CN1788863A - Method for removing impurity of porous material - Google Patents
Method for removing impurity of porous material Download PDFInfo
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- CN1788863A CN1788863A CN 200410098756 CN200410098756A CN1788863A CN 1788863 A CN1788863 A CN 1788863A CN 200410098756 CN200410098756 CN 200410098756 CN 200410098756 A CN200410098756 A CN 200410098756A CN 1788863 A CN1788863 A CN 1788863A
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- supercritical fluid
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- aqueous vapor
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Abstract
The present invention relates to method of eliminating impurity from porous material, and is especially method of utilizing supercritical fluid to eliminate impurity from the porous material with nanometer pores. By means of utilizing the physical and chemical characteristics of supercritical fluid and adding decorating agent to the supercritical fluid, and under proper operating temperature and pressure, fluid is led to the porous material to be cleaned and made to penetrate into nanometer pores to eliminate impurity. The present invention uses no acid, alkali and solvent in the cleaning process, and has water saving, high efficiency and environment friendship.
Description
Technical field
The invention relates to a kind of method that removes impurity in the porous material, especially relevant a kind of method of utilizing supercritical fluid to remove impurity from porous material with nano aperture.
Background technology
How effectively and environmental protection reach the assembly surface cleaning, the new material purifying has become the following process requirement of each high-tech industry problem anxious to be overcome to promote product fine rate and reliability.The clean method that the past manufacturing process for cleaning uses, comprise and make apparatus Acidity of Aikalinity, strong oxidizing property solution and organic solvent etc., though quite effective and row year arranged, but the negative issue of also deriving relatively, for example a large amount of pure water and chemical reagent be must use, product and environmental pollution so not only very easily caused, in addition drying that still must be time-consuming after cleaning.Yet, when assembly has zanjon or high aspect ratio structure (high aspect ratio) or assembly for porous crack composition (porous media), traditional soda acid cleaning procedure is because the surface tension of liquid is excessive, can't be effectively and clean the thin portion structure of this class component rapidly or enter the nanoscale hole of assembly.That is can't realize comprehensive clean level, all there are the pollutant of varying degree and aqueous vapor residual no matter be at process stage or wash phase.And assembly is through traditional soda acid, the organic solvent cleaning procedure drying stage of still must arranging in pairs or groups later, in the process of drying, the surface tension of cleaning solvent is crossed conference and is caused assembly pattern collapse (pattern collapse), destruction assembly original structure to cause deterioration in characteristics.In addition, required drying time is longer relatively, and drying effect is also undesirable, and the collocation that has a strong impact on successive process is connected, so conventional liquid solvent clean mode can't meet the demand of effectively cleaning that will have labyrinth or porous novel materials future.
The physical property of supercritical fluid is between gas, liquid.Supercritical fluid with the low-viscosity as gas (during conveying the power of palpus be low then) than liquid, (diffusion coefficient is higher than 10 to 100 times of liquid to high diffusion coefficient, that is mass transfer resistance is little far beyond liquid, on quality is transmitted than liquid for fast), low surface tension (penetrating in the porous tissue easily), (can carry just like the high density as the liquid than the more supercritical fluid of gas; Can increase the dead time of fluid in reactor, so can use the operation of continous way).Except that physical property, the chemical property of supercritical fluid also with its at gas, different when liquid, for example carbon dioxide is not had an extracting power under gaseous state, but after entering supercriticality, carbon dioxide changes close organic property into, thereby having the ability of dissolved organic matter, this solvability changes with temperature and pressure adjustment.Supercritical fluid after the use only need reduce pressure promptly can return gas phase, and with other solid, liquid separating substances mutually, therefore easily reclaim and re-use, this is one of advantage of supercritical fluid.In numerous fluids again with the application of carbon dioxide most popular with pay attention to, because of its critical condition gentleness, critical point easily reach, 31.2 ℃ of critical-temperatures are near room temperature, the about 72.8atm of critical pressure.Do not have simultaneously toxicity, a flammability of not having, stable in properties, the source can by reclaim in the fossil fuel combustion by-products and price not high, for the related application of high-tech industry, will have its advantages for development and potentiality.
