CN104909336A - Growing method for nanowire array based on metal electrodes - Google Patents
Growing method for nanowire array based on metal electrodes Download PDFInfo
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- CN104909336A CN104909336A CN201510194994.XA CN201510194994A CN104909336A CN 104909336 A CN104909336 A CN 104909336A CN 201510194994 A CN201510194994 A CN 201510194994A CN 104909336 A CN104909336 A CN 104909336A
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Abstract
The invention belongs to the field of microelectronics technologies and instrument technologies, and particularly relates to a growing method for a nanowire array based on metal electrodes. The method includes the steps that firstly, the electrode A and the electrode B are prepared on the two sides of a porous template respectively, wherein it needs to be ensured that the electrode B does not block holes of the porous template, the electrode A is the metal electrode obtained through sputtering, and the electrode B is the metal electrode obtained through sputtering; secondly, the electrode A and the electrode B are connected with a power source and immersed into a solution groove containing electrolyte until the even nanowire array is grown. Compared with a method for ensuring the consistency of the lengths of nanowires through chemical-mechanical polishing, the lengths of the nanowires can be controlled more easily the growing method, and the polishing technology is not needed any more. Meanwhile, the technology route provided by the growing method prevents the porous template from being damaged in the polishing process, and the yield is easily increased.
Description
Technical field
The invention belongs to microelectronic technique field and technology of instrument and meter field, particularly a kind of growing method of the nano-wire array based on metal electrode.
Background technology
Monodimension nanometer material is one of current study hotspot [Yao Aili, Lv Guiqin, Hu Changwen, the preparation of silver nanoparticle modified electrode and electrochemical behavior [J], Chinese Journal of Inorganic Chemistry, 2006,22 (6): 1099-1102].This material all has a wide range of applications in fields such as focus device, luminescent devices.Effect [Guo Yuguo specific to the nano materials such as bulk effect, skin effect, quantum size effect and tunnel-effect that monodimension nanometer material has, the Electrochemical Template UV absorber of nano wire, University Of Qingdao's master thesis, 2001], its application also receives and notes more and more widely.
All the time, people mainly concentrate on the sign of its performance to the research of nano wire and apply, such as thermo-electric device [Mildred S.Dresselhaus etc., New Directions for Low-DimensionalThermoelectric Materials [J], Adv.Mater.2007, 19, 1043 – 1053], solar cell [Xavier Mathew etc., Structural and opto-electronic properties of electrodeposited CdTe on stainless steel foil, Solar Energy Materials & Solar Cells, 1999, 59:99-114] etc. aspect.The growth technique of nano wire is often only introduced as a part for device research, especially lacks effective control device to the homogeneity of nanowire growth.The main following points of reason: the diameter (tens nanometer scale) of (1) nano wire differs about 5 orders of magnitude with the overall dimensions (several millimeters of magnitudes) of device, make the growing environment that can not control nano wire one by one, can only be controlled from macroscopic view; (2) micro under macroscopic growth environment has a lot of inhomogeneities, as the concentration gradient of solution, electric field all to affect the growth of nano wire with the Temperature Distribution etc. in space distribution situation and solution.The Changing Pattern of these conditions under microcosmic is usually difficult to directly describe with macroscopic view distribution, and it is more difficult to control, and makes different nano wire often have different growth rates; (3) many times different nano aperture is different by the speed of solution impregnation, and make the time that in different space, electro-deposition starts also different, this result also in the inhomogeneities of nanowire growth.
Work before us adopts the method for chemically mechanical polishing [Guo Tianwei, the nano-wire array for miniature thermal generator is prepared with integrated, Tsing-Hua University's Engineering Master academic dissertation, 2014] to ensure the uniformity of resulting devices nanowire length.But the method for chemically mechanical polishing easily causes damage to device, as wearing and tearing or fragmentation etc., this method is made to have certain limitation.
