CN101857971A - Bismuth/bismuth-antimony extensional superlattice nanowire and preparation method thereof - Google Patents
Bismuth/bismuth-antimony extensional superlattice nanowire and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a bismuth/bismuth-antimony extensional superlattice nanowire and a preparation method thereof. The nanowire is a bismuth/bismuth-antimony superlattice nanowire with the diameter of 30-120 nanometers, which is formed by extensionally connecting a bismuth nanowire and a bismuth-antimony nanowire, wherein the lengths of each segment of the bismuth nanowire and the bismuth-antimony nanowire are respectively 3-99 nanometers and 3-99 nanometers; and the bismuth-antimony nanowire contains 80-50 percent of bismuth and 20-50 percent of stibium. The preparation method comprises the following steps of: firstly, preparing an electrodeposition solution by using bismuth chloride, antimony chloride, hydrochloric acid, tartaric acid, citric acid, sodium chloride and glycerol; then placing a gold film plated porous alumina template as a cathode into the electrodeposition solution for electrodeposition under two pulse voltages alternately connected in series; and finally, placing the porous alumina template electrodeposited with the bismuth/bismuth-antimony extensional superlattice nanowire into an alkali solution to corrode the alumina template so as to prepare the bismuth/bismuth-antimony extensional superlattice nanowire. The bismuth/bismuth-antimony extensional superlattice nanowire can be widely used in the fields of thermo-electric generation, thermoelectric refrigeration, and the like; in addition, the method is easy to implement and suitable for large-scale industrialized production.
Description
Technical field
The present invention relates to a kind of superlattice nano line and preparation method, especially a kind of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire and preparation method thereof.
Background technology
The basic one dimension thermoelectric material of bismuth (Bi) is because the electronics Fermi surface of the anisotropic elliposoidal of height of bismuth, the energy-band overlap that conduction band and valence band are little (being 38meV when 77K), atomic mass is big, can make its performance excellent properties such as have greatly improved become the favorite of thermoelectric research by carrying out chemical combination with other element such as antimony (Sb), tellurium (Te), tin (Sn) etc.At present, people are in order to obtain it, some trials and effort have been done, as at the 5th Chinese functional materials in 2004 and the 3087th～3089 page of article that is entitled as " controllable growth of monocrystalline bismuth nano-wire array " of having reported that Li Liang etc. delivers of application academic meeting paper collection II thereof, this article discloses a kind of preparation method of monocrystalline bismuth nano-wire array.It is to adopt the pulse electrochemical deposition technique, utilizes the alumina formwork of same diameter, has prepared the monocrystalline bismuth nano-wire array of different diameter by the regulating impulse parameter.Yet, bismuth antimony nano wire openly in this method, and the also concrete preparation process of unexposed bismuth/bismuth/bismuth-antimony extensional superlattice nanowire, also promptly this method has and both can not prepare bismuth antimony nano wire, more can not prepare the deficiency of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire.And superlattice nano line structure thermoelectric material is compared to common simple substance owing to it and the alloy nano line structure has higher figure of merit, thereby at many key areas such as thermo-electric generation and thermoelectric refrigerations the potential application prospect is arranged all.
Summary of the invention
The technical problem to be solved in the present invention is for overcoming weak point of the prior art, the bismuth/bismuth/bismuth-antimony extensional superlattice nanowire that provides a kind of bismuth nano-wire to be connected with bismuth antimony nano wire extension.
Another technical problem that the present invention will solve is the preparation method of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire that a kind of epitaxially grown cycle, composition, controllable diameter are provided.
For solving technical problem of the present invention, the technical scheme that is adopted is: bismuth/bismuth/bismuth-antimony extensional superlattice nanowire comprises bismuth nano-wire, particularly,
Described bismuth nano-wire and bismuth antimony nano wire extension connect into bismuth/bismuth antimony superlattice nano line;
The diameter of described bismuth/bismuth antimony superlattice nano line is 30～120nm, and every segment length of bismuth nano-wire wherein is that every segment length of 3～99nm, bismuth antimony nano wire is 3～99nm;
Bi content in the described bismuth antimony nano wire is 80～50%, antimony content is 20～50%.
