CN102583235A - Method for preparing organic micro/nano structure by liquid phase chemical reaction method and patterning in situ - Google Patents
Method for preparing organic micro/nano structure by liquid phase chemical reaction method and patterning in situ Download PDFInfo
- Publication number
- CN102583235A CN102583235A CN2012100763102A CN201210076310A CN102583235A CN 102583235 A CN102583235 A CN 102583235A CN 2012100763102 A CN2012100763102 A CN 2012100763102A CN 201210076310 A CN201210076310 A CN 201210076310A CN 102583235 A CN102583235 A CN 102583235A
- Authority
- CN
- China
- Prior art keywords
- solution
- radical anion
- reaction
- organic
- micro
- 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.)
- Granted
Links
Images
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method for preparing an organic micro/nano structure by a liquid phase chemical reaction method and patterning in situ. The invention adopts the main scheme that: anion radical salt of organic molecules is prepared by a reduction method; and the anion radical salt of the organic molecules is oxidized into the original substance with a certain structure by an oxidation method. The method has wide prospect for application of organic nano materials, in particular N-type functional molecules to integrated circuits, solar batteries, sensors, information storage and integrated photonics.
Description
Technical field
The present invention relates to a kind ofly, belong to organic micro-nano structure technical field with organic micro-nano structure of the controlled preparation of liquid-phase chemical reaction method and former bit-patterned method.
Background technology
In recent decades, nanosecond science and technology are in the ascendant.Compare with traditional block and monomer solution,, received researcher's growing interest thus, and expedited the emergence of very application prospects because metal and inorganic semiconductor micro-nano material have the physics and the chemical property of many excellences.Up to now, scientist has successfully realized the controlled preparation of many metals and inorganic semiconductor nano material size and pattern, and finds that the electronic structure of these materials and performance often have size and pattern correlation.Meanwhile; Compare with inorganic material; Organic material also has its incomparable advantage; Such as structure cutting property, plasticity and the low-cost raw material that is easy to get etc., this makes the research of organic micro-nano material aspect become an important hot fields in the micro-nano material research contents rapidly, also widens and enriched simultaneously the research category of micro-nano material.More noticeable is that the photoelectric properties of the uniqueness that the organic semi-conductor micro-nano structure is displayed also make it become display of future generation, integrated circuit, solar cell, sensor, information storage, the research object in fields such as integrated photon.
Research for many years is verified; Because organic molecule effect each other mainly relies on weak Van der Waals force, hydrogen bond, π-active forces such as π interaction to combine; Rising material to the organic compound photoelectric property is not Wannier exciton in semiconductor and the metallic crystal, but the electric charge in Frenkle exciton or " transition " organic molecule semiconductor shifts (charge-transfer CT) exciton.Therefore, the function element that organic compound constitutes not only depends on the molecular structure of itself, also depends on its package assembly on micro/nano-scale to a certain extent consumingly.That is to say; In the organic nano device; The pattern of organic molecule, structure, assembling form all will influence its performance to a great extent; Therefore how to realize the controlled preparation of organic micro-nano material, realize in order extensive or the original position self assembly also become gradually the current technical problem of needing solution badly it
In the controlled technology of preparation method of present organic micro-nano material, common has: 1. physical vapor transmission after pair substrate is modified or chemical gaseous phase transmission; 2. utilize soft or hard template (surfactant micella or anodic oxidation aluminium formwork) that the assembling of organic molecule is regulated and control; 3. utilize again deposition (normal temperature or high temperature) method that thermodynamics or dynamics regulation and control are carried out in the growth of organic micro-nano structure; 4. realize that by the weak force between other organic molecule the collaborative self assembly of organic molecule forms micro-nano structure.These methods have obtained effective application in the preparation of organic micro-nano structure, but still have certain limitation.For example: it is certain for heat endurance that method 1 needs raw material to have, and needed device is also complicated simultaneously, and energy consumption is high, and raw material availability is not high, and is uneconomical; Method 2,3,4 all need raw molecule certain solubility to be arranged conveniently to carry out liquid phase processing in solvent.Therefore; Good to those photoelectric properties; But solubility does not satisfy the nanostructured preparation and the former bit-patterned challenge that caused thereof of the organic photoelectric molecule of liquid phase low cost, low energy consumption processing, has limited simultaneously yet the research of its inherent problem in science is used with large-scale device preparation.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the liquid-phase chemical reaction legal system to have machine micro-nano structure and reaction in-situ patterning.
Major programme of the present invention is to utilize reducing process to prepare the radical anion salt of organic molecule, and then through oxidizing process the radical anion salt of organic molecule is oxidized to the former material with a fixed structure.
Liquid-phase chemical reaction legal system provided by the invention has machine micro-nano structure method, and step is following:
(1) utilizes reduction reaction to prepare the radical anion salt of organic molecule, and be made into solution;
(2) configure the solution that contains oxidant, the radical anion salting liquid of removing step (1) is injected in the solution that contains oxidant, and the amount of oxidant makes the abundant oxidation of radical anion, stirs or ultrasonicly makes it abundant mixing, and lucifuge leaves standstill then, reacts;
(3) after reaction finished, washing can obtain one dimension or two-dimentional organic micro-nano structure.
