CN102401633A - 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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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; People such as Masuda have invented two step anodizing (Science; 1995,268,1466～1468) since the Woelm Alumina of the cellular structure of preparation large tracts of land 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, the restraining barrier of therefore before the electro-deposition nano wire, wanting elder generation to remove porous alumina membrane with acid solution, the film of sputter layer of metal again carries out electro-deposition as electrode.Influenced by several factors because acid liquid corrosion is removed the process on restraining barrier, this just makes the removal degree on restraining barrier be difficult to control, therefore presses at present to seek a kind of easy monitoring and the removal degree methods that detects the restraining barrier of porous alumina membrane.
The ultraviolet-visible-near-infrared spectrum detection technique is simple with its specimen preparation, detected object extensive, can realize that advantages such as non-destructive detects, detection speed is fast are applied to a lot of fields; People (Thin Solid Films such as Jian Wang; 2008; 516; 7689～7694) utilize the ultraviolet-visible-near-infrared spectrum detection technique to test the transmitted spectrum of the porous alumina membrane that contains the 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 the match transmitted spectrum to draw the thickness and the barrier layer thickness of porous alumina membrane; Its spectrum test scope is merely 190nm～900nm; But the transmitted spectrum for the porous alumina membrane that removes the restraining barrier is not studied; Therefore can only utilize The above results to detect the thickness and the barrier layer thickness of the porous alumina membrane of firm preparation; And, do not see document and patent report at present for the research of the through-hole porous aluminum oxide film that is generally used for preparing nano wire with the transmitted spectrum technology for detection.
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.
Inventor of the present invention is surprised to find that; When this porous alumina membrane contains the restraining barrier; Its transmitted spectrum vibration can occur in 200nm～2500nm scope; And this porous alumina membrane is not when containing the restraining barrier (when the restraining barrier is removed fully), and vibration does not appear in its transmitted spectrum in 200nm～2500nm scope, accomplished the present invention thus.
The invention provides a kind of detection method of barrier layer thickness of porous alumina membrane; It is characterized in that; This method comprises that the transmitted spectrum in the 200nm～2500nm scope according to porous alumina membrane judges whether porous alumina membrane contains the restraining barrier; Wherein, if vibration appears in transmitted spectrum in 200nm～2500nm scope, the thickness on restraining barrier of then judging this porous alumina membrane is greater than 0; If vibration does not appear in transmitted spectrum in 200nm～2500nm scope, the thickness of then judging 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 the ultraviolet-visible-near-infrared spectrum detection technique that porous alumina membrane and the film that removes the restraining barrier are carried out the transmitted spectrum test, the result of transmitted spectrum can be used to characterize thickness and the through-hole rate of porous alumina membrane on the restraining barrier of porous alumina membrane.
Method of the present invention is a kind of lossless detection method; This method can be easy, quick, efficient, the removal degree on the restraining barrier of porous alumina membrane is monitored harmlessly and detected to sample, in large-scale production, can be used as the important means of the control of product and quality testing.
Description of drawings
Fig. 1 is the ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane among the embodiment 1.
Fig. 2 is the FESEM shape appearance figure at the resulting porous alumina membrane back side among the embodiment 1.
Fig. 3 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier among the embodiment 1.
Fig. 4 is the ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane among the embodiment 3.
Fig. 5 is the FESEM shape appearance figure at the resulting porous alumina membrane back side among the embodiment 3.
Fig. 6 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier among the embodiment 3.
Fig. 7 is the ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane among the embodiment 5.
Fig. 8 is the FESEM shape appearance figure at the resulting porous alumina membrane back side among the embodiment 5.
Fig. 9 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier among the embodiment 5.
Figure 10 is the ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane among the embodiment 7.
Figure 11 is the FESEM shape appearance figure at the resulting porous alumina membrane back side among the embodiment 7.
Figure 12 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier among the embodiment 7.
Figure 13 is the ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane among the embodiment 9.
Figure 14 is the FESEM shape appearance figure at the resulting porous alumina membrane back side among the embodiment 9.
Figure 15 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier among the embodiment 9.
Figure 16 is the ultraviolet-visible-near-infrared transmission spectrogram of resulting porous alumina membrane among the embodiment 11.
