CN102021626B - Annealing method for preventing porous anodic aluminum oxide (AAO) template from curling - Google Patents
Annealing method for preventing porous anodic aluminum oxide (AAO) template from curling Download PDFInfo
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Abstract
The invention provides an annealing method for preventing a porous anodic aluminum oxide (AAO) template from curling, comprising the following steps: (1) manufacturing the porous AAO template by adopting a conventional technology and carrying out through hole enlarging treatment; (2) taking a vacuum tubular furnace as an annealing furnace, placing the porous AAO template which is subject to through hole enlarging treatment into the tubular furnace, sealing off the discharge end of the annealing furnace, and introducing pressure preserving gas from the inlet end of the annealing furnace to ensure the gas pressure in the annealing furnace reaches 1.01 MPa; and (3) performing heating annealing on the porous AAO template, wherein air inflow and air displacement are regulated so as to ensure the pressure value of the pressure preserving gas in the annealing furnace is in the range of 1.01-1.10 MPa in the process until the annealing operation is finished. The annealing method for preventing the porous AAO template from curling has the beneficial effects of solving the difficulties which bother researchers in the field for a long time, and playing an important role in broadening applied research of the AAO template and pushing technical progress in the field.
Description
(1) technical field
The present invention relates to the synthetic and micro-nano technical field of nanometer, particularly a kind of method for annealing that porous anodic alumina template is not curled.
(2) background technology
Porous anodic aluminium oxide (Anodic Aluminum Oxide is hereinafter to be referred as AAO) template is as a kind of ideal template material, has a wide range of applications with micro-nano technical field in that nanometer is synthetic.The AAO template has the vesicular structure of rule, is to be close to accurate six side's solid matter periodic arrangement, and the cylindricality duct is parallel; It is controlled that the cycle of solid matter and the aperture in duct are all adjustable, and have higher dielectric constant etc., the vesicular structure of this uniqueness and the good characteristic of aluminum oxide; Make AAO become the ideal carrier of the orderly composite structure of assemble nanometer (referring to document R.C.Furneaux, W.R.Rigby, A.P.Davidson; Nature; 337 (1989) 147 and H.Masuda, K.Fukuda, Science 268 (1995) 1466).With AAO is that materials such as template synthetic nano wire, nanometer rod and nanotube usually have peculiar physical and chemical performance.It should be noted that a large amount of building-up processes,, all under hot conditions, carry out such as molecular beam epitaxy, chemical Vapor deposition process, electrochemical deposition method etc.Yet AAO is when high temperature annealing, and template can be curled, and this is a global technical barrier, its big limitations the application of AAO template.Report that the earliest this phenomenon is in 1972, at that time, people such as Neufeld were (referring to document P.Neufeld; N.K.Nagpaul, R.Ashdown, and M.Akbar; Electrochimica Acta 17,1972,1543) find that the AAO template can undergo phase transition and follow shrinkage phenomenon when heating.Nineteen ninety-five, and people such as Mardilovich (referring to document P.P.Mardilovich, A.N.Govyadinov; N.I.Mukhurov, A.M.Rzhevskii, and R.Paterson; J.Membrane Sci.98; 1995,131) systematically studied curling phenomenon after the AAO heat that in oxalic acid, prepares, they find that the impurity in the AAO template reduces near several transformation temperatures; For example 830-840 ℃ (becoming polycrystalline state mutually) from amorphous state, 1075-1150 ℃ (becoming six side's solid matter structures mutually) from cubic(al)grating; And the template behind the discovery high temperature annealing produced a large amount of inferior holes, thinks that the generation in time hole is relevant with the phase transformation of aluminum oxide.2006, and people such as I.W.M.Brown (referring to document I.W.M.Brown, M.E.Bowden; T.Kemmitt, and K.J.D.MacKenzie, Current Applied Physics 6; 2006,557) detail analysis has been carried out in the thermal treatment of the AAO that in phosphoric acid, prepares, thought after the AAO template is heated to 850 ℃; It can curl under the effect of internal mechanical stresses or cracking, and thinks that this stress is because impurity (AlPO