Present organic molecule applicatory is mainly common N-type semiconductor material in the above-mentioned steps (1), and is for example preferred: perfluoro metallo phthalocyanine (fluorinated metal phthalocyanine), cyanic acid benzoquinone compound (TCNQ, F
4-TCNQ), fullerene compound (C
60, C
70) perylene diimide (Perylenediimide) and derivative (comprise and carry out N position Qu Dai De perylene diimide and waist position halo De perylene diimide (halogenated perylenediimide)) thereof, adopt conventional liquid phase one-step reducing process to make the radical anion salt or the solution of corresponding organic molecule; Solution described in the step 1, its solvent are acetonitrile, oxolane etc.
In the step (2); The said solution that contains oxidant; Its solvent is generally alcohols, water or the solvent (acetonitrile, oxolane etc.) identical with the free radical salting liquid, and oxidant is saturated oxygen, liquor ferri trichloridi, hydrogen peroxide solution, the potassium ferricyanide, and the consumption of oxidant is for guaranteeing to make the abundant oxidation of radical anion salt; If increase the concentration of oxidant, then can accelerate the speed of the oxidized zeroth order monomer of radical anion simultaneously.Stir or the preferred 30s～1min of ultrasonic time the preferred 30min～4h of time of repose.
The concentration of the radical anion solution of being taken is generally 0.5mmol/L～2mmol/L.The volume ratio that contains oxidizing agent solution and free-atom aqueous solution through control; Can regulate and control the concentration of precursor and the generating rate of zeroth order monomer; Regulate and control the growth rate of micro-nano structure thus, obtain the micro-nano structure of different pattern (one dimension or two dimension) and size.For instance, for N position unsubstituted Lu Dai perylene diimide compounds, when the liquor capacity that contains oxidant is 5 times of the free-atom aqueous solution volume ratio and when above, resulting structure is a two-dimensional structure; When the liquor capacity that contains oxidant is 2 times of the free-atom aqueous solution volume ratio and when following, what obtain is the structure of one dimension.
The cleaning solvent that step (3) is selected for use is preferably the used solvent of dissolved oxidant in the corresponding step (2).
Said method is through the suitable oxidant of above-mentioned selection; Utilize the power of their oxidability to regulate the speed that radical anion is oxidizing to neutral molecule; The speed of conditioned reaction can realize the regulation and control to the micro-nano structure growth rate, to obtain the structure of different-shape, different size.Meanwhile; If the nonionic surface active agent of adding 0.05mmol/L～0.5mmol/L (for example: F127; P123 etc.) as the growth and the assembling of soft template aided nano structure; Can realize further regulation and control, for example on specific dimension or direction, carry out limiting growth the size of micro-nano structure.
Another kind of liquid-phase chemical reaction legal system provided by the invention is equipped with the method for original position patterned devices, and step is following:
Utilize reduction reaction to prepare the radical anion salt of organic molecule, and be made into solution; The array electrode base sheet of handling well impregnated in the radical anion solution, under airtight lucifuge condition, make anion carry out the in-situ oxidation reaction, after reaction finishes, wash substrate, obtain one dimension or two-dimentional organic micro-nano structure of array at electrode surface.
Present organic molecule applicatory is mainly common N-type semiconductor material in the above-mentioned steps, and is for example preferred: perfluoro metallo phthalocyanine (fluorinated metal phthalocyanine), cyanic acid benzoquinone compound (TCNQ, F
4-TCNQ), fullerene compound (C
60, C
70) perylene diimide (Perylenediimide) and derivative thereof; Comprise and carry out the substituted derivative in N position, and the derivative of waist position halo (halogenated perylenediimide), adopt conventional liquid phase one-step reducing process to make the radical anion salt or the solution of corresponding organic molecule; The solution of radical anion salt, its solvent are acetonitrile, oxolane etc. (preferred acetonitrile); In this step,, and join solution before in advance with nitrogen bubble deoxygenation 30min if the solution of selecting for use dissolution with solvents free radical salt to be made into is then selected anhydrous acetonitrile for use; If usefulness is the radical anion solution that directly reaction obtains, survey and need not to carry out this deoxygenation operation, only need to shift utensil and get final product at the solution that the condition of starvation pipettes respective volume with syringe or other solution.
The preparation method of the array electrode base sheet of handling well; May further comprise the steps: the monocrystalline silicon piece that (1) height N mixes, resistivity is the 0.05-0.20 ohmcm, the plane is [100] direction; Then silicon chip is carried out thermal oxide, make its surface generate the SiO of a layer thickness 20nm-500nm
2Thermal oxide layer, and carry out single-sided polishing, as substrate; (2) selecting in the substrate under the vacuum condition, through reticle vapor deposition one deck Cr of patterning (preferred 2nm) is as adhesion layer in advance, vapor deposition one deck (preferred 30nm) metal A g or Cu realizes array again; (3) use acetone respectively, washing with alcohol, and dry up gently with nitrogen, place 60 ℃ baking oven to keep 30min afterwards, perhaps carry out the about 5～10min of surface oxidation treatment with the uv ozone cleaning machine.
