CN102401633B - Detection method for detecting thickness of barrier layer of porous alumina film - Google Patents
Detection method for detecting thickness of barrier layer of porous alumina film Download PDFInfo
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- CN102401633B CN102401633B CN201010280022.XA CN201010280022A CN102401633B CN 102401633 B CN102401633 B CN 102401633B CN 201010280022 A CN201010280022 A CN 201010280022A CN 102401633 B CN102401633 B CN 102401633B
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Abstract
The invention provides a detection method for detecting the thickness of a barrier layer of a porous alumina film, which is characterized in that the detection method judges whether the porous alumina film comprises the barrier layer according to the transmission spectrum of the porous alumina film in the range of 200 nm-2500 nm, wherein if oscillation appears in the transmission spectrum in the range of 200 nm-2500 nm, the detection method judges that the thickness of the barrier layer of the porous alumina film is more than 0; if oscillation does not appear in the transmission spectrum in the range of 200 nm-2500 nm, the detection method judges that the thickness of the barrier layer of the porous alumina film is 0. The detection method provided by the invention is a lossless detection method, can conveniently, quickly and efficiently monitor a sample in a lossless way and detect the removal degree of the barrier layer of the porous alumina film, therefore, in mass production, the detection method can be used as an important measure for product control and quality detection.
Description
Technical field
What the present invention relates to is a kind of detection method of barrier layer thickness of porous alumina membrane.
Background technology
From nineteen ninety-five, the human hairs such as Masuda understand two step anodizing (Science, 1995,268,1466～1468) since preparing the Woelm Alumina of cellular structure of large area high-sequential, porous alumina membrane is widely used in metal, semiconductor or the polymer nano-wire (nanotube) of synthetic high-sequential as template, because aluminium oxide is non-conductive, therefore before electro-deposition nano wire, will first by acid solution, remove the restraining barrier of porous alumina membrane, then sputter layer of metal film carries out electro-deposition as electrode.The process of removing restraining barrier due to acid liquid corrosion is affected by several factors, and this just makes the removal degree on restraining barrier be difficult to control, therefore a kind of method of removal degree in the urgent need to finding easy monitoring and detecting the restraining barrier of porous alumina membrane at present.
Ultraviolet-visible-near-infrared spectrum detection technique is simple with its sample preparation, detected object extensive, can realize the advantages such as non-destructive detects, detection speed is fast is applied to a lot of fields, people (the Thin Solid Films such as Jian Wang, 2008,516,7689～7694) utilize ultraviolet-visible-near-infrared spectrum detection technique to test the transmitted spectrum of the porous alumina membrane that contains restraining barrier, and use transmission extreme value envelope method to calculate refractive index, absorption coefficient and the optical energy gap of porous alumina membrane.Thereby CN200510027581.9 utilizes four layers of dielectric model to come matching transmitted spectrum to draw thickness and the barrier layer thickness of porous alumina membrane, its spectrum test scope is only 190nm～900nm, but do not study for the transmitted spectrum that removes the porous alumina membrane on restraining barrier, therefore can only utilize the above results to detect thickness and the barrier layer thickness of the porous alumina membrane of firm preparation, and for the research that is generally used for preparing the through-hole porous aluminum oxide film of nano wire by transmitted spectrum technology for detection, have no at present document and patent report.
Summary of the invention
The object of the present invention is to provide a kind of method of thickness of restraining barrier of simple detection porous alumina membrane.
The present inventor is surprised to find that, when this porous alumina membrane contains restraining barrier, its transmitted spectrum there will be vibration within the scope of 200nm～2500nm, and this porous alumina membrane is not while containing restraining barrier (when restraining barrier is completely removed), there is not vibration in its transmitted spectrum, completed thus the present invention within the scope of 200nm～2500nm.
The invention provides a kind of detection method of barrier layer thickness of porous alumina membrane, it is characterized in that, the method comprises according to the transmitted spectrum within the scope of the 200nm～2500nm of porous alumina membrane and judges whether porous alumina membrane contains restraining barrier, wherein, if vibration appears in transmitted spectrum within the scope of 200nm～2500nm, judge that the thickness on the restraining barrier of this porous alumina membrane is greater than 0; If vibration does not appear in transmitted spectrum within the scope of 200nm～2500nm, the thickness that judges the restraining barrier of this porous alumina membrane is 0.
