CN106854775B - The method for preparing organic semiconductive small molecule monocrystal thin films using water-air-organic solvent three phase boundary - Google Patents
The method for preparing organic semiconductive small molecule monocrystal thin films using water-air-organic solvent three phase boundary Download PDFInfo
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- CN106854775B CN106854775B CN201610991732.0A CN201610991732A CN106854775B CN 106854775 B CN106854775 B CN 106854775B CN 201610991732 A CN201610991732 A CN 201610991732A CN 106854775 B CN106854775 B CN 106854775B
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/54—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
- C30B7/06—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using non-aqueous solvents
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- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Abstract
The invention discloses the method for preparing organic semiconductive small molecule monocrystal thin films using water-air-organic solvent three phase boundary, this method key steps are as follows: 1) makees surface hydrophobicity processing to the surface on the surface of container inner wall and auxiliary piece；2) appropriate first solution is then injected into hydrophobic container, the first solution forms meniscus, forms slit between the edge and container inner wall of meniscus arc；It will be added in slit dissolved with the organic solution of small organic molecule, hydrophobic auxiliary piece is slowly back and forth inserted into the first solution, under the action of the first liquid level of solution tension and auxiliary piece, organic solution is sprawled in the first liquid level of solution orientation, as solvent is constantly volatilized, small organic molecule deposits to form organic single crystal thin film in the first solution surface.Large area, uniform, ultra-thin organic semiconductor small molecule monocrystal thin films are just obtained under the action of water surface tension and external force.
Description
Technical field
Water-air-organic solvent three phase boundary preparation large area, uniform, ultra-thin organic half are utilized the invention belongs to a kind of
The method of conductor small molecule monocrystal thin films.Specifically, the present invention relates to efficiently quickly the uniform organic film of preparation large area,
The self assembly of solvent volatilization from top to bottom grows small organic molecule monocrystal thin films at three phase boundary.
Background technique
The discovery of graphene demonstrates the presence of two-dimensional atomic crystal, and theory thinks that two dimensional crystal is to be not present before this
, using graphene as the two dimensional crystal of representative because its distinctive electrical properties is more and more applied to micro-nano electronics and biography
In sensor.And small organic molecule is because the self-assembly ability of " from bottom to top ", regulatable molecular structure make it in growth course
In available large area two-dimensional molecular crystal film.
Go preparation equal currently, the prior art has existed many methods waved using physical vapour deposition (PVD) (PVT) and solution
Even organic crystal film.But the crystal that PVT method obtains is mostly polycrystalline, and crystal quality is not high, and crystalline areas is limited, therefore is made
Device performance is obtained to have a greatly reduced quality.Although and the film crystal quality that solwution method obtains is very high, is mostly made of crystal band, direction
Property strong and uniformity it is not high.Therefore by a kind of simple and efficient way, it is brilliant to prepare the uniform two-dimensional molecular of growing large-area
Body thin film is highly important.
Summary of the invention
The present invention utilizes orderly self assembly behavior of the small organic molecule at water-air-organic solvent three-phase line of contact, and
Under the assisting growth of water surface tension and applied force, the uniform organic film of large area.Also there is high mobility simultaneously, solve
The small non-uniform problem of the area of small organic molecule crystal film, for the development of organic crystal film and its answering on device
With being of great significance.
Area to solve the problems, such as small organic molecule crystal film is small, uneven, high directivity, and the present invention provides one
For kind using small organic molecule in water-air-organic solvent three phase boundary volatilization self assembly method, this method has operation letter
Single, universality is strong, and use scope is wide, and obtained organic crystal film large area is uniform, and crystal quality is preferable, and mobility is higher,
Photoelectric properties are good.
To realize above-mentioned technical purpose and the technique effect, the invention is realized by the following technical scheme:
A method of organic semiconductive small molecule monocrystal thin films being prepared using water-air-organic solvent three phase boundary,
It is characterized in that, comprising the following steps:
Step 1) makees surface hydrophobicity processing to the surface of container inner wall and the surface of auxiliary piece；
Then step 2 injects appropriate first solution into hydrophobic container, the first solution forms meniscus, meniscus arc
Slit is formed between the edge and container inner wall of shape；It will be added in slit dissolved with the organic solution of small organic molecule, it will be hydrophobic
Auxiliary piece be constantly slowly back and forth inserted into the first solution, under the action of the first liquid level of solution tension and auxiliary piece, have
Machine solution is sprawled in the first liquid level of solution orientation, and as solvent constantly volatilizees in organic solution, small organic molecule is in the first solution
Surface deposits to form organic single crystal thin film.