Certain hour is soaked in array metal electrode substrate of handling well and radical anion solution reaction, and the sealing lucifuge leaves standstill.Thereby can control the growth of organic nanostructure through control anion concentration, reaction time at substrate surface.
The washing substrate preferably soaked 2 minutes with reaction dissolvent, and nitrogen dries up gently.
Operation is simple for preparation method provided by the invention, also can adopt different subsequent treatment as required, can directly utilize the organic micro-nano material of the extensive controlled preparation of method of liquid-phase chemical reaction, obtains the structure of required pattern and size.Meanwhile; Utilize the radical anion of preparation; Can also be on the electrode basement that patterning is good in advance; Realizations original position micro-nano materials such as the kind through regulating the different metal electrode, size, raceway groove length and width, reaction time, concentration are grown and the constructing of device; Choose the different oxidation agent or add different surface active agents and carry out assisting growth, can be effectively the size and the pattern of organic micro-nano structure of finally obtaining be regulated and control, can realize the growth of material in tens nano level sizes to the tens micron-scale scope.The corresponding organic molecule radical anion solution that makes; The solution reaction that contains oxidant with different volumes; Can realize the transformation of sample from the one dimension to the two-dimensional growth; In the time of concentration height (volume of reactant liquor is little), generate one-dimentional structure, generate two-dimensional structure in the time of concentration low (volume of reactant liquor is big).
Method provided by the invention be organic nano material particularly the application of N type functional molecular in the middle of integrated circuit, solar cell, sensor, information storage, integrated photon are learned wide prospect is provided.
Description of drawings
Fig. 1 is UV, visible light (Uv-Vis) absorption spectrum of the sample 1# of the embodiment of the invention 1;
Fig. 2 is field emission scanning electron microscope (FESEM) image of the sample 2# of the embodiment of the invention 1;
Fig. 3 is X-ray diffraction (XRD) image of the sample 2# of the embodiment of the invention 1;
Fig. 4 is field emission scanning electron microscope (FESEM) image of the sample 3# of the embodiment of the invention 1;
Fig. 5 is field emission scanning electron microscope (FESEM) image of the sample 4# of the embodiment of the invention 1;
Fig. 6 is field emission scanning electron microscope (FESEM) image of the sample 5# of the embodiment of the invention 1;
Fig. 7 is SEAD (the Selected Area Electron Diffraction) image of the sample 5# of the embodiment of the invention 1;
Fig. 8 is field emission scanning electron microscope (FESEM) image of the sample 6# of the embodiment of the invention 2, reaction time 30min;
Fig. 9 is field emission scanning electron microscope (FESEM) image of the sample 6# of the embodiment of the invention 2,1 hour reaction time;
Figure 10 is field emission scanning electron microscope (FESEM) image of the sample 6# of the embodiment of the invention 2,4 hours reaction time;
Figure 11 is field emission scanning electron microscope (FESEM) image of the sample 6# of the embodiment of the invention 2,4 hours reaction time, the wherein photo of raceway groove multiplication factor.
Figure 12 is field emission scanning electron microscope (FESEM) image of the sample 6# of the embodiment of the invention 2, less multiplication factor, large tracts of land photo;
Figure 13 is the micro-Raman collection of illustrative plates of laser co-focusing of the sample 6# of the embodiment of the invention 2;
Figure 14 is UV, visible light (Uv-Vis) absorption spectrum of the sample 7# of the embodiment of the invention 3;
Figure 15 is field emission scanning electron microscope (FESEM) image of the sample 8# of the embodiment of the invention 3;
Figure 16 is SEAD (the Selected Area Electron Diffraction) image of the sample 8# of the embodiment of the invention 3;
Figure 17 is UV, visible light (Uv-Vis) absorption spectrum of the sample 9# of the embodiment of the invention 4;
Figure 18 is field emission scanning electron microscope (FESEM) image of the sample 10# of the embodiment of the invention 4;
Figure 19 is SEAD (the Selected Area Electron Diffraction) image of the sample 10# of the embodiment of the invention 4;
Figure 20 is field emission scanning electron microscope (FESEM) image of the sample 11# of the embodiment of the invention 4;
Figure 21 is field emission scanning electron microscope (FESEM) image of the sample 12# of the embodiment of the invention 5.
The specific embodiment
Organic micro-nano structure of controlled preparation provided by the invention and former bit-patterned core content are for preparing its radical anion solution through each organic molecule bulk material of reduction; React with the oxide on debita spissitudo organic molecule radical anion solution and various oxidizing agent solution or the metal electrode afterwards; Oxidation reaction takes place generate neutral molecule, neutral molecule is assembled and is piled up organic nanostructure or the former bit-patterned structure that obtains pattern, size adjustable then.
