CN100427381C - Diameter thinning method of one-dimensional micro-nanometer structural material of metal organic complex - Google Patents

Abstract

The present invention relates to a novel one-dimensional micro nanometer material diameter thinning method, particularly to a steaming induced reaction method. Since the diameter dimension of a metal organic complex (M-TCNQ) one-dimensional structure generated by the traditional solution chemical reaction method has the order of magnitude of a plurality of microns, the preparation of a nanometer structure by the method is a problem. Based on the solution chemical reaction method, the present invention provides a novel preparation method, namely the steaming induced reaction method. In the method, firstly, a metal film with the nanometer thickness is plated on a substrate by the conventional method; secondly, part of the metal nanometer film is immersed in a hot TCNQ acetonitrile solution; by the induction of steam, the non-immersed part of the metal nanometer film forms nanometer bands, nanometer wires or micro nanometer tubes. Compared with the traditional solution chemical reaction method, a generated one-dimensional structure has thinner diameter and longer length. The method has the advantages of simple experimental facilities, controllable processes and wide application range.

Description

The diameter thinning method of one-dimensional micro-nanometer structural material of metal organic complex

Technical field

The present invention is the preparation method of monodimension nanometer material, belongs to the chemical material field.

Background technology

Since Iijima in 1991 (Ijima S.[J] .Nature 1991 354:56) finds CNT, the monodimension nanometer material of various novelties such as nanotube, nano wire, nanometer rods, nanometer band and nano coaxial cable etc. are found in succession, have caused in the world to pay close attention to widely.They in mesoscopic physics and nano-device are constructed, have its uniqueness application (Y.Xia, P.Yang, Y.Sun, et al.Adv.Mater.2003 15 (5): 353).

From Potember (Potember, R.S.; Poehler, T.O.; Cowan, D.O.Appl.Phys.Lett., 1979,34:405) grade at first finds 7,7,8, the charge transfer type complex of 8-four cyano 1,4-benzoquinone bismethane (TCNQ) and some electron donor has unique photoelectric property, and people have carried out deep research to electricity, optics and optoelectronic switch phenomenon and the mechanism thereof of its thin-film device.

Because the direction that the high conducting direction of metal organic complex M-TCNQ is just piled up along the TCNQ column, and be the insulation attitude on other direction, so M-TCNQ is quasi-one-dimensional conductor or semiconductor.How research prepares the one-dimensional nano structure of this metal organic complex, can lay the foundation for its application in nano electron device, has not yet to see the report of such research.

Summary of the invention

The objective of the invention is to obtain the diameter thinning method of easy, the respond well one-dimensional micro-nanometer structural material of metal organic complex of a kind of method.

It is as follows to utilize steam inducing solution chemical reaction method to prepare the concrete steps of metal organic complex one-dimensional micro-nanometer structure:

(1) on substrate, prepares the metallic film of one deck 5-20 nanometer thickness with vacuum evaporation or sputtering method;

(2) in little flask, prepare 7,7,8, the 8-tetracyano-p-quinodimethane, i.e. TCNQ acetonitrile saturated solution,

Be placed on then in the hot bath, the temperature maintenance that makes the fine solution of TCNQ second is at 40-60 ℃;

(3) metallic film is partly immersed in the above-mentioned TCNQ acetonitrile solution, under the effect of the acetonitrile of water vapour and volatilization, the TCNQ molecule can be climbed to substrate and not immerse part in the solution, immersing and the part that does not immerse all chemical reaction can take place, generate the metal organic complex of the one-dimensional micro-nanometer structure of different-shape.

(4) after question response 1-3 minute, take out sample, the residual substance on the washing sample.

