CN101105468B - Porous anode alumina humidity sensor and its preparing process - Google Patents
Porous anode alumina humidity sensor and its preparing process Download PDFInfo
- Publication number
- CN101105468B CN101105468B CN2007100279096A CN200710027909A CN101105468B CN 101105468 B CN101105468 B CN 101105468B CN 2007100279096 A CN2007100279096 A CN 2007100279096A CN 200710027909 A CN200710027909 A CN 200710027909A CN 101105468 B CN101105468 B CN 101105468B
- Authority
- CN
- China
- Prior art keywords
- porous
- aluminium oxide
- humidity sensor
- membrane
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Investigating Or Analyzing Materials By The Use Of Fluid Adsorption Or Reactions (AREA)
Abstract
The invention discloses a porous anodic alumina humidity transducer and the preparation method thereof. The metal film electrode of the transducer is a porous metal film electrode. Porous anodic aluminum membrane is communicated with the porous metal film electrode by holes along the thickness direction of the membrane, with via-holes provided in upper and lower surfaces thereof. The preparation method that the combination technique of two-step anode oxidation and acid corrosion is adopted to prepare the anodic aluminum membrane with the two via-holes; then the metal electrode is deposited on the upper and the lower surfaces of the anodic aluminum membrane by using RF magnetron sputtering to form the humidity transducer with the intercommunication between the electrode holes and the anodic aluminum holes on the metal electrode replica-surfaces of the anodic aluminum membrane The transducer can measure in the whole scope of relative humidity, and is characterized in simple structure, small volume, rapid response, good repeatability, and stable performance, etc., therefore, particularly suitable for being used in the precision electronic instruments.
Description
Technical field
The present invention relates to the humidity sensor technology, be specifically related to a kind of porous anode alumina humidity sensor and preparation method thereof.
Background technology
Humidity sensor is a kind of important electron element, at aspects such as warehousing, commercial production, process control, environmental monitoring, household electrical appliance, meteorologies purposes is widely arranged.The kind of humidity sensor has a lot, with regard to its employed wet sensory material, roughly can be divided into four big classes: Electrolyte type, high molecular polymer type, semiconductor ceramics type and porous metal oxide semi-conductor type.The Electrolyte type measurement range is narrow, repeatability is poor, serviceable life short; High molecular polymer type wet sensing performance is good, highly sensitive, but the stability under high temperature and high humidity environment, anticorrosive and anti-contamination ability; But semiconductor ceramics type wet sensing performance is good, it is simple to produce, cost is low, the fast heated wash of moisture absorption/dehumidification response speed, but reproducibility is relatively poor.Comparatively speaking, the advantage of porous metal oxide semi-conductor type is fairly obvious, have highly sensitive, moisture absorption/the dehumidification response speed is fast, reproducibility good, chemical stability is better, bear advantages such as high temperature and low temperature ability be strong.
Document " Effect of moisture on the dielectric properties of porous alumina films; Sensors and Actuator; 1984; 5:187～198 " has been reported a kind of porous anode alumina humidity sensor, this sensor is a wet sensory material with the single-pass hole anodic aluminium oxide membrane of average pore size 13nm, at diaphragm through-hole surfaces sputter gold as top electrode, remaining aluminum substrate is as bottom electrode after the anodic oxidation, can measure in 2～98% relative humidity scopes, have highly sensitive, advantages such as the linearity is better, but moisture absorption/dehumidification response speed is slower.Document " Highly ordered nanoporous alumina films:Effect ofpore size and uniformity on sensing performance; J.Mater.Res.; Vol.17 (2002): 1162-1171 " has been reported another kind of porous anodic aluminium oxide moisture sensor, this sensor is a wet sensory material with the single-pass hole anodic aluminium oxide membrane of average pore size 13.6nm, form surperficial interdigital electrode at diaphragm through-hole surfaces vacuum evaporation gold, can measure in 20～90% relative humidity scopes, has the precision height, reproducibility is good, advantages such as manufacture craft is simple, but the linearity is relatively poor, and particularly the sensitivity under low humidity is lower.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of porous anode alumina humidity sensor is provided, make its not only moisture absorption/dehumidification response speed fast, and under the low humidity condition, have good linearity and higher sensitivity.