Figure 17 is the FESEM shape appearance figure at the resulting porous alumina membrane back side among the embodiment 11.
Figure 18 is the FESEM shape appearance figure on resulting porous alumina membrane restraining barrier among the embodiment 11.
Embodiment
The invention provides a kind of detection method of barrier layer thickness of porous alumina membrane; It is characterized in that; This method comprises that the transmitted spectrum in the 200nm～2500nm scope according to porous alumina membrane judges whether porous alumina membrane contains the restraining barrier; Wherein, if vibration appears in transmitted spectrum in 200nm～2500nm scope, the thickness on restraining barrier of then judging this porous alumina membrane is greater than 0; If vibration does not appear in transmitted spectrum in 200nm～2500nm scope, the thickness of then judging the restraining barrier of this porous alumina membrane is 0.
Inventor of the present invention further finds following characteristic
1, the detection method of the barrier layer thickness of above-mentioned porous alumina membrane; Wherein, vibration only appears in transmitted spectrum in 500nm～2500nm scope, and the number of oscillation peaks is 17; Then 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, vibration only appears in transmitted spectrum in 1000nm～2500nm scope, and the number of oscillation peaks is 16; Then 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, vibration only appears in transmitted spectrum in 1000nm～2500nm scope, and the number of oscillation peaks is 8; Then 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, vibration only appears in transmitted spectrum in 1500nm～2500nm scope, and the number of oscillation peaks is 4; Then 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 above-mentioned characteristic 4 described porous alumina membranes, 70%～80%, then the through-hole rate of porous alumina membrane is 50%-65% as if transmittance, the thickness on restraining barrier is about 15nm～25nm.
6, the detection method of the barrier layer thickness of above-mentioned characteristic 4 described porous alumina membranes, 85%～90%, then the through-hole rate of porous alumina membrane is 70%-80% as if transmittance, the thickness on restraining barrier is about 5nm～10nm.
Among the present invention, the ratio of the number in the hole that the number that through-hole rate is meant through hole and porous alumina membrane are total, described through hole is meant the hole of not containing the restraining barrier.
The detection method of the barrier layer thickness of above-mentioned porous alumina membrane, wherein, said 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 said 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 said porous alumina membrane is the 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 through the method that may further comprise the steps:
1) pre-service
(ultrasonic cleaning 10 minutes respectively of 18.2M Ω/cm), using volume ratio subsequently is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water with high-purity Al sheet (99.999%).
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.2M～0.4M in concentration, under 40V～60V voltage; Environment temperature is carried out first step anodic oxidation, oxidization time 1 hour～12 hours during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 2 hours～12 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.2M～0.4M in concentration, under 40V～60V voltage; Environment temperature is carried out first step anodic oxidation, oxidization time 1 minute～30 minutes during less than 10 ℃.
5) peel off aluminium substrate
The product that step 4) is obtained soaks with saturated cupric chloride, takes out immediately when not having bubble to emerge, and has obtained pellumina.
6) go to the restraining barrier
The product that step 5) is obtained 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, the ultraviolet-visible-near-infrared spectrum of utilization transmitted spectrum technical testing porous alumina membrane.The wavelength coverage of test is 200nm～2500nm.
Following embodiment will be further described the present invention.
This embodiment is used to explain 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; Purchase and cover Thailand in Beijing and grind) (18.2M Ω/cm) distinguishes ultrasonic cleaning 10 minutes, and the use volume ratio is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water.
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is a negative electrode with graphite in the electrolytic tank of organic glass or teflon, and aluminium flake is an anode; In concentration is in the oxalic acid electrolyte aqueous solution of 0.3M; Under the 60V voltage, environment temperature is carried out first step anodic oxidation, oxidization time 1 hour during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 4 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.3M, under the 60V voltage in concentration; Environment temperature is carried out the second step anodic oxidation, oxidization time 5 minutes during less than 10 ℃.
5) peel off aluminium substrate
With in the step 4) product that obtains, soak with saturated cupric chloride, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to the restraining barrier
The product that step 5) is obtained is immersed in the phosphate aqueous solution of 5wt% 5 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
The ultraviolet-visible-near-infrared spectrum of utilization transmitted spectrum technical testing porous alumina membrane; Test condition is that employed instrument is Lambda 950 serial ultraviolet-visible-near infrared spectrometers that Perkin Elmer company produces; Metering system is scanning; Wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.The result is as shown in Figure 1, and the wavelength coverage of employing is 200nm～2500nm.Vibration appears in transmitted spectrum in 500nm～2500nm scope, the number of oscillation peaks is 17, judges that the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 80nm～90nm.