Known utilize supercritical fluid carry out the porous low dielectric constant films (low dielectric constantfilm, lowk) in the relevant patent that removes of impurity have 3.US6306754 utilizes impurity and the photoresistance residue in the hole of the etched back of supercritical fluid cleaning porous low dielectric constant films, supercritical fluid is ethene or carbon dioxide and adds alcohol, ketone or its mixture and be used as dressing agent that operating pressure is that 70～200atm, operating temperature are 35～100 ℃.US6669785 utilizes supercritical fluid to clean the oxide (oxide) that removes the porous advanced low-k materials, photoresistance or etch residue and environmental contaminants; Supercritical fluid is CO
2, comprising first washing fluid and second washing fluid, operational densities is 0.150g/cc～1.1g/cc, and operating temperature is 0～80 ℃, and the cosolvent kind is amine (morpholine (morpholine), aniline (aniline) or dibutyl amine (dibutylamine) or C
1～C
4Alcohol, adding proportion are 0.1～40%w/w; 0.1～5%w/w interfacial agent.US2004018452 utilizes the back residue of supercritical fluid interpolation passivator (passivating agent) cleaning porous dielectric material surface etching to lower material degradation, and supercritical fluid is CO
2, passivator is acid or fluoride.After analyzing above-mentioned patented technology content, find that the type of fluid of utilizing supercritical fluid to clean the porous low dielectric constant material film at present mainly still is carbon dioxide, but all need follow the dressing agent that adds heterogeneity, ratio to reach the purpose that pollutant removes.The pollutant kind that is removed great majority are organic substances such as photoresistance, photoresistance residue, etch residue, still do not have patent at present and deliver specific aqueous vapor and remove or utilize simultaneously with a kind of dressing agent and clean and the surface characteristic upgrading at impurity such as aqueous vapor, organic pollution in the processing procedure.Yet, for the porous low dielectric constant material film, through very easily causing after the etching thin-film material deterioration, aqueous vapor absorption residual porosity to cause dielectric constant values to rise, so aqueous vapor can not be ignored with the common problem that exists of organic pollution and suddenly to be solved.Reach assembly surface activation and upgrading if can't remove organic pollution and aqueous vapor simultaneously, so for the cleaning of porous material and processing procedure integration and development application potential with limited.
Up to now, still acomia having now utilizes supercritical fluid to remove the Prior Art of impurity in the CNT.
Summary of the invention
Main purpose of the present invention is for providing a kind of method of utilizing supercritical fluid to remove the impurity that comprises aqueous vapor from the porous material with nano aperture.
Another object of the present invention is for providing a kind of method of utilizing supercritical fluid to remove impurity from CNT.
For realizing the invention described above purpose, the present invention utilizes supercritical CO
2With the interpolation of certain proportion, kind dressing agent, the cleaning of carrying out aqueous vapor, organic pollution in the porous material under suitable temperature, pressure operation condition removes.Supercritical CO
2Low surface tension, high diffusibility and good solvent compatibility make it become the quite good fluid (carrier) that carries, enter the nanoscale hole of porous material after the dressing agent that additionally adds evenly can being disperseed, under the prerequisite of not destroying original characteristic of material and structure, further impurity such as aqueous vapor and organic pollution are taken out of in hole, supercritical fluid through separate be depressed into normal pressure after, impurity can separate with fluid with dressing agent, and problems such as noresidue produce.The waste liquid of cleaning produces the advantage of present technique in order almost to have after cleaning, water-saving is economized and can, be subtracted that useless, required scavenging period is short, efficient is high, non-secondary pollution, also is one of environment friendliness processing method.The present invention also assesses and verifies that the porous material after finding to clean more can show its characteristic at the assembly surface characteristic after cleaning.
