effect.And n-type semiconductor is divided
The orderly nanostructured of son can significantly improve the electron mobility of bpmi unimolecular layer membrane, makes opto-electronic device and solar energy
Battery has higher efficiency, and the self-assembled structures discovery of therefore bpmi molecule is significant.
Because cdi and bpmi molecule is multi-ring pi-conjugated acid imide molecule, there are different symmetry, but but all may be used
To form thermodynamics stable state self-assembled structures.Thus, it can be known that multi-ring pi-conjugated molecule is it is easy to form ordered structure, but by
Cause its intermolecular force in substituent group and symmetric difference, molecule is different from hopg substrate effect power, thus being had
There is the two-dimensional molecular self-assembled monolayer membrane structure of different structure.Symmetry has to the sequential 2 D nanostructured of its self assembly props up
The effect of auxiliary tone section.By the research of molecular level, obtain multi-ring pi-conjugated be how Molecular regulator self-assembled structures, and orderly
Self-assembled structures to the exploitation of micro-nano device and molecular device, there is highly important using value.
Applicant states, the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, do not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The interpolation of the equivalence replacement to each raw material of product of the present invention and auxiliary element, selection of concrete mode etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (10)
1. a kind of two-dimentional solid matter unimolecular layer membrane nanostructured of symmetrical cool diamides molecule is it is characterised in that by cdi in base
Basal surface is formed along the direction of minimum energy with substrate effect, and molecular film passes through internal situation change, progressivelyes reach heating power
That learns stablizes, and defines the two-dimensional structure of high-density array.
2. nanostructured according to claim 1 is it is characterised in that described cdi has a following molecular structure:
.
3. a kind of two dimension of asymmetrical benzo list acid imide molecule poroid chirality unimolecular layer membrane nanostructured, its feature exists
In, formed along the direction of minimum energy with substrate effect in substrate surface by bpmi, molecular film passes through internal situation change,
Progressively reach thermodynamic (al) stable, define the two-dimensional structure of poroid arrangement.
4. nanostructured according to claim 3 is it is characterised in that described bpmi has a following molecular structure:
.
5. the two-dimentional solid matter unimolecular layer membrane nano junction of the symmetrical cool diamides molecule described in a kind of any one of claim 1-4
The preparation method of the two dimension poroid chirality unimolecular layer membrane nanostructured of structure or asymmetrical benzo list acid imide molecule, including
Following steps:
(1) solution containing cdi or bpmi is prepared using the solvent that can dissolve cdi or bpmi；
(2) cleaning treatment substrate；
(3) solution containing cdi or bpmi configuring step (1) is added drop-wise in the substrate of step (2), and solute expands in substrate surface
Dissipate, solution evaporation, can get the unimolecular layer membrane nanostructured of cdi or bpmi of sequential 2 D after Thermodynamically stable.
6. preparation method according to claim 5 it is characterised in that in step (1) preparation carry out at room temperature.
7. the preparation method according to claim 5 or 6 it is characterised in that in step (1) solvent for use be 1- octyl group benzene,
The 1- octyl group benzene of a kind of the long chain alkane apoplexy due to endogenous wind of c8-c20, preferably purity >=99%；
Preferably, purity >=95% of described cdi or bpmi；
Preferably, the concentration of the solution of described cdi or bpmi is 10-4-10-6mol/l.
8. the preparation method according to any one of claim 5-7 is it is characterised in that adopt ultrasonic when preparing in step (1)
Dispersion；
Preferably, power when ultrasonic is 100w, and the ultrasonic time is more than 10 minutes, preferably more than 20 minutes, more preferably
For 1 hour.
9. the preparation method according to any one of claim 5-8 is it is characterised in that substrate described in step (2) is Gao Ding
To pyrolytic graphite, the preferably smooth highly oriented pyrolytic graphite of surface atom level；
Preferably, described cleaning is carried out by the method that adhesive tape is peeled off.
10. the preparation method according to any one of claim 5-9 it is characterised in that in step (3) Deca containing cdi or
The amount of the 1- octyl group benzole soln of bpmi is 0.5-15 μ l, preferably 1-5 μ l；
Preferably, the time of solution evaporation is more than 5 minutes, preferably 10-50 minute.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108191903A (en) * | 2017-12-21 | 2018-06-22 | 上海师范大学 | A kind of synthetic method of cool imidodicarbonic diamide and its derivative based on imidodicarbonic diamide |
| CN111172594A (en) * | 2020-01-15 | 2020-05-19 | 深圳大学 | Method for preparing single crystal by electric stimulation induction |
| CN112062993A (en) * | 2020-09-18 | 2020-12-11 | 中国科学院微电子研究所 | Preparation method of monolayer semiconductor high polymer film |
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2016
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| MIN-MIN SHI,等: "π-π Interaction among Violanthrone Molecules: Observation, Enhancement, and Resulting Charge Transport Properties", 《J. PHYS. CHEM. B》 * |
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| XIANG SHAO,等: "Chain-Length Effects on Molecular Conformation in and Chirality of Self-Assembled Monolayers of Alkoxylated Benzo[c]cinnoline Derivatives on Highly Oriented Pyrolytic Graphite", 《J. PHYS. CHEM. B》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108191903A (en) * | 2017-12-21 | 2018-06-22 | 上海师范大学 | A kind of synthetic method of cool imidodicarbonic diamide and its derivative based on imidodicarbonic diamide |
| CN108191903B (en) * | 2017-12-21 | 2020-03-17 | 上海师范大学 | Method for synthesizing coronadimide and derivative thereof based on perylene diimide |
| CN111172594A (en) * | 2020-01-15 | 2020-05-19 | 深圳大学 | Method for preparing single crystal by electric stimulation induction |
| CN111172594B (en) * | 2020-01-15 | 2021-08-17 | 深圳大学 | Method for preparing single crystal by electric stimulation induction |
| CN112062993A (en) * | 2020-09-18 | 2020-12-11 | 中国科学院微电子研究所 | Preparation method of monolayer semiconductor high polymer film |
| CN112062993B (en) * | 2020-09-18 | 2022-07-01 | 中国科学院微电子研究所 | Preparation method of monolayer semiconductor high polymer film |
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