Observe pattern (seeing Fig. 2, Fig. 3) with field emission scanning electron microscope (Hitachi S4800), 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 who 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; Purchase and cover Thailand in Beijing and grind) (18.2M Ω/cm) distinguishes ultrasonic cleaning 10 minutes, and the use volume ratio is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water.
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is a negative electrode with graphite in the electrolytic tank of organic glass or teflon, and aluminium flake is an anode; In concentration is in the oxalic acid electrolyte aqueous solution of 0.4M; Under the 40V voltage, environment temperature is carried out first step anodic oxidation, oxidization time 12 hours during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 12 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.4M, under the 40V voltage in concentration; Environment temperature is carried out the second step anodic oxidation, oxidization time 30 minutes during less than 10 ℃.
5) peel off aluminium substrate
With in the step 4) product that obtains, soak with saturated cupric chloride, take out immediately when not having bubble to emerge, obtained pellumina.
6) go to the restraining barrier
The aluminium flake that step 5) is obtained is immersed in the phosphate aqueous solution of 5wt% 10 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
The ultraviolet-visible-near-infrared spectrum of utilization transmitted spectrum technical testing porous alumina membrane; Test condition is that employed instrument is Lambda 950 serial ultraviolet-visible-near infrared spectrometers that Perkin Elmer company produces; Metering system is scanning; Wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.Vibration appears in transmitted spectrum in 500nm～2500nm scope, the number of oscillation peaks is 17, judges that the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 80nm～85nm.
Observe pattern with field emission scanning electron microscope (Hitachi S4800), the through-hole rate that shows porous alumina membrane is 0, and the thickness on restraining barrier is about 80nm～85nm, and is consistent with the result who 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; Purchase and cover Thailand in Beijing and grind) (18.2M Ω/cm) distinguishes ultrasonic cleaning 10 minutes, and the use volume ratio is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water.
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is a negative electrode with graphite in the electrolytic tank of organic glass or teflon, and aluminium flake is an anode; In concentration is in the oxalic acid electrolyte aqueous solution of 0.3M; Under the 60V voltage, environment temperature is carried out first step anodic oxidation, oxidization time 8 hours during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 4 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.3M, under the 60V voltage in concentration; Environment temperature is carried out the second step anodic oxidation, oxidization time 5 minutes during less than 10 ℃.
5) peel off aluminium substrate
The product that step 4) is obtained soaks with saturated cupric chloride, takes out immediately when not having bubble to emerge, and has obtained pellumina.
6) go to the restraining barrier
The product that step 5) is obtained is immersed in the phosphate aqueous solution of 5wt% 15 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
The ultraviolet-visible-near-infrared spectrum of utilization transmitted spectrum technical testing porous alumina membrane; Test condition is that employed instrument is Lambda 950 serial ultraviolet-visible-near infrared spectrometers that Perkin Elmer company produces; Metering system is scanning; Wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.The result is as shown in Figure 4, and vibration appears in transmitted spectrum in 1000nm～2500nm scope, and the number at concussion peak is 16, judges that the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 65nm～75nm.
Observe pattern (referring to Fig. 5, Fig. 6) with field emission scanning electron microscope (Hitachi S4800), the through-hole rate that proves porous alumina membrane is 0, and the thickness on restraining barrier is about 65nm～75nm, and is consistent with the result who 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; Purchase and cover Thailand in Beijing and grind) (18.2M Ω/cm) distinguishes ultrasonic cleaning 10 minutes, and the use volume ratio is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water.
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is a negative electrode with graphite in the electrolytic tank of organic glass or teflon, and aluminium flake is an anode; In concentration is in the oxalic acid electrolyte aqueous solution of 0.2M; Under the 50V voltage, environment temperature is carried out first step anodic oxidation, oxidization time 8 hours during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 4 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.2M, under the 50V voltage in concentration; Environment temperature is carried out the second step anodic oxidation, oxidization time 15 minutes during less than 10 ℃.