It further include by organic single crystal thin film in a preferred embodiment of the present invention, after step 2 using transfer sheet from the
One solution surface is transferred to the step in target substrate.
In a preferred embodiment of the present invention, the film after transfer slowly dries in constant-temperature enclosed drier.
In a preferred embodiment of the present invention, hydrophobic treatment in step 1) are as follows: using the toluene of octadecyl trichlorosilane alkane
Solution impregnates appropriate time.
In a preferred embodiment of the present invention, the solvent and first solution in the organic solution are immiscible.
In a preferred embodiment of the present invention, first solution is water.
In a preferred embodiment of the present invention, the movement speed of the auxiliary piece is controlled by step-by-step movement translation stage.
In a preferred embodiment of the present invention, the auxiliary piece is slowly inserted into not cause the first solution surface visible ripple
Subject to.
In a preferred embodiment of the present invention, the auxiliary piece is glass slide.
It is a kind of using water-air-organic solvent three phase boundary preparation large area, uniform, ultra-thin organic semiconductor small molecule
The method of monocrystal thin films, comprising the following steps:
The cleaning of step 1) silicon wafer and container: the silicon wafer and vessel surface cleaned up is hydrophilic, and hydrophilic silicon wafer is to shift
Monocrystal thin films, container are operated to second step.
Step 2 glass container and glass slide hydrophobic treatment: clean glass container and glass slide is molten with analytically pure toluene
Liquid, which is swung, to be washed, after in OTS solution closed immersion appropriate time.Again successively with toluene, acetone ultrasound, such glass container inner wall and
The surface of glass slide becomes hydrophobic from hydrophilic.
The growth of step 3) organic film: the water of proper volume is then injected in the hydrophobic container of inward wall, because hydrophobic
Inner wall, water level become meniscus from concave meniscus, and meniscus and container inner wall form slit；By micro dissolved with small organic molecule
Organic solution is added drop-wise in the slit that the water surface and chamber wall are formed along inner wall.As solvent volatilizees, solution concentration increases, one
A hydrophobic glass slide is slowly inserted into solution, and under the action of water surface tension and external force, organic solution is sprawled to liquid level center
It comes, and then solvent volatilization organic film is formed in water level.
The transfer of step 4) organic film: after organic film is formed, slowly removing glass slide, then with hydrophilic SiO2/Si base
Bottom, organic film is transferred out from the water surface slowly.It is dried on blotting paper.
In a preferred embodiment of the present invention, the OTS solution is the toluene solution of octadecyl trichlorosilane alkane (OTS)
Water-wetted surface can be modified to hydrophobic surface by the solution of silane of (toluene: OTS=100:1).
In a preferred embodiment of the present invention, container must carry out hydrophobic treatment, organic molten for storing to provide slit
Liquid.
In a preferred embodiment of the present invention, selected organic solvent must be immiscible with water, could successfully obtain
Water-air-solvent three phase boundary.
In a preferred embodiment of the present invention, the small organic molecule must be completely insoluble in bottom phase (water phase).
In a preferred embodiment of the present invention, the organic solution need to be slowly dropped in slit along chamber wall.
In a preferred embodiment of the present invention, the small organic molecule be pentacene type, benzothiophene kind etc. there are commonly
Machine semiconductor molecule.
The invention solves the defect existing in the background technology, the present invention have it is following the utility model has the advantages that
1, organic crystal thin film growth process is easy to operate, is not necessarily to large scale equipment instrument and ultra-clean condition；
2, organic crystal film is grown under normal temperature environment, does not need high temperature requirement, energy saving；
3, it is suitable for using the method for water-air-organic solution three phase boundary auxiliary volatilization most readily soluble organic
Small molecule；
4, the small organic molecule crystal film being prepared is monocrystalline, relative to amorphous or polycrystalline sample, mobility
Higher, photoelectric properties are more preferable.
