CN117567494A - Oxygen scavenging process for metal alkyl precursors - Google Patents
Oxygen scavenging process for metal alkyl precursors Download PDFInfo
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- CN117567494A CN117567494A CN202311532188.XA CN202311532188A CN117567494A CN 117567494 A CN117567494 A CN 117567494A CN 202311532188 A CN202311532188 A CN 202311532188A CN 117567494 A CN117567494 A CN 117567494A
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- metal
- oxygen
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- oxygen scavenging
- trimethylaluminum
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 105
- 239000002184 metal Substances 0.000 title claims abstract description 105
- 239000001301 oxygen Substances 0.000 title claims abstract description 74
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 74
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 63
- 239000002243 precursor Substances 0.000 title claims abstract description 33
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 21
- 230000002000 scavenging effect Effects 0.000 title claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000012535 impurity Substances 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 230000009467 reduction Effects 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 239000012445 acidic reagent Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 abstract description 40
- 229910052749 magnesium Inorganic materials 0.000 abstract description 38
- 239000000126 substance Substances 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 60
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 238000005086 pumping Methods 0.000 description 15
- 238000005406 washing Methods 0.000 description 14
- 239000011261 inert gas Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 238000007781 pre-processing Methods 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 238000005070 sampling Methods 0.000 description 7
- 229910000574 NaK Inorganic materials 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 description 6
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000012279 sodium borohydride Substances 0.000 description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 235000012431 wafers Nutrition 0.000 description 3
- 229910002704 AlGaN Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910001508 alkali metal halide Inorganic materials 0.000 description 2
- 150000008045 alkali metal halides Chemical class 0.000 description 2
- -1 aluminum halide Chemical class 0.000 description 2
- 238000004871 chemical beam epitaxy Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/062—Al linked exclusively to C
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses an oxygen removal method of an alkyl metal precursor, which comprises the following steps: contacting a metal alkyl precursor containing oxygen impurities with a selected metal and heating to react so that the oxygen impurities are reduced; the standard hydrogen reduction potential of the selected metallic magnesium is-2.37V. According to the deoxidization method provided by the invention, the metal elemental magnesium reacts with the oxygen-containing component, then the good deoxidization purification effect can be realized through heating and stirring, the stable low-oxygen alkyl metal precursor is obtained, the inorganic purity of the precursor reaches 99.9999%, the oxygen content is less than 5ppm, the metal elemental potentiometer is low, the impurity removal reaction rate can be obviously improved, the chemical property of the metal elemental is stable, and the precursor can be recycled. The method has the advantages of simple process flow, no introduction of new impurities, high treatment efficiency and impurity removal efficiency, convenient operation and wide application prospect.
Description
Technical Field
The invention relates to the technical field of preparation of semiconductor materials, in particular to an oxygen removal method of an alkyl metal precursor.
Background
Organometallic compounds are common precursors in the field of material preparation, especially in the field of semiconductor thin film or structure growth, where for example Trimethylaluminum (TMA) is an important raw material for growing optoelectronic materials during metal organic vapor deposition techniques (MOCVD), chemical Beam Epitaxy (CBE). The method is mainly used for growing epitaxial wafers of III-nitride semiconductor materials mainly comprising AlGaN/AlN, is a core raw material for growing epitaxial wafers of third-generation semiconductors such as AlGaN, alN and the like, and is one of core raw materials of phase-change memories, radio frequency integrated circuit chips and the like.
The quality of the compound semiconductor material epitaxially grown by taking trimethylaluminum as a precursor is mainly influenced by impurities in the trimethylaluminum. Due to the process of trimethylaluminum preparation, organic impurities are introduced during the synthesis stage. Organic oxygen generally has a higher vapor pressure than trimethylaluminum or similar vapor pressure, and thus, oxygen atoms are incorporated in a semiconductor thin layer during the production of a compound semiconductor material, thereby causing serious degradation of the quality and lifetime of a downstream wafer in a chain reaction, and ultimately affecting the performance of the compound semiconductor. For aluminum oxide impurities in trimethylaluminum, which have similar boiling points to products, purification by a conventional rectifying device is difficult, and the impurities must be removed by a new impurity removal method to purify the precursor.