Summary of the invention
Not enough for prior art, the invention provides a kind of growing method of the nano-wire array based on metal electrode, aim to provide a kind of method controlling electrochemical deposition nanowire length homogeneity.Its principle is: the present invention, by making the method for electrode (electrode A and electrode B) in foraminous die plate both sides, forms pressure drop in the both sides of pattern hole.When template is infiltrated by electrolyte time, described pressure drop will be loaded on electrolyte, thus causes the beginning of electrodeposition process, and the nano wire namely in stencil apertures starts to grow from a lateral electrode (electrode A).In nanowire growth process, because the electrical conductivity of nano wire is far away higher than the electrical conductivity of electrolyte, the overwhelming majority of pressure drop added by template both sides is still loaded on electrolyte, and does not reduce rapidly with the growth of nano wire, this can ensure that nanowire growth process is relatively steady.Time near some nanowire growth to template opposite side electrode B, because electrode B and nano wire top distance become very little, make the obvious step-down of pressure drop on electrolyte, and then nanowire growth in corresponding space is stopped, in other holes, growth phase is to nano wire then continued growth slowly, until all nano wires grow near electrode B, in all holes, nanowire growth stops, the uniform nano-wire array of final acquisition.
Based on a growing method for the nano-wire array of metal electrode, comprise the steps:
Step 1, makes electrode A and electrode B respectively in foraminous die plate both sides, and wherein electrode B guarantees the hole that can not block foraminous die plate; Described electrode A is sputter the metal electrode obtained, and described electrode B is the metal electrode that sputtering or ald obtain;
Step 2, electrode A is connected with power supply respectively with electrode B, and immersion is equipped with in the solution tank of electrolyte, until grow uniform nano-wire array.
The thickness of described electrode A is greater than the thickness of electrode B.
Not blocked for ensureing foraminous die plate hole, the thickness of described electrode B is no more than 2/3rds of foraminous die plate aperture.The thickness of described electrode A is more than 100nm; The thickness of described electrode B is about 20nm, generally not higher than the diameter in nano-form aperture.
The foraminous die plate adopted in described step 1 is porous alumina formwork, and be called for short " AAO " template, its thickness is 300 microns.
The foraminous die plate adopted in described step 1 is polymer template.
This technique is applicable to electrochemical process depositing nano line.But this uses Bi ion and Te ion electrochemical deposition Bi on porous alumina formwork
xte
ynano wire, wherein x>0, y>0.In described step 2, electrolyte is TeO
2, BiNO
5hBi (OH) and HNO
3mixed solution, wherein TeO
2concentration be 10mmol/L, BiNO
5the concentration of HBi (OH) is 7.5mmol/L, HNO
3concentration be 1mol/L.
The sedimentation potential that described in described step 2, power supply provides is-0.068V ~-10V.
The invention provides a kind of growing method of the nano-wire array based on metal electrode, concrete principle is described as follows:
The present invention, by making the method for electrode (electrode A and electrode B) in foraminous die plate both sides, forms pressure drop in the both sides of pattern hole.As shown in Figure 1, as shown in Figure 1,1 is electrode B to sample structure needed for technique, and 2 is foraminous die plate, and 3 is electrode A, and 4 is intact sample schematic diagram.
Fig. 2 is principle schematic of the present invention, and wherein 5 is circuit connection, and 6 is power supply, and 7 is electrolytic bath; There is electrolyte in 7 electrolytic baths, intact sample 4 can be soaked.
The more detailed principle of the present invention describes in Fig. 3, Fig. 4, Fig. 5, for convenience, assuming that get 3 different holes in a certain foraminous die plate, respectively they is numbered 8,9,10.
Situation when electro-deposition just starts as shown in Figure 3, now soaked by the electrolyte in electrolytic bath 7 by intact sample 4, provides potential difference between electrode A (3) and electrode B (1) by power supply 6.Now nano wire (in 8,9,10, black block represents) has just started growth.Because micro is not quite similar, their length is also incomplete same.