5, the small organic molecule crystal film being prepared, overlarge area is uniform, collects on a large scale for subsequent possible device
It may at providing；
6, organic crystal film is can be transferred in any substrate of growing on the water surface, facilitates the preparation of flexible device；
7, since preparation manipulation process of the present invention is simple and easy, favorable repeatability, reaction process is mild, has universality,
Therefore there is the value promoted the use.
Detailed description of the invention
Fig. 1 be a preferred embodiment of the present invention utilization water-air-organic solvent three phase boundary preparation large area,
Uniformly, the step schematic diagram of ultra-thin organic semiconductor small molecule monocrystal thin films；
Fig. 2 is what a preferred embodiment of the present invention obtained, and small organic molecule hexichol 1,4-Dithiapentalene (C10-BTBT) is single
Brilliant film.
In figure: 1, glass container, 2, glass slide, 3, organic solution, 4, water, 5, crystal film, 6, SiO2/ Si piece substrate.
Specific embodiment
To achieve the above object of the invention, a kind of technical solution of the present invention is: a kind of organic using water-air-
The method that solvent three phase boundary prepares organic semiconductive small molecule monocrystal thin films:
1) cleaning of silicon wafer: a part of SiO is taken2/ Si piece immerses piranha solution and heats appropriate time, then successively uses
Acetone, dehydrated alcohol, deionized water ultrasonic cleaning, with after being dried with nitrogen with oxygen plasma treatment, finally with a large amount of ultrapure waters
It rinses and uses and be dried with nitrogen.
2) glass container and glass slide hydrophobic treatment: clean glass container and glass slide is swung with toluene wash after be immersed in
Appropriate time in OTS solution, then successively with toluene solution repeated flushing repeatedly, acetone, ethyl alcohol, water ultrasound appropriate time.In this way
The surface of glass container inner wall and glass slide becomes hydrophobic from hydrophilic.
3) organic film is grown: the water of proper volume is then injected in the hydrophobic container of inward wall, because of hydrophobic inner wall,
Water level becomes meniscus from concave meniscus, and meniscus and container inner wall form slit；By micro dissolved with the organic of small organic molecule
Solution is added drop-wise in the slit that the water surface and chamber wall are formed along inner wall.As solvent volatilizees, solution concentration increases, and one is dredged
The glass slide of water is slowly inserted into solution, and under the action of water surface tension and external force, organic solution is come to liquid level center drawout,
And then solvent volatilization organic film is formed in water level.
4) organic film shift: after organic film is formed, slowly remove glass slide after again with hydrophilic SiO2/Si piece slowly
Organic film is transferred out from the water surface.It is dried on blotting paper.
In a preferred embodiment of the present invention, piranha solution described in step 1) is the concentrated sulfuric acid: hydrogen peroxide=
The strong oxidizing solution of 3:1, can be by SiO2The oxidation operation on surface falls and increases significantly SiO2The hydroxy number on surface increases
Its wellability.SiO2SiO in/Si piece substrate2Layer with a thickness of 300 nm, cleaning solvent is respectively acetone, ethyl alcohol, deionized water,
Each ultrasound appropriate time.
In a preferred embodiment of the present invention, OTS solution described in step 2 is octadecyl trichlorosilane alkane (OTS)
Toluene solution (toluene: OTS=100:1) solution of silane, water-wetted surface can be modified to hydrophobic surface.
In a preferred embodiment of the present invention, when organic solution described in step 3) is added dropwise, using liquid-transfering gun by 200
μ L organic solution is slowly dropped in groove along chamber wall.The concentration of organic solution is controlled in 2mg/mL, the movement of glass slide
Speed is 2mm/s.
In a preferred embodiment of the present invention, SiO described in step 4)2/ Si piece substrate is hydrophobic substrate, after transfer
Sample 30min or so is needed in closed drier, dry completely.
It is below with reference to the accompanying drawings and in conjunction with the embodiments, next that the present invention will be described in detail.