Various purification methods are provided in the prior art, for example, methods using complex coordination are available in the prior art to remove the amount of oxa in trimethylaluminum; furthermore, japanese patent publication No. 112991/1991 (JP-A-3-112991) proposes a method for purifying an aluminum alkyl containing an oxygen-containing component, wherein the oxygen-containing component is treated with an aluminum halide-containing component such as aluminum bromide, aluminum iodide or the like; japanese patent publication No. JP31338893 (43) proposes a method of using an alkali metal halide which is reacted with an oxygen-containing component to form a complex, and then rectifying the complex to thereby achieve an oxygen-removing effect; the Chinese patent with publication number of CN1749260B proposes a method for adding sodium to remove oxygen; chinese patent publication No. CN1769289B proposes an oxygen removal method using an inert gas (e.g., high purity helium) to purge trimethylaluminum vapor; the Chinese patent with publication No. CN109879900A proposes a method for reducing the oxygen impurity in trimethylaluminum by using inorganic salt; U.S. patent publication No. US4797500 proposes a method of removing oxygen impurities by adding a reflux of a potassium-sodium alloy.
Some technical problems exist in various methods for deoxidizing and purifying various MO sources in the prior art, such as a complex compound matching method in the prior art, but the method has complex process operation, high temperature required during the decomposition and possibility of introducing new impurities; some aluminum halide reagents used in the prior art also have a high tendency to decompose moisture themselves, while halides can increase the risk of corrosion of the stainless steel reactor; some prior arts propose an alkali metal halide which reacts with an oxygen-containing component to form a complex, and then rectifying to achieve the deoxidization effect, but the method requires other solvents to treat the mixture during the operation process, so the process operation is complex; some prior art suggests a purification method using inert gas (such as high purity helium) to blow through trimethylaluminum vapor, which can cause part of trimethylaluminum vapor to be lost along with the inert gas, cause trimethylaluminum loss, and increase the safety treatment steps of tail gas; some prior art proposes a method for adding sodium, refluxing and deoxidizing, wherein part of trimethylaluminum reacts with sodium metal at high temperature to produce sodium tetramethylaluminum, so that the loss of trimethylaluminum is caused; some prior art proposes a method for reducing the oxygen impurity in trimethylaluminum by using inorganic salt, the method needs to carry out secondary long-time vacuumizing treatment on the treated product, and the production period of the product is increased; some prior art proposes a reflux purification method by adding potassium-sodium alloy, in which the potassium-sodium alloy can form large particles in trimethylaluminum, so that the potassium-sodium alloy is difficult to be completely dispersed in trimethylaluminum, the potassium-sodium alloy and the trimethylaluminum cannot be effectively contacted, the impurity removal effect of a product is finally affected, and the trimethylaluminum body and the potassium-sodium alloy are easy to react at high temperature, so that the loss of trimethylaluminum is caused.
Therefore, the development of the precursor deoxidizing method which has high treatment rate, high deoxidizing efficiency and convenient operation and can be repeatedly recycled has important significance for the mass preparation of the precursor.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide an oxygen removal method for an alkyl metal precursor.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
the invention provides an oxygen removal method of an alkyl metal precursor, which comprises the following steps: contacting and reacting a metal alkyl precursor containing oxygen impurities with a selected metal to remove at least the oxygen impurities; the standard hydrogen reduction potential of the selected metal is around-2.37V, for example-2.35 to-2.40V.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
according to the deoxidization method provided by the invention, the selected metal simple substance reacts with the oxygen-containing component, then the deoxidization effect can be realized through heating and stirring, the inorganic purity of the deoxidization method reaches 99.9999%, the oxygen content is less than 5ppm, the standard hydrogen reduction potential of the selected metal magnesium is-2.37 v, the preferred alkyl metal precursor comprises trimethylaluminum and trimethylgallium, wherein the standard hydrogen reduction potential of aluminum is-1.66 v, the standard hydrogen reduction potential of gallium is-0.32 v, magnesium plays a role in reducing and transferring oxygen impurities in the two alkyl metal precursors, the impurity removal reaction rate is improved, and the selected metal has stable chemical properties and can be recycled; the method has the advantages of simple process flow, no introduction of new impurities, higher treatment efficiency and impurity removal efficiency, convenient operation and wide application prospect.