5) peel off aluminium substrate
The product that step 4) is obtained soaks with saturated cupric chloride, takes out immediately when not having bubble to emerge, and has obtained pellumina.
6) go to the restraining barrier
The product that step 5) is obtained is immersed in the phosphate aqueous solution of 5wt% 20 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
The ultraviolet-visible-near-infrared spectrum of utilization transmitted spectrum technical testing porous alumina membrane; Test condition is that employed instrument is Lambda 950 serial ultraviolet-visible-near infrared spectrometers that Perkin Elmer company produces; Metering system is scanning; Wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.Vibration appears in transmitted spectrum in 1000nm～2500nm scope, the number of oscillation peaks is 16, judges that the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 65nm～75nm.
Observe pattern with field emission scanning electron microscope (Hitachi S4800), the through-hole rate that shows porous alumina membrane is 0, and the thickness on restraining barrier is about 65nm～75nm, and is consistent with the result who 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; Purchase and cover Thailand in Beijing and grind) (18.2M Ω/cm) distinguishes ultrasonic cleaning 10 minutes, and the use volume ratio is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water.
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is a negative electrode with graphite in the electrolytic tank of organic glass or teflon, and aluminium flake is an anode; In concentration is in the oxalic acid electrolyte aqueous solution of 0.3M; Under the 60V voltage, environment temperature is carried out first step anodic oxidation, oxidization time 4 hours during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 4 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.3M, under the 60V voltage in concentration; Environment temperature is carried out the second step anodic oxidation, oxidization time 1 minute during less than 10 ℃.
5) peel off aluminium substrate
The product that step 4) is obtained soaks with saturated cupric chloride, takes out immediately when not having bubble to emerge, and has obtained pellumina.
6) go to the restraining barrier
The product that step 5) is obtained is immersed in the phosphate aqueous solution of 5wt% 30 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
The ultraviolet-visible-near-infrared spectrum of utilization transmitted spectrum technical testing porous alumina membrane; Method of testing is that employed instrument is Lambda 950 serial ultraviolet-visible-near infrared spectrometers that Perkin Elmer company produces; Metering system is scanning; Wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.The result is as shown in Figure 7, and vibration only appears in transmitted spectrum in 1000nm～2500nm scope, and the number at concussion peak is 8, judges that the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 30nm～40nm.
Observe pattern (referring to Fig. 8, Fig. 9) with field emission scanning electron microscope (Hitachi S4800), prove that the through-hole rate of porous alumina membrane is 0, barrier layer thickness is about 30nm～40nm, and is consistent with the result who 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; Purchase and cover Thailand in Beijing and grind) (18.2M Ω/cm) distinguishes ultrasonic cleaning 10 minutes, and the use volume ratio is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water.
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is a negative electrode with graphite in the electrolytic tank of organic glass or teflon, and aluminium flake is an anode; In concentration is in the oxalic acid electrolyte aqueous solution of 0.4M; Under the 60V voltage, environment temperature is carried out first step anodic oxidation, oxidization time 4 hours during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 8 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.4M, under the 60V voltage in concentration; Environment temperature is carried out the second step anodic oxidation, oxidization time 20 minutes during less than 10 ℃.
5) peel off aluminium substrate
The product that step 4) is obtained soaks with saturated cupric chloride, takes out immediately when not having bubble to emerge, and has obtained pellumina.
6) go to the restraining barrier
The product that step 5) is obtained is immersed in the phosphate aqueous solution of 5wt% 35 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
The ultraviolet-visible-near-infrared spectrum of utilization transmitted spectrum technical testing porous alumina membrane; Method of testing is that employed instrument is Lambda 950 serial ultraviolet-visible-near infrared spectrometers that Perkin Elmer company produces; Metering system is scanning; Wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.Vibration appears in transmitted spectrum in 1000nm～2500nm scope, the number of oscillation peaks is 8, judges that the through-hole rate of porous alumina membrane is 0, and the thickness on restraining barrier is 30nm～40nm.
Observe pattern with field emission scanning electron microscope (Hitachi S4800), the through-hole rate that shows porous alumina membrane is 0, and the thickness on restraining barrier is about 30nm～40nm, and is consistent with the result who 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; Purchase and cover Thailand in Beijing and grind) (18.2M Ω/cm) distinguishes ultrasonic cleaning 10 minutes, and the use volume ratio is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water.
