CN102380358A - Metal porous material, preparation method thereof and nitrogenous compound detection method - Google Patents
Metal porous material, preparation method thereof and nitrogenous compound detection method Download PDFInfo
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- CN102380358A CN102380358A CN2010102741024A CN201010274102A CN102380358A CN 102380358 A CN102380358 A CN 102380358A CN 2010102741024 A CN2010102741024 A CN 2010102741024A CN 201010274102 A CN201010274102 A CN 201010274102A CN 102380358 A CN102380358 A CN 102380358A
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Abstract
The invention relates to a metal porous material, a preparation method thereof and a nitrogenous compound detection method. The invention provides the preparation method of the metal porous material, which comprises the steps of: mixing siloxane, metal or metallic compound and water, and obtaining the mixture after stirring; adjusting the pH value of the mixture to be smaller than 7; after adjusting the pH, drying the mixture for the first time, and obtaining solid; and grinding the solid, drying for the second time, obtaining the metal porous material, wherein the preparation method of the metal porous material dose not use any annealing manufacturing technology.
Description
Technical field
The present invention relates to metal polyporous material, particularly a kind of metal polyporous material that can be used as the sensing element of detector.
Background technology
Along with science and technology is constantly progressive, many novel key technologies become the development priority of high-tech industry, and wherein the little contamination monitoring technology of high-tech factory building has been classified as one of key technology of Mirae Corp.'s competition.
(the International Technology Roadmap for Semiconductors of the ITRS committee; ITRS) estimate to wafer key size (critical dimension in 2013; CD) will be contracted to 32 nanometers (nm), little pollution is controlled to be one of its key technology.Semiconductor fabrication process with 32nm is an example, the manufacturing process key area in dust free room, and little pollution sensibility district advises maintaining in the scope below the 10-150ppt for the air quality recommended value of acid, alkali, organic class, admixture (dopants) class respectively.Therefore, desire confirms whether dustless indoor air quality meets the requirement on the semiconductor fabrication process, and what need is the gas monitor of extremely low concentration.
Ammonia concentration is carried out the monitoring and the control of part per billion (ppb) grade, is a very important problem for wafer factory.In little shadow technology (lithography) manufacturing process; As long as the ammonia concentration of manufacturing process environment reaches the spectrochemical property that 1/10000000000th (sub-ppb) grade will change photoresistance; And then cause photoresistance to produce T type top (t-topping) phenomenon, as shown in Figure 1.In addition, ammonia is a kind of gas with light reaction characteristic, can be at the eyeglass (lens) of yellow light area surface and sulfide (SO for example
2) reaction generation (NH
4)
2SO
2And the atomizing minute surface causes the infringement of board even causes equipment to be stopped work.
Ammonia the pollution of semiconductor factory generate the source has CVD, chip cleaning (wafer cleaning) and even, photoresistance coating, the CMP operating personnel gas of breathing out all contains ammonia.Though in dust free room with in the board inside, all have the air air return system to be equipped with various filter in order to guarantee the cleanliness factor of air; Yet, can't learn whether the inner air of board meets job requirements to reach the lifting of yield if there is not the gas monitoring system of suitable sensitivity to cooperate with it so that the little dusty gas change in concentration in operation and the manufacturing process environment in time to be provided.In the past under the consideration of technology,, upkeep operation personnel's health and environment safety often is merely 1,000,000/(ppm) grades to ten million/one (sub-ppm) grade for developing the ammonia monitor sensitivity that.
For semiconductor factory; Detectable limit only can't satisfy the requirement to fabrication process monitoring to the ammonia sensing device of ppm grade; Therefore in order to reach the requirement of the ammonia concentration that can measure the ppb grade, the mode that at semiconductor factory low concentration ammonia is detected has at present adopted the ion chromatography (Impinger+ion chromatography:IC) that comprises that Ion mobility spectrometry (Ion Mobility Spectroscopy:IMS), chemoluminescence method (Chemiluminescence:CI), cavity ring-down spectroscopy (Cavity Ring-Down Spectroscopy:CRDS) and traditional sampling are analyzed.Yet these analytical methods are not the instrument and equipments that needs high unit price, have tediously long analysis time exactly, and then cause high-tech factory often to face the threat of yield loss.