The foregoing description is only an overview of the present invention and is intended to enable those skilled in the art to make more clear the scope of the present invention and to be practiced in accordance with the present invention as described below with reference to the preferred embodiments thereof.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
Moreover, relational terms such as "first" and "second", and the like, may be used solely to distinguish one from another component or method step having the same name, without necessarily requiring or implying any actual such relationship or order between such components or method steps.
The embodiment of the invention provides an oxygen removal method of an alkyl metal precursor, which comprises the following steps of:
contacting a metal alkyl precursor containing oxygen impurities with a selected metal and heating to react so that the oxygen impurities are reduced; the standard hydrogen reduction potential of the selected metal magnesium is-2.37V, and of course, the actually adopted magnesium simple substance can cause the standard hydrogen reduction potential to float up and down to a certain extent due to the different contents of impurity elements, which is a normal phenomenon, namely, the pure metal magnesium is preferably adopted as a reducing agent and a catalyst, but the metal magnesium used in the invention does not exclude other alloy elements or doping elements.
In the invention, the reducibility of selected metal Mg to oxa is utilized to reduce and remove the oxa, while the technical scheme of reducing the oxa by adopting a reducing agent also exists in the prior art, for example, some prior arts adopt borohydride to reduce the oxa after pretreatment, however, the inventor of the invention discovers that the borohydride only plays a role of the reducing agent in the prior arts, and the selected metal surface selected by the invention has lower metal potentiometer, oxidized alkyl aluminum is unstable, and oxygen heteroatom is transferred to the surface of the selected metal, so that the method has better reaction rate and improves the impurity removal efficiency; and the metal Mg can be recycled and reused, and has good reusability.
With respect to specific process ratios, in some embodiments, the mass ratio of the metal alkyl precursor to the selected metal is from 1 to 100:1;
in some embodiments, the macroscopic morphology of the selected metal may include, for example, any one or a combination of two or more of powder, network, flakes. Of course, the reduction can be achieved by using the block, but the specific surface area of the block is low, and the preferable form is still the form with the large specific surface area.
In some embodiments, the oxygen scavenging process may specifically include the steps of:
mixing the metal alkyl precursor with a selected metal to obtain a mixture;
heating and stirring the mixture at a selected temperature to obtain an deoxidized alkyl metal precursor;
and with respect to specific operating conditions, in some embodiments, the selected temperature is 80 to 127 ℃ and the time of heating and stirring is 1 to 10 hours; in some embodiments, the oxygen scavenging process further comprises:
a step of surface activation treatment of the selected metal before the selected metal is contacted with the metal alkyl precursor.
In some embodiments, the surface activation treatment comprises at least contacting the selected metal with an acidic reagent to remove at least oxides from the surface of the selected metal.
The technical scheme provided by the invention not only can realize the reducibility and the oxa-transfer, but also has the advantages that the selected reducer can be reused, and the method is characterized in that: in some embodiments, the oxygen scavenging process further comprises the step of organic solvent cleaning the selected metal remaining after oxygen scavenging and re-use after the surface activation treatment.
