CN101811888B - Method for preparing composite air-sensitive membrane of carbon nano tube embedded with oxide quantum dots - Google Patents
Method for preparing composite air-sensitive membrane of carbon nano tube embedded with oxide quantum dots Download PDFInfo
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- CN101811888B CN101811888B CN2010101535320A CN201010153532A CN101811888B CN 101811888 B CN101811888 B CN 101811888B CN 2010101535320 A CN2010101535320 A CN 2010101535320A CN 201010153532 A CN201010153532 A CN 201010153532A CN 101811888 B CN101811888 B CN 101811888B
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Abstract
The invention discloses a method for preparing a composite air-sensitive membrane of a carbon nano tube embedded with oxide quantum dots. The composite air-sensitive membrane is prepared by preparing a layer of an oxide nano particle membrane layer on a silicon substrate, sintering the silicon substrate in a sintering furnace at a high temperature and then growing a carbon nano tube on the oxide nano particle membrane through high-temperature pyrolysis. The composite air-sensitive membrane is the dendritic carbon nano tube embedded with the oxide quantum dots. The air-sensitive membrane with a composite structure increases passages for electron transportation and absorption, increases surface area and contributes to improvement on air sensitivity and selectivity. The preparation process of the composite air-sensitive membrane has the advantages of simple operation and low cost.
Description
Technical field
The invention belongs to gas sensor sensitive thin film preparation field, relate to a kind of preparation method who is embedded with the composite air-sensitive membrane of carbon nano tube of oxide quantum dots.
Background technology
The cardinal principle of gas sensor is that detected gas and gas sensitization film react; The attribute such as material structure, surface state that causes air-sensitive film changes; This attribute change is changed into electric signal outputs such as resistance, electricity are led, electric capacity, the electric signal through output can analyze information such as component and the concentration of gas.Therefore for gas detection, the effect of sensitive membrane is crucial.Sensitive membrane has often determined structure, power consumption, life-span, sensitivity, the response time of gas sensor, the key characteristics such as scope of detection to a great extent.Metal oxide semiconductor such as tin oxide, zinc paste, titanium dioxide, zirconia etc. are the widest gas sensitives of present range of application; Because metal oxide materials has physics, chemical stability is good; Reliability is high; Gas absorption, desorption time weak point, advantages such as sensitivity height are fit to do gas sensitive very much.But metal oxide air-sensitive film sensor, the working temperature universal demand is than higher (at least more than 200 ℃), and selectivity is relatively poor under the room temperature, and the life-span is short, and the complicated cost of manufacture of device architecture is higher.Thereby how to develop new sensitive membrane material and preparation technology thereof, the characteristics such as sensitivity, stability, selectivity and life-span that improve gas sensor become the problem that current gas sensor field presses for solution.CNT is as a kind of novel nano material, has that specific surface area is big, electron mobility is high, an advantage such as can work under the room temperature, is well suited for doing gas sensitive and air-sensitive conductive material.Have highly sensitive, advantages such as response is fast, work under the room temperature, anti-electromagnetic-radiation based on the gas sensor of CNT.But the air-sensitive selectivity ratios of CNT is relatively poor, is difficult to accurately distinguish the kind of gas.This patent proposes embed oxide quantum dot formation composite air-sensitive material on CNT; Take into account the CNT good electron and transport performance and oxide quantum dots selectivity gaseous species, realize at room temperature high precision, selectively, the fast detecting all gases.The advantage of compound substance is 1+1＞2, and the development of novel gas sensitive is that solid foundation has been established in the research of gas sensor.
Summary of the invention
The objective of the invention is to, a kind of preparation method who is embedded with the composite air-sensitive membrane of carbon nano tube of oxide quantum dots is provided, this method can provide a kind of air-sensitive film technology of preparing of practicality for gas sensor.