What therefore, need is a kind of new material and technology of measuring ammonia.
Summary of the invention
The present invention provides a kind of preparation method of metal polyporous material, and it comprises: hybrid silicone, metal or metallic compound and water obtain mixture after the stirring; Regulate this mixture so that it has the pH value less than 7; After regulating pH, this mixture is carried out first dried to obtain solid; And, grind this solid, after carrying out second dried, obtain said metal polyporous material, it should be noted that the preparation method of said metal polyporous material does not use any calcination manufacturing process.The present invention provides a kind of metal polyporous material that is made by said method.
The present invention also provides a kind of detection method of nitrogen-containing compound, and it comprises: aforesaid metal polyporous material is provided; Import the reaction of gas to be measured and this metal polyporous material; And analytical reactions result.
For letting above-mentioned and other purposes of the present invention, characteristic and the advantage can be more obviously understandable, the hereinafter spy enumerates preferred embodiment, and is described with reference to the accompanying drawings as follows:
Description of drawings
Fig. 1 is the image of photoresistance because of the T type top phenomenon that ammonia caused of environment.
Fig. 2 is the preparation flow figure of the described metal polyporous material of one embodiment of the present of invention.
Fig. 3 contains the detector means figure of the gas of nitrogen molecular for embodiments of the invention 9 described measurements.
Fig. 4 is embodiments of the invention 9 described absorption test results with the metal polyporous material absorbing ammonia.
Fig. 5 is the images of embodiments of the invention 9 described metal polyporous materials before absorbing ammonia.
Fig. 6 is the images of embodiments of the invention 9 described metal polyporous materials behind absorbing ammonia.
Fig. 7 has shown at different N H
3Under the concentration (ppb), metal polyporous material absorbs the absorption intensity discrepancy delta A before and after the ammonia.
Fig. 8 has shown the repeated experiment result of embodiments of the invention 15 described metal polyporous materials.
The main element symbol description
11-16: step;
101: gas to be measured;
102: carrier gas;
103,104: mass flow controller;
105: valve;
106: the test cavity;
107: metal polyporous material;
108: the ultraviolet-visible light spectroscopic system; And
109: discharge gas.
The specific embodiment
The invention provides a kind of metal polyporous material, it has the colour generation sensed characteristic to nitrogen-containing compound.Said metal polyporous material because its preparation method, can make metal or metallic compound stably be present among the silicon porous material, thereby provides enough spaces to increase itself and object gas (NH for example
3) chance that combines, and then improve detectable limit.The principle that this metal polyporous material has a colour generation sensed characteristic to nitrogen-containing compound be metallic compound and nitrogen-containing compound combine can produce specific change color.The present invention also provides a kind of detection method of nitrogen-containing compound; Ultraviolet-visible light spectrum capable of using quantizes the optical absorption intensity of metal polyporous material; And then set up the linear relationship between nitrogen-containing compound concentration and the optical absorption intensity variation, finally reach the purpose of measuring nitrogen-containing compound concentration.
In one embodiment of the invention; Metal polyporous material of the present invention is made by following steps; Referring to metal polyporous material preparation flow figure shown in Figure 2: at first, (step 11) obtains mixture (step 12) after the stirring for hybrid silicone, metal or metallic compound and water.Then, regulate this mixture so that it has the pH value (step 13) less than 7.After regulating pH, leave standstill this mixture a period of time (for example 24 hours), and this mixture is carried out first dried (for example at room temperature carrying out), thereby obtain solid (step 14).Then; (carry out second dried (for example under 60 ℃, carrying out) after the step 15) at this solid of grinding; Thereby obtain said metal polyporous material; Wherein, dried of the present invention (comprising first and second dried) refers in room temperature or is not higher than that (relative humidity is preferably less than RH=50%) carries out air dry under 60 ℃ the temperature, and the preparation method of said metal polyporous material does not use any calcination manufacturing process.The whole manufacturing process temperature of this metal polyporous material is not higher than 60 ℃.