4Group) along the direction uneven distribution in hole and cause.2007, and people such as A.Kirchner (referring to document K.J.D.M.A.Kirchner, I.W.M.Brown; T.Kemmitt, and M.E.Bowden, J.Membrane Sci.287; 2007; 264) the AAO template that in sulfuric acid, prepares has been carried out the bent analysis of hot rolling, thought that the AAO template through 970 ℃ of annealing, changes γ-Al into from amorphous state
2O
3, and follow SO
2, O
2Deng the release of material, after 1228 ℃ of annealing, become the most stable α-Al through phase transformation
2O
3Structure.2008, and people such as Fern á ndez-Romero (referring to document L.Fern á dez-Romero, J.M.Montero-Moreno, E.Pellicer; F.Peir, A.Cornet, J.R.Morante, M.Sarret; And C.Muler, Mater.Chem.Phys.111,2008; 542) once tested the certain weight of storing on template, observed the anneal act of template under the effect of weight pressure, found when template is annealed under weight pressure cracked.People's such as Fern á ndez Romero research is also found; Do not remove the template on blocking layer and can effectively improve the curling phenomenon of template; But what in plurality of applications, need is the AAO template of having removed blocking layer, through hole, and therefore this way can not solve the hot rolling Qu Wenti of AAO template effectively.Above document shows that the problem that the AAO template takes place to curl once received extensive attention and research, but did not still have effective solution so far when high temperature annealing.
(3) summary of the invention
The objective of the invention is provides a kind of effective method for annealing to above-mentioned existing problems, makes the AAO template when high temperature annealing, can hold its shape, and does not curl.
Technical scheme of the present invention:
A kind of method for annealing that porous anodic alumina template is not curled, step is following:
1) adopting routine techniques to prepare the go forward side by side hole reaming that works of porous anodic alumina template handles;
2) with the vacuum tube furnace be lehre, the porous anodic alumina template after the through hole reaming is handled is put into tube furnace, the exhaust side of closed annealing stove, and the inlet end feeding pressurize gas from lehre makes furnace gas pressure reach 1.01 normal atmosphere;
3) to the porous anodic alumina template annealing that heats up, in this process, make the atmospheric pressure value of pressurize gas in the lehre constant at 1.01 normal atmosphere-1.10 normal atmosphere through adjustment inlet and outlet amount, accomplish until annealing.
Said pressurize gas is air, oxygen, nitrogen or argon gas.
Said annealing temperature is not for being higher than 1000 ℃.
Principle of work of the present invention: the AAO template is divided positive and negative two surfaces, and usually, the front is meant that one side that in the preparation process, is close to electrolytic solution, and reverse side is meant that one side by aluminium substrate.Experiment shows, when under normal pressure, annealing, places in any case, and the AAO template is always curled towards positive.Our research shows that the front of annealed AAO template has produced in a large number " inferior hole " (sub-pores, the light-colored part that around some hole, occurs among the SEM figure of annealing back front face template) under the normal pressure, is the immediate cause that causes template to be curled.And the generation in inferior hole is owing to due to front face template inner remaining " hole nuclear " (pore nuclear) and the stress; Therefore; If making the AAO template anneals in airtight furnace chamber; And make the gaseous tension in the lehre balance each other with the inner unrelieved stress of template, and then the hole of pore-forming nuclear will no longer not grown and will be inferior hole, and template will be no longer curling at this moment.
The invention has the beneficial effects as follows: this method for annealing has solved a difficult problem that troubles this area investigator for a long time, for the applied research of expansion AAO template, the technical progress of promotion this area important meaning is arranged.
(4) description of drawings
Fig. 1 is the SEM picture of AAO template (reverse side).