As some typical application examples of the above technical solutions, the above technical solutions may be implemented, for example, by the following specific procedures:
step one, selecting and preprocessing a metal simple substance
Three shapes of magnesium powder (diameter is 100-300 meshes)/net/sheet are selected, the selected metal powder/net/sheet is placed in a 100-1000 ml dry conical flask, 20-400 ml of acetone-concentrated hydrochloric acid (1:1) mixed solvent is added, and the mixture is vigorously stirred for 5-20 min, and then the sand core is filtered. Repeating the steps twice, washing with acetone and anhydrous diethyl ether, pumping, and storing in a dryer;
step two, treating trimethylaluminum by metal simple substance
1-100 kg of trimethylaluminum can be treated per 1kg of metal single body, and the treatment method is as follows:
the method comprises the following steps: under the protection of inert gas in a glove box, mixing the pretreated metal powder/net/sheet with trimethylaluminum in a flask, stirring, setting the rotating speed of a stirring device to be 20-500 r/min, heating the mixture to 80-120 ℃, and stirring for 1-10h;
step three, detecting the oxygen content of trimethyl aluminum after deoxidization
Detecting the collected product by using a nuclear magnetic resonance spectrometer, wherein the detection result is that the oxa is less than 5ppm, namely the qualified product;
step four, recovering metal simple substance
Under the protection of inert gas in a glove box, placing the used metal powder/net/sheet in a glass vessel, adding tri-n-octylamine with the mass of 5-50 times of the metal powder/net/sheet for soaking, standing for 5-20 h, filtering by using a sand core, washing the filtered metal powder/net/sheet by using ethanol with the mass of 5-50 times of the metal powder/net/sheet, pumping, and storing in a dryer for next activation.
With respect to preferred application results, in some embodiments, the oxygen content of the oxygen-scavenging metal alkyl precursor may be, for example, less than 5ppm. Of course, if the purity of the product is not very critical, the reaction time may be suitably shortened to obtain a product having a slightly higher oxygen content, which is still within the practical scope of the present invention, and is not limited to the absolute requirement to reduce the oxygen content of the product to the above-mentioned value.
The technical scheme of the invention is further described in detail through a plurality of embodiments. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention.
In addition, because of the physicochemical characteristics of water explosion and air spontaneous combustion of the trimethylaluminum, all the works related in the invention are carried out under the inert gas atmosphere such as nitrogen or argon, so that the environmental factors such as air and moisture are strictly removed, and the used experimental instrument is cleaned according to strict cleaning standards, so that the influence of the contamination of the experimental instrument on the detection result is eliminated. Of course, this is a common technical means of handling the relevant substances and the raw materials involved, such as the trimethylaluminum synthesized or the metals used, are all available or commercially by conventional methods.
Example 1
This example illustrates a process for preparing high purity trimethylaluminum, as follows:
step one, selecting and preprocessing a metal simple substance
50g of magnesium net is selected as deoxidizing medicine, 50g of magnesium net is placed in a 500ml dry conical flask, 300ml of acetone-concentrated hydrochloric acid (1:1) mixed solvent is added, and the mixture is vigorously stirred for 20min, and then the sand core is filtered. Repeating the steps twice, washing with acetone and anhydrous diethyl ether, pumping, and storing in a dryer;
step two, treating trimethylaluminum by metal simple substance
Under the protection of inert gas in a glove box, adding 50g of pretreated magnesium net into 2L of trimethylaluminum filled with 1000g, heating for 1h at 120 ℃ under the condition of stirring speed of 60r/min, and sampling after the completion;
step three, detecting the oxygen content of trimethyl aluminum after deoxidization
The trimethylaluminum after oxygen removal was examined by nuclear magnetic resonance spectroscopy, and the analysis results are shown in Table 1.
TABLE 1
| Before deoxidization (ppm) | Deoxidization (ppm) | |
| Oxygen-containing component | 17.2 | 1.2 |
Step four, recovering metal simple substance
Placing 50g of used magnesium net in a glass vessel, adding 100g of tri-n-octylamine, uniformly mixing, stirring for 10min, standing for 15h after stirring, filtering by using a sand core, washing the filtered magnesium net by using 1000g of ethanol, pumping, and storing in a dryer for next activation.
