CN102380358B - 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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- CN102380358B CN102380358B CN201010274102.4A CN201010274102A CN102380358B CN 102380358 B CN102380358 B CN 102380358B CN 201010274102 A CN201010274102 A CN 201010274102A CN 102380358 B CN102380358 B CN 102380358B
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- containing compound
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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 of the sensing element that can be used as 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 micro-contamination monitoring technology of high-tech factory building has been listed in 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), one of micro-pollution control is its key technology.Taking the semiconductor fabrication process of 32nm as example, manufacturing process key area in dust free room, micro-pollution sensibility district advises maintaining in the scope below 10-150ppt for the air quality recommended value of acid, alkali, organic, admixture (dopants) class respectively.Therefore, wish confirms whether dustless indoor air quality meets the requirement on semiconductor fabrication process, and what need is the gas monitor of extremely low concentration.
Ammonia concentration being carried out to monitoring and the control of part per billion (ppb) grade, is a very important problem for wafer factory.In micro-shadow technology (lithography) manufacturing process, as long as reaching 1/10000000000th (sub-ppb) grade, the ammonia concentration of manufacturing process environment will change the spectrochemical property of photoresistance, and then cause photoresistance to produce T-shaped top (t-topping) phenomenon, as shown in Figure 1.In addition, ammonia is a kind of gas with light reaction characteristic, can for example, on eyeglass (lens) surface and sulfide (SO of yellow light area
2) reaction generation (NH
4)
2sO
2and atomization minute surface causes the infringement of board even to cause equipment to be stopped work.
Ammonia the pollution the generating resource of semiconductor factory have CVD, chip cleaning (wafer cleaning) and even, light blockage coating, the CMP operating personnel gas of breathing out all contains ammonia.Although all have air air return system to be equipped with various filter in order to guarantee the cleanliness factor of air in dust free room with board inside, if but the gas monitoring system that there is no suitable sensitivity coordinates with it to provide in time the micro-dusty gas change in concentration in operation and manufacturing process environment, cannot learn whether the air of board inside meets job requirements to reach the lifting of yield.Under the consideration of technique, the ammonia monitor sensitivity developing for upkeep operation personnel's health and environment safety was only often 1,000,000/(ppm) extremely ten million/mono-(sub-ppm) grade of grade in the past.
For semiconductor factory, detectable limit only cannot meet 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 ppb grade, the mode at semiconductor factory, low concentration ammonia being detected has at present adopted and has comprised Ion mobility spectrometry (Ion Mobility Spectroscopy:IMS), chemoluminescence method (Chemiluminescence:CI), the ion chromatography (Impinger+ion chromatography:IC) that cavity ring-down spectroscopy (Cavity Ring-Down Spectroscopy:CRDS) and traditional sampling are analyzed.But these analytical methods are not the instrument and equipments that needs high unit price, have exactly tediously long analysis time, 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 preparation method who the invention provides a kind of metal polyporous material, it comprises: hybrid silicone, metal or metallic compound and water, obtain mixture after stirring; Regulate this mixture to make it have the pH value that is less than 7; After regulating pH, this mixture is carried out to the first dry processing to obtain solid; And, grind this solid, carrying out obtaining described metal polyporous material after the second dry processing, it should be noted that the preparation method of described metal polyporous material does not use any calcination manufacturing process.The invention provides a kind of metal polyporous material being made by said method.
The present invention also provides a kind of detection method of nitrogen-containing compound, and it comprises: metal polyporous material as above is provided; Importing gas to be measured reacts with this metal polyporous material; And analytical reactions result.
For above and other object of the present invention, feature and advantage can be become apparent, cited below particularly go out preferred embodiment, and be described with reference to the accompanying drawings as follows:
Brief description of the drawings
The image of the T-shaped top phenomenon that Fig. 1 causes because of the ammonia of environment for photoresistance.
Fig. 2 is the preparation flow figure of the metal polyporous material described in one embodiment of the present of invention.
Fig. 3 is the detector means figure that the measurement described in embodiments of the invention 9 contains the gas of nitrogen molecular.
Fig. 4 is the absorption test result with metal polyporous material absorbing ammonia described in embodiments of the invention 9.
Fig. 5 is metal polyporous material described in embodiments of the invention 9 image before absorbing ammonia.
Fig. 6 is metal polyporous material described in embodiments of the invention 9 image after absorbing ammonia.
Fig. 7 has shown at different N H
3under concentration (ppb), metal polyporous material absorbs the absorption intensity discrepancy delta A before and after ammonia.
Fig. 8 has shown the repeated experiment result of the metal polyporous material described in embodiments of the invention 15.
Main element symbol description
11-16: step;
101: gas to be measured;
102: carrier gas;
103,104: mass flow controller;
105: valve;
106: test cavity;
107: metal polyporous material;
108: ultraviolet-visible light spectroscopic system; And
109: Exhaust Gas.