To achieve these goals; The technical scheme that the present invention adopts is: the process using thick-film technique prepares one deck oxide nano particles rete on silicon substrate; High temperature sintering is as growth substrates in sintering furnace; Adopt FePC high-temperature catalytic cracking process carbon nano-tube composite structure in mono temperature area resistance furnace then above that; The CNT that obtains is dendroid and has oxide quantum dots to be embedded in its pipe and tube wall; Said method comprising the steps of: 1) the substrate pretreatment base material is silicon or silicon dioxide or other metal substrate, successively uses acetone, absolute ethyl alcohol and deionized water to each ultrasonic cleaning of substrate 20～30 minutes respectively, in baking oven, dries then; 2) oxide printing pulp preparation takes by weighing 8～15 gram oxides; Particle diameter is less than 1 micron; Measure 30～50 milliliters of terpinols and pour in the clean beaker, load weighted oxide is poured in the top beaker, with the glass bar back ultrasonic concussion 5～10 minutes in ultrasonic cleaner that stirs; Add 3～4 gram ethyl celluloses then, stir and ultrasonic concussion 3～5 minutes with glass bar.Beaker is placed in the electric heating constant temperature heating cabinet heats, keep 80～100 ℃ of temperature and constantly stir, finally process the oxide nano particles slurry; 3) substrate preparation through thick-film technique, comprises serigraphy with the oxide nano particles slurry, gets rid of and be coated with and other coating processes moulding on silicon or silicon dioxide or other metal substrate; 4) the sintering substrate that will prepare oxide slurry is put in the sintering furnace, and 540～560 ℃ of sintering temperatures are set, and keeps constant temperature 30～40 minutes, naturally cools to room temperature then; 5) oxide substrate of carbon nano-tube after with sintering is as growth substrates; With FePC as carbon source; Hydrogen adopts FePC catalystic pyrolysis carbon nano-tube sandwich (seeing patent (GL200510096426) " technology of mono temperature area resistance furnace pyrolysis for growing and purifying carbon nano-tube ") as reducing gas in mono temperature area resistance furnace.
Oxide is the multiple metal oxide of zinc paste, tin oxide, titanium dioxide or zirconia.
The technology that is embedded with the composite air-sensitive membrane of carbon nano tube of oxide quantum dots of the present invention can be carried out in multiple substrate, such as backing materials such as silicon, monox, other metals.Oxide membranous layer wherein can be multiple metal oxides such as zinc paste, tin oxide, titanium dioxide, zirconia.The present invention establishes certain basis for the development and the development of gas sensor.
Description of drawings
Fig. 1 is an air-sensitive film structures of samples synoptic diagram.
1 expression substrate; 2 oxide particle retes; 3 carbon nano-tube films.
Fig. 2 is the electromicroscopic photograph of carbon nano-tube compound film.
Below in conjunction with accompanying drawing content of the present invention is done further explain.
Embodiment
With reference to shown in Figure 1,1 is substrate, and 2 is the oxide particle rete, and 3 is carbon nano-tube film.Substrate is provided with one deck sull, and growth has the dendroid carbon nano-tube compound film that is embedded with oxide quantum dots on sull.
With reference to the SEM photo of CNT tin oxide composite membrane shown in Figure 2, the oxidized tin particles of dendritic CNT is wrapped in, and the CNT that grows is the ring shape, and can be clear that the tin oxide quantum dot is embedded in the tube wall and pipe of CNT.
According to technical scheme of the present invention; Preparation method's the specific requirement that is embedded with the dendroid composite air-sensitive membrane of carbon nano tube of oxide quantum dots is: 1) oxide particle obtains through ball milling; Oxide membranous layer is through being screen-printed on the silicon substrate; What 450～560 ℃ of sintering formed in constant temperature oven afterwards, the thickness of oxide particle rete is approximately 10um.
2) carbon nano tube compound material is to be grown on the oxide particle rete.
3) CNT is to grow in single warm area tubular furnace through the FePC high-temperature cracking method.