The present invention is with the basis that is prepared as of porous alumina membrane, utilize ultraviolet-visible-near-infrared spectrum detection technique to carry out transmitted spectrum test to porous alumina membrane and the film that removes restraining barrier, the result of transmitted spectrum can be for characterizing the thickness on restraining barrier and the through-hole rate of porous alumina membrane of porous alumina membrane.
Method of the present invention is a kind of lossless detection method, the method can be easy, quick, efficient, to sample nondestructive harmful monitor and detect the removal degree on the restraining barrier of porous alumina membrane, in large-scale production, can be used as the important means of the control of product and quality testing.
Accompanying drawing explanation
Fig. 1 is ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane in embodiment 1.
Fig. 2 is the FESEM shape appearance figure at the resulting porous alumina membrane back side in embodiment 1.
Fig. 3 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier in embodiment 1.
Fig. 4 is ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane in embodiment 3.
Fig. 5 is the FESEM shape appearance figure at the resulting porous alumina membrane back side in embodiment 3.
Fig. 6 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier in embodiment 3.
Fig. 7 is ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane in embodiment 5.
Fig. 8 is the FESEM shape appearance figure at the resulting porous alumina membrane back side in embodiment 5.
Fig. 9 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier in embodiment 5.
Figure 10 is ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane in embodiment 7.
Figure 11 is the FESEM shape appearance figure at the resulting porous alumina membrane back side in embodiment 7.
Figure 12 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier in embodiment 7.
Figure 13 is ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane in embodiment 9.
Figure 14 is the FESEM shape appearance figure at the resulting porous alumina membrane back side in embodiment 9.
Figure 15 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier in embodiment 9.
Figure 16 is ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane in embodiment 11.
Figure 17 is the FESEM shape appearance figure at the resulting porous alumina membrane back side in embodiment 11.
Figure 18 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier in embodiment 11.
Embodiment
The invention provides a kind of detection method of barrier layer thickness of porous alumina membrane, it is characterized in that, the method comprises according to the transmitted spectrum within the scope of the 200nm～2500nm of porous alumina membrane and judges whether porous alumina membrane contains restraining barrier, wherein, if vibration appears in transmitted spectrum within the scope of 200nm～2500nm, judge that the thickness on the restraining barrier of this porous alumina membrane is greater than 0; If vibration does not appear in transmitted spectrum within the scope of 200nm～2500nm, the thickness that judges the restraining barrier of this porous alumina membrane is 0.
The present inventor further finds following characteristics
1, the detection method of the barrier layer thickness of above-mentioned porous alumina membrane, wherein, only there is vibration in transmitted spectrum, and the number of oscillation peaks is 17 within the scope of 500nm～2500nm, the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 80nm～90nm.
2, the detection method of the barrier layer thickness of above-mentioned porous alumina membrane, wherein, only there is vibration in transmitted spectrum, and the number of oscillation peaks is 16 within the scope of 1000nm～2500nm, the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 65nm～75nm.
3, the detection method of the barrier layer thickness of above-mentioned porous alumina membrane, wherein, only there is vibration in transmitted spectrum, and the number of oscillation peaks is 8 within the scope of 1000nm～2500nm, the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 30nm～40nm.
4, the detection method of the barrier layer thickness of above-mentioned porous alumina membrane, wherein, only there is vibration in transmitted spectrum, and the number of oscillation peaks is 4 within the scope of 1500nm～2500nm, the through-hole rate of porous alumina membrane is 50%-80%, and the thickness on restraining barrier is 5nm～25nm.
5, the detection method of the barrier layer thickness of the porous alumina membrane described in above-mentioned feature 4, if transmittance 70%～80%, the through-hole rate of porous alumina membrane is 50%-65%, the thickness on restraining barrier is about 15nm～25nm.
6, the detection method of the barrier layer thickness of the porous alumina membrane described in above-mentioned feature 4, if transmittance 85%～90%, the through-hole rate of porous alumina membrane is 70%-80%, the thickness on restraining barrier is about 5nm～10nm.