Detailed description of the invention
The invention provides a kind of metal polyporous material, it has colour generation sensed characteristic to nitrogen-containing compound.Described metal polyporous material, due to its preparation method, can make metal or metallic compound stably be present among silicon porous material, thereby provides enough spaces to increase itself and object gas (for example NH
3) chance of combination, and then improve detectable limit.The principle that this metal polyporous material has colour generation sensed characteristic to nitrogen-containing compound is that the combination meeting of metallic compound and nitrogen-containing compound produces specific change color.The present invention also provides a kind of detection method of nitrogen-containing compound, can utilize ultraviolet-visible light spectrum that the optical absorption intensity of metal polyporous material is quantized, and then set up the linear relationship between nitrogen-containing compound concentration and optical absorption intensity variation, finally reach the object of measuring nitrogen-containing compound concentration.
In one embodiment of the invention, metal polyporous material of the present invention is made by following steps, metal polyporous material preparation flow figure shown in Figure 2: first, hybrid silicone, metal or metallic compound and water (step 11), obtain mixture (step 12) after stirring.Then, regulate this mixture to make it have the pH value (step 13) that is less than 7.After regulating pH, leave standstill this mixture a period of time (for example 24 hours), and this mixture is carried out to the first dry processing (for example at room temperature carrying out), thereby obtain solid (step 14).Then, carry out afterwards the second dry processing (for example carrying out) at this solid (step 15) of grinding at 60 DEG C, thereby obtain described metal polyporous material, wherein, dry processing of the present invention (comprise first and second dry process) refers to that in room temperature or at not higher than the temperature of 60 DEG C (relative humidity is preferably less than RH=50%) carry out natural dryingly, and the preparation method of described metal polyporous material does not use any calcination manufacturing process.The whole manufacture process temperature of this metal polyporous material is not higher than 60 DEG C.
The proportion of composing (atom %) of metal polyporous material of the present invention for: come from used metal or the metallic atom of metallic compound (such as iron, copper, vanadium, manganese, chromium etc.) and account 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 is owing to not carrying out calcination, so its decomposition temperature is 150-250 DEG C, be different from the general burning material (300 DEG C of decomposition temperature >) through calcining.
The chemical formula of siloxanes as herein described is Si (OR)
4, R is the alkyl containing 1-8 carbon atom, can be for example titanium tetraisopropylate (titanium (IV) isopropoxide; TTIP), 3-aminopropyl triethoxysilane (3-aminopropyltriethoxysilane; APTES), tetramethoxy-silicane (TMOS), tetraethoxysilane (TEOS) or aforesaid combination.Described metal is iron, copper, vanadium, manganese, chromium, cobalt, or its combination, in addition, described metallic compound is halide, sulfide, nitrate, nitronic acid salt, the sulfate of iron, copper, vanadium, manganese, chromium or cobalt, or its combination, be for example ferric nitrate, cobalt nitrate, chromic nitrate, or there is 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 is greater than 0.95, easily form larger particle, reduce activity site surface area, cause reactivity to decline.If the ratio of metal is less than 0.05, may reduce because activated positions is not enough reaction rate.
Regulating in the process of pH value, can use acidic materials to regulate the pH value of mixture.In one embodiment of the invention, described acidic materials can be hydrochloric acid, sulfuric acid, nitronic acid, nitric acid or aforesaid combination.For example, in the time that the metal adding or metallic compound comprise cobalt, preferably regulate the pH value of mixture with hydrochloric acid.In some embodiments of the invention, the pH value of described mixture can be 7.0-1.0, is preferably 5.0-2.0, the friendly environment of being combined with alkaline molecules of ammonia to promote metal.
According to another embodiment of the present invention, the present invention also provides a kind of detection method of above-mentioned metal polyporous material to nitrogen-containing compound of utilizing, and it comprises: metal polyporous material of the present invention is provided, and imports gas to be measured and react with this metal polyporous material.Finally, 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 containing the detector of 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 containing nitrogen molecular.Method of testing can comprise: whether gas to be measured and carrier gas (carrier flow), respectively via mixing after different mass flow controllers, and are sent in the test cavity with metal polyporous material by valve control.Send the air-flow in test cavity to, need guarantee to discharge again after it runs through metal polyporous material powder.Because this metal polyporous material can change himself color after absorption nitrogen-containing compound, therefore in conjunction with after ultraviolet-visible light spectroscopic system, can immediately measure the optical absorption intensity of this metal polyporous material in particular range of wavelengths.It should be noted that, the concentration of the nitrogen-containing compound adsorbing to this metal polyporous material in the absorption intensity of particular range of wavelengths due to this measured metal polyporous material of ultraviolet-visible light spectroscopic system is directly proportional, therefore can, via the variation of the optical absorption intensity of metal polyporous material, obtain the concentration of the nitrogen-containing compound of gas to be measured.