Purpose of the present invention is achieved through the following technical solutions:
A kind of porous anode alumina humidity sensor, comprise porous anodic aluminium oxide membrane, the porous anodic aluminium oxide membrane upper and lower surface is provided with metal film electrode, described metal film electrode is the porous metals membrane electrode, and the hole on porous anodic aluminium oxide membrane and the porous metals membrane electrode is along the connection of porous anodic aluminium oxide membrane thickness direction and at the upper and lower surface opening.
Described porous metals membrane electrode is gold or aluminum film electrode.
The hole diameter of described anodic aluminium oxide membrane is 40～90nm, and thickness is 50～120 μ m.
The hole diameter of described porous metals membrane electrode is that 10～70nm, thickness are 150～300nm.
The preparation method of porous anode alumina humidity sensor: at first adopt two step anodizings to prepare porous anodic aluminium oxide membrane, adopt magnetron sputtering method to prepare the porous metals membrane electrode then, form porous anode alumina humidity sensor in the porous anodic aluminium oxide membrane upper and lower surface;
It is to carry out in 0.3～0.5mol/L oxalic acid solution that described two step anodizings prepare porous anodic aluminium oxide membrane; After the first step anodic oxidation, with phosphoric acid and the complete dissolved oxygen aluminium lamination of chromic acid mixture; After the second step anodic oxidation, at room temperature remove not oxidized metallic aluminium matrix by displacement reaction, remove the porous anodic aluminium oxide membrane of potential barrier layer, corrosion reaming acquisition doubled via structure with phosphoric acid with saturated cupric chloride or mercuric chloride solution.
It is to be target with purity High Purity Gold or aluminium that described magnetron sputtering method prepares the porous metals membrane electrode in the porous anodic aluminium oxide membrane upper and lower surface, in base vacuum＞1 * 10
-4Under Pa, deposition vacuum 0.5～2Pa, argon flow amount 1～5sccm, sputtering power 10～20W, 25～500 ℃ of conditions of underlayer temperature, in the anodic aluminium oxide membrane upper and lower surface, prepare porous anode alumina humidity sensor by rf magnetron sputtering.
With respect to existing porous anode alumina humidity sensor technology, the present invention has following advantage and beneficial effect:
(1) hole on porous anodic aluminium oxide membrane and the porous metals membrane electrode is along the connection of diaphragm thickness direction and at the upper and lower surface opening, for air flow provides an effective passage, can avoid capillary condensation aqueous water gathering in hole, improve the moisture absorption/dehumidification speed of hydrone, obtain good reproducibility at the hole inside surface;
(2) equipment of preparation porous anodic aluminium oxide membrane is simple, only need electrolytic tank and D.C. regulated power supply, aperture and thickness are may command by time quantum, process stabilizing and reproducibility are good, the equipment of preparation porous metals membrane electrode only needs the rf magnetron sputtering platform, and porous anodic aluminium oxide membrane need not other processing, and aperture and thickness also can be controlled by time quantum, qualitative control is easy, is beneficial to steady production in batches.
Description of drawings
Fig. 1 is a porous anode alumina humidity sensor structural representation of the present invention.1 is the porous metals membrane electrode; 2 is porous anodic aluminium oxide membrane.
Fig. 2 is embodiment 1 a prepared porous anodic aluminium oxide surface topography sem photograph.
Fig. 3 is embodiment 1 a prepared porous electrode surface topography sem photograph.
Fig. 4 is the made porous electrode cross-section morphology sem photograph of embodiment 1.
Fig. 5 is the impedance of embodiment 1 made humidity sensor and the relation of relative humidity.
Fig. 6 is the moisture absorption/dehumidification response curve of embodiment 1 made humidity sensor.