Specific embodiment of the present invention is the composite air-sensitive membrane of carbon nano tube of in the substrate of sensor component silicon structure, using that is embedded with the tin oxide quantum dot.
1) the substrate pretreatment base material is the low-resistance silicon substrate, successively uses acetone, absolute ethyl alcohol and deionization to each ultrasonic cleaning of substrate half an hour, 120 ℃ of bakings oven dry in 20～30 minutes in baking oven then respectively.
2) the tin oxide pulp preparation a) the ball milling putty powder then through 300 purpose screen filtrations.Take by weighing 8～10 gram ball milling rear oxidation tin.
B) measuring 30～50 milliliters of terpinols pours in the clean beaker.Load weighted tin oxide is poured in the top beaker, with the glass bar back ultrasonic concussion 5～10 minutes in ultrasonic cleaner that stirs.
C) take by weighing ethyl cellulose 3～4 grams then, pour in the top beaker, stir 5～10 minutes d of ultrasonic concussion in ultrasonic cleaner with glass bar) beaker is placed in the electric heating constant temperature heating cabinet heats, and constantly stir, process oxide printing slurry.
3) serigraphy is fixed to ready made silk screen on the screen process press, fixes silicon chip according to alignment patterns, presses silk screen.Get an amount of tin oxide and print the place ahead that slurry is positioned over the silk screen graph window, one hand is holding up scraper plate to scrape the graphics field to tin oxide printing slurry then, and tin oxide printing slurry sees through silk screen and stays formation tin oxide rete on the silicon chip.
4) the sintering silicon chip that will print the tin oxide slurry is put on the ceramic tile of constant temperature oven, puts into constant temperature oven to ceramic tile again, and 540～560 ℃ of sintering temperatures are set, and keeps constant temperature 30～40 minutes, naturally cools to room temperature then.
5) silicon chip behind the effective top tin oxide sintering of Growth of Carbon is as substrate, and as carbon source, hydrogen is reducing gas with FePC, and argon gas is protection gas and carrier gas, and the silicon chip that burns down after tying is put into single warm area tubular furnace carbon nano-tube.
Use the present invention and finally on oxidation film, grow dendritic CNT, and discovery there is the embedding of oxide quantum dots in the tube wall of CNT and pipe.The composite air-sensitive film of this new construction had both increased surface area, and for gas absorption and electron transport increase many passages, gas-sensitive property is significantly strengthened again.The good advantage of highly sensitive, the mature and stable property of the existing oxide material of this NEW TYPE OF COMPOSITE air-sensitive film has carbon nano-tube material ambient operation, anti-electromagnetic interference (EMI), highly sensitive, advantage such as reaction is fast again.
Claims (2)
1. be embedded with the preparation method of the composite air-sensitive membrane of carbon nano tube of oxide quantum dots; It is characterized in that; Adopt thick-film technique on silicon substrate, to prepare one deck oxide nano particles rete, high temperature sintering adopts FePC high-temperature catalytic cracking process carbon nano-tube composite structure in mono temperature area resistance furnace above that then as growth substrates in sintering furnace; The CNT that obtains is dendroid and has oxide quantum dots to be embedded in its pipe and tube wall, said method comprising the steps of:
1) substrate pretreatment
Base material is silicon or silicon dioxide substrates, successively uses acetone, absolute ethyl alcohol and deionized water to each ultrasonic cleaning of substrate 20～30 minutes respectively, in baking oven, dries then;
2) oxide printing pulp preparation
Take by weighing 8～15 gram oxides; Particle diameter is measured 30～50 milliliters of terpinols and is poured in the clean beaker less than 1 micron, and load weighted oxide is poured in the top beaker; With the glass bar back ultrasonic concussion 5～10 minutes in ultrasonic cleaner that stirs; Add 3～4 gram ethyl celluloses then, stir and ultrasonic concussion 3～5 minutes, beaker is placed in the electric heating constant temperature heating cabinet heats with glass bar; Keep 80～100 ℃ of temperature and constantly stirring, finally process the oxide nano particles slurry;
3) substrate preparation
The oxide nano particles slurry through thick-film technique, is comprised serigraphy, gets rid of and be coated with and other coating processes moulding on silicon or silicon dioxide substrates;
4) sintering
The substrate for preparing oxide slurry is put in the sintering furnace, 540～560 ℃ of sintering temperatures are set, kept constant temperature 30～40 minutes, naturally cool to room temperature then;
5) carbon nano-tube
Oxide substrate behind the sintering as growth substrates, is adopted FePC catalystic pyrolysis carbon nano-tube sandwich in mono temperature area resistance furnace.