Example 2
Step one, selecting and preprocessing a metal simple substance
50g of magnesium net is selected as deoxidizing medicine, 50g of magnesium net is placed in a 500ml dry conical flask, 300ml of acetone-concentrated hydrochloric acid (1:1) mixed solvent is added, and the mixture is vigorously stirred for 20min, and then the sand core is filtered. Repeating the steps twice, washing with acetone and anhydrous diethyl ether, pumping, and storing in a dryer;
step two, treating trimethylaluminum by metal simple substance
Under the protection of inert gas in a glove box, adding 50g of pretreated magnesium net into 2L of trimethylaluminum filled with 1000g, heating for 1h at the temperature of 100 ℃ under the condition of stirring speed of 60r/min, and sampling after the completion;
step three, detecting the oxygen content of trimethyl aluminum after deoxidization
The trimethylaluminum after oxygen removal was examined by nuclear magnetic resonance spectroscopy, and the analysis results are shown in Table 2.
TABLE 2
| Before deoxidization (ppm) | Deoxidization (ppm) | |
| Oxygen-containing component | 17.2 | 5.4 |
Step four, recovering metal simple substance
Placing 50g of used magnesium net in a glass vessel, adding 100g of tri-n-octylamine, uniformly mixing, stirring for 10min, standing for 15h after stirring, filtering by using a sand core, washing the filtered magnesium net by using 1000g of ethanol, pumping, and storing in a dryer for next activation.
Example 3
Step one, selecting and preprocessing a metal simple substance
50g of magnesium net is selected as deoxidizing medicine, 50g of magnesium net is placed in a 500ml dry conical flask, 300ml of acetone-concentrated hydrochloric acid (1:1) mixed solvent is added, and the mixture is vigorously stirred for 20min, and then the sand core is filtered. Repeating the steps twice, washing with acetone and anhydrous diethyl ether, pumping, and storing in a dryer;
step two, treating trimethylaluminum by metal simple substance
Under the protection of inert gas in a glove box, adding 50g of pretreated magnesium net into 2L of trimethylaluminum filled with 1000g, heating for 1h at 80 ℃ under the condition of stirring speed of 60r/min, and sampling after the completion;
step three, detecting the oxygen content of trimethyl aluminum after deoxidization
The trimethylaluminum after oxygen removal was examined by nuclear magnetic resonance spectroscopy, and the analysis results are shown in Table 3.
TABLE 3 Table 3
| Before deoxidization (ppm) | Deoxidization (ppm) | |
| Oxygen-containing component | 17.2 | 3.4 |
Step four, recovering metal simple substance
Placing 50g of used magnesium net in a glass vessel, adding 100g of tri-n-octylamine, uniformly mixing, stirring for 10min, standing for 15h after stirring, filtering by using a sand core, washing the filtered magnesium net by using 1000g of ethanol, pumping, and storing in a dryer for next activation.
Example 4
Step one, selecting and preprocessing a metal simple substance
50g of magnesium net is selected as deoxidizing medicine, 50g of magnesium net is placed in a 500ml dry conical flask, 300ml of acetone-concentrated hydrochloric acid (1:1) mixed solvent is added, and the mixture is vigorously stirred for 20min, and then the sand core is filtered. Repeating the steps twice, washing with acetone and anhydrous diethyl ether, pumping, and storing in a dryer;
step two, treating trimethylaluminum by metal simple substance
Under the protection of inert gas in a glove box, adding 50g of pretreated magnesium net into 2L of trimethylaluminum filled with 1000g, heating at 80 ℃ for 8 hours under the condition of stirring speed of 60r/min, and sampling after the completion;
step three, detecting the oxygen content of trimethyl aluminum after deoxidization
The trimethylaluminum after oxygen removal was examined by nuclear magnetic resonance spectroscopy, and the analysis results are shown in Table 4.
TABLE 4 Table 4
| Before deoxidization (ppm) | Deoxidization (ppm) | |
| Oxygen-containing component | 17.2 | 2.0 |
Step four, recovering metal simple substance
Placing 50g of used magnesium net in a glass vessel, adding 100g of tri-n-octylamine, uniformly mixing, stirring for 10min, standing for 15h after stirring, filtering by using a sand core, washing the filtered magnesium net by using 1000g of ethanol, pumping, and storing in a dryer for next activation.