The processing method of metal electrode in following examples: the monocrystalline silicon piece that height N mixes is purchased in (1), and resistivity is the 0.05-0.20 ohmcm, and the plane is [100] direction, then silicon chip is carried out thermal oxide, makes its surface generate the SiO of a layer thickness 20nm-500nm
2Thermal oxide layer, and carry out single-sided polishing, as substrate; (2) selecting in the substrate under the vacuum condition, through reticle vapor deposition one deck Cr of patterning (preferred 2nm) is as adhesion layer in advance, vapor deposition one deck (preferred 30nm) metal A g or Cu realizes array again.Electrode raceway groove length and width sizes and electrode size can be according to actual demand value (live width of processing can be decided according to the working ability of the litho machine of reality, generally can reach 1 μ m, and the metal electrode substrate for preparing after finishing array cuts into small pieces by 1cm * 1cm); (3) use acetone respectively, washing with alcohol, and dry up gently with nitrogen, place 60 ℃ baking oven to keep 30min afterwards, perhaps carry out the about 5～10min of surface oxidation treatment with the uv ozone cleaning machine.
Below in conjunction with specific embodiment the present invention is further specified, but the present invention is not limited to following instance.
The preparation of radical anion salt:
10gTCNQ (structure is shown in structural formula 1) is joined in the high-purity acetonitrile solution of 1000ml, place round-bottomed flask to carry out reflux condensation mode and be heated to the intimate boiling of acetonitrile.The lithium iodide (LiI) that takes by weighing 20g then is dissolved in the acetonitrile of 50ml, and establishes according to circumstances when heating promotion dissolving, subsequently this solution is added rapidly in the acetonitrile solution of TCNQ while hot, is continuing under the situation of the nearly boiling of solution about stirring 4h.Use the filter paper suction filtration afterwards while hot, obtain wine-colored needle-like solid, with high-purity acetonitrile washing 3～4 times, till filtrating is bright green.Use a large amount of ether or petroleum ether solid subsequently again, and carry out vacuum chamber temperature drying, it is for use to keep in Dark Place; The absorption spectrum of resulting ion acetonitrile solution is shown in Fig. 1; 680nm wherein, 744nm, the absworption peak at 843nm place are negative univalent anion (sample 1#) characteristic absorption peak of TCNQ.
Reaction equation is: 2TCNQ+3LiI → 2Li
+TCNQ
-.+ LiI
3
The controlled preparation of micro-nano structure:
A. the condition and the step that prepare two-dimentional hexagonal plate TCNQ structure:
At first, the TCNQ radical anion salt LiTCNQ that takes by weighing an amount of employing method for preparing is made into the acetonitrile solution of about 1mM, pipettes 5ml and joins and contain 1mM K
3Fe (CN)
6(oxidant) among the aqueous solution 30ml of 0.2mM F127 (surfactant), stirs 30s～1min, and lucifuge leaves standstill 2h, leaches deposition, and washs with secondary water washing, and centrifugal removal filtrating is preserved.Gained sample 2# presents the laminated structure of two-dimentional hexagonal, and size is about 2 μ m * 5 μ m, and thickness is approximately about 1 micron, has showed good mono-crystalline structures simultaneously, and index turns to monoclinic system well.Corresponding electron scanning micrograph and X-ray diffraction photo are shown in Fig. 2 and Fig. 3.Wherein corresponding oxidation reaction is following:
TCNQ
-+Fe(CN)
6 3-→Fe(CN)
6 4-+TCNQ
(s)↓
B. the condition and the step that prepare two-dimentional TCNQ losenges:
The LiTCNQ precursor solution of preparation 2mM concentration pipettes 100ul and joins 2ml and contain 10mMFeCl
3Water in, stir or sonic oscillation 30s～1min, and lucifuge leaves standstill 2h, leach deposition, and wash with secondary water washing, centrifugal removal filtrating is preserved.Reaction will obtain the losenges (sample 3#) of 5 μ m * 5 μ m size, and thickness is near 1 μ m.Corresponding scanned photograph is shown among Fig. 4.The oxidation reaction that takes place is following:
TCNQ
-+Fe
3+→Fe
2++TCNQ
(s)↓
C. the condition and the step that prepare the two-dimentional hexagonal TCNQ slice, thin piece of large-size (with the comparison among a):
The LiTCNQ precursor solution of preparation 2mM concentration pipettes 100ul and joins the FeCl that 2ml contains 0.2mM F127 and 10mM
3The aqueous solution in, stir or sonic oscillation 30s, and lucifuge leaves standstill 2h, leach deposition, and wash with secondary water washing, centrifugal removal filtrating is preserved.Will obtain size is the two-dimentional hexagonal slice, thin piece (sample 4#) of 10 μ m～20 μ m, and corresponding scanned photograph is shown among Fig. 5.The same b of reaction equation wherein.