In the present invention, the ratio of the number in the hole that the number that through-hole rate refers to through hole and porous alumina membrane are total, described through hole refers to the hole of not containing restraining barrier.
The detection method of the barrier layer thickness of above-mentioned porous alumina membrane, wherein, described transmitted spectrum is ultraviolet-visible-near-infrared transmission spectrum.
The detection method of the barrier layer thickness of above-mentioned porous alumina membrane, wherein, the condition of obtaining described transmitted spectrum comprises that metering system is scanning, and wavelength coverage can be 200nm～2500nm, and sweep speed is 900-950nm/min, is preferably 924nm/min.
The detection method of the barrier layer thickness of porous alumina membrane of the present invention, wherein, the thickness of described porous alumina membrane is 1-30 micron.The thickness of porous alumina membrane adopts field emission scanning electron microscope (Hitachi S4800) to record.
The preparation method of above-mentioned porous alumina membrane has been that art technology is known, for example, can prepare by the method comprising the following steps:
1) pre-service
High-purity Al sheet (99.999%) use acetone and deionized water (18.2M Ω/cm) are distinguished to ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio subsequently, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.2M～0.4M in concentration, under 40V～60V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 1 hour～12 hours.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, places 2 hours～12 hours in 65 ℃ of baking ovens, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.2M～0.4M in concentration, under 40V～60V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 1 minute～30 minutes.
5) peel off aluminium substrate
By step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) product that obtains is immersed in the phosphate aqueous solution of 5wt% 5 minutes～70 minutes.
The mensuration of porous alumina membrane of the present invention adopts ultraviolet-visible-near-infrared transmission spectral detection, uses the ultraviolet-visible-near-infrared spectrum of transmitted spectrum technical testing porous alumina membrane.The wavelength coverage of test is 200nm～2500nm.
The present invention is further illustrated for the following examples.
This embodiment is for illustrating the detection method of the barrier layer thickness of porous alumina membrane provided by the invention
1. the preparation of porous alumina membrane
1) pre-service
Purity is that high-purity Al sheet of 99.999% (is of a size of 2cm*2cm*0.025cm, being purchased from Beijing illiteracy Thailand grinds) with acetone and deionized water (18.2M Ω/cm), distinguish ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 1 hour.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 4 hours, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out second step anodic oxidation, oxidization time 5 minutes.
5) peel off aluminium substrate
By in step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) product that obtains is immersed in the phosphate aqueous solution of 5wt% 5 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
Use the ultraviolet-visible-near-infrared spectrum of transmitted spectrum technical testing porous alumina membrane, test condition is the serial ultraviolet-visible-near infrared spectrometer of Lambda 950 that used instrument is produced for Perkin Elmer company, metering system is scanning, wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.As shown in Figure 1, the wavelength coverage of employing is 200nm～2500nm to result.There is vibration in transmitted spectrum, the number of oscillation peaks is 17 within the scope of 500nm～2500nm, and the through-hole rate of judging porous alumina membrane is 0, and the thickness on restraining barrier is 80nm～90nm.
With field emission scanning electron microscope (Hitachi S4800), observe pattern (seeing Fig. 2, Fig. 3), the through-hole rate that proves porous alumina membrane is 0, and the thickness on restraining barrier is about 80nm～90nm.Consistent with the result that adopts method of the present invention to detect.
1. the preparation of porous alumina membrane
1) pre-service
Purity is that high-purity Al sheet of 99.999% (is of a size of 2cm*2cm*0.025cm, being purchased from Beijing illiteracy Thailand grinds) with acetone and deionized water (18.2M Ω/cm), distinguish ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.4M in concentration, under 40V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 12 hours.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 12 hours, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.4M in concentration, under 40V voltage, when being less than 10 ℃, environment temperature carries out second step anodic oxidation, oxidization time 30 minutes.