After the magnesium net is repeatedly used for 3 times, the deoxidization efficiency is reduced by only 4 percent;
comparative example 1
Step one, selecting and preprocessing a metal simple substance
10g of aluminum powder (aluminum standard hydrogen reduction potential is-1.66 v, diameter is 250-300 meshes) is selected as deoxidized medicine, 10g of aluminum powder is placed in a 100ml dry conical flask, 50ml of acetone-concentrated hydrochloric acid (1:1) mixed solvent is added, and the mixture is vigorously stirred for 10min, and then sand core filtration is performed. Repeating the steps twice, washing with acetone and anhydrous diethyl ether, pumping, and storing in a dryer;
step two, treating trimethylaluminum by metal simple substance
Under the protection of inert gas in a glove box, adding 10g of pretreated aluminum powder and 100g of trimethylaluminum into a 2L flask, gradually heating the mixture to 120 ℃, heating and stirring for 1h under the condition of stirring speed of 60r/min, and then sampling and detecting;
step three, detecting the oxygen content of trimethyl aluminum after deoxidization
The collected trimethylaluminum was examined by nuclear magnetic resonance spectroscopy, and the results of the middle distillate analysis are shown in Table 5.
TABLE 5
| Before deoxidization (ppm) | Deoxidization (ppm) | |
| Oxygen-containing component | 17.2 | 17.8 |
This comparison demonstrates that not all reducing metals are capable of achieving efficient removal of the oxa from trimethylaluminum, and that the metals selected are desirable.
Comparative example 2
Step one, selecting and preprocessing a metal simple substance
Magnesium net as deoxidizing agent, 10g of magnesium net was placed in a 500ml dry conical flask, 300ml of acetone-concentrated hydrochloric acid (1:1) mixed solvent was added, vigorously stirred for 20min, and then the sand core was filtered. Repeating the steps twice, washing with acetone and anhydrous diethyl ether, pumping, and storing in a dryer;
step two, treating trimethylaluminum by metal simple substance
Under the protection of inert gas in a glove box, adding 10g of pretreated magnesium net into 2L of trimethylaluminum with 1000g, heating for 10h at 120 ℃ under the condition of stirring speed of 60r/min, and sampling after the completion.
Step three, detecting the oxygen content of trimethyl aluminum after deoxidization
The collected middle distillate was examined by nuclear magnetic resonance spectroscopy, and the results of the middle distillate analysis are shown in Table 6.
TABLE 6
| Before deoxidization (ppm) | Deoxidization (ppm) | |
| Oxygen-containing component | 17.2 | 8.7 |
Step four, recovering metal simple substance
Placing 10g of used magnesium net in a glass vessel, adding 100g of tri-n-octylamine, uniformly mixing, stirring for 10min, standing for 15h after stirring, filtering by using a sand core, washing the filtered magnesium net by using 1000g of ethanol, pumping, and storing in a dryer for next activation.
This comparative example shows that the ratio of the selected metal to trimethylaluminum is in a range that has a great influence on obtaining a superior impurity removing effect, and the amount of the selected metal to be added should be well controlled in practical applications.
Comparative example 3
This example also illustrates a method for preparing high purity trimethylaluminum, which is substantially the same as example 1, except that:
the reducing agent is replaced by borohydride, and specifically:
selecting commercial sodium borohydride as a reducing agent, weighing 100g of sodium borohydride, and placing the sodium borohydride in an oven for heating and drying at a drying temperature of 100 ℃ for 10 hours; and simultaneously, pumping the pressure to the steel cylinder by using a vacuum pump to 1-5 kpa, maintaining the pressure for 30 minutes, supplementing nitrogen to normal pressure through a pipeline, and repeating the process for 5 times to prepare the reducing agent.
The reducing agent had the same particle size and the same specific surface area as in example 1, and was mixed with trimethylaluminum in the same ratio as in example 1, followed by removal of impurities by the same treatment process and the same condition parameters.