D. the condition and the step that prepare the two-dimentional TCNQ losenges of thinner thickness (with the comparison among the b):
Correspondingly, if with the LiTCNQ precursor solution of 2mM concentration, pipette 100ul and join 2ml and contain 0.2mM amphiphilic surfactant F127 and 10mM K
3Fe (CN)
6The aqueous solution in, and to keep the temperature in reaction time be 80 ℃, stirs simultaneously or sonic oscillation 30s, cools to room temperature then naturally, leaches deposition, and wash with secondary water washing, the preservation of centrifugal removal filtrating.Will obtain size is the two-dimentional rhombus slice, thin piece (sample 5#) of 10 μ m～20 μ m, thinner thickness (being about 300nm), and corresponding stereoscan photograph is shown among Fig. 6.The corresponding same a of reaction equation.The two-dimentional rhombus micron film that the electronic diffraction proof obtains among Fig. 7 is a mono-crystalline structures, is expected in organic electro-optic device, be well used.
This shows, utilize the TCNQ anion as presoma, through changing the kind of the oxidant in the subsequent oxidation reaction, whether liquor capacity adds suitable surfactant and reaction temperature, can regulate and control to obtain the pattern and the size of micro-nano structure effectively.
At first, take by weighing the acetonitrile solution that an amount of LiTCNQ is made into about 1mM, the Cu electrode of the patterning that wash passing through in advance, surface oxidation treatment is good is dipped in wherein; Airtight lucifuge is static deposits certain hour (30min～4h, the length of time will determine the size of the extent of reaction, detailed presentations sees below); Take out then; With acetonitrile cyclic washing gently, vacuum drying obtains the device (sample 6#) of CuTCNQ array of the patterning of growth in situ.Corresponding ESEM picture is shown in Fig. 8 (reaction 30min), and Fig. 9 (reacting 1 hour) and Figure 10 (reacting 4 hours) are among Figure 11 (enlarged photograph of raceway groove among Figure 10).Figure 12 is the photo of the electrode basement of large-area array.Figure 13 then is the collection of illustrative plates of the micro-Raman of laser co-focusing of gained array device, 2200cm
-1, 2132cm
-1, 1603cm
-1, 1312cm
-1, 1186cm
-1Be the characteristic Raman scattering peak of CuTCNQ.
Visible by figure, the organic structure that adopts preparation method of the present invention to obtain distributes regular, and pattern is adjustable, and growth in situ on the metal electrode of handling optionally, carries out the mass preparation patterned devices easily.
The radical anion and the controlled preparation of nanostructured thereof of embodiment 3, preparation De perylene diimide
The preparation of radical anion:
Get 3.9mg De perylene diimide solid (structure is shown in structural formula 2) and 174mg sulfo-sodium dithionite (amount of reducing agent can change as required); 400mg NaOH chip solid places 50ml reaction there-necked flask; Sealing also connects biexhaust pipe; Vacuumize,, be full of there-necked flask with nitrogen again with high-purity nitrogen washing 2～3 times.Oxolane or the acetonitrile solution that will pass through the nitrogen bubble deoxygenation pipette 20ml and join in this system, under nitrogen protection, stir 20min, add the secondary water that 5ml passes through the nitrogen deoxygenation in advance afterwards, proceed to stir.Along with the reaction carrying out, the color of solution by before wine-colored turbid solution become carmine settled solution, shown the generation of dianion.With the static 20min of solution, the layering gradually of organic facies and water is got supernatant liquor and then can be obtained corresponding anion sodium salt solution (sample 7#).The absorption spectrum of corresponding negative dianion free radical is illustrated among Figure 14.Corresponding chemical equation is following:
PDINH+Na
2S
2O
4+4NaOH→Na
+ 2PDINH
2-+2Na
2SO
3+2H
2O
The condition and the step of the nano wire that the preparation width is controlled:
Pipette above-mentioned radical anion solution 0.5ml, join the methyl alcohol 1ml of saturated oxygen respectively, among 3ml and the 5ml, 30s～1min is stirred in ultrasonic or vibration, and static lucifuge is placed about 4h, and the taking-up deposition is centrifugal, washing.Corresponding chemical equation is following:
2PDINH
2-+O
2+2H
2O→2PDINH(s)+4OH
-
Consumption according to the methyl alcohol that reacts usefulness is increased to 5ml from 1ml, and we will obtain size in a large number and be respectively 220nm, 120nm, and the nano wire of 80nm (sample 8#) is shown in the stereoscan photograph among Figure 15.If change the solvent of reaction into the 3ml oxolane again from methyl alcohol 5ml, we will obtain the littler nano wire of size, and width is about about 35nm, and thickness also will diminish to the 8nm.Choose electronic diffraction and prove that also obtaining nano wire is mono-crystalline structures, shown in figure 16.
This shows, sharp with perylene diimide dianion free radical as precursor, the volume of the solvent that we can be simply through the adjusting subsequent reactions be is regulated and control the size of the structure of resultant organic nano.Therefore, but this preparation method is expected to the large-scale application of molecule in organic electro-optic device of the low poor processability of this function admirable solubility of Tuo Zhan perylene diimide.