As the further improvement of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire, the bismuth nano-wire in described bismuth/bismuth antimony superlattice nano line and the hop count of bismuth antimony nano wire are 3～10000 sections; Described bismuth/bismuth antimony superlattice nano line is arranged in porous alumina formwork.
For solving another technical problem of the present invention, another technical scheme that is adopted is: the preparation method of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire comprises the pulse electrochemical sedimentation, and particularly completing steps is as follows,
Step 1, earlier be that the bismuth chloride of 0.02～0.06M and antimony chloride that concentration is 0.06～0.1M are dissolved in the hydrochloric acid that concentration is 0.08～0.12M with concentration, the mixing solutions that gets, add the tartrate that concentration is 0.25～0.29M successively in the mixing solutions under stirring again, citric acid and the concentration that concentration is 0.22～0.26M is the sodium-chlor of 0.1～0.14M, treat that it is the glycerol of 0.08～0.12M that its dissolving back adds concentration, and continue to stir 1h at least, afterwards, regulating its pH value with alkaline solution is 0.8～0.84, obtains electrodeposit liquid;
Step 2, one side is coated with the porous alumina formwork of golden film as negative electrode, placing temperature is 30～40 ℃ electrodeposit liquid, under pulsed voltage, carry out galvanic deposit, described pulsed voltage is made of two groups of pulses that alternately are connected in series, a set of pulses wherein is the pulse delay voltage and the bismuth pulsed deposition voltage of space, another group pulse is the pulse delay voltage and the bismuth antimony pulsed deposition voltage of space, the pulse width of described pulse delay voltage is 12ms, voltage is 0V, the pulse width of described bismuth pulsed deposition voltage is 8ms, voltage is-1.4～-1.6V, the pulse width of described bismuth antimony pulsed deposition voltage is 8ms, voltage is-1.7～-2V;
Step 3 has the porous alumina formwork of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire to place strong base solution to erode alumina formwork galvanic deposit, makes bismuth/bismuth/bismuth-antimony extensional superlattice nanowire.
As the preparation method's of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire further improvement, described alkaline solution is that concentration is that sodium hydroxide solution or the concentration of 0.05M is the ammoniacal liquor of 0.1M; The thickness of described golden film is 150～250nm; The aperture of described porous alumina formwork is 30～120nm; Anode during described galvanic deposit is a graphite; The accumulative total pulse width of described every group of bismuth pulsed deposition voltage is 1～33s, and the accumulative total pulse width of every group of bismuth antimony pulsed deposition voltage is 0.3～10s; Described strong base solution is sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution.
Beneficial effect with respect to prior art is, one, use transmission electron microscope, x-ray diffractometer and field emission scanning electron microscope and incidental power spectrum tester to carry out the sign of form, structure, composition, crystalline quality and epitaxy respectively to the product that makes, from the transmission electron microscope photo that obtains, X-ray diffraction spectrogram, stereoscan photograph and scanning can spectrogram as can be known, product is the numerous nano wire that is ordered arrangement.Nano wire is to be made of two kinds of different metabolies, promptly connect into the bismuth that diameter is 30～120nm/bismuth antimony superlattice nano line by bismuth nano-wire and bismuth antimony nano wire extension, wherein, the hop count of bismuth nano-wire and bismuth antimony nano wire is more than 3 sections, every segment length of bismuth nano-wire is that every segment length of 3～99nm, bismuth antimony nano wire is 3～99nm, and the bi content in the bismuth antimony nano wire is 80～50%, antimony content is 20～50%.The crystallinity of bismuth/bismuth antimony superlattice nano line is good, and its preferred orientation is consistent with optimization gained direction, and the interface is clear, and is epitaxy; They are two years old, the preparation method uses the proportioning raw materials of science and preparation steps to obtain electrodeposit liquid, and adopt controlled pulse electrochemical to deposit, promptly control the length of every section bismuth nano-wire or bismuth antimony nano wire by the time of control galvanic deposit, control the bismuth in the bismuth antimony nano wire and the component proportions of antimony by the height of control galvanic deposit voltage, brought the technique effect of the technological line of the bismuth/bismuth antimony superlattice nano line that accurately prepares epitaxially grown cycle, composition, controllable diameter; Its three, the preparation method is easy to implement, is suitable for large-scale industrial production.Depositing temperature in the method is low, and controlled pulse electrochemical sedimentation prepares high-quality epitaxially grown bismuth/bismuth antimony superlattice nano line except that being suitable for, and also can be extended to the preparation of other superlattice nano lines.