5) peel off aluminium substrate
By in step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) aluminium flake that obtains is immersed in the phosphate aqueous solution of 5wt% 10 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
Use the ultraviolet-visible-near-infrared spectrum of transmitted spectrum technical testing porous alumina membrane, test condition is the serial ultraviolet-visible-near infrared spectrometer of Lambda 950 that used instrument is produced for Perkin Elmer company, metering system is scanning, wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.There is vibration in transmitted spectrum, the number of oscillation peaks is 17 within the scope of 500nm～2500nm, and the through-hole rate of judging porous alumina membrane is 0, and the thickness on restraining barrier is 80nm～85nm.
With field emission scanning electron microscope (Hitachi S4800), observe pattern, the through-hole rate that shows porous alumina membrane is 0, and the thickness on restraining barrier is about 80nm～85nm, consistent with the result that adopts method of the present invention to detect.
1. the preparation of porous alumina membrane
1) pre-service
Purity is that high-purity Al sheet of 99.999% (is of a size of 2cm*2cm*0.025cm, being purchased from Beijing illiteracy Thailand grinds) with acetone and deionized water (18.2M Ω/cm), distinguish ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 8 hours.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 4 hours, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out second step anodic oxidation, oxidization time 5 minutes.
5) peel off aluminium substrate
By step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) product that obtains is immersed in the phosphate aqueous solution of 5wt% 15 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
Use the ultraviolet-visible-near-infrared spectrum of transmitted spectrum technical testing porous alumina membrane, test condition is the serial ultraviolet-visible-near infrared spectrometer of Lambda 950 that used instrument is produced for Perkin Elmer company, metering system is scanning, wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.As shown in Figure 4, there is vibration in transmitted spectrum to result within the scope of 1000nm～2500nm, and the number at concussion peak is 16, and the through-hole rate of judging porous alumina membrane is 0, and the thickness on restraining barrier is 65nm～75nm.
With field emission scanning electron microscope (Hitachi S4800), observe pattern (referring to Fig. 5, Fig. 6), the through-hole rate that proves porous alumina membrane is 0, and the thickness on restraining barrier is about 65nm～75nm, consistent with the result that adopts method of the present invention to detect.
1. the preparation of porous alumina membrane
1) pre-service
Purity is that high-purity Al sheet of 99.999% (is of a size of 2cm*2cm*0.025cm, being purchased from Beijing illiteracy Thailand grinds) with acetone and deionized water (18.2M Ω/cm), distinguish ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.2M in concentration, under 50V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 8 hours.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 4 hours, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.2M in concentration, under 50V voltage, when being less than 10 ℃, environment temperature carries out second step anodic oxidation, oxidization time 15 minutes.
5) peel off aluminium substrate
By step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) product that obtains is immersed in the phosphate aqueous solution of 5wt% 20 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
Use the ultraviolet-visible-near-infrared spectrum of transmitted spectrum technical testing porous alumina membrane, test condition is the serial ultraviolet-visible-near infrared spectrometer of Lambda 950 that used instrument is produced for Perkin Elmer company, metering system is scanning, wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.There is vibration in transmitted spectrum, the number of oscillation peaks is 16 within the scope of 1000nm～2500nm, and the through-hole rate of judging porous alumina membrane is 0, and the thickness on restraining barrier is 65nm～75nm.
With field emission scanning electron microscope (Hitachi S4800), observe pattern, the through-hole rate that shows porous alumina membrane is 0, and the thickness on restraining barrier is about 65nm～75nm, consistent with the result that adopts method of the present invention to detect.
Embodiment 5
1. the preparation of porous alumina membrane
1) pre-service
Purity is that high-purity Al sheet of 99.999% (is of a size of 2cm*2cm*0.025cm, being purchased from Beijing illiteracy Thailand grinds) with acetone and deionized water (18.2M Ω/cm), distinguish ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 4 hours.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 4 hours, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out second step anodic oxidation, oxidization time 1 minute.
5) peel off aluminium substrate
By step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) product that obtains is immersed in the phosphate aqueous solution of 5wt% 30 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
Use the ultraviolet-visible-near-infrared spectrum of transmitted spectrum technical testing porous alumina membrane, method of testing is the serial ultraviolet-visible-near infrared spectrometer of Lambda 950 that used instrument is produced for Perkin Elmer company, metering system is scanning, wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.As shown in Figure 7, only there is vibration in transmitted spectrum to result within the scope of 1000nm～2500nm, and the number at concussion peak is 8, and the through-hole rate of judging porous alumina membrane is 0, and the thickness on restraining barrier is 30nm～40nm.