Among the present invention, be example, detailed process following (as shown in Figure 1) with micron tube, nanotube, the nano wire/rod/structures such as band of using the steam revulsion to prepare Ag-TCNQ and Cu-TCNQ:

1) at first on substrate, prepares the Ag or the Cu metallic film of one deck 5-20 nanometer thickness with vacuum evaporation or sputtering method;

2) preparation TCNQ acetonitrile saturated solution (3) in little flask is placed on (1) in the hot bath then, and the temperature maintenance that makes the fine solution of TCNQ second is at 40-60 ℃;

3) metallic film is partly immersed in the TCNQ acetonitrile solution of heat, under the effect of the acetonitrile of water vapour and volatilization, the TCNQ molecule can be climbed to substrate and not immerse part in the solution.Therefore immersing and the part that does not immerse all chemical reaction can take place, thereby generating the Ag-TCNQ or the Cu-TCNQ of different-shape;

4) after question response 1-3 minute, take out sample, put into acetonitrile solution and rinse out residual substance on the sample.

The present invention is partly immersed at metallic film and formed three zones in the TCNQ acetonitrile solution: immersing part is thermal reaction area (4); The critical surface that film immerses the TCNQ acetonitrile solution is that transition region (5) and not immersion part are induced reaction district (6).By the SEM test, main pattern has: the micron tube (as shown in Figure 2) that the Ag-TCNQ thermal reaction area generates; The micro-nano mitron that Ag-TCNQ induced reaction district generates is (as shown in Figure 3, about diameter 400nm; Visible longer pipe among Fig. 4, length is about 50 microns) and nanometer rods diameter (as shown in Figure 5); The Cu-TCNQ thermal reaction area generates core micron tube (as shown in Figure 6); The cross section that the Cu-TCNQ transition region generates is foursquare nanometer rods (as shown in Figure 7, diameter is 200-400nm); The nanometer band (as shown in Figure 8, diameter is about 100nm) that Cu-TCNQ induced reaction district generates.This shows in the sample diameter of transition region and induced reaction district preparation carefullyyer, played the effect of refinement.

Among the present invention used metal must be can and the metal of TCNQ oxidation-reduction reaction, as Ag, Cu, K, Na etc., but with Ag, Cu is for well.

For well, acetonitrile solution can dissolve the remaining TCNQ that stays substrate surface with acetonitrile solution when washing among the present invention, and Ag-TCNQ and the Cu-TCNQ dissolving in acetonitrile is very little.

The mechanism primary explanation that steam induced reaction legal system of the present invention is equipped with the thinner metal organic complex one-dimensional micro-nanometer structure of diameter is as follows: because TCNQ solution places hot bath, water vapour evaporation also condenses upon the surface that metal film does not enter into that part of film of solution, TCNQ just along the passage of these moisture films " climb " arrive above.Because metal is that good electron is given body; And TCNQ is the good electron acceptor, so metal, TCNQ and water formation galvanic cell structure, and wherein metal is an anode; TCNQ is a negative electrode.Though the TCNQ concentration ratio saturated solution that this part is regional is low, because the existence of water, therefore the generation of electrochemical reaction has quickened the speed of generation M-TCNQ.Thereby nucleation and the speed of growing up are all accelerated than under the normal condition, and diameter obtains refinement.Simultaneously because the CONCENTRATION DISTRIBUTION difference of TCNQ, thereby make varying in size of nucleation.Generally speaking, the size of inducing district's nucleation that concentration is lower is less, therefore advantage diameter refinement to a certain extent.The general micro-nanometer structural material that in the induced reaction district, generates band shape, wire, transition region generates bar-shaped micro-nanometer structural material, and thermal reaction area generates tubulose micrometer structure material.

The inventive method is easy, processing ease, and band, line, rod, tubular material that each reaction zone obtains are very satisfactory.

Description of drawings

Fig. 1 is a steam induced reaction method experimental provision schematic diagram.

Fig. 2 is the micron tube figure that the Ag-TCNQ thermal reaction area generates.

Fig. 3 is the micro-nano mitron figure that Ag-TCNQ induced reaction district generates.

Fig. 4 is the long micro-nano mitron figure that Ag-TCNQ induced reaction district generates.