Illustrate that by the following example the synthesis mode of metal polyporous material of the present invention and character thereof measure below, in order to further to illustrate technical characterictic of the present invention.
Embodiment 1
First, get Co (NO
3)
26H
2o (0.4g) and TEOS (8ml) are mixed in 4ml water (H
2o) in, and fully stir.Then, 2M HCl (2ml) is added in said mixture and fully and stirred, make the pH value of gained solution be less than 7.By above-mentioned solution at room temperature leave standstill within 24 hours, be dried after, the solid of gained is ground.Finally, the powder that grinds gained is placed at 60 DEG C and is dried 6 hours, obtain having the silicon porous material 1 of cobalt metal.
Use EDX (energy dispersion x-ray spectrometer, energy disperse X-ray) to carry out surface-element analysis to the silicon porous material with cobalt metal 1 of gained, the weight ratio that obtains cobalt and silicon is 12: 88.
Embodiment 2
First, get Co (NO
3)
26H
2o (0.4g) and TEOS (8ml) are mixed in 4ml water (H
2o) in, and fully stir.Then, 0.1M HCl (0.12ml) is added in said mixture and fully and stirred, make the pH value of gained solution be less than 7.By above-mentioned solution at room temperature leave standstill within 24 hours, be dried after, the solid of gained is ground.Finally, the powder that grinds gained is placed at 60 DEG C and is dried 6 hours, obtain having the silicon porous material 2 of cobalt metal.
Embodiment 3
First, get Co (NO
3)
26H
2o (0.8g) and TEOS (8ml) are mixed in 4ml water (H
2o) in, and fully stir.Then, 0.1M HCl (0.12ml) is added in said mixture and fully and stirred, make the pH value of gained solution be less than 7.By above-mentioned solution at room temperature leave standstill within 24 hours, be dried after, the solid of gained is ground.Finally, the powder that grinds gained is placed at 60 DEG C and is dried 6 hours, obtain having the silicon porous material 3 of cobalt metal.
Embodiment 4-8
Embodiment 4-8 carries out as the same way of embodiment 1 respectively, but replaces Co (NO with different metallic oxide precursor things
3)
26H
2o.The metallic compound that embodiment 4-8 uses is respectively as shown in table 1.
Table 1
| Embodiment numbering | 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
The silicon porous material 1 with cobalt metal that embodiment 1 is obtained is placed in the test cavity 106 of device as shown in Figure 3, to measure it to NH
3adsorption capacity, metering system is as follows: utilize mass flowmenter 103 and 104 to control respectively gas (NH to be measured
3) 101 and the flow of carrier gas (nitrogen) 102, (NH after mixing after fully mixing
3concentration is 500ppb), control and send the test cavity 106 with metal polyporous material 107 to and adsorb by valve 105, air-flow is entered by cavity top, run through after metal polyporous material 107 by cavity 106 below Exhaust Gas 109, within during permeate gas stream every 2.5 minutes, measure one group of data, utilize ultraviolet-visible light spectroscopic system to record powder surface ultraviolet-visible optical absorption characteristics collection of illustrative plates (temperature is that 21.3 DEG C, humidity are 44.1%), and record 100 times, 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 1700cc per minute, powder surface becomes bluish violet (Fig. 6) from pink (Fig. 5).Please refer to Fig. 4, between wavelength 600-700nm, absorption intensity becomes large along with passing into the increase of ammonia amount gradually.This result confirms that described metal polyporous material can be used as NH really
3colour generation sensing material, its instant measurement in conjunction with ultraviolet-visible light spectroscopic system can be used as NH
3gas monitor.
Embodiment 10-11
Embodiment 10-11 carries out as the same way of embodiment 9 respectively, but replaces respectively the metal polyporous material of embodiment 1 gained with the metal polyporous material of embodiment 2 and 3 gained.Metal polyporous material described in embodiment 9-11 is as shown in table 2 in the absorption intensity difference results at 640nm place before and after absorption ammonia.
Table 2
Embodiment 12-14
Embodiment 12-14 carries out as the same way of embodiment 9 respectively, but respectively with 60ppbNH
3, 115ppb NH
3with 230ppb NH
3replace the 500ppb NH that embodiment 9 uses
3concentration.Metal polyporous material described in embodiment 12-14 is as shown in table 3 in the absorption intensity difference results at 640nm place before and after absorption ammonia.