As shown in Figs. 1-2, the first preferred embodiment of the invention the following steps are included:
1) cleaning of silicon wafer: a part of SiO is taken2/ Si piece immerses piranha solution and heats appropriate time, then successively uses
Acetone, dehydrated alcohol, deionized water ultrasonic cleaning, with after being dried with nitrogen with oxygen plasma treatment, finally with a large amount of ultrapure waters
It rinses and uses and be dried with nitrogen.
2) glass container and glass slide hydrophobic treatment: clean glass container and glass slide is swung with toluene wash after be immersed in
Appropriate time in OTS solution, successively use toluene solution repeated flushing repeatedly, acetone, ethyl alcohol, water ultrasound.Such glass container
The surface of inner wall and glass slide becomes hydrophobic from hydrophilic.
3) organic film is grown: the water of proper volume is then injected in the hydrophobic container of inward wall, because of hydrophobic inner wall,
Water level becomes meniscus from concave meniscus, and meniscus and container inner wall form slit；By micro dissolved with the organic of small organic molecule
Solution is added drop-wise in the slit that the water surface and chamber wall are formed along inner wall.As solvent volatilizees, solution concentration increases, and one is dredged
The glass slide of water is slowly inserted into solution, and under the action of water surface tension and external force, organic solution is come to liquid level center drawout,
And then solvent volatilization organic film is formed in water level.
4) organic film shifts: after organic film is formed, slowly again with hydrophilic SiO after removal glass slide2/ Si piece is slowly
Organic film is transferred out from the water surface.It is dried on blotting paper.
Based on the above description of the preferred embodiments of the present invention, through the above description, related personnel completely can be with
Without departing from the scope of the technological thought of the present invention', various changes and amendments are carried out.The technical scope of this invention
It is not limited to the contents of the specification, it is necessary to determine the technical scope according to the scope of the claims.
Claims (6)
1. a kind of method for preparing organic semiconductive small molecule monocrystal thin films using water-air-organic solvent three phase boundary, special
Sign is, comprising the following steps:
Step 1) makees surface hydrophobicity processing to the surface of container inner wall and the surface of auxiliary piece；
Step 2) then injects appropriate first solution into hydrophobic container, and the first solution forms meniscus, meniscus arc
Slit is formed between edge and container inner wall；It will be added in slit dissolved with the organic solution of small organic molecule, it will be hydrophobic auxiliary
Piece is helped slowly back and forth to be inserted into the first solution, under the action of the first liquid level of solution tension and auxiliary piece, organic solution is
One liquid level of solution orientation is sprawled, and as solvent constantly volatilizees in organic solution, small organic molecule deposits shape in the first solution surface
At organic single crystal thin film；
First solution is water, solvent and the first solution objectionable intermingling in the organic solution；
The auxiliary piece, which is slowly inserted into be subject to, does not cause the first solution surface visible ripple.
2. method according to claim 1, it is characterised in that: further include using transfer sheet by organic single-crystal after step 2)
Film is transferred to the step in target substrate from the first solution surface.
3. method according to claim 2, it is characterised in that: the film after transfer slowly dries in the air in constant-temperature enclosed drier
It is dry.
4. method according to claim 1, it is characterised in that: hydrophobic treatment in step 1) are as follows: use octadecyl trichlorosilane
The toluene solution of alkane impregnates appropriate time.
5. method according to claim 1, it is characterised in that: the movement speed of the auxiliary piece, by step-by-step movement translation stage control
System.
6. according to claim 1 or 5 the methods, it is characterised in that: the auxiliary piece is glass slide.
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| WO2009031434A1 (en) * | 2007-09-03 | 2009-03-12 | Fujifilm Corporation | Single crystal thin film of organic semiconductor compound and method for producing the same |
| CN103436949A (en) * | 2013-09-04 | 2013-12-11 | 清华大学 | Single crystal thin film of organic semiconductor compound as well as preparation method and application of single crystal thin film |
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| WO2009031434A1 (en) * | 2007-09-03 | 2009-03-12 | Fujifilm Corporation | Single crystal thin film of organic semiconductor compound and method for producing the same |
| CN103436949A (en) * | 2013-09-04 | 2013-12-11 | 清华大学 | Single crystal thin film of organic semiconductor compound as well as preparation method and application of single crystal thin film |
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