Embodiment
The invention provides a kind of method that removes the impurity that comprises aqueous vapor from porous material with nano aperture, comprise a supercritical fluid is contacted with a porous material, wherein this porous material has nano aperture or canal, and be positioned at the impurity that comprises aqueous vapor of this nano aperture or canal, go out for this supercritical fluid is entrained so be positioned at the impurity that comprises aqueous vapor of this nano aperture or canal, and separate with this porous material.
Preferable, this supercritical fluid comprises the dressing agent that an inert gas and is selected from alcohol or ketone.Better, this inert gas is a carbon dioxide.Better, this dressing agent comprises methyl alcohol, ethanol, propyl alcohol, butanols, acetone or their mixing.
Preferable, this contact is to carry out in a treatment trough, and this supercritical fluid is by continuous this treatment trough of flowing through.Better, the inventive method further comprises and stops to flow of this supercritical fluid, makes this supercritical fluid be transformed into gas by step-down, and shift out this porous material in this treatment trough.
Preferable, this porous material comprises CNT.
Preferable, this supercritical fluid has one between 40 to 80 ℃ temperature, the pressure between 1000psi to 5000psi, and a dressing agent between 0.5 to 15 volume %, is benchmark with the volume of this supercritical fluid.
Preferable, this contact continues 1 minute to 60 minutes.
Below, a preferred embodiment of the present invention will be described with reference to the flow chart of figure 1.
Liquid carbon dioxide is delivered to through thermostatically controlled test piece treatment trough with a firm discharge after the pressurization of heating reaches the setting supercritical fluid, before supercritical carbon dioxide fluid enters this treatment trough dressing agent is added into supercritical carbon dioxide fluid with certain volume than (firm discharge).The adorned supercritical carbon dioxide fluid that is produced is continuous is imported into this test piece treatment trough, arrive a predetermined pressure after, discharge the useless stream of same traffic from this test piece treatment trough.After a period of time, stop the discharge of the influent stream and the useless stream of adorned supercritical carbon dioxide fluid.The test piece treatment trough takes out test piece and finishes the cleaning action behind cooling, decompress(ion).Test piece after the cleaning is carried out correlation Analysis and checking work.
The present invention will further be understood by the following example, and these embodiment but not are used to limit the scope of the invention as illustrative purposes only.
Description of drawings
Fig. 1 is the schematic flow sheet of preferred embodiment of the present invention.
Fig. 2 shows the electrical performance of two utmost point CNT field emission devices of supercritical CO 2 processing preceding (Diamond spot)/back (square dot), and wherein the x axle is the operation electric field, and the y axle is the current density (J) of CNT field emission device.
The specific embodiment
Embodiment 1
In the present embodiment take two utmost point CNT (CNT) field emission devices as cleaning object. On a glass substrate Form earlier silver electrode, on silver electrode, be coated with again a slurry that contains CNT, through high temperature (400～500 ℃) behind the sintering, be made into two utmost point CNT field emission devices. The employed CNT of present embodiment is by Taiwan Worker Yan Yuan electron institute provides. Two utmost point CNT field emission devices that just prepared are first through soaked processing, carry out again water The experiment that gas removes.
Do not need in the processing procedure of two utmost point CNT field emission devices soaked, but in processing procedure the process of patterning will connect Touch wet type solvent (solution such as acid, alkali), also will import the pollutions such as acid, alkali, aqueous vapor this moment, cause group The electrical defective of part. The soaked purpose of this experiment only for simple analog two utmost point CNT field emission devices behind wet process Whether the phenomenon of its electrical defective can be activated improvement by the supercritical fluid cleaning mode. The soaked time is More than one day, until the electrical reflex action reduction of assembly or complete obiteration. Test piece after soaked directly is put into again Oven oven dry about 103 ℃ 10～20 minutes.
Carry out cleaning experiment, experiment condition according to method shown in Figure 1: the pressure 3000psi in the test piece treatment trough, Temperature is 50 ℃. Supercritical carbon dioxide adds 7 volume % normal propyl alcohols as dressing agent. Scavenging period is 5 Minute.