Electro-deposition carries out the situation after a period of time as shown in Figure 4, and now intact sample 4 is soaked by the electrolyte in electrolytic bath 7, provides potential difference between electrode A (3) and electrode B (1) by power supply 6.In nanowire growth process, because the electrical conductivity of nano wire is far away higher than the electrical conductivity of electrolyte, when nano wire top distance electrode B (1) is still distant, the overwhelming majority of the added pressure drop of foraminous die plate 2 liang of lateral electrodes (1 and 3) is still loaded on electrolyte, namely the dividing potential drop on electrolyte can't reduce rapidly with the growth of nano wire, and this can ensure that nano wire keeps growth.Meanwhile, because the microcosmic condition in hole different in growth course is not quite similar, in different hole, the speed of nanowire growth may be different, becomes when in same hole, the growth rate of nano wire also may be.
At the end of electro-deposition is close, conveniently describes, three phases can be divided into artificially: namely minority nanowire growth terminates, most nanowire growth terminates and all nanowire growths terminate.
Electro-deposition is close to terminating and having situation at the end of minority nanowire growth as shown in Figure 5.Now, the still continued growth of most nano wire, but very fast with the nanowire growth speed in the second hole 9, to such an extent as to the top of nano wire is first close to electrode B (1).Because top distance electrode B (1) of nano wire in the second hole 9 is very near, the length that electrolyte is occupied is very short, to such an extent as in the second hole 9 resistance of nano wire and the resistance sizes of electrolyte comparable, now on electrolyte, dividing potential drop has been not enough to electrodeposition process is continued, and the nanowire growth in the second hole 9 terminates.
Electro-deposition is close to terminating and having situation at the end of most nanowire growth as shown in Figure 6.The resistance of most hole (first hole 8 and the second hole 9) interior nano wire and the resistance sizes of electrolyte comparable, now on electrolyte, dividing potential drop has been not enough to electrodeposition process is continued, and the nanowire growth in the first hole 8, second hole 9 terminates.But minority hole (the 3rd hole 10) nano wire top distance electrode B (1) is still distant, the overwhelming majority of the added pressure drop of foraminous die plate 2 liang of lateral electrodes (1 and 3) is still loaded on electrolyte, and the electrodeposition process in the 3rd hole 10 continues.
Situation at the end of electro-deposition as shown in Figure 7.The resistance of all holes (the first hole 8, second hole 9 and the 3rd hole 10) interior nano wire and the resistance sizes of electrolyte comparable, now on electrolyte, dividing potential drop has been not enough to electrodeposition process is continued, nanowire growth in all holes terminates, and obtains uniform nano-wire array.
Beneficial effect of the present invention is:
Compared to the conforming method adopting chemically mechanical polishing to ensure nanowire length, the inventive method is more simple for the cut to lengthen of nano wire, no longer needs glossing to get involved.Meanwhile, process routes provided by the present invention avoids the damage of polishing process to foraminous die plate, is conducive to the raising of yields.
Accompanying drawing explanation
Fig. 1 is sample schematic diagram needed for the growing method of a kind of nano-wire array based on metal electrode of the present invention;
The apparatus structure schematic diagram that the growing method that Fig. 2 is a kind of nano-wire array based on metal electrode of the present invention uses;
Fig. 3 is the schematic diagram of the growing method technique of a kind of nano-wire array based on metal electrode of the present invention when starting;
Fig. 4 is the schematic diagram of the growing method technique of a kind of nano-wire array based on metal electrode of the present invention when carrying out middle;
Fig. 5 is the schematic diagram at the end of the growing method technique later stage individual nanowires growth of a kind of nano-wire array based on metal electrode of the present invention;
Fig. 6 is the schematic diagram at the end of growing method technique later stage most nanowire growth of a kind of nano-wire array based on metal electrode of the present invention;
Fig. 7 is the schematic diagram that the growing method technique of a kind of nano-wire array based on metal electrode of the present invention terminates at the end of all nanowire growths;
Fig. 8 (a) ~ Fig. 8 (d) is the embodiment of the present invention 1 and 3 one kind of growing method process flow diagram based on the nano-wire array of metal electrode;
Fig. 9 (a) ~ Fig. 9 (d) is for the embodiment of the present invention 2 one kinds is based on the growing method process flow diagram of the nano-wire array of metal electrode;
Number in the figure: 1-electrode B, 2-foraminous die plate, 3-electrode A, 4-intact sample, 5-circuit connection, 6-power supply, 7-electrolytic bath, 8-first hole, 9-second hole, 10-the 3rd hole, 11-porous alumina formwork, 12-first gold electrode, 13-second gold electrode, 14-electrochemical workstation, 15-porous polyethylene template.