The proportion of composing of metal polyporous material of the present invention (atom %) is: the metallic atom (for example iron, copper, vanadium, manganese, chromium etc.) that comes from employed metal or metallic compound accounts for 1-10%; The silicon atom that comes from siloxanes accounts for 20-40%; Oxygen atom accounts for 50-70%.It should be noted that metal polyporous material of the present invention owing to do not carry out calcination,, be different from general burning material (decomposition temperature＞300 ℃) through calcining so its decomposition temperature is 150-250 ℃.
The chemical formula of siloxanes as herein described is Si (OR)
4, R is the alkyl that contains 1-8 carbon atom, can for example be titanium tetraisopropylate (titanium (IV) isopropoxide; TTIP), 3-aminopropyl triethoxysilane (3-aminopropyltriethoxysilane; APTES), tetramethoxy-silicane (TMOS), tetraethoxysilane (TEOS) or aforesaid combination.Said metal is iron, copper, vanadium, manganese, chromium, cobalt; Or its combination; In addition, said metallic compound is halide, sulfide, nitrate, nitronic acid salt, the sulfate of iron, copper, vanadium, manganese, chromium or cobalt, or its combination; Be ferric nitrate, cobalt nitrate, chromic nitrate for example, or have the aforesaid compound of the crystallization water.The silicon that metal polyporous material is contained and the weight ratio of metal are 0.95: 0.05 to 0.05: 0.95.If the ratio of metal greater than 0.95, then is prone to form bigger particle, reduce the activity site surface area, cause reactivity to descend.If the ratio of metal less than 0.05, then possibly reduce reaction rate because of activated positions is not enough.
In the process of regulating the pH value, can use acidic materials to regulate the pH value of mixture.In one embodiment of the invention, said acidic materials can be hydrochloric acid, sulfuric acid, nitronic acid, nitric acid or aforesaid combination.For example, when the metal that adds or metallic compound comprise cobalt, preferably use hydrochloric acid to regulate the pH value of mixture.In some embodiments of the invention, the pH value of said mixture can be 7.0-1.0, is preferably 5.0-2.0, to promote the friendly environment that metal combines with alkaline molecules of ammonia.
According to another embodiment of the present invention, the present invention also provides a kind of detection method of utilizing above-mentioned metal polyporous material to nitrogen-containing compound, and it comprises: metal polyporous material of the present invention is provided, and imports gas to be measured and the reaction of this metal polyporous material.At last, analytical reactions result.Detectable nitrogen-containing compound is for example ammonia (NH
3).Than the method for traditional detection ammonia, metal polyporous material of the present invention has high sensitivity for ammonia.Therefore, it also can be used as the sensing element of the detector that contains nitrogen molecular, and the detection lower limit of this sensing element can reach 100ppt.
In one embodiment of the invention, this sensing element also can be connected with ultraviolet-visible light spectrum (ultraviolet-visible spectroscopy) system as the detector that contains nitrogen molecular.Method of testing can comprise: whether gas to be measured and carrier gas (carrier flow) respectively via mixing behind the different mass flow controllers, and are sent in the test cavity with metal polyporous material by valve control.Send the air-flow in the test cavity to, need guarantee to discharge again after it runs through the metal polyporous material powder.Because this metal polyporous material can change himself color after absorbing nitrogen-containing compound, so after combining the ultraviolet-visible light spectroscopic system, can measure the optical absorption intensity of this metal polyporous material in particular range of wavelengths immediately.It should be noted that; Because measured this metal polyporous material of ultraviolet-visible light spectroscopic system is directly proportional in the concentration of the adsorbed nitrogen-containing compound of the absorption intensity of particular range of wavelengths and this metal polyporous material; Therefore can obtain the concentration of the nitrogen-containing compound of gas to be measured via the variation of the optical absorption intensity of metal polyporous material.