As the further embodiment of beneficial effect, the one, the bismuth nano-wire in bismuth/bismuth antimony superlattice nano line and the hop count of bismuth antimony nano wire all are preferably 3～10000 sections, have satisfied the needs of practical application fully; The 2nd, bismuth/bismuth antimony superlattice nano line is preferably placed in the porous alumina formwork, is beneficial to its practical application; The 3rd, it is the ammoniacal liquor of 0.1M that alkaline solution is preferably sodium hydroxide solution or the concentration that concentration is 0.05M, is easy to obtain the electrodeposit liquid of required pH value; The 4th, the thickness of golden film is preferably 150～250nm, is convenient to the galvanic deposit of bismuth/bismuth antimony superlattice nano line; The 5th, the accumulative total pulse width of every group of bismuth pulsed deposition voltage is preferably 1～33s, the accumulative total pulse width of every group of bismuth antimony pulsed deposition voltage is preferably 0.3～10s, and every segment length of having guaranteed the bismuth nano-wire in bismuth/bismuth antimony superlattice nano line is that every segment length of 3～99nm, bismuth antimony nano wire is 3～99nm; The 6th, strong base solution is preferably sodium hydroxide solution or potassium hydroxide solution or lithium hydroxide solution, not only makes the source of raw material than horn of plenty, also makes the easier enforcement of preparation technology and flexibly.
Description of drawings
Below in conjunction with accompanying drawing optimal way of the present invention is described in further detail.
Fig. 1 be take the photograph after using JEOL-2010 type transmission electron microscope (TEM) to observe to the product that makes one of TEM photo.Can be found out that by this TEM photo nano wire is to be connected in series mutually by the multistage thread to form, wherein, dark section is a bismuth nano-wire, and the light color section is a bismuth antimony nano wire;
Fig. 2 is one of TEM photo of obtaining after using JEOL-2010 type transmission electron microscope (TEM) and Philips PW 1700x type X-ray diffraction (XRD) instrument to observe and test respectively to the product that makes and one of XRD spectra.Wherein, Fig. 2 a is the TEM photo, can find out that by it nano wire is that thread by different sections is concatenated into.Fig. 2 b is the high resolution TEM photo at square frame position among Fig. 2 a, and by wherein striped facies analysis as can be known, this nano wire is along the growth of [110] direction, and does not observe room and dislocation from this high resolution TEM photo, and this has shown the coupling of epitaxy lattice.Fig. 2 c is the selected area electron diffraction figure at square frame position among Fig. 2 a, electron-diffraction diagram this nano wire edge [110] direction growth equally as can be seen thus, and from the enlarged view of [003] direction point diffraction as can be seen point diffraction occur separating, and it is increasing, be the sign of extension periodic modulation structural growth, thereby proved that further the superlattice nano line that uses the inventive method to make is epitaxy.Fig. 2 d is an XRD spectra, ordinate zou in the spectrogram is that relative intensity, X-coordinate are angle (2 θ), and by this XRD spectra as can be known, nano-wire array has well (110) preferential growth orientation, the result is consistent with the parameter optimization gained, has illustrated that it is epitaxially grown by (110) preferential direction;