Detailed description of the invention
The invention provides a kind of growing method of the nano-wire array based on metal electrode, below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment 1
Composition graphs 8, describes first specific embodiment of the present invention in detail, but is not limited in any way claim of the present invention.Technique described in the present embodiment is divided into 4 steps, (a) standby sheet respectively, b () sputtering obtains the first gold electrode 12 (electrode A), (c) sputtering obtains the second gold electrode 13 (electrode B), (d) nanowire deposition.Wherein, foraminous die plate 2 adopts commercial porous alumina formwork 11, and its aperture is less than 100nm; The thickness of the first gold electrode 12 is 300nm; The thickness of the second gold electrode 13 is 20nm, and electron microscopic examination gold electrode B does not cover the micropore of porous alumina formwork.Circuit connection is provided by figure d, and electrochemical workstation 14 can provide constant voltage and record current change curve in time.In this example, voltage is-0.7V.Electrolyte is TeO
2, BiNO
5hBi (OH) and HNO
3mixed solution, wherein TeO
2concentration be 10mmol/L, BiNO
5the concentration of HBi (OH) is 7.5mmol/L, HNO
3concentration be 1mol/L.After electro-deposition starts, can see that electric current is first relatively stable, after part nanowire growth, have the phenomenon appearance that electric current rises to.After this, when no longer occurring in a period of time that electric current rises to, and size of current keep stable after, can think that all nanowire growths complete, technique terminates.Total growth time is 5 hours, and the nanowire length uniformity that microscopy visible growth goes out is good, has no the part nanowire growth caused because nanowire growth speed is inconsistent long, and produces the situation of reuniting at template surface.
Embodiment 2
Composition graphs 9, describes the 3rd specific embodiment of the present invention in detail, but is not limited in any way claim of the present invention.Technique described in the present embodiment is divided into 4 steps, (a) standby sheet respectively, b () sputtering obtains the first gold electrode 12 (electrode A), (c) sputtering obtains the second gold electrode 13 (electrode B), (d) nanowire deposition.Wherein, foraminous die plate 2 adopts porous polyethylene template 15, and its aperture is less than 1 micron; The thickness of the first gold electrode 12 is 300nm; The thickness of the second gold electrode 13 is 20nm, and electron microscopic examination gold electrode B does not cover the micropore of porous alumina formwork.Circuit connection is provided by figure d, and 14 electrochemical workstations can provide constant voltage and record current change curve in time.In this example, voltage is-0.7V.Electrolyte is TeO
2, BiNO
5hBi (OH) and HNO
3mixed solution, wherein TeO
2concentration be 10mmol/L, BiNO
5the concentration of HBi (OH) is 7.5mmol/L, HNO
3concentration be 1mol/L.After electro-deposition starts, can see that electric current is first relatively stable, after part nanowire growth, have the phenomenon appearance that electric current rises to.After this, when no longer occurring in a period of time that electric current rises to, and size of current keep stable after, can think that all nanowire growths complete, technique terminates.Total growth time is 5 hours, and the nanowire length uniformity that microscopy visible growth goes out is good, has no the part nanowire growth caused because nanowire growth speed is inconsistent long, and produces the situation of reuniting at template surface.