The radical anion of embodiment 4, preparation Si Lv perylene diimide and the controlled preparation of micro-nano structure
Get the Si Lv perylene diimide solid (TCPDINH of 10.0mg; Structure is shown in structural formula 3) and 100mg sulfo-sodium dithionite; 400mg NaOH chip solid places 50ml reaction there-necked flask, seals and connect biexhaust pipe, vacuumizes; With high-purity nitrogen washing 2～3 times, be full of there-necked flask with nitrogen again.Oxolane or the acetonitrile solution that will pass through the nitrogen bubble deoxygenation pipette 20ml and join in this system, under nitrogen protection, stir 20min, add the secondary water that 5ml passes through the nitrogen deoxygenation in advance afterwards, proceed to stir.Along with the carrying out of reaction, the color of solution by before the turbid solution of cervinus become carmine settled solution, shown the generation (sample 9#) of dianion free radical.Figure 17 has showed Si Lv perylene diimide monomer (line 1), negative univalent anion free radical (line 3) and the ultra-violet absorption spectrum of negative dianion free radical (line 2) in acetonitrile; Shown that we can obtain the anion free radical of Si Lv perylene diimide different valence state effectively through the consumption of control reducing agent; And can stable in the airly there be the long period, be convenient to follow-up experimental implementation.With the static 20min of solution, the layering gradually of organic facies and water is got supernatant liquor and then can be obtained corresponding anion sodium salt solution.Corresponding reaction equation is following:
Preparation monovalence anion free radical:
2TCPDINH+Na
2S
2O
4+4NaOH→2Na
+TCPDINH
-+2Na
2SO
3+2H
2O
Preparation divalence anion free radical:
TCPDINH+Na
2S
2O
4+4NaOH→Na
+ 2TCPDINH
2-+2Na
2SO
3+2H
2O
A. the preparation condition of two-dimentional micro-nano structure and step:
Getting above-mentioned divalence anion free-atom aqueous solution 0.5ml is injected in the methanol solution of the saturated oxygen in the 5ml left and right sides fast; And stir simultaneously or ultrasonic 30s～1min; Lucifuge leaves standstill about about 4h; Deposition is taken out in centrifugal filtration, and is dispersed in again in the methanol solution, under the illumination of fluorescent lamp, it will be appreciated that glittering crystal (sample 10#).Carrying out sign such as Figure 18 of ESEM, is the losenges of the 5 μ m length of sides, and thickness is greatly about about 300nm.The SEAD of the transmission electron microscope among Figure 19 characterizes proves that also the two-dimentional slice, thin piece that obtains is a mono-crystalline structures.The oxidation reaction that takes place is:
2TCPDINH
2-+O
2+2H
2O→2TCPDINH(s)↓+4OH
-
B. the condition and the step of one dimension micro-nano structure preparation:
Getting above-mentioned divalence anion free-atom aqueous solution 0.5ml is injected in the methanol solution of the saturated oxygen of 0.5ml fast; And stir simultaneously or ultrasonic 30s～1min; Lucifuge leaves standstill about about 1h, and deposition is taken out in centrifugal filtration, and is dispersed in the methanol solution again; Sample preparation is observed, and we will find the micro-nano line structure (sample 11#) of one dimension.Shown in figure 20.The same a of chemical reaction that wherein takes place.
This shows; We utilize radical anion to be equipped with the precursor of micro-nano structure as the liquid phase reactor legal system; Solve a poorly soluble unmanageable difficult problem on the one hand, on the other hand, can regulate and control the pattern and the size of resulting micro-nano structure effectively through kinetics.Therefore and resulting mono-crystalline structures also is easy to processing, is expected on single-crystal field effect transistor, organic photocon and photovoltaic device, be widely used.
The anionic preparation of Si Lv perylene diimide is with reference to the step among the embodiment 5; Pipette the acetonitrile solution 5ml～10ml of univalent anion free radical afterwards; The Cu electrode of the patterning that process is washed in advance, surface oxidation treatment is good is dipped in wherein, and airtight lucifuge is placed about 4h, takes out; With the flushing gently respectively of acetonitrile, ethanolic solution, dry up substrate gently with nitrogen.Obtain the device architecture (sample 12#) of the growth in situ of patterning.Carrying out ESEM characterizes shown in figure 21.This shows that utilize the anion free radical to carry out the preparation that reaction in-situ is realized patterned devices as precursor, method is simple, cost is low, can realize large-scale device preparation quickly.
Claims (9)
1. a liquid-phase chemical reaction legal system has machine micro-nano structure method, it is characterized in that, may further comprise the steps:
(1) utilizes reduction reaction to prepare the radical anion salt of organic molecule, and be made into solution;
(2) configure the solution that contains oxidant, the radical anion salting liquid of removing step (1) is injected in the solution that contains oxidant, and the amount of oxidant makes the abundant oxidation of radical anion, stirs or ultrasonicly makes it abundant mixing, and lucifuge leaves standstill then, reacts;
(3) after reaction finished, washing can obtain one dimension or two-dimentional organic micro-nano structure; Organic molecule in the above-mentioned steps (1) is the N-type semiconductor material, adopts the liquid phase one-step reducing process to make the radical anion salt or the solution of corresponding organic molecule; Solution described in the step (1), its solvent are acetonitrile or oxolane; In the step (2), the said solution that contains oxidant, its solvent are alcohols, water or the solvent identical with the free radical salting liquid, and oxidant is saturated oxygen, liquor ferri trichloridi, hydrogen peroxide solution, the potassium ferricyanide.