Fig. 5 is the nanometer rods figure that Ag-TCNQ induced reaction district generates.

Fig. 6 be the Cu-TCNQ thermal reaction area generate core micron tube figure arranged.

Fig. 7 is that the cross section that the Cu-TCNQ transition region generates is foursquare nanometer rods figure.

Fig. 8 is the nanometer band figure that Cu-TCNQ induced reaction district generates.

1 is hot bath among the above-mentioned figure; The 2nd, metal film; The 3rd, the TCNQ saturated solution; The 4th, thermal reaction area; The 5th, transition region; The 6th, the induced reaction district.

The specific embodiment

The preparation of embodiment 1:Ag-TCNQ micro nano structure sample

At first the Si substrate is cleaned; Use the thick Ag film of vacuum vapor deposition method evaporation one deck 10nm then.The filamentary silver purity of using is 99.999%, and the vacuum during evaporation is 1 * 10 ^-3Pa, sedimentation rate 0.1nm/s, and utilize the measured film thickness instrument to monitor the thickness of evaporation in real time; Preparation TCNQ acetonitrile saturated solution is placed in the hot bath of big flask then in little flask, and the temperature maintenance that makes the fine solution of TCNQ second is about 40 ℃; The Ag membrane portions is immersed in the TCNQ acetonitrile solution of heat, under the effect of the acetonitrile of water vapour and volatilization, the TCNQ molecule can be climbed to substrate and not immerse part in the solution.Therefore immersing and the part that does not immerse all chemical reaction can take place, thereby generating the Ag-TCNQ of different-shape; Behind the question response 1min, take out sample, put into acetonitrile solution and rinse out residual substance on the sample.

The SEM photo of gained sample is shown in Fig. 2,3,4,5.

The preparation of embodiment 2:Cu-TCNQ micro nano structure sample

At first the Si substrate is cleaned; Use the thick Cu film of vacuum vapor deposition method evaporation one deck 20nm then.The copper billet purity of using is 99.99%, and the vacuum during evaporation is 1 * 10 ^-3Pa, sedimentation rate 0.1nm/s, and utilize the measured film thickness instrument to monitor the thickness of evaporation in real time; Preparation TCNQ acetonitrile saturated solution is placed in the hot bath of big flask then in little flask, and the temperature maintenance that makes the fine solution of TCNQ second is about 60 ℃; The Cu membrane portions is immersed in the TCNQ acetonitrile solution of heat, under the effect of the acetonitrile of water vapour and volatilization, the TCNQ molecule can be climbed to substrate and not immerse part in the solution.Therefore immersing and the part that does not immerse all chemical reaction can take place, thereby generating the Cu-TCNQ of different-shape; Behind the question response 3min, take out sample, put into acetonitrile solution and rinse out residual substance on the sample.

The SEM photo of gained sample is shown in Fig. 6,7,8.

Claims (2)

1, the method for a kind of metal organic complex one-dimensional micro-nanometer diameter of movement refinement is characterized in that steam inducing solution chemical reaction method, and concrete steps are as follows:

(1) on substrate, prepares the Ag or the Cu metallic film of one deck 5-20 nanometer thickness with vacuum evaporation or sputtering method;

(2) preparation 7,7,8, the 8-tetracyano-p-quinodimethane, promptly the TCNQ acetonitrile saturated solution is placed in the hot bath then, and the temperature maintenance that makes the TCNQ acetonitrile solution is at 40-60 ℃;

(3) Ag or Cu metallic film are partly immersed in the above-mentioned TCNQ acetonitrile solution, under the effect of the acetonitrile of water vapour and volatilization, the TCNQ molecule can be climbed to substrate and not immerse part in the solution, immersing and the part that does not immerse all chemical reaction can take place, generate the metal organic complex of the one-dimensional micro-nanometer structure of different-shape;

(4) after question response 1-3 minute, take out sample, the residual substance on the washing sample.

2, method according to claim 1 is used acetonitrile solution when it is characterized in that washing.

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