Fig. 2 is pressurization annealing device structural representation, wherein: 1. gas pipeline, 2. vent valve, 3. sealing-ring, 4. corundum system boiler tube, 5. intake valve, 6. high pressure valve, 7. gas cylinder, 8. temp-controlling element.
Fig. 3 is AAO template pictorial diagram after 700 ℃ of annealing under the different pressure, and wherein (c) sample does not have the generation of curling, (a) P=1.00 P
0(normal pressure); (b) P=1.05 P
0(c) P=1.06 P
0(d) P=1.07P
0, P is a gas pressure intensity in the lehre, P
0Be normal atmosphere.
Fig. 4 is the positive SEM photo of annealed AAO template under 700 ℃, different pressure, and wherein gas pressure intensity P is respectively in the lehre: Fig. 4 (a) 1.04 P
0, Fig. 4 (b) 1.05 P
0, Fig. 4 (c) 1.06 P
0, Fig. 4 (d) 1.07P
0, P
0Be normal atmosphere.Unlabeled data is mean pore size and pitch of holes (data in the bracket), and unit is nm.
(5) embodiment
Embodiment:
1) preparation of porous anodic aluminium oxide (AAO) template
High-purity aluminum foil (purity is more than 99.99%) is put into retort furnace 550 ℃ of down annealing 6 hours, eliminating the internal stress of aluminium foil, the aluminium foil after the annealing respectively in acetone and ethanol solution with ultrasonic cleaning 15 minutes, to remove surperficial grease.Then, it is that 1: 4 perchloric acid absolute ethyl alcohol mixed solution carries out electropolishing that the aluminium foil after cleaning is put into volume ratio, removes organic pollutant and zone of oxidation, and polished aluminium foil surface very light is clean.Pretreated aluminium foil is negative electrode as anode with the copper sheet more than inciting somebody to action, and in oxalic acid, carries out anodic oxidation (once oxidation), and strength of solution is 0.3mol/L, and electrolysis voltage is 40V, and the time is 10 hours.Template behind the once oxidation is put into the mixed solution of chromic acid (1.8%wt) and phosphoric acid (5%wt) and is removed sull, and the upper surface of aluminum substrate stays the indenture of ordered arrangement at this moment.Carry out the anodic oxidation second time on this basis, its condition is identical with once oxidation, can obtain having initial stage AAO template aluminium substrate, that be made up of blocking layer and porous layer.Use saturated CuCl then
2The solution removal aluminium substrate, and in phosphoric acid (5%wt) solution, 30 ℃ down reaction took out the back and clean to remove blocking layer (through hole) in 30 minutes with deionized water, immerse 5% phosphoric acid solution, and put into about 5 minutes of UW concussion, handle to carry out reaming.
Sem (SEM) picture of the AAO template (reverse side) that process through hole, reaming obtain after handling is as shown in Figure 1.
2) AAO template pressurization annealed equipment configuration and enforcement
Shown in Figure 2ly be AAO template pressurization annealing device synoptic diagram; Pressurize nitrogen is stored in the gas cylinder 7; Get into corundum system boiler tube 4 through high pressure valve 6 and intake valve 5; The gas pipeline 1 of corundum system boiler tube 4 the other ends is provided with vent valve 2, and the two ends of corundum system boiler tube 4 are through sealing-ring 3 sealings, and corundum system boiler tube 4 is through temp-controlling element 8 control annealing temperatures.
Select for use the GSL1300X vacuum tube furnace as lehre, the AAO template after the through hole reaming is put into tube furnace, the exhaust side of closed annealing stove; Feed pressurize gas nitrogen from the inlet end of lehre, heating on one side then, on one side suitable adjustment air input or free air delivery; Setting annealing temperature is 700 ℃; Temperature rise rate is 10 ℃/min, and soaking time is 30 minutes, and pressurize gas atmosphere value is made as 1.00 P respectively in the lehre
0, 1.05 P
0, 1.06 P
0, 1.07 P
0, P
0Be normal atmosphere, and keep steady state value, accomplish until annealing.