Embodiment
The invention will be further described below in conjunction with embodiment, and the inventor has many successful examples to the present invention after research and testing, enumerates the part specific embodiment below, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
Purity 99.99%, length and width is high for after the aluminium flake of 35mm * 15mm * 0.3mm at room temperature places volume ratio to be 1: 4 perchloric acid and the electropolishing of absolute ethyl alcohol mixed solution, under 0 ℃ of temperature conditions, carry out two-step anodic oxidization in 0.3mol/L oxalic acid, anodic oxidation voltage is 40V.Behind the first step anodic oxidation 12h, be the complete dissolved oxygen aluminium lamination of 6% phosphoric acid and 1.5% chromic acid mixture with mass percent concentration; Behind the second step anodic oxidation 24h, remove aluminum substrate, remove potential barrier layer, corrosion reaming, obtain the porous anodic aluminium oxide membrane of average pore size 85nm, thickness 110 μ m as shown in Figure 2 with 5% (quality) phosphoric acid with saturated copper chloride solution.
With purity is that 99.99% High Purity Gold is a target, at base vacuum 1 * 10
-5Under Pa, deposition vacuum 1.2Pa, argon flow amount 3.5sccm, sputtering power 17W, 250 ℃ of conditions of underlayer temperature, prepare the porous anode alumina humidity sensor that electrode size is φ 8mm in 10mm * 10mm anodic aluminium oxide membrane (sample of previous step preparation cuts into fritter) upper and lower surface by rf magnetron sputtering.As shown in Figure 3, the electrode of this sensor has porous oldered array surface topography, and average pore size is about 60nm, and thickness of electrode is 190nm.As shown in Figure 4, hole on the electrode and anodised aluminium hole are interconnected.The porous anode alumina humidity sensor structural representation of preparation as shown in Figure 1, porous anodic aluminium oxide membrane 2 upper and lower surfaces are provided with porous metals membrane electrode 1, and the hole on porous anodic aluminium oxide membrane 2 and the porous metals membrane electrode 1 is along the connection of diaphragm thickness direction and at the upper and lower surface opening.
The moisture absorption of humidity sensor/dehumidification measure of merit: by room temperature following 5 kinds of inorganic salts saturated aqueous solution LiCl, MgCl
2, Mg (NO
3)
2, NaCl, K
2SO
4Obtain 12%, 33%, 53%, 75% and 97% relative humidity environment, measure the impedance of 10kHz with HP4194A impedance-gain frequency analyser | Z|, data presentation as Fig. 5: the linearity in 12～97% relative humidity scopes is better, increase to relative humidity and to reduce circulation change (each humidity environment keep down 5min), extraordinary repeatability is arranged.
Impedance variation curve when relative humidity 12% and 75% environment are alternately changed under the test room temperature, by impedance | Z| reaches 90% and 10% calculated response time and release time of variable quantity, the data presentation of Fig. 6: the moisture absorption response time is about 18s, and the dehumidification response time is about 5s.
Purity 99.99%, length and width is high for after the aluminium flake of 35mm * 15mm * 0.3mm at room temperature places perchloric acid and absolute ethyl alcohol (1: 4) mixed solution electropolishing, in 0 ℃, 0.5mol/L oxalic acid, carry out two-step anodic oxidization, anodic oxidation voltage is 40V.Behind the first step anodic oxidation 12h, with the complete dissolved oxygen aluminium lamination of 6% phosphoric acid+1.5% chromic acid mixture; Behind the second step anodic oxidation 12h, remove aluminum substrate, remove potential barrier layer, corrosion reaming, obtain the porous anodic aluminium oxide membrane of average pore size 45nm, thickness 60 μ m with 5% phosphoric acid with saturated copper chloride solution.