Table 3
Then,, by the result mapping of table 3 gained, show at different N H
3under concentration (ppb), metal polyporous material is absorbing the absorption intensity discrepancy delta A of ammonia front and back at 640nm place, as shown in Figure 7.As shown in Figure 7, absorption intensity discrepancy delta A is directly proportional to ammonia concentration, and the ammonia concentration passing into and absorption intensity 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, if when it is connected with ultraviolet-visible light spectrometer system, also can carry out instant ammonia quantitative analysis of measuring.
Embodiment 15
The silicon porous material 1 (metal polyporous material) with cobalt metal that embodiment 1 is obtained is placed in test cavity, utilizes ultraviolet-visible light spectrometer system to measure this metal polyporous material and does not absorb NH
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 entered by cavity top, after running through metal polyporous material, discharged by cavity below, continue to carry out, after 60 minutes, to utilize ultraviolet-visible light spectrometer system to measure the absorption spectrum of this metal polyporous material.Then, contain NH stopping sending into
3gas enter cavity after 30 minutes, utilize ultraviolet-visible light spectrometer system to measure the absorption spectrum of this metal polyporous material.Then, contain NH stopping sending into
3gas enter cavity after 24 hours, utilize ultraviolet-visible light spectrometer system to measure the absorption spectrum of this metal polyporous material.Finally, again pass into and contain NH
3gas (concentration is 46ppm, 50sccm), and continue two hours, recycling ultraviolet-visible light spectrometer system is measured the absorption spectrum of this metal polyporous material, the result of above-mentioned measurement is as shown in Figure 8.As shown in Figure 8, metal polyporous material of the present invention has reusability, is suitable for very much the detection to ammonia.
In sum, because the metal center atom of positively charged in the metallic compound on metal polyporous material of the present invention can be combined and form metal complex with the right amido of lone pair electrons in nitrogen-containing compound, thereby cause the change of absorption intensity, therefore can utilize ultraviolet-visible spectrometer to carry out qualitative and quantitative analysis.In addition, metal polyporous material of the present invention has high sensitivity, high selectivity, repeatability and low detectable limit, and detection method and the device that therefore can further be used in nitrogen-containing compound are upper, are 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
Although the present invention with several preferred embodiments openly as above; but described embodiment is not in order to limit the present invention; any those skilled in the art without departing from the spirit and scope of the present invention, can make and changing arbitrarily and retouching, and therefore protection scope of the present invention is as the criterion with claims.
Claims (9)
1. a detection method for nitrogen-containing compound, it comprises:
Metal polyporous material is provided;
Importing gas to be measured reacts with this metal polyporous material; And
Analytical reactions result;
Wherein said metal polyporous material makes by the preparation method who comprises the steps:
Hybrid silicone, metal or metallic compound and water, obtain mixture after stirring;
Regulate this mixture to make it have the pH value that is less than 7;
After regulating pH, this mixture is carried out to the first dry processing to obtain solid; And,
Grind this solid, carrying out obtaining described metal polyporous material after the second dry processing, the wherein said first dry processing and the second dry temperature of processing are not more than 60 DEG C,
Wherein said preparation method does not use any calcination manufacturing process.
2. the detection method of nitrogen-containing compound according to claim 1, the chemical formula of wherein said siloxanes is Si (OR)
4, R is the alkyl containing 1-8 carbon atom.
3. the detection method of nitrogen-containing compound according to claim 1, wherein said siloxanes is 3-aminopropyl triethoxysilane, tetramethoxy-silicane, tetraethoxysilane, or its combination.
4. the detection method of nitrogen-containing compound according to claim 1, wherein said metal is iron, copper, vanadium, manganese, chromium, cobalt, or its combination.
5. the detection method of nitrogen-containing compound according to claim 1, wherein said metallic compound is halide, sulfide, nitrate, the sulfate of iron, copper, vanadium, manganese, chromium or cobalt, or its combination.
6. the detection method of nitrogen-containing compound 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 detection method of nitrogen-containing compound according to claim 1, wherein said nitrogen-containing compound comprises ammonia.
8. the detection method of nitrogen-containing compound according to claim 1, it further comprises described metal polyporous material is connected with ultraviolet-visible light spectroscopic system, immediately to measure the optical absorption intensity of this metal polyporous material in particular range of wavelengths.
9. the detection method of nitrogen-containing compound according to claim 8, wherein said particular range of wavelengths is 300-900nm.
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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 |
-
2010
- 2010-09-01 CN CN201010274102.4A patent/CN102380358B/en active Active
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 (4)
| 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》.1992,第146卷 |
| The preparation and characterisation of silica aerogels and xerogels doped with transition metal species;A.M. Buckley et al;《Journal of Non-Crystalline Solids》;19921231;第146卷;97-110 * |
| 强磁性纳米Fe3O4/SiO2复合粒子的制备及其性能研究;陈令允等;《材料科学与工程学报》;20051031;第23卷(第05期);556-559、567 * |
| 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》.2005,第23卷(第05期),556-559、567. |
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