AAO template after the pressurization annealing is carried out appearance observes, shown in Figure 3 for normal pressure and different air pressure down through the outward appearance photo of the AAO template of 700 ℃ of annealing (temperature rise rate is 10 ℃/min, and soaking time is 30 minutes).Visible by Fig. 3 (c), in the time of 700 ℃, pressurize gas pressure intensity P=1.06 P
0Be best annealing conditions, the AAO template after annealing this moment is not curled, and its positive and negative all do not have inferior hole and produce.
AAO template to after the pressurization annealing is carried out electron microscopic observation; Fig. 4 is the positive SEM photo of pressurization annealed AAO template under the different pressure, and the annealing temperature of sample is 700 ℃, and temperature rise rate is 10 ℃/min; Soaking time is 30 minutes, and pressurize gas pressure intensity P is respectively among Fig. 4: (a) 1.04 P
0, (b) 1.05 P
0x, (c) 1.06 P
0, (d) 1.07 P
0, the mean pore size and average pitch of holes (bracket in data) of the data in the upper left corner for calculating among the figure with Image-pro plus software measurement, unit is nm.Visible by Fig. 4, the aperture of annealing specimen under the different pressure, pitch of holes are basic identical, and still, Fig. 4 (a) and (b), (d) show that P is respectively 1.04 P when the pressurize gas pressure intensity
0, 1.05 P
0With 1.07 P
0The time, the front of annealing specimen still has a large amount of inferior holes to occur, and at Fig. 4 (c) (P=1.06 P
0) in, inferior hole almost disappear (number significantly reduces in other words).This shows that template will not produce time hole in the condition annealing of following time of suitably pressurization, this moment, template was not curled yet.For 700 ℃, P=1.06 P
0Be suitable, and under other pressure, anneal that pressure is excessive or too small, all can make the nuclear continued growth of remaining hole, form time hole, make template that curling in various degree arranged.
Claims (2)
1. method for annealing that porous anodic alumina template is not curled is characterized in that step is following:
1) adopting routine techniques to prepare the go forward side by side hole reaming that works of porous anodic alumina template handles;
2) with the vacuum tube furnace be lehre, the porous anodic alumina template after the through hole reaming is handled is put into tube furnace, the exhaust side of closed annealing stove, and the inlet end feeding pressurize gas from lehre makes furnace gas pressure reach 1.01 normal atmosphere;
3) to the porous anodic alumina template annealing that heats up, annealing temperature is 700 ℃, in this process, makes the atmospheric pressure value of pressurize gas in the lehre constant in 1.06 normal atmosphere through adjustment inlet and outlet amount, accomplishes until annealing.
2. according to the said method for annealing that porous anodic alumina template is not curled of claim 1, it is characterized in that: said pressurize gas is air, oxygen, nitrogen or argon gas.
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| CN101139081A (en) * | 2007-08-10 | 2008-03-12 | 中国科学院上海技术物理研究所 | Method for preparing nanometer line material with nanometer bore and complex structure thereof |
| CN101499417A (en) * | 2008-01-30 | 2009-08-05 | 中国科学院半导体研究所 | Method for implementing image transfer on semiconductor material by anodised aluminum template |
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| DE10221866A1 (en) * | 2002-05-15 | 2003-11-27 | Marconi Comm Gmbh | Production of aluminum oxide ceramic used as a dielectric material comprises sintering a mixture consisting of an aluminum oxide powder and titanium-containing oxide powder, and calcining the body formed at a calcining temperature |
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| CN101139081A (en) * | 2007-08-10 | 2008-03-12 | 中国科学院上海技术物理研究所 | Method for preparing nanometer line material with nanometer bore and complex structure thereof |
| CN101499417A (en) * | 2008-01-30 | 2009-08-05 | 中国科学院半导体研究所 | Method for implementing image transfer on semiconductor material by anodised aluminum template |
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