At base vacuum 1.5 * 10
-4Under Pa, deposition vacuum 0.5Pa, argon flow amount 1sccm, sputtering power 12W, 25 ℃ of conditions of underlayer temperature, with 99.99% High Purity Gold is target, prepares average pore size 30nm, thickness 210nm porous metals membrane electrode formation humidity sensor with embodiment 1 described method.The method of testing of Application Example 1 detects, and the linearity of this sensor in 12～97% relative humidity scopes is better, and extraordinary repeatability is arranged, and the moisture absorption response time is about 10s, and the dehumidification response time is about 8s.
Embodiment 3
Purity 99.99%, length and width is high for after the aluminium flake of 35mm * 15mm * 0.3mm at room temperature places perchloric acid and absolute ethyl alcohol (1: 4) mixed solution electropolishing, in 0 ℃, 0.3mol/L oxalic acid, carry out two-step anodic oxidization, anodic oxidation voltage is 40V.Behind the first step anodic oxidation 12h, with the complete dissolved oxygen aluminium lamination of 6% phosphoric acid+1.5% chromic acid mixture; Behind the second step anodic oxidation 18h, remove aluminum substrate, remove potential barrier layer, corrosion reaming, obtain the porous anodic aluminium oxide membrane of average pore size 73nm, thickness 85 μ m with 5% phosphoric acid with saturated copper chloride solution.
At base vacuum 8 * 10
-6Under Pa, deposition vacuum 1.9Pa, argon flow amount 5sccm, sputtering power 20W, 500 ℃ of conditions of underlayer temperature, with 99.99% rafifinal is target, prepares average pore size 70nm, thickness 150nm porous metals membrane electrode formation humidity sensor with embodiment 1 described method.The method of testing of Application Example 1 detects, and the linearity of this sensor in 12～97% relative humidity scopes is better, and extraordinary repeatability is arranged, and the moisture absorption response time is about 20s, and the dehumidification response time is about 6s.
Embodiment 4
Purity 99.99%, length and width is high for after the aluminium flake of 35mm * 15mm * 0.3mm at room temperature places perchloric acid and absolute ethyl alcohol (1: 4) mixed solution electropolishing, in 0 ℃, 0.5mol/L oxalic acid, carry out two-step anodic oxidization, anodic oxidation voltage is 40V.Behind the first step anodic oxidation 12h, with the complete dissolved oxygen aluminium lamination of 6% phosphoric acid+1.5% chromic acid mixture; Behind the second step anodic oxidation 24h, remove aluminum substrate, remove potential barrier layer, corrosion reaming, obtain the porous anodic aluminium oxide membrane of average pore size 85nm, thickness 110 μ m with 5% phosphoric acid with saturated copper chloride solution.
At base vacuum 1.2 * 10
-5Under Pa, deposition vacuum 1.2Pa, argon flow amount 3sccm, sputtering power 10W, 300 ℃ of conditions of underlayer temperature, with 99.99% High Purity Gold is target, prepares average pore size 12nm, thickness 290nm porous metals membrane electrode formation humidity sensor with embodiment 1 described method.The method of testing of Application Example 1 detects, and the linearity of this sensor in 12～97% relative humidity scopes is better, and extraordinary repeatability is arranged, and the moisture absorption response time is about 25s, and the dehumidification response time is about 18s.
Claims (6)
1. porous anode alumina humidity sensor, comprise porous anodic aluminium oxide membrane, the porous anodic aluminium oxide membrane upper and lower surface is provided with metal film electrode, it is characterized in that, described metal film electrode is the porous metals membrane electrode, and the hole on porous anodic aluminium oxide membrane and the porous metals membrane electrode is along the connection of porous anodic aluminium oxide membrane thickness direction and at the upper and lower surface opening.
2. according to the described porous anode alumina humidity sensor of claim 1, it is characterized in that described porous metals membrane electrode is gold or aluminum film electrode.
3. according to the described porous anode alumina humidity sensor of claim 1, the hole diameter that it is characterized in that described porous anodic aluminium oxide membrane is 40～90nm, and thickness is 50～120 μ m.