Embodiment 3
Composition graphs 8, describes the 3rd specific embodiment of the present invention in detail, but is not limited in any way claim of the present invention.Technique described in the present embodiment is divided into 4 steps, (a) standby sheet respectively, b () sputtering obtains the first gold electrode 12 (electrode A), (c) atomic layer deposition obtains the second gold electrode 13 (electrode B), (d) nanowire deposition.Wherein, foraminous die plate 2 adopts commercial porous alumina formwork 11, and its aperture is less than 100nm; The thickness of the first gold electrode 12 is 300nm; The thickness of the second gold electrode 13 is 20nm, and electron microscopic examination gold electrode B does not cover the micropore of porous alumina formwork.Circuit connection is provided by Fig. 8 (d), and electrochemical workstation 14 can provide constant voltage and record current change curve in time.In this example, voltage is-0.7V.Electrolyte is TeO
2, BiNO
5hBi (OH) and HNO
3mixed solution, wherein TeO
2concentration be 10mmol/L, BiNO
5the concentration of HBi (OH) is 7.5mmol/L, HNO
3concentration be 1mol/L.After electro-deposition starts, can see that electric current is first relatively stable, after part nanowire growth, have the phenomenon appearance that electric current rises to.After this, when no longer occurring in a period of time that electric current rises to, and size of current keep stable after, can think that all nanowire growths complete, technique terminates.Total growth time is 5 hours, and the nanowire length uniformity that microscopy visible growth goes out is good, has no the part nanowire growth caused because nanowire growth speed is inconsistent long, and produces the situation of reuniting at template surface.
Claims (5)
1. based on a growing method for the nano-wire array of metal electrode, it is characterized in that, comprise the steps:
Step 1, makes electrode A and electrode B respectively in foraminous die plate both sides, and wherein electrode B guarantees the hole that can not block foraminous die plate; Described electrode A is sputter the metal electrode obtained, and described electrode B is the metal electrode that sputtering or ald obtain;
Step 2, electrode A is connected with power supply respectively with electrode B, and immersion is equipped with in the solution tank of electrolyte, until grow uniform nano-wire array.
2. the growing method of a kind of nano-wire array based on metal electrode according to claim 1, is characterized in that, the thickness of described electrode A is greater than the thickness of electrode B.
3. the growing method of a kind of nano-wire array based on metal electrode according to claim 1, is characterized in that, not blocked for ensureing foraminous die plate hole, the thickness of described electrode B is no more than 2/3rds of foraminous die plate aperture.
4. the growing method of a kind of nano-wire array based on metal electrode according to claim 1, is characterized in that, the foraminous die plate adopted in described step 1 is porous alumina formwork.
5. the growing method of a kind of nano-wire array based on metal electrode according to claim 1, is characterized in that, the foraminous die plate adopted in described step 1 is polymer template.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020118027A1 (en) * | 2000-10-24 | 2002-08-29 | Dmitri Routkevitch | Nanostructured ceramic platform for micromachined devices and device arrays |
| CN101306795A (en) * | 2008-06-13 | 2008-11-19 | 中国科学院光电技术研究所 | Optical band artificial composite structure material made by AAO template |
| CN103733388A (en) * | 2011-07-01 | 2014-04-16 | 安普雷斯股份有限公司 | Template electrode structures with enhanced adhesion characteristics |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020118027A1 (en) * | 2000-10-24 | 2002-08-29 | Dmitri Routkevitch | Nanostructured ceramic platform for micromachined devices and device arrays |
| CN101306795A (en) * | 2008-06-13 | 2008-11-19 | 中国科学院光电技术研究所 | Optical band artificial composite structure material made by AAO template |
| CN103733388A (en) * | 2011-07-01 | 2014-04-16 | 安普雷斯股份有限公司 | Template electrode structures with enhanced adhesion characteristics |
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Effective date of registration: 20210122 Address after: No. 102, 113, 209, 210, 211 and the third floor of Guotai building a (gong'an Building No. 2), 440 Wenchang West Road, Hanjiang District, Yangzhou City, Jiangsu Province, 225012 Patentee after: Jiangsu intelligent microsystem Industrial Technology Co.,Ltd. Address before: 100084 Beijing City, Haidian District, Haidian District, 100084 mailbox Patentee before: TSINGHUA University |