With field emission scanning electron microscope (Hitachi S4800), observe pattern (referring to Fig. 8, Fig. 9), prove that the through-hole rate of porous alumina membrane is 0, barrier layer thickness is about 30nm～40nm, consistent with the result that adopts method of the present invention to detect.
Embodiment 6
1. the preparation of porous alumina membrane
1) pre-service
Purity is that high-purity Al sheet of 99.999% (is of a size of 2cm*2cm*0.025cm, being purchased from Beijing illiteracy Thailand grinds) with acetone and deionized water (18.2M Ω/cm), distinguish ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.4M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 4 hours.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 8 hours, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.4M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out second step anodic oxidation, oxidization time 20 minutes.
5) peel off aluminium substrate
By step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) product that obtains is immersed in the phosphate aqueous solution of 5wt% 35 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
Use the ultraviolet-visible-near-infrared spectrum of transmitted spectrum technical testing porous alumina membrane, method of testing is the serial ultraviolet-visible-near infrared spectrometer of Lambda 950 that used instrument is produced for Perkin Elmer company, metering system is scanning, wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.There is vibration in transmitted spectrum, the number of oscillation peaks is 8 within the scope of 1000nm～2500nm, and the through-hole rate of judging porous alumina membrane is 0, and the thickness on restraining barrier is 30nm～40nm.
With field emission scanning electron microscope (Hitachi S4800), observe pattern, the through-hole rate that shows porous alumina membrane is 0, and the thickness on restraining barrier is about 30nm～40nm, consistent with the result that adopts method of the present invention to detect.
Embodiment 7
1. the preparation of porous alumina membrane
1) pre-service
Purity is that high-purity Al sheet of 99.999% (is of a size of 2cm*2cm*0.025cm, being purchased from Beijing illiteracy Thailand grinds) with acetone and deionized water (18.2M Ω/cm), distinguish ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 1 hour.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 2 hours, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out second step anodic oxidation, oxidization time 5 minutes.
5) peel off aluminium substrate
By step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) product that obtains is immersed in the phosphate aqueous solution of 5wt% 40 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
Use the ultraviolet-visible-near-infrared spectrum of transmitted spectrum technical testing porous alumina membrane, method of testing is the serial ultraviolet-visible-near infrared spectrometer of Lambda 950 that used instrument is produced for Perkin Elmer company, metering system is scanning, wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.As shown in figure 10, only there is vibration in transmitted spectrum to result within the scope of 1500nm～2500nm, and the number at concussion peak is 4, and transmittance is 70%, and the through-hole rate of judging porous alumina membrane is 50%, and the thickness on restraining barrier is 15nm～25nm.
With field emission scanning electron microscope (Hitachi S4800), observe pattern (referring to Figure 11, Figure 12), prove that the through-hole rate of porous alumina membrane is 50%, barrier layer thickness is about 15nm～25nm, consistent with the result that adopts method of the present invention to detect.
1. the preparation of porous alumina membrane
1) pre-service
Purity is that high-purity Al sheet of 99.999% (is of a size of 2cm*2cm*0.025cm, being purchased from Beijing illiteracy Thailand grinds) with acetone and deionized water (18.2M Ω/cm), distinguish ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 40V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 12 hours.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 12 hours, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 40V voltage, when being less than 10 ℃, environment temperature carries out second step anodic oxidation, oxidization time 10 minutes.
5) peel off aluminium substrate
By step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) product that obtains is immersed in the phosphate aqueous solution of 5wt% 45 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
Use the ultraviolet-visible-near-infrared spectrum (seeing accompanying drawing 22) of transmitted spectrum technical testing porous alumina membrane, method of testing is the serial ultraviolet-visible-near infrared spectrometer of Lambda 950 that used instrument is produced for Perkin Elmer company, metering system is scanning, wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.Only there is vibration in transmitted spectrum, the number at concussion peak is 4 within the scope of 1500nm～2500nm, and transmittance is 80%, and the through-hole rate of judging porous alumina membrane is 65%, and the thickness on restraining barrier is 15nm～25nm.