4. according to the described porous anode alumina humidity sensor of claim 1, the hole diameter that it is characterized in that the porous metals membrane electrode is that 10～70nm, thickness are 150～300nm.
5. the preparation method of the described porous anode alumina humidity sensor of claim 1, it is characterized in that at first adopting two step anodizings to prepare porous anodic aluminium oxide membrane, adopt magnetron sputtering method to prepare the porous metals membrane electrode then, form porous anode alumina humidity sensor in the porous anodic aluminium oxide membrane upper and lower surface;
It is to carry out in 0.3～0.5mol/L oxalic acid solution that described two step anodizings prepare porous anodic aluminium oxide membrane; After the first step anodic oxidation, with phosphoric acid and the complete dissolved oxygen aluminium lamination of chromic acid mixture; After the second step anodic oxidation, at room temperature remove not oxidized metallic aluminium matrix by displacement reaction, remove the porous anodic aluminium oxide membrane of potential barrier layer, corrosion reaming acquisition doubled via structure with phosphoric acid with saturated cupric chloride or mercuric chloride solution.
6. the preparation method of porous anode alumina humidity sensor according to claim 5, it is characterized in that it is to be target with purity High Purity Gold or aluminium that described magnetron sputtering method prepares the porous metals membrane electrode in the porous anodic aluminium oxide membrane upper and lower surface, in base vacuum＞1 * 10
-4Under Pa, deposition vacuum 0.5～2Pa, argon flow amount 1～5sccm, sputtering power 10～20W, 25～500 ℃ of conditions of underlayer temperature, in the anodic aluminium oxide membrane upper and lower surface, prepare porous anode alumina humidity sensor by rf magnetron sputtering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100279096A CN101105468B (en) | 2007-04-30 | 2007-04-30 | Porous anode alumina humidity sensor and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100279096A CN101105468B (en) | 2007-04-30 | 2007-04-30 | Porous anode alumina humidity sensor and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101105468A CN101105468A (en) | 2008-01-16 |
| CN101105468B true CN101105468B (en) | 2011-04-27 |
Family
ID=38999462
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100279096A Expired - Fee Related CN101105468B (en) | 2007-04-30 | 2007-04-30 | Porous anode alumina humidity sensor and its preparing process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101105468B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102645455B (en) * | 2012-03-22 | 2014-02-26 | 南京工业大学 | Preparation method for sensitive humidity sensor material |
| CN103698358B (en) * | 2012-09-27 | 2015-11-18 | 中国科学院金属研究所 | A kind of preparation method of porous ceramics alumina type humidity sensor |
| CN102967634A (en) * | 2012-12-04 | 2013-03-13 | 中国科学院合肥物质科学研究院 | Capacitive humidity-sensitive sensor based on anodic alumina film coplanar electrode structure and preparation method thereof |
| CN103424439A (en) * | 2013-09-04 | 2013-12-04 | 浙江工商大学 | Gas sensor for detecting trace benzene |
| CN108226236A (en) * | 2018-01-29 | 2018-06-29 | 黑龙江大学 | A kind of integrated humidity sensor and its manufacture craft |
| CN113514106B (en) * | 2021-07-14 | 2022-09-27 | 天津工业大学 | Preparation method and application of multifunctional sensor for synchronously measuring temperature, pressure and humidity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86102535A (en) * | 1986-10-17 | 1988-05-11 | 中国科学院上海冶金研究所 | Metal-aluminium oxide one silicon structure humidity sensor and preparation technology thereof |
| CN2129414Y (en) * | 1992-06-27 | 1993-04-07 | 中国科学院上海冶金研究所 | Humidity-measuring probe |
-
2007