Below explain that through the following example synthesis mode and the character thereof of metal polyporous material of the present invention measure, in order to further to illustrate technical characterictic of the present invention.
Embodiment 1
At first, get Co (NO
3)
26H
2O (0.4g) and TEOS (8ml) are mixed in 4ml water (H
2O) in, and fully stir.Then, add in the said mixture 2M HCl (2ml) and fully stirring, the pH value that makes gained solution is less than 7.Above-mentioned solution is at room temperature left standstill carried out drying in 24 hours after, the solid of gained is ground.At last, the powder that grinds gained is placed 60 ℃ of following dryings 6 hours, obtain having the silicon porous material 1 of cobalt metal.
Use EDX (energy dispersion x-ray spectrometer, energy disperse X-ray) that the silicon porous material with cobalt metal 1 of gained is carried out the surface-element analysis, the weight ratio that obtains cobalt and silicon is 12: 88.
At first, get Co (NO
3)
26H
2O (0.4g) and TEOS (8ml) are mixed in 4ml water (H
2O) in, and fully stir.Then, add in the said mixture 0.1M HCl (0.12ml) and fully stirring, the pH value that makes gained solution is less than 7.Above-mentioned solution is at room temperature left standstill carried out drying in 24 hours after, the solid of gained is ground.At last, the powder that grinds gained is placed 60 ℃ of following dryings 6 hours, obtain having the silicon porous material 2 of cobalt metal.
Embodiment 3
At first, get Co (NO
3)
26H
2O (0.8g) and TEOS (8ml) are mixed in 4ml water (H
2O) in, and fully stir.Then, add in the said mixture 0.1M HCl (0.12ml) and fully stirring, the pH value that makes gained solution is less than 7.Above-mentioned solution is at room temperature left standstill carried out drying in 24 hours after, the solid of gained is ground.At last, the powder that grinds gained is placed 60 ℃ of following dryings 6 hours, obtain having the silicon porous material 3 of cobalt metal.
Embodiment 4-8
Embodiment 4-8 carries out like the same way as of embodiment 1 respectively, but replaces Co (NO with different metallic oxide precursor thing
3)
26H
2O.The metallic compound that embodiment 4-8 uses respectively is as shown in table 1.
Table 1
| The embodiment numbering | The metallic oxide precursor thing |
| 4 | Fe(NO 3) 3·9H 2O |
| 5 | Cu(NO 3) 2·6H 2O |
| 6 | ?VOSO 4·xH 2O(x＞1) |
| 7 | Mn(NO 3) 2·4H 2O |
| 8 | Cr(NO 3) 2·9H 2O |
Embodiment 9
Embodiment 1 resulting silicon porous material 1 with cobalt metal is placed the test cavity 106 of device as shown in Figure 3, to measure it to NH
3Adsorption capacity, metering system is following: utilize mass flowmenter 103 and 104 to control gas (NH to be measured respectively
3) 101 and the flow of carrier gas (nitrogen) 102, fully mix the back and (mix back NH
3Concentration is 500ppb); Control through valve 105 and to send the test cavity 106 with metal polyporous material 107 to and adsorb, air-flow is got into by the cavity top, runs through metal polyporous material 107 backs and discharges gas 109 by cavity 106 belows; One group of data of measurement in per 2.5 minutes during the permeate gas stream; Utilize ultraviolet-visible light spectroscopic system record powder surface ultraviolet-visible optical absorption characteristics collection of illustrative plates (temperature is that 21.3 ℃, humidity are 44.1%), and write down 100 times, the absorption intensity result of variations is shown in Fig. 4.At 500ppb NH
3Under the test condition that gas runs through with the flow velocity of per minute 1700cc, powder surface becomes bluish violet (Fig. 6) by pink (Fig. 5).Please with reference to Fig. 4, between wavelength 600-700nm, it is big that absorption intensity becomes along with the increase that feeds the ammonia amount gradually.This result confirms that said metal polyporous material can be used as NH really
3The colour generation sensing material, it combines the instant measurement of ultraviolet-visible light spectroscopic system to can be used as NH
3Gas monitor.