2. the preparation method of the composite air-sensitive membrane of carbon nano tube that is embedded with oxide quantum dots described in the claim 1 is characterized in that, oxide is the multiple metal oxide of zinc paste, tin oxide, titanium dioxide or zirconia.
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| CN101881667B (en) * | 2010-06-24 | 2015-09-09 | 电子科技大学 | A kind of uncooled microbolometer and preparation method thereof |
| CN102592840B (en) * | 2012-03-19 | 2013-11-20 | 天津师范大学 | Quantum-dot sensitized oxide/carbon nanotube composite fiber solar cell photo-anode |
| CN102953059B (en) * | 2012-08-28 | 2015-03-11 | 河北工业大学 | Manufacture method of acetone gas sensitive sensor based on titanium dioxide doped by zinc oxide |
| CN103115947B (en) * | 2013-03-05 | 2014-04-23 | 济南大学 | Preparation method and application of carbon-doped mesoporous metal oxide acetone sensor |
| CN104078367B (en) * | 2013-03-29 | 2017-10-13 | 天水天光半导体有限责任公司 | A kind of manufacture craft of flip chip package Schottky diode salient point |
| CN105924871A (en) * | 2016-06-06 | 2016-09-07 | 怀远县金浩电子科技有限公司 | Preparation method of gas-sensitive slurry for semiconductor gas-sensitive element |
| CN109060893B (en) * | 2018-07-05 | 2020-11-13 | 太原理工大学 | Humidity sensor based on carbon nanotube/zinc oxide/chitosan composite membrane |
| CN108906013B (en) * | 2018-07-23 | 2021-09-14 | 合肥工业大学 | Method for preparing titanium dioxide quantum dots through ultrasonic crushing |
| CN110779958B (en) * | 2019-10-31 | 2020-09-22 | 山东交通学院 | Ship tail gas sensing material and preparation process thereof |
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| CN1632557A (en) * | 2004-12-22 | 2005-06-29 | 浙江大学 | Multi-wall carbon nano-tube film gas sensor |
| CN101435795A (en) * | 2007-11-15 | 2009-05-20 | 中国科学院合肥物质科学研究院 | Thin film type gas-sensitive sensor of multi-layer classification nanostructure ordered hole and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1632557A (en) * | 2004-12-22 | 2005-06-29 | 浙江大学 | Multi-wall carbon nano-tube film gas sensor |
| CN101435795A (en) * | 2007-11-15 | 2009-05-20 | 中国科学院合肥物质科学研究院 | Thin film type gas-sensitive sensor of multi-layer classification nanostructure ordered hole and preparing method thereof |
Non-Patent Citations (2)
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| JP特开2010-8122A 2010.01.14 |
| 张勇 等.PECVD法制备的SnOx气敏膜的色变机理.《功能材料》.1998,第29卷(第4期),第375-377页. * |
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Effective date of registration: 20170306 Address after: 213000 Jiangsu province west of the city of Changzhou Taihu science and Technology Industrial Park orchid Road No. 8 Patentee after: Changzhou Ruifeng Technology Co., Ltd. Address before: 710049 Xianning Road, Shaanxi, China, No. 28, No. Patentee before: Xi'an Jiaotong University |