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is a negative electrode with graphite in the electrolytic tank of organic glass or teflon, and aluminium flake is an anode; In concentration is in the oxalic acid electrolyte aqueous solution of 0.3M; Under the 60V voltage, environment temperature is carried out first step anodic oxidation, oxidization time 1 hour during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 2 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.3M, under the 60V voltage in concentration; Environment temperature is carried out the second step anodic oxidation, oxidization time 5 minutes during less than 10 ℃.
5) peel off aluminium substrate
The product that step 4) is obtained soaks with saturated cupric chloride, takes out immediately when not having bubble to emerge, and has obtained pellumina.
6) go to the restraining barrier
The product that step 5) is obtained is immersed in the phosphate aqueous solution of 5wt% 40 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
The ultraviolet-visible-near-infrared spectrum of utilization transmitted spectrum technical testing porous alumina membrane; Method of testing is that employed instrument is Lambda 950 serial ultraviolet-visible-near infrared spectrometers that Perkin Elmer company produces; Metering system is scanning; Wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.The result is shown in figure 10, and vibration only appears in transmitted spectrum in 1500nm～2500nm scope, and the number at concussion peak is 4, and transmittance is 70%, judges that the through-hole rate of porous alumina membrane is 50%, and the thickness on restraining barrier is 15nm～25nm.
Observe pattern (referring to Figure 11, Figure 12) with field emission scanning electron microscope (Hitachi S4800), prove that the through-hole rate of porous alumina membrane is 50%, barrier layer thickness is about 15nm～25nm, and is consistent with the result who 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; Purchase and cover Thailand in Beijing and grind) (18.2M Ω/cm) distinguishes ultrasonic cleaning 10 minutes, and the use volume ratio is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water.
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is a negative electrode with graphite in the electrolytic tank of organic glass or teflon, and aluminium flake is an anode; In concentration is in the oxalic acid electrolyte aqueous solution of 0.3M; Under the 40V voltage, environment temperature is carried out first step anodic oxidation, oxidization time 12 hours during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 12 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.3M, under the 40V voltage in concentration; Environment temperature is carried out the second step anodic oxidation, oxidization time 10 minutes during less than 10 ℃.
5) peel off aluminium substrate
The product that step 4) is obtained soaks with saturated cupric chloride, takes out immediately when not having bubble to emerge, and has obtained pellumina.
6) go to the restraining barrier
The product that step 5) is obtained is immersed in the phosphate aqueous solution of 5wt% 45 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
The ultraviolet-visible-near-infrared spectrum (seeing accompanying drawing 22) of utilization transmitted spectrum technical testing porous alumina membrane; Method of testing is that employed instrument is Lambda 950 serial ultraviolet-visible-near infrared spectrometers that Perkin Elmer company produces; Metering system is scanning; Wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.Vibration only appears in transmitted spectrum in 1500nm～2500nm scope, the number at concussion peak is 4, and transmittance judges that 80% the through-hole rate of porous alumina membrane is 65%, and the thickness on restraining barrier is 15nm～25nm.
Observe pattern with field emission scanning electron microscope (Hitachi S4800), show that the through-hole rate of porous alumina membrane is 65%, barrier layer thickness is about 15nm～25nm, and is consistent with the result who 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; Purchase and cover Thailand in Beijing and grind) (18.2M Ω/cm) distinguishes ultrasonic cleaning 10 minutes, and the use volume ratio is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water.
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is a negative electrode with graphite in the electrolytic tank of organic glass or teflon, and aluminium flake is an anode; In concentration is in the oxalic acid electrolyte aqueous solution of 0.3M; Under the 60V voltage, environment temperature is carried out first step anodic oxidation, oxidization time 2 hours during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 2 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.3M, under the 60V voltage in concentration; Environment temperature is carried out the second step anodic oxidation, oxidization time 5 minutes during less than 10 ℃.
5) peel off aluminium substrate
The product that step 4) is obtained soaks with saturated cupric chloride, takes out immediately when not having bubble to emerge, and has obtained pellumina.