The electrical performance that supercritical CO 2 is processed two front/rear utmost point CNT field emission devices is shown in Fig. 2. Fig. 2 Middle x axle is the operation electric field, and the y axle is the current density of CNT field emission device. The operation electric field will more little more power saving, The curve of current density will the more precipitous control that more is conducive to assembly. The result of Fig. 2 show after cleaning two The field emission effciency of utmost point CNT field emission device obviously increases.
This case inventor also once carries out the experiment of similar embodiment 1, but the volume % that changes normal propyl alcohol be 3% and 5%, experimental result finds to have the cleaning performance that is same as embodiment 1.
The present invention is described in, and person skilled in the art scholar still can make and not break away from the following model of applying for a patent Multiple variation and the modification of enclosing.
Claims (9)
1. method that removes the impurity that comprises aqueous vapor from porous material with nano aperture, comprise a supercritical fluid is contacted with a porous material, wherein this porous material has nano aperture or canal, and be positioned at the impurity that comprises aqueous vapor of this nano aperture or canal, go out for this supercritical fluid is entrained so be positioned at the impurity that comprises aqueous vapor of this nano aperture or canal, and separate with this porous material.
2. the method for claim 1, wherein this supercritical fluid comprises the dressing agent that an inert gas and is selected from alcohol or ketone.
3. the method for claim 1, wherein this contact is to carry out in a treatment trough, and this supercritical fluid is by continuous this treatment trough of flowing through.
4. method as claimed in claim 3, it further comprises and stops to flow of this supercritical fluid, makes this supercritical fluid be transformed into gas by step-down, and shift out this porous material in this treatment trough.
5. the method for claim 1, wherein this porous material comprises CNT.
6. method as claimed in claim 2, wherein this inert gas is a carbon dioxide.
7. method as claimed in claim 2, wherein this dressing agent comprises methyl alcohol, ethanol, propyl alcohol, butanols, acetone or their mixing.
8. the method for claim 1, wherein this supercritical fluid has one between 40 to 80 ℃ temperature, the pressure between 1000psi to 5000psi, and a dressing agent between 0.5 to 15 volume %, is benchmark with the volume of this supercritical fluid.
9. the method for claim 1 wherein should contact continue 1 minute to 60 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410098756 CN1788863A (en) | 2004-12-15 | 2004-12-15 | Method for removing impurity of porous material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410098756 CN1788863A (en) | 2004-12-15 | 2004-12-15 | Method for removing impurity of porous material |
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| Publication Number | Publication Date |
|---|---|
| CN1788863A true CN1788863A (en) | 2006-06-21 |
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|---|---|---|---|
| CN 200410098756 Pending CN1788863A (en) | 2004-12-15 | 2004-12-15 | Method for removing impurity of porous material |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105321805A (en) * | 2015-08-13 | 2016-02-10 | 安徽亿能机械有限公司 | High-pressure hole flushing device |
| CN109175355A (en) * | 2018-08-17 | 2019-01-11 | 宁波瑞丰汽车零部件有限公司 | A kind of iron-based connection pressing plate |
| CN115385335A (en) * | 2022-08-23 | 2022-11-25 | 浙江浙能技术研究院有限公司 | Supercritical cleaning method for deeply purifying super-capacitive porous carbon material |
-
2004
- 2004-12-15 CN CN 200410098756 patent/CN1788863A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105321805A (en) * | 2015-08-13 | 2016-02-10 | 安徽亿能机械有限公司 | High-pressure hole flushing device |
| CN109175355A (en) * | 2018-08-17 | 2019-01-11 | 宁波瑞丰汽车零部件有限公司 | A kind of iron-based connection pressing plate |
| CN109175355B (en) * | 2018-08-17 | 2020-10-27 | 宁波瑞丰汽车零部件有限公司 | Iron-based connecting pressing plate |
| CN115385335A (en) * | 2022-08-23 | 2022-11-25 | 浙江浙能技术研究院有限公司 | Supercritical cleaning method for deeply purifying super-capacitive porous carbon material |
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