Embodiment 10-11
Embodiment 10-11 carries out like the same way as of embodiment 9 respectively, but replaces the metal polyporous material of embodiment 1 gained with the metal polyporous material of embodiment 2 and 3 gained respectively.The described metal polyporous material of embodiment 9-11 is as shown in table 2 in the absorption intensity difference results at 640nm place before and after the absorption ammonia.
Table 2
Embodiment 12-14
Embodiment 12-14 carries out like the same way as of embodiment 9 respectively, but respectively with 60ppbNH
3, 115ppb NH
3With 230ppb NH
3Replace embodiment 9 employed 500ppb NH
3Concentration.The described metal polyporous material of embodiment 12-14 is as shown in table 3 in the absorption intensity difference results at 640nm place before and after the absorption ammonia.
Table 3
Then, the result's mapping with table 3 gained shows at different N H
3Under the concentration (ppb), metal polyporous material is absorbing the absorption intensity discrepancy delta A of ammonia front and back at the 640nm place, and is as shown in Figure 7.Can know that by Fig. 7 absorption intensity discrepancy delta A is directly proportional with ammonia concentration, and the ammonia concentration and the absorption intensity that feed present good linear relationship.Hence one can see that, and metal polyporous material of the present invention not only can carry out qualitative analysis to ammonia, when being connected with the ultraviolet-visible light spectrometer system as if it, and the ammonia quantitative analysis that also can measure immediately.
Embodiment 1 resulting silicon porous material 1 (metal polyporous material) with cobalt metal is placed the test cavity, utilize the ultraviolet-visible light spectrometer system to measure not absorption of N H of this metal polyporous material
3Uv-visible absorption spectroscopy before.Then, will contain NH
3Gas (concentration is 46ppm, 50sccm); Sending the test cavity with metal polyporous material to adsorbs; Air-flow is got into by the cavity top; Discharge by the cavity below after running through metal polyporous material, after continuing to carry out 60 minutes, utilize the ultraviolet-visible light spectrometer system to measure the absorption spectrum of this metal polyporous material.Then, contain NH stopping to send into
3Gas get into cavity after 30 minutes, utilize the ultraviolet-visible light spectrometer system to measure the absorption spectrum of this metal polyporous material.Then, contain NH stopping to send into
3Gas get into cavity after 24 hours, utilize the ultraviolet-visible light spectrometer system to measure the absorption spectrum of this metal polyporous material.At last, feeding contains NH once more
3Gas (concentration is 46ppm, 50sccm), and continue two hours, utilize the ultraviolet-visible light spectrometer system to measure the absorption spectrum of this metal polyporous material again, the result of above-mentioned measurement is as shown in Figure 8.Can know that by Fig. 8 metal polyporous material of the present invention has reusable property, is suitable for very much the detection to ammonia.
In sum; Since in the metallic compound on the metal polyporous material of the present invention the metal center atom of positively charged can with nitrogen-containing compound in have lone pair electrons right amido combine the formation metal complex; Thereby cause the change of absorption intensity, therefore ultraviolet-visible spectrometer capable of using carries out qualitative and quantitative analysis.In addition, metal polyporous material of the present invention has high sensitivity, high selectivity, repeatable and low detectable limit, therefore can further be used on the detection method and device of nitrogen-containing compound, is suitable for very much monitoring low concentration ammonia.Table 4 is the detection method of nitrogen-containing compound of the present invention and the comparison of the ion chromatography that Ion mobility spectrometry of the prior art, chemoluminescence method, cavity ring-down spectroscopy and traditional sampling are analyzed.