2. according to the method for claim 1, it is characterized in that the N-type semiconductor material is perfluoro metallo phthalocyanine, cyanic acid benzoquinone compound, fullerene compound 、 perylene diimide, N position Qu Dai De perylene diimide, waist position halo De perylene diimide.
3. according to the method for claim 1, it is characterized in that, stir or the preferred 30s～1min of ultrasonic time the preferred 30min～4h of time of repose in the step (2).
4. according to the method for claim 1, it is characterized in that the concentration of step (1) radical anion solution is 0.5mmol/L～2mmol/L.
5. according to the method for claim 1, it is characterized in that the cleaning solvent that step (3) is selected for use is preferably the used solvent of dissolved oxidant in the corresponding step (2).
6. according to the method for claim 1, it is characterized in that, in step (2), also add the nonionic surface active agent of 0.05mmol/L～0.5mmol/L.
7. a liquid-phase chemical reaction legal system is equipped with the method for original position patterned devices, it is characterized in that, may further comprise the steps: utilize reduction reaction to prepare the radical anion salt of organic molecule, and be made into solution; The array electrode base sheet of handling well impregnated in the radical anion solution, under airtight lucifuge condition, make anion carry out the in-situ oxidation reaction, after reaction finishes, wash substrate, obtain one dimension or two-dimentional organic micro-nano structure of array at electrode surface;
Organic molecule in the above-mentioned steps is the N-type semiconductor material; The solution of radical anion salt, its solvent are acetonitrile or oxolane;
The preparation method of the array electrode base sheet of handling well; May further comprise the steps: the monocrystalline silicon piece that (1) height N mixes, resistivity is the 0.05-0.20 ohmcm, the plane is [100] direction; Then silicon chip is carried out thermal oxide, make its surface generate the SiO of a layer thickness 20nm-500nm
2Thermal oxide layer, and carry out single-sided polishing, as substrate; (2) under the vacuum condition in selected substrate, the reticle vapor deposition one deck Cr through patterning in advance is as adhesion layer, vapor deposition layer of metal Ag or Cu realize array again; (3) use acetone respectively, washing with alcohol, and dry up gently with nitrogen, place 60 ℃ baking oven to keep 30min afterwards, perhaps carry out the about 5～10min of surface oxidation treatment with the uv ozone cleaning machine.
8. according to the method for claim 7; It is characterized in that; The N-type semiconductor material is selected from perfluoro metallo phthalocyanine, cyanic acid benzoquinone compound, fullerene compound 、 perylene diimide, its derivative, comprises carrying out N position Qu Dai De perylene diimide or waist position halo De perylene diimide.
9. according to the method for claim 7, it is characterized in that, adopt the liquid phase one-step reducing process to make the radical anion salt or the solution of corresponding organic molecule; If the solution of selecting for use dissolution with solvents free radical salt to be made into is then selected anhydrous acetonitrile for use, and join solution before in advance with nitrogen bubble deoxygenation 30min; If usefulness is the radical anion solution that directly reaction obtains, survey and need not to carry out this deoxygenation operation, only need to shift utensil and get final product at the solution that the condition of starvation pipettes respective volume with syringe or other solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210076310.2A CN102583235B (en) | 2012-03-22 | 2012-03-22 | Method for preparing organic micro/nano structure by liquid phase chemical reaction method and patterning in situ |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210076310.2A CN102583235B (en) | 2012-03-22 | 2012-03-22 | Method for preparing organic micro/nano structure by liquid phase chemical reaction method and patterning in situ |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102583235A true CN102583235A (en) | 2012-07-18 |
| CN102583235B CN102583235B (en) | 2015-07-22 |
Family
ID=46472603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210076310.2A Expired - Fee Related CN102583235B (en) | 2012-03-22 | 2012-03-22 | Method for preparing organic micro/nano structure by liquid phase chemical reaction method and patterning in situ |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102583235B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104253225A (en) * | 2013-06-27 | 2014-12-31 | 中国科学院化学研究所 | Preparation method of large-area ordered organic p-n junction nanowire array |
| US11084816B2 (en) * | 2018-01-05 | 2021-08-10 | South China University Of Technology | Anionic imide material having ferromagnetism at room temperature and the use thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005088089A (en) * | 2003-09-12 | 2005-04-07 | Inst Of Research & Innovation | Manufacturing method of three-dimensional network structure |
| WO2005104260A1 (en) * | 2004-04-20 | 2005-11-03 | Riken | Element, thin film transistor and sensor using the same, and method for manufacture of element |