6) go to the restraining barrier
The product that step 5) is obtained is immersed in the phosphate aqueous solution of 5wt% 50 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
The ultraviolet-visible-near-infrared spectrum (seeing accompanying drawing 22) of utilization transmitted spectrum technical testing porous alumina membrane; Method of testing is that employed instrument is Lambda 950 serial ultraviolet-visible-near infrared spectrometers that Perkin Elmer company produces; Metering system is scanning; Wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.The result is shown in figure 13, and vibration only appears in transmitted spectrum in 1500nm～2500nm scope, and the number at concussion peak is 4, and transmittance judges that 85% the through-hole rate of porous alumina membrane is 70%, and the thickness on restraining barrier is 5nm～10nm.
Observe pattern (referring to Figure 14, Figure 15) with field emission scanning electron microscope (Hitachi S4800), prove that the through-hole rate of porous alumina membrane is 70%, barrier layer thickness is about 5nm～10nm, and is consistent with the result who 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; Purchase and cover Thailand in Beijing and grind) (18.2M Ω/cm) distinguishes ultrasonic cleaning 10 minutes, and the use volume ratio is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water.
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is a negative electrode with graphite in the electrolytic tank of organic glass or teflon, and aluminium flake is an anode; In concentration is in the oxalic acid electrolyte aqueous solution of 0.3M; Under the 60V voltage, environment temperature is carried out first step anodic oxidation, oxidization time 4 hours during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 6 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.3M, under the 60V voltage in concentration; Environment temperature is carried out the second step anodic oxidation, oxidization time 10 minutes during less than 10 ℃.
5) peel off aluminium substrate
The product that step 4) is obtained soaks with saturated cupric chloride, takes out immediately when not having bubble to emerge, and has obtained pellumina.
6) go to the restraining barrier
The product that step 5) is obtained is immersed in the phosphate aqueous solution of 5wt% 60 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
The ultraviolet-visible-near-infrared spectrum of utilization transmitted spectrum technical testing porous alumina membrane; Method of testing is that employed instrument is Lambda 950 serial ultraviolet-visible-near infrared spectrometers that Perkin Elmer company produces; Metering system is scanning; Wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.Vibration only appears in transmitted spectrum in 1500nm～2500nm scope, the number at concussion peak is 4, and transmittance judges that 90% the through-hole rate of porous alumina membrane is 80%, and the thickness on restraining barrier is 5nm～10nm.
Observe pattern with field emission scanning electron microscope (Hitachi S4800), show that the through-hole rate of porous alumina membrane is 80%, barrier layer thickness is about 5nm～10nm, and is consistent with the result who 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; Purchase and cover Thailand in Beijing and grind) (18.2M Ω/cm) distinguishes ultrasonic cleaning 10 minutes, and the use volume ratio is that 7: 1: 2 the mixed liquor of SPA, the concentrated sulphuric acid and red fuming nitric acid (RFNA) was 120 ℃ of chemical polishings 1 minute with acetone and deionized water.
2) first step anodic oxidation
The aluminium flake that step 1) is obtained is a negative electrode with graphite in the electrolytic tank of organic glass or teflon, and aluminium flake is an anode; In concentration is in the oxalic acid electrolyte aqueous solution of 0.3M; Under the 60V voltage, environment temperature is carried out first step anodic oxidation, oxidization time 3 hours during less than 10 ℃.
3) corrosion primary oxide film
With step 2) aluminium flake that obtains places the mixed solution of phosphoric acid and chromic acid, in 65 ℃ of baking ovens, places 3 hours, and concentration of phosphoric acid is 5wt%, and the concentration of chromic acid is 1.5wt%.
4) the second step anodic oxidation
The good aluminium flake of the corrosion that step 3) is obtained is in the electrolytic tank of organic glass or teflon; With graphite is negative electrode; Aluminium flake is an anode, is in the oxalic acid electrolyte aqueous solution of 0.3M, under the 60V voltage in concentration; Environment temperature is carried out the second step anodic oxidation, oxidization time 5 minutes during less than 10 ℃.
5) peel off aluminium substrate
The product that step 4) is obtained soaks with saturated cupric chloride, takes out immediately when not having bubble to emerge, and has obtained pellumina.
6) go to the restraining barrier
The product that step 5) is obtained is immersed in the phosphate aqueous solution of 5wt% 70 minutes.