Fig. 3 uses FEI Sirion-200 type field emission scanning electron microscope (SEM) and incidental power spectrum (EDS) tester to observe and test resulting SEM photo in back and EDS spectrogram to bismuth nano-wire that makes respectively and bismuth antimony nano wire, and the ordinate zou in the EDS spectrogram is that relative intensity, X-coordinate are energy (KeV).Wherein, Fig. 3 a is in the EDS spectrogram of deposition voltage for the bismuth nano-wire array that obtains under-the 1.5V, can find out that by it bismuth nano-wire array is that pure bismuth constitutes, illustration in this EDS spectrogram is the SEM photo of bismuth nano-wire array, the SEM photo can find out that the crystallinity of bismuth nano-wire is good thus, and linear diameter is about 60nm.Fig. 3 b is in the EDS spectrogram of deposition voltage for the bismuth antimony nano-wire array that obtains under-the 2.0V, can find out that by it element bismuth and antimony atoms per-cent in bismuth antimony nano-wire array respectively account for 50%, illustration in this EDS spectrogram is the SEM photo of bismuth antimony nano-wire array, the SEM photo can find out that the crystallinity of bismuth antimony nano wire is good thus, and linear diameter is about 60nm.Thus, the bismuth section that we can draw among bismuth/bismuth antimony superlattice nano line only is pure bismuth, and the content of bismuth antimony section antimony is 50% or can be 20～50% behind the modulating pulse deposition voltage;
Fig. 4 be to take the photograph after adopting product that the different pulsed deposition time makes to use JEOL-2010 type transmission electron microscope (TEM) to observe the TEM photo.Wherein, the long 17nm of bismuth nano-wire among Fig. 4 a, bismuth antimony nanometer line length 24nm.The long 10nm of bismuth nano-wire among Fig. 4 b, bismuth antimony nanometer line length 20nm.The long 10nm of bismuth nano-wire among Fig. 4 c, bismuth antimony nanometer line length 10nm.The long 3nm of bismuth nano-wire among Fig. 4 d, bismuth antimony nanometer line length 10nm.Can find out that by this TEM photo the cycle length of bismuth/bismuth antimony superlattice nano line is to reach by the depositing time of modulation bismuth nano-wire section and bismuth antimony nanowire segment; Simultaneously as can be known, the average speed of growth of bismuth nano-wire section is 3nm/s, and the average speed of growth of bismuth antimony nanowire segment is 10nm/s.
Embodiment
At first make or buy bismuth chloride, antimony chloride, hydrochloric acid, tartrate, citric acid, sodium-chlor and glycerol from market with ordinary method, sodium hydroxide solution and ammoniacal liquor as alkaline solution, be coated with the porous alumina formwork of golden film, as sodium hydroxide solution, potassium hydroxide solution and the lithium hydroxide solution of strong base solution.Then,
Embodiment 1
The concrete steps of preparation are: step 1 earlier is that the bismuth chloride of 0.02M and antimony chloride that concentration is 0.06M are dissolved in the hydrochloric acid that concentration is 0.08M with concentration, mixing solutions.In stirring mixing solutions down, add the tartrate that concentration is 0.25M successively again, citric acid and the concentration that concentration is 0.22M is the sodium-chlor of 0.1M, treat that it is the glycerol of 0.08M that its dissolving back adds concentration, and continue stirring 1h.Afterwards, regulating its pH value with alkaline solution is 0.8, obtains electrodeposit liquid; Wherein, alkaline solution is that concentration is the sodium hydroxide solution (or concentration is the ammoniacal liquor of 0.1M) of 0.05M.Step 2, the porous alumina formwork that one side is coated with golden film is as negative electrode, and placing temperature is 30 ℃ electrodeposit liquid, carries out galvanic deposit under pulsed voltage; Wherein, the thickness of golden film