| WO2007024323A2 (en) * | 2005-06-17 | 2007-03-01 | The University Of North Carolina At Chapel Hill | Nanoparticle fabrication methods, systems, and materials |
| CN101704502A (en) * | 2009-09-11 | 2010-05-12 | 中国科学院化学研究所 | Method for preparing arrayed organic nanoparticles |
| CN101757882A (en) * | 2008-12-25 | 2010-06-30 | 中国科学院理化技术研究所 | Method for preparing organic nano-structure material by chemical reaction |
| CN102041556A (en) * | 2009-10-20 | 2011-05-04 | 中国科学院理化技术研究所 | Method for preparing single crystal one-dimensional or quasi one-dimensional organic nano material by solution method |
-
2012
- 2012-03-22 CN CN201210076310.2A patent/CN102583235B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005088089A (en) * | 2003-09-12 | 2005-04-07 | Inst Of Research & Innovation | Manufacturing method of three-dimensional network structure |
| WO2005104260A1 (en) * | 2004-04-20 | 2005-11-03 | Riken | Element, thin film transistor and sensor using the same, and method for manufacture of element |
| WO2007024323A2 (en) * | 2005-06-17 | 2007-03-01 | The University Of North Carolina At Chapel Hill | Nanoparticle fabrication methods, systems, and materials |
| CN101757882A (en) * | 2008-12-25 | 2010-06-30 | 中国科学院理化技术研究所 | Method for preparing organic nano-structure material by chemical reaction |
| CN101704502A (en) * | 2009-09-11 | 2010-05-12 | 中国科学院化学研究所 | Method for preparing arrayed organic nanoparticles |
| CN102041556A (en) * | 2009-10-20 | 2011-05-04 | 中国科学院理化技术研究所 | Method for preparing single crystal one-dimensional or quasi one-dimensional organic nano material by solution method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104253225A (en) * | 2013-06-27 | 2014-12-31 | 中国科学院化学研究所 | Preparation method of large-area ordered organic p-n junction nanowire array |
| US11084816B2 (en) * | 2018-01-05 | 2021-08-10 | South China University Of Technology | Anionic imide material having ferromagnetism at room temperature and the use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102583235B (en) | 2015-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Song et al. | Overall photocatalytic water splitting by an organolead iodide crystalline material | |
| Zhang et al. | Ultrathin oxygen-vacancy abundant WO3 decorated monolayer Bi2WO6 nanosheet: A 2D/2D heterojunction for the degradation of Ciprofloxacin under visible and NIR light irradiation | |
| CN103265020B (en) | Method for preparing graphene quantum dot powder on large scale | |
| Kong et al. | Incorporation of well-dispersed sub-5-nm graphitic pencil nanodots into ordered mesoporous frameworks | |
| Chen et al. | Nitrogen-doped carbon quantum dots/Ag3PO4 complex photocatalysts with enhanced visible light driven photocatalytic activity and stability | |
| CN102275908B (en) | Preparation method of graphene material | |
| Liu et al. | Dendritic CuSe with hierarchical side-branches: synthesis, efficient adsorption, and enhanced photocatalytic activities under daylight | |
| Gao et al. | Freestanding atomically-thin cuprous oxide sheets for improved visible-light photoelectrochemical water splitting | |
| Hu et al. | Metal-catalyzed electroless etching of silicon in aerated HF/H2O vapor for facile fabrication of silicon nanostructures | |
| Wang et al. | Controllable green synthesis of crassula peforata-like TiO2 with high photocatalytic activity based on deep eutectic solvent (DES) | |
| Cao et al. | Large scale fabrication of quasi-aligned ZnO stacking nanoplates | |
| CN103539805B (en) | A kind of CuCN complex based on flexible dual-triazole ligand and preparation method thereof | |
| Singh et al. | Novel synthesis process of methyl ammonium bromide and effect of particle size on structural, optical and thermodynamic behavior of CH3NH3PbBr3 organometallic perovskite light harvester | |
| CN102897724B (en) | Tin selenide nano-flowers and preparation method thereof | |
| CN101752094B (en) | Electrode in a photonic crystal structure mixed with nano metal and making method thereof | |
| CN105883909B (en) | A kind of CsPbBrxI3‑xThe preparation method of nanometer rods | |
| Xu et al. | Size-and surface-determined transformations: from ultrathin InOOH nanowires to uniform c-In2O3 Nanocubes and rh-In2O3 nanowires | |
| Chen et al. | One-pot photochemical synthesis of ultrathin Au nanocrystals on co-reduced graphene oxide and its application | |
| CN103449429A (en) | Preparation method of Janus graphene sheet layer | |
| Li et al. | Fabrication of black phosphorus nanosheets/BiOBr visible light photocatalysts via the co-precipitation method | |
| Wei et al. | Preparation and optical properties of In2Se3 nanospheres using CTAB as surface modifier | |
| Liu et al. | Single-crystalline indium hydroxide and indium oxide microcubes: synthesis and characterization | |
| Zhu et al. | Size-tunable bismuth quantum dots for self-powered photodetectors under ambient conditions | |
| Wei et al. | Preparation of Cu2O nanorods by a simple solvothermal method | |
| CN102583235B (en) | Method for preparing organic micro/nano structure by liquid phase chemical reaction method and patterning in situ |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150722 Termination date: 20180322 |