Table 4
Though the present invention with several preferred embodiments openly as above; But said embodiment is not in order to limit the present invention; Any those skilled in the art are not breaking away from the spirit and scope of the present invention, can make changing arbitrarily and retouching, so protection scope of the present invention are as the criterion with claims.
Claims (12)
1. the preparation method of a metal polyporous material, it comprises:
Hybrid silicone, metal or metallic compound and water obtain mixture after the stirring;
Regulate this mixture so that it has the pH value less than 7;
After regulating pH, this mixture is carried out first dried to obtain solid; And,
Grind this solid, after carrying out second dried, obtain said metal polyporous material, the preparation method of wherein said metal polyporous material does not use any calcination manufacturing process.
2. the preparation method of metal polyporous material according to claim 1, the chemical formula of wherein said siloxanes is Si (OR)
4, R is the alkyl that contains 1-8 carbon atom.
3. the preparation method of metal polyporous material according to claim 1, wherein said siloxanes is titanium tetraisopropylate, 3-aminopropyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, or its combination.
4. the preparation method of metal polyporous material according to claim 1, wherein said metal is iron, copper, vanadium, manganese, chromium, cobalt, or its combination.
5. the preparation method of metal polyporous material according to claim 1, wherein said metallic compound is halide, sulfide, nitrate, nitronic acid salt, the sulfate of iron, copper, vanadium, manganese, chromium or cobalt, or its combination.
6. the preparation method of metal polyporous material according to claim 1, the silicon that wherein said metal polyporous material is contained and the weight ratio of metal are 0.95: 0.05 to 0.05: 0.95.
7. the preparation method of metal polyporous material according to claim 1, the temperature of wherein said first dried and second dried is not more than 60 ℃.
8. the detection method of a nitrogen-containing compound, it comprises:
Metal polyporous material as claimed in claim 1 is provided;
Import the reaction of gas to be measured and this metal polyporous material; And analytical reactions result.
9. the detection method of nitrogen-containing compound according to claim 8, wherein said nitrogen-containing compound comprises ammonia.
10. the detection method of nitrogen-containing compound according to claim 8, it further comprises said metal polyporous material is connected with the ultraviolet-visible light spectroscopic system, with the optical absorption intensity of this metal polyporous material of instant measurement in particular range of wavelengths.
11. the detection method of nitrogen-containing compound according to claim 10, wherein said particular range of wavelengths are 300-900nm.
12. a metal polyporous material, it is made up of following atom:
Metallic atom, this metallic atom are iron, copper, vanadium, manganese, chromium, cobalt or its combination, and the atom number ratio of wherein said metallic atom is the 1-10% of this metal polyporous material;
Silicon atom, the atom number ratio of this silicon atom are the 20-40% of this metal polyporous material;
Oxygen atom, the atom number ratio of this oxygen atom are the 50-70% of this metal polyporous material;
Wherein said metal polyporous material without any calcination manufacturing process, and has 150-250 ℃ decomposition temperature in manufacture process.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772833A (en) * | 2005-10-25 | 2006-05-17 | 上海师范大学 | Infrared absorbing material and its prepn |
| US20090301878A1 (en) * | 2008-06-05 | 2009-12-10 | Da Yu Wang | Ammonia sensor element, method of making thereof, and ammonia sensor derived therefrom |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772833A (en) * | 2005-10-25 | 2006-05-17 | 上海师范大学 | Infrared absorbing material and its prepn |
| US20090301878A1 (en) * | 2008-06-05 | 2009-12-10 | Da Yu Wang | Ammonia sensor element, method of making thereof, and ammonia sensor derived therefrom |
Non-Patent Citations (2)
| Title |
|---|
| A.M. BUCKLEY ET AL: "The preparation and characterisation of silica aerogels and xerogels doped with transition metal species", 《JOURNAL OF NON-CRYSTALLINE SOLIDS》 * |
| 陈令允等: "强磁性纳米Fe3O4/SiO2复合粒子的制备及其性能研究", 《材料科学与工程学报》 * |
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