is 150nm, and the aperture of porous alumina formwork is 30nm, and the anode during galvanic deposit is a graphite.Above-mentioned pulsed voltage is made of two groups of pulses that alternately are connected in series, and a set of pulses wherein is the pulse delay voltage of space and pulse delay voltage and the bismuth antimony pulsed deposition voltage that bismuth pulsed deposition voltage, another group pulse are the space; Wherein, the pulse width of pulse delay voltage is that 12ms, voltage are 0V, and the pulse width of bismuth pulsed deposition voltage is that 8ms, voltage are-1.4V, and the pulse width of bismuth antimony pulsed deposition voltage is that 8ms, voltage are-2V.The accumulative total pulse width of aforesaid every group of bismuth pulsed deposition voltage is 1s, and the accumulative total pulse width of every group of bismuth antimony pulsed deposition voltage is 10s.Step 3 has the porous alumina formwork of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire to place strong base solution to erode alumina formwork galvanic deposit, and wherein, strong base solution is sodium hydroxide solution (or potassium hydroxide solution or lithium hydroxide solution).Make and be similar to shown in Fig. 1, Fig. 2 a～Fig. 2 c, as among Fig. 2 d and the bismuth/bismuth/bismuth-antimony extensional superlattice nanowire shown in the curve among Fig. 3.
Embodiment 2
The concrete steps of preparation are: step 1 earlier is that the bismuth chloride of 0.03M and antimony chloride that concentration is 0.07M are dissolved in the hydrochloric acid that concentration is 0.09M with concentration, mixing solutions.In stirring mixing solutions down, add the tartrate that concentration is 0.26M successively again, citric acid and the concentration that concentration is 0.23M is the sodium-chlor of 0.11M, treat that it is the glycerol of 0.09M that its dissolving back adds concentration, and continue stirring 2h.Afterwards, regulating its pH value with alkaline solution is 0.81, obtains electrodeposit liquid; Wherein, alkaline solution is that concentration is the sodium hydroxide solution of 0.05M.Step 2, the porous alumina formwork that one side is coated with golden film is as negative electrode, and placing temperature is 33 ℃ electrodeposit liquid, carries out galvanic deposit under pulsed voltage; Wherein, the thickness of golden film is 180nm, and the aperture of porous alumina formwork is 50nm, and the anode during galvanic deposit is a graphite.Above-mentioned pulsed voltage is made of two groups of pulses that alternately are connected in series, and a set of pulses wherein is the pulse delay voltage of space and pulse delay voltage and the bismuth antimony pulsed deposition voltage that bismuth pulsed deposition voltage, another group pulse are the space; Wherein, the pulse width of pulse delay voltage is that 12ms, voltage are 0V, and the pulse width of bismuth pulsed deposition voltage is that 8ms, voltage are-1.45V, and the pulse width of bismuth antimony pulsed deposition voltage is that 8ms, voltage are-1.95V.The accumulative total pulse width of aforesaid every group of bismuth pulsed deposition voltage is 3s, and the accumulative total pulse width of every group of bismuth antimony pulsed deposition voltage is 3s.Step 3 has the porous alumina formwork of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire to place strong base solution to erode alumina formwork galvanic deposit, and wherein, strong base solution is a sodium hydroxide solution.Make as shown in Figure 1, be similar to shown in Fig. 2 b and Fig. 2 c, be similar to shown in the curve among Fig. 2 d and Fig. 3, and be similar to the bismuth/bismuth/bismuth-antimony extensional superlattice nanowire shown in Fig. 4 a.