With field emission scanning electron microscope (Hitachi S4800), observe pattern, show that the through-hole rate of porous alumina membrane is 65%, barrier layer thickness is about 15nm～25nm, consistent with the result that adopts method of the present invention to detect.
Embodiment 9
1. the preparation of porous alumina membrane
1) pre-service
Purity is that high-purity Al sheet of 99.999% (is of a size of 2cm*2cm*0.025cm, being purchased from Beijing illiteracy Thailand grinds) with acetone and deionized water (18.2M Ω/cm), distinguish ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 2 hours.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 2 hours, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out second step anodic oxidation, oxidization time 5 minutes.
5) peel off aluminium substrate
By step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) product that obtains is immersed in the phosphate aqueous solution of 5wt% 50 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
Use the ultraviolet-visible-near-infrared spectrum (seeing accompanying drawing 22) of transmitted spectrum technical testing porous alumina membrane, method of testing is the serial ultraviolet-visible-near infrared spectrometer of Lambda 950 that used instrument is produced for Perkin Elmer company, metering system is scanning, wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.As shown in figure 13, only there is vibration in transmitted spectrum to result within the scope of 1500nm～2500nm, and the number at concussion peak is 4, and transmittance is 85%, and the through-hole rate of judging porous alumina membrane is 70%, and the thickness on restraining barrier is 5nm～10nm.
With field emission scanning electron microscope (Hitachi S4800), observe pattern (referring to Figure 14, Figure 15), prove that the through-hole rate of porous alumina membrane is 70%, barrier layer thickness is about 5nm～10nm, consistent with the result that adopts method of the present invention to detect.
1. the preparation of porous alumina membrane
1) pre-service
Purity is that high-purity Al sheet of 99.999% (is of a size of 2cm*2cm*0.025cm, being purchased from Beijing illiteracy Thailand grinds) with acetone and deionized water (18.2M Ω/cm), distinguish ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 4 hours.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 6 hours, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out second step anodic oxidation, oxidization time 10 minutes.
5) peel off aluminium substrate
By step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) product that obtains is immersed in the phosphate aqueous solution of 5wt% 60 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
Use the ultraviolet-visible-near-infrared spectrum of transmitted spectrum technical testing porous alumina membrane, method of testing is the serial ultraviolet-visible-near infrared spectrometer of Lambda 950 that used instrument is produced for Perkin Elmer company, metering system is scanning, wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.Only there is vibration in transmitted spectrum, the number at concussion peak is 4 within the scope of 1500nm～2500nm, and transmittance is 90%, and the through-hole rate of judging porous alumina membrane is 80%, and the thickness on restraining barrier is 5nm～10nm.
With field emission scanning electron microscope (Hitachi S4800), observe pattern, show that the through-hole rate of porous alumina membrane is 80%, barrier layer thickness is about 5nm～10nm, consistent with the result that adopts method of the present invention to detect.
Embodiment 11
1. the preparation of porous alumina membrane
1) pre-service
Purity is that high-purity Al sheet of 99.999% (is of a size of 2cm*2cm*0.025cm, being purchased from Beijing illiteracy Thailand grinds) with acetone and deionized water (18.2M Ω/cm), distinguish ultrasonic cleaning 10 minutes, and the mixed liquor of the strong phosphoric acid that is 7: 1: 2 by volume ratio, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute.
2) first step anodic oxidation
By step 1) aluminium flake that obtains in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out first step anodic oxidation, oxidization time 3 hours.
3) corrosion primary oxide film
By step 2) aluminium flake obtaining is placed in the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 3 hours, and the concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) second step anodic oxidation
By step 3) the good aluminium flake of the corrosion that obtains is in the electrolytic tank of organic glass or teflon, take graphite as negative electrode, aluminium flake is anode, in the oxalic acid electrolyte aqueous solution that is 0.3M in concentration, under 60V voltage, when being less than 10 ℃, environment temperature carries out second step anodic oxidation, oxidization time 5 minutes.