- 2007-04-30 CN CN2007100279096A patent/CN101105468B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86102535A (en) * | 1986-10-17 | 1988-05-11 | 中国科学院上海冶金研究所 | Metal-aluminium oxide one silicon structure humidity sensor and preparation technology thereof |
| CN2129414Y (en) * | 1992-06-27 | 1993-04-07 | 中国科学院上海冶金研究所 | Humidity-measuring probe |
Non-Patent Citations (7)
| Title |
|---|
| 凌志远等.基于阳极氧化铝模板的金属纳米孔阵列膜制备.电子元件与材料26 2.2007,26(2),5，6，10. |
| 凌志远等.基于阳极氧化铝模板的金属纳米孔阵列膜制备.电子元件与材料26 2.2007,26(2),5,6,10. * |
| 史青等.α-Al2O3电容薄膜湿度传感器.电子科技大学学报26 4.1997,26(4),387-390. |
| 史青等.α-Al2O3电容薄膜湿度传感器.电子科技大学学报26 4.1997,26(4),387-390. * |
| 张会锐.基于纳米材料的湿度传感器的研究.中国优秀硕士学位论文全文数据库.2004,50-64. * |
| 张会锐等.室温下纳米多孔氧化铝湿度传感器的研究.浙江大学学报38 4.2004,38(4),420-424. |
| 张会锐等.室温下纳米多孔氧化铝湿度传感器的研究.浙江大学学报38 4.2004,38(4),420-424. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101105468A (en) | 2008-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101105468B (en) | Porous anode alumina humidity sensor and its preparing process | |
| Gong et al. | Highly ordered nanoporous alumina films: Effect of pore size and uniformity on sensing performance | |
| CN105021120B (en) | A kind of capacitance strain transducer and preparation method thereof | |
| KR101217972B1 (en) | Thin film capacitor and method of fabrication thereof | |
| CN102507660B (en) | Humidity-sensitive sensor based on aluminum oxide nanowire film and preparation method of humidity-sensitive sensor | |
| CN105842313A (en) | Micro-nano textured graphene-based bionic pH sensor and manufacturing method thereof | |
| CN101775586A (en) | Preparation method of electrochemical oriented growth of polyporous Al2O3 film on non-aluminum base | |
| US8132457B2 (en) | Nano-porous alumina sensor | |
| US7820587B2 (en) | Porous anodic aluminum oxide membranes for nanofabrication | |
| Khatko et al. | Tungsten trioxide sensing layers on highly ordered nanoporous alumina template | |
| CN102183558A (en) | Graded porous nano alumina/gold composite film electrode and preparation method thereof | |
| Liu et al. | Synthesis of an ordered nanoporous Cu/Ni/Au film for sensitive non-enzymatic glucose sensing | |
| CN102517558B (en) | Porous metal/dielectric micro tube, and preparation method and application thereof | |
| US20140361794A1 (en) | Silicon dioxide moisture sensors | |
| Shrestha et al. | Investigation of Volmer-Weber growth during the nucleation phase of ALD platinum thin films and template based platinum nanotubes | |
| CN101629927A (en) | Porous aluminum oxide film humidity-dependent sensor preparation method | |
| Li et al. | Capacitive humidity sensor with a coplanar electrode structure based on anodised porous alumina film | |
| Zahedi et al. | Preparation of a Pd membrane on a WO3 modified porous stainless steel for hydrogen separation | |
| Sberveglieri et al. | Capacitive humidity sensor with controlled performances, based on porous Al2O3 thin film growm on SiO2-Si substrate | |
| CN106350058B (en) | The preparation method of fluorescence enhancement substrate based on nano-porous gold | |
| CN107884316A (en) | Surface tension of liquid sensor based on ordered carbon nanotube film and preparation method thereof | |
| Li et al. | Influence of the microstructure of sputtered Ti films on the anodization toward TiO2 nanotube arrays | |
| CN106645329B (en) | A kind of double-deck film modified pH of GO-Nafion, water content compound sensor and preparation method thereof | |
| CN1117196A (en) | Inorganic thin film humidity-sensitive element with high performance and its producing method | |
| Lan et al. | Fabrication and characteristics of the high-sensitivity humidity sensor of anodic aluminum oxide based on silicon substrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110427 Termination date: 20150430 |
|
| EXPY | Termination of patent right or utility model |