Embodiment 3
The concrete steps of preparation are: step 1 earlier is that the bismuth chloride of 0.04M and antimony chloride that concentration is 0.08M are dissolved in the hydrochloric acid that concentration is 0.1M with concentration, mixing solutions.In stirring mixing solutions down, add the tartrate that concentration is 0.27M successively again, citric acid and the concentration that concentration is 0.24M is the sodium-chlor of 0.12M, treat that it is the glycerol of 0.1M that its dissolving back adds concentration, and continue stirring 3h.Afterwards, regulating its pH value with alkaline solution is 0.82, obtains electrodeposit liquid; Wherein, alkaline solution is that concentration is the sodium hydroxide solution of 0.05M.Step 2, the porous alumina formwork that one side is coated with golden film is as negative electrode, and placing temperature is 35 ℃ electrodeposit liquid, carries out galvanic deposit under pulsed voltage; Wherein, the thickness of golden film is 200nm, and the aperture of porous alumina formwork is 80nm, and the anode during galvanic deposit is a graphite.Above-mentioned pulsed voltage is made of two groups of pulses that alternately are connected in series, and a set of pulses wherein is the pulse delay voltage of space and pulse delay voltage and the bismuth antimony pulsed deposition voltage that bismuth pulsed deposition voltage, another group pulse are the space; Wherein, the pulse width of pulse delay voltage is that 12ms, voltage are 0V, and the pulse width of bismuth pulsed deposition voltage is that 8ms, voltage are-1.5V, and the pulse width of bismuth antimony pulsed deposition voltage is that 8ms, voltage are-1.9V.The accumulative total pulse width of aforesaid every group of bismuth pulsed deposition voltage is 17s, and the accumulative total pulse width of every group of bismuth antimony pulsed deposition voltage is 5s.Step 3 has the porous alumina formwork of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire to place strong base solution to erode alumina formwork galvanic deposit, and wherein, strong base solution is a sodium hydroxide solution.Make and be similar to shown in Fig. 2 a～Fig. 2 c, be similar to shown in the curve among Fig. 2 d, and be similar to the bismuth/bismuth/bismuth-antimony extensional superlattice nanowire shown in Fig. 4 b～Fig. 4 d.
Embodiment 4
The concrete steps of preparation are: step 1 earlier is that the bismuth chloride of 0.05M and antimony chloride that concentration is 0.09M are dissolved in the hydrochloric acid that concentration is 0.11M with concentration, mixing solutions.In stirring mixing solutions down, add the tartrate that concentration is 0.28M successively again, citric acid and the concentration that concentration is 0.25M is the sodium-chlor of 0.13M, treat that it is the glycerol of 0.11M that its dissolving back adds concentration, and continue stirring 4h.Afterwards, regulating its pH value with alkaline solution is 0.83, obtains electrodeposit liquid; Wherein, alkaline solution is that concentration is the sodium hydroxide solution of 0.05M.Step 2, the porous alumina formwork that one side is coated with golden film is as negative electrode, and placing temperature is 38 ℃ electrodeposit liquid, carries out galvanic deposit under pulsed voltage; Wherein, the thickness of golden film is 230nm, and the aperture of porous alumina formwork is 100nm, and the anode during galvanic deposit is a graphite.Above-mentioned pulsed voltage is made of two groups of pulses that alternately are connected in series, and a set of pulses wherein is the pulse delay voltage of space and pulse delay voltage and the bismuth antimony pulsed deposition voltage that bismuth pulsed deposition voltage, another group pulse are the space; Wherein, the pulse width of pulse delay voltage is that 12ms, voltage are 0V, and the pulse width of bismuth pulsed deposition voltage is that 8ms, voltage are-1.55V, and the pulse width of bismuth antimony pulsed deposition voltage is that 8ms, voltage are-1.8V.The accumulative total pulse width of aforesaid every group of bismuth pulsed deposition voltage is 26s, and the accumulative total pulse width of every group of bismuth antimony pulsed deposition voltage is 2s.Step 3 has the porous alumina formwork of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire to place strong base solution to erode alumina formwork galvanic deposit, and wherein, strong base solution is a sodium hydroxide solution.Make and be similar to shown in Fig. 2 a～Fig. 2 c, be similar to the bismuth/bismuth/bismuth-antimony extensional superlattice nanowire shown in the curve among Fig. 2 d.