Finally, it was found that the same amount of oxa was achieved, the time required for heating and stirring was 5 hours, obviously longer than in example 1, and that sodium borohydride was more difficult to recover and reuse. The selected metal provided by the invention has good recycling property.
Example 5
This example also illustrates the use of a metal magnesium mesh as an oxygen scavenger for the removal of oxygen from trimethylgallium, as follows:
step one, selecting and preprocessing a metal simple substance
50g of magnesium net is selected as deoxidizing medicine, 50g of magnesium net is placed in a 500ml dry conical flask, 300ml of acetone-concentrated hydrochloric acid (1:1) mixed solvent is added, and the mixture is vigorously stirred for 20min, and then the sand core is filtered. Repeating the steps twice, washing with acetone and anhydrous diethyl ether, pumping, and storing in a dryer;
step two, processing the trimethylgallium by the metal simple substance
Under the protection of inert gas in a glove box, adding 50g of pretreated magnesium net into 2L of trimethylgallium filled with 1000g, heating for 1h at 50 ℃ under the condition of stirring speed of 60r/min, and sampling after the completion;
step three, detecting oxygen content of trimethyl gallium after deoxidization
The trimethylaluminum after oxygen removal was examined by nuclear magnetic resonance spectroscopy, and the analysis results are shown in Table 7.
TABLE 7
| Before deoxidization (ppm) | Deoxidization (ppm) | |
| Oxygen-containing component | 46 | 4.3 |
In addition, the inventors of the present invention have conducted oxygen scavenging tests on other metal alkyl precursors, such as triethyl or monomethyl diethyl or dimethyl monoethyl compounds, to achieve good technical results.
Based on the above examples and comparative examples, it is clear that the embodiment of the present invention can prepare low-oxygen trimethylaluminum/trimethylgallium by pre-treating the powder/net/sheet of the selected metal element, then mixing and heating the pretreated powder/net/sheet of the metal element with trimethylaluminum, thereby obtaining stable low-oxygen trimethylaluminum with inorganic purity up to 99.9999% and oxygen content <5ppm, and finally recovering the powder/net/sheet of the metal element after use; the invention can realize the deoxidization and purification effect by reacting the metal simple substance with the oxygen-containing component and heating and stirring. The method has simple process flow, does not introduce new impurities, and the used metal simple substance has stable chemical property and can be recycled.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (9)
1. A method for deoxidizing a metal alkyl precursor, comprising:
contacting and reacting a metal alkyl precursor containing oxygen impurities with a selected metal to remove at least the oxygen impurities;
wherein the standard hydrogen reduction potential of the selected metal is-2.35 to-2.40V.
2. The oxygen scavenging process of claim 1 wherein said selected metal is elemental magnesium metal.
3. The oxygen scavenging process of claim 1 wherein the mass ratio of the metal alkyl precursor to the selected metal is 1-100:1;
and/or the macroscopic form of the selected metal comprises any one or more than two of powder, network and sheet.
4. The oxygen scavenging process of claim 1, comprising in particular:
mixing the metal alkyl precursor with a selected metal to obtain a mixture;
and heating and stirring the mixture at a selected temperature to obtain the deoxidized alkyl metal precursor.
5. The oxygen scavenging process of claim 4 wherein the selected temperature is 80-127 ℃ and the time of heating and stirring is 1-10 hours.
6. The oxygen scavenging method of claim 1 further comprising:
a step of surface-activating the selected metal prior to contacting the selected metal with the metal alkyl precursor.
7. The oxygen scavenging process of claim 7 wherein the surface activation treatment comprises at least contacting the selected metal with an acidic reagent to remove at least oxides from the surface of the selected metal.
8. The oxygen scavenging process of claim 7 further comprising the step of subjecting said selected metal remaining after oxygen scavenging to an organic solvent wash and re-use after said surface activation treatment.
9. The oxygen scavenging process of claim 1 wherein the oxygen content of the deoxygenated metal alkyl precursor is less than 5ppm.
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