2. the ultraviolet-visible-near-infrared spectrum of porous alumina membrane test
The ultraviolet-visible-near-infrared spectrum of utilization transmitted spectrum technical testing porous alumina membrane; Method of testing is that employed instrument is Lambda 950 serial ultraviolet-visible-near infrared spectrometers that Perkin Elmer company produces; Metering system is scanning; Wavelength coverage 200nm～2500nm, sweep speed is 924nm/min.The result is shown in figure 16, and vibration does not appear in transmitted spectrum in 200nm～2500nm scope, judges that the through-hole rate of porous alumina membrane is 100%, and the thickness on restraining barrier is 0nm.
Observe pattern (referring to Figure 17, Figure 18) with field emission scanning electron microscope (Hitachi S4800), the through-hole rate that proves porous alumina membrane is 100%, and barrier layer thickness is 0nm, and is consistent with the result who 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; This method comprises according to the transmitted spectrum of porous alumina membrane in 200nm～2500nm scope judges whether porous alumina membrane contains the restraining barrier; Wherein, if vibration appears in transmitted spectrum in 200nm～2500nm scope, the thickness on restraining barrier of then judging this porous alumina membrane is greater than 0; If vibration does not appear in transmitted spectrum in 200nm～2500nm scope, the thickness of then judging 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, vibration only appears in transmitted spectrum in 500nm～2500nm scope, and the number of oscillation peaks is 17; Then 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, vibration only appears in transmitted spectrum in 1000nm～2500nm scope, and the number of oscillation peaks is 16; Then 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, vibration only appears in transmitted spectrum in 1000nm～2500nm scope, and the number of oscillation peaks is 8; Then 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, Vibration only appears in transmitted spectrum in 1500nm～2500nm scope; And the number of oscillation peaks is 4, and then 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 is 70%～80% as if transmittance, and then the through-hole rate of porous alumina membrane is 50%-65%, and the thickness on restraining barrier is about 15nm～25nm.
7. the detection method of the barrier layer thickness of porous alumina membrane according to claim 5 is 85%～90% as if transmittance, and then the through-hole rate of porous alumina membrane is 70%-80%, and the thickness on restraining barrier is about 5nm～10nm.
8. according to the detection method of the barrier layer thickness of any described porous alumina membrane among the claim 1-7, wherein, said 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 said 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 said porous alumina membrane is the 1-30 micron.
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| CN103606528A (en) * | 2013-10-23 | 2014-02-26 | 上海华力微电子有限公司 | Pre-tungsten-growth silicon detection device and method |
| CN110657752A (en) * | 2019-10-23 | 2020-01-07 | 成都飞机工业（集团）有限责任公司 | Array hole through-void ratio measuring method based on optical fiber displacement sensor |
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| US6190153B1 (en) * | 1997-05-01 | 2001-02-20 | Mitsui Chemicals Inc. | Oriented film producing facility with thickness and orientation control means |
| 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 |
| US20070115486A1 (en) * | 2001-12-19 | 2007-05-24 | Nikon Corporation | Film forming device, and production method for optical member |
| CN101294795A (en) * | 2007-04-25 | 2008-10-29 | 横河电机株式会社 | Apparatus and method for measuring film thickness |
| CN101363768A (en) * | 2008-09-28 | 2009-02-11 | 厦门大学 | Method for detecting optical constant and thickness of mono-layer optical film |
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| US6190153B1 (en) * | 1997-05-01 | 2001-02-20 | Mitsui Chemicals Inc. | Oriented film producing facility with thickness and orientation control means |
| US20070115486A1 (en) * | 2001-12-19 | 2007-05-24 | Nikon Corporation | Film forming device, and production method for optical member |
| 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 |
| CN101363768A (en) * | 2008-09-28 | 2009-02-11 | 厦门大学 | Method for detecting optical constant and thickness of mono-layer optical film |
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| CN103606528A (en) * | 2013-10-23 | 2014-02-26 | 上海华力微电子有限公司 | Pre-tungsten-growth silicon detection device and method |
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| CN110657752A (en) * | 2019-10-23 | 2020-01-07 | 成都飞机工业（集团）有限责任公司 | Array hole through-void ratio measuring method based on optical fiber displacement sensor |
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