The concrete steps of preparation are: step 1 earlier is that the bismuth chloride of 0.06M and antimony chloride that concentration is 0.1M are dissolved in the hydrochloric acid that concentration is 0.12M with concentration, mixing solutions.In stirring mixing solutions down, add the tartrate that concentration is 0.29M successively again, citric acid and the concentration that concentration is 0.26M is the sodium-chlor of 0.14M, treat that it is the glycerol of 0.12M that its dissolving back adds concentration, and continue stirring 5h.Afterwards, regulating its pH value with alkaline solution is 0.84, obtains electrodeposit liquid; Wherein, alkaline solution is that concentration is the sodium hydroxide solution of 0.05M.Step 2, the porous alumina formwork that one side is coated with golden film is as negative electrode, and placing temperature is 40 ℃ electrodeposit liquid, carries out galvanic deposit under pulsed voltage; Wherein, the thickness of golden film is 250nm, and the aperture of porous alumina formwork is 120nm, and the anode during galvanic deposit is a graphite.Above-mentioned pulsed voltage is made of two groups of pulses that alternately are connected in series, and a set of pulses wherein is the pulse delay voltage of space and pulse delay voltage and the bismuth antimony pulsed deposition voltage that bismuth pulsed deposition voltage, another group pulse are the space; Wherein, the pulse width of pulse delay voltage is that 12ms, voltage are 0V, and the pulse width of bismuth pulsed deposition voltage is that 8ms, voltage are-1.6V, and the pulse width of bismuth antimony pulsed deposition voltage is that 8ms, voltage are-1.7V.The accumulative total pulse width of aforesaid every group of bismuth pulsed deposition voltage is 33s, and the accumulative total pulse width of every group of bismuth antimony pulsed deposition voltage is 0.3s.Step 3 has the porous alumina formwork of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire to place strong base solution to erode alumina formwork galvanic deposit, and wherein, strong base solution is a sodium hydroxide solution.Make and be similar to shown in Fig. 2 a～Fig. 2 c, be similar to shown in the curve among Fig. 2 d, and be similar to the bismuth/bismuth/bismuth-antimony extensional superlattice nanowire shown in Fig. 4 d.
If desire obtains to be arranged in the bismuth/bismuth antimony superlattice nano line of porous alumina formwork, only need save step 3 and get final product.
Obviously, those skilled in the art can carry out various changes and modification to bismuth/bismuth/bismuth-antimony extensional superlattice nanowire of the present invention and preparation method thereof and not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1. a bismuth/bismuth/bismuth-antimony extensional superlattice nanowire comprises bismuth nano-wire, it is characterized in that:
Described bismuth nano-wire and bismuth antimony nano wire extension connect into bismuth/bismuth antimony superlattice nano line;
The diameter of described bismuth/bismuth antimony superlattice nano line is 30～120nm, and every segment length of bismuth nano-wire wherein is that every segment length of 3～99nm, bismuth antimony nano wire is 3～99nm;
Bi content in the described bismuth antimony nano wire is 80～50%, antimony content is 20～50%.
2. bismuth/bismuth/bismuth-antimony extensional superlattice nanowire according to claim 1 is characterized in that the bismuth nano-wire in bismuth/bismuth antimony superlattice nano line and the hop count of bismuth antimony nano wire are 3～10000 sections.
3. bismuth/bismuth/bismuth-antimony extensional superlattice nanowire according to claim 1 is characterized in that bismuth/bismuth antimony superlattice nano line is arranged in porous alumina formwork.