5) peel off aluminium substrate
By step 4) product that obtains, with saturated cupric chloride, soak, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to restraining barrier
By step 5) product that obtains is immersed in the phosphate aqueous solution of 5wt% 70 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
Use the ultraviolet-visible-near-infrared spectrum of transmitted spectrum technical testing porous alumina membrane, method of testing is the serial ultraviolet-visible-near infrared spectrometer of Lambda 950 that used instrument is produced for Perkin Elmer company, metering system is scanning, wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.As shown in figure 16, there is not vibration in transmitted spectrum to result within the scope of 200nm～2500nm, and the through-hole rate of judging porous alumina membrane is 100%, and the thickness on restraining barrier is 0nm.
With field emission scanning electron microscope (Hitachi S4800), observe pattern (referring to Figure 17, Figure 18), the through-hole rate that proves porous alumina membrane is 100%, and barrier layer thickness is 0nm, consistent with the result that adopts method of the present invention to detect.
Claims (10)
1. the detection method of the barrier layer thickness of a porous alumina membrane, it is characterized in that, the method comprises that according to porous alumina membrane the transmitted spectrum within the scope of 200nm～2500nm judges whether porous alumina membrane contains restraining barrier, wherein, if vibration appears in transmitted spectrum within the scope of 200nm～2500nm, judge that the thickness on the restraining barrier of this porous alumina membrane is greater than 0; If vibration does not appear in transmitted spectrum within the scope of 200nm～2500nm, the thickness that judges the restraining barrier of this porous alumina membrane is 0.
2. the detection method of the barrier layer thickness of porous alumina membrane according to claim 1, wherein, only there is vibration in transmitted spectrum, and the number of oscillation peaks is 17 within the scope of 500nm～2500nm, the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 80nm～90nm.
3. the detection method of the barrier layer thickness of porous alumina membrane according to claim 1, wherein, only there is vibration in transmitted spectrum, and the number of oscillation peaks is 16 within the scope of 1000nm～2500nm, the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 65nm～75nm.
4. the detection method of the barrier layer thickness of porous alumina membrane according to claim 1, wherein, only there is vibration in transmitted spectrum, and the number of oscillation peaks is 8 within the scope of 1000nm～2500nm, the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 30nm～40nm.
5. the detection method of the barrier layer thickness of porous alumina membrane according to claim 1, wherein, only within the scope of 1500nm～2500nm, there is vibration in transmitted spectrum, and the number of oscillation peaks is 4, the through-hole rate of porous alumina membrane is 50%-80%, and the thickness on restraining barrier is 5nm～25nm.
6. the detection method of the barrier layer thickness of porous alumina membrane according to claim 5, if transmittance is 70%～80%, the through-hole rate of porous alumina membrane is 50%-65%, the thickness on restraining barrier is 15nm～25nm.
7. the detection method of the barrier layer thickness of porous alumina membrane according to claim 5, if transmittance is 85%～90%, the through-hole rate of porous alumina membrane is 70%-80%, the thickness on restraining barrier is 5nm～10nm.
8. according to the detection method of the barrier layer thickness of the porous alumina membrane described in any one in claim 1-7, wherein, described transmitted spectrum is ultraviolet-visible-near-infrared transmission spectrum.
9. the detection method of the barrier layer thickness of porous alumina membrane according to claim 8, wherein, the condition of obtaining described transmitted spectrum comprises wavelength coverage 200nm～2500nm, sweep speed is 900-950nm/min.
10. the detection method of the barrier layer thickness of porous alumina membrane according to claim 8, wherein, the thickness of described porous alumina membrane is 1-30 micron.
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| CN1715871A (en) * | 2005-07-07 | 2006-01-04 | 上海交通大学 | Method for testing ordered nano hole aluminium oxide template optical constant |
| CN101294795A (en) * | 2007-04-25 | 2008-10-29 | 横河电机株式会社 | Apparatus and method for measuring film thickness |
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| CN1715871A (en) * | 2005-07-07 | 2006-01-04 | 上海交通大学 | Method for testing ordered nano hole aluminium oxide template optical constant |
| CN101294795A (en) * | 2007-04-25 | 2008-10-29 | 横河电机株式会社 | Apparatus and method for measuring film thickness |
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