4. the preparation method of the described bismuth/bismuth/bismuth-antimony extensional superlattice nanowire of claim 1 comprises the pulse electrochemical sedimentation, it is characterized in that completing steps is as follows:
Step 1, earlier be that the bismuth chloride of 0.02～0.06M and antimony chloride that concentration is 0.06～0.1M are dissolved in the hydrochloric acid that concentration is 0.08～0.12M with concentration, the mixing solutions that gets, add the tartrate that concentration is 0.25～0.29M successively in the mixing solutions under stirring again, citric acid and the concentration that concentration is 0.22～0.26M is the sodium-chlor of 0.1～0.14M, treat that it is the glycerol of 0.08～0.12M that its dissolving back adds concentration, and continue to stir 1h at least, afterwards, regulating its pH value with alkaline solution is 0.8～0.84, obtains electrodeposit liquid;
Step 2, one side is coated with the porous alumina formwork of golden film as negative electrode, placing temperature is 30～40 ℃ electrodeposit liquid, under pulsed voltage, carry out galvanic deposit, described pulsed voltage is made of two groups of pulses that alternately are connected in series, a set of pulses wherein is the pulse delay voltage and the bismuth pulsed deposition voltage of space, another group pulse is the pulse delay voltage and the bismuth antimony pulsed deposition voltage of space, the pulse width of described pulse delay voltage is 12ms, voltage is 0V, the pulse width of described bismuth pulsed deposition voltage is 8ms, voltage is-1.4～-1.6V, the pulse width of described bismuth antimony pulsed deposition voltage is 8ms, voltage is-1.7～-2V;
Step 3 has the porous alumina formwork of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire to place strong base solution to erode alumina formwork galvanic deposit, makes bismuth/bismuth/bismuth-antimony extensional superlattice nanowire.
5. the preparation method of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire according to claim 4 is characterized in that alkaline solution is that concentration is that sodium hydroxide solution or the concentration of 0.05M is the ammoniacal liquor of 0.1M.
6. the preparation method of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire according to claim 4, the thickness that it is characterized in that golden film is 150～250nm.
7. the preparation method of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire according to claim 4, the aperture that it is characterized in that porous alumina formwork is 30～120nm.
8. the preparation method of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire according to claim 4, the anode when it is characterized in that galvanic deposit is a graphite.
9. the preparation method of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire according to claim 4, the accumulative total pulse width that it is characterized in that every group of bismuth pulsed deposition voltage is 1～33s, the accumulative total pulse width of every group of bismuth antimony pulsed deposition voltage is 0.3～10s.
10. the preparation method of bismuth/bismuth/bismuth-antimony extensional superlattice nanowire according to claim 4 is characterized in that strong base solution is a sodium hydroxide solution, or potassium hydroxide solution, or lithium hydroxide solution.
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| CN102637765A (en) * | 2011-02-12 | 2012-08-15 | 同济大学 | Preparation method of multilayer nanometer wire |
| CN103088388A (en) * | 2013-01-15 | 2013-05-08 | 中国科学院合肥物质科学研究院 | Silver-bismuth superlattice nanowire array and preparation method and application thereof |
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| CN1234599C (en) * | 2003-12-21 | 2006-01-04 | 浙江大学 | Bi2Te3 base compound nano line and its preparing method |
| CN100453707C (en) * | 2004-10-22 | 2009-01-21 | 中国科学院合肥物质科学研究院 | Method for preparing diameter different monocrystal bismuth nanowire microarray by using uniform hole diameter alumina template |
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| CN102637765A (en) * | 2011-02-12 | 2012-08-15 | 同济大学 | Preparation method of multilayer nanometer wire |
| CN102637765B (en) * | 2011-02-12 | 2014-12-10 | 同济大学 | Preparation method of multilayer nanometer wire |
| CN103088388A (en) * | 2013-01-15 | 2013-05-08 | 中国科学院合肥物质科学研究院 | Silver-bismuth superlattice nanowire array and preparation method and application thereof |
| CN103088388B (en) * | 2013-01-15 | 2015-04-29 | 中国科学院合肥物质科学研究院 | Silver-bismuth superlattice nanowire array and preparation method and application thereof |
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