CN115584482B - Purification method of tantalum source precursor - Google Patents
Purification method of tantalum source precursor Download PDFInfo
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- CN115584482B CN115584482B CN202211324335.XA CN202211324335A CN115584482B CN 115584482 B CN115584482 B CN 115584482B CN 202211324335 A CN202211324335 A CN 202211324335A CN 115584482 B CN115584482 B CN 115584482B
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- source precursor
- tantalum
- adsorbent
- tantalum source
- purification
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- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 153
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 151
- 239000002243 precursor Substances 0.000 title claims abstract description 147
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000746 purification Methods 0.000 title abstract description 114
- 239000003463 adsorbent Substances 0.000 claims abstract description 102
- 238000001179 sorption measurement Methods 0.000 claims abstract description 62
- 239000012535 impurity Substances 0.000 claims abstract description 40
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 230000008020 evaporation Effects 0.000 claims abstract description 5
- VSLPMIMVDUOYFW-UHFFFAOYSA-N dimethylazanide;tantalum(5+) Chemical compound [Ta+5].C[N-]C.C[N-]C.C[N-]C.C[N-]C.C[N-]C VSLPMIMVDUOYFW-UHFFFAOYSA-N 0.000 claims description 60
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 50
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 36
- -1 (diethylamino) tert-butanamide tantalum Chemical compound 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000126 substance Substances 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000011261 inert gas Substances 0.000 claims description 14
- 239000002608 ionic liquid Substances 0.000 claims description 13
- 238000011068 loading method Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 150000002696 manganese Chemical class 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- MTHYQSRWPDMAQO-UHFFFAOYSA-N diethylazanide;tantalum(5+) Chemical compound CCN(CC)[Ta](N(CC)CC)(N(CC)CC)(N(CC)CC)N(CC)CC MTHYQSRWPDMAQO-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000007833 carbon precursor Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 1
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 30
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000003756 stirring Methods 0.000 description 44
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- 238000009833 condensation Methods 0.000 description 23
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- 239000007789 gas Substances 0.000 description 20
- 229910052786 argon Inorganic materials 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 238000000859 sublimation Methods 0.000 description 10
- 230000008022 sublimation Effects 0.000 description 10
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 7
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 5
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- 230000005540 biological transmission Effects 0.000 description 5
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 229940099607 manganese chloride Drugs 0.000 description 5
- 235000002867 manganese chloride Nutrition 0.000 description 5
- 239000011565 manganese chloride Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
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- PBIDWHVVZCGMAR-UHFFFAOYSA-N 1-methyl-3-prop-2-enyl-2h-imidazole Chemical compound CN1CN(CC=C)C=C1 PBIDWHVVZCGMAR-UHFFFAOYSA-N 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
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- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
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- 238000001914 filtration Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 2
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- TYOCDPIZUIQUSO-UHFFFAOYSA-N 1-butyl-2,3-dimethyl-2h-imidazole Chemical compound CCCCN1C=CN(C)C1C TYOCDPIZUIQUSO-UHFFFAOYSA-N 0.000 description 1
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- BYJYUVOOHAFSKS-UHFFFAOYSA-N trityloxyphosphane Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OP)C1=CC=CC=C1 BYJYUVOOHAFSKS-UHFFFAOYSA-N 0.000 description 1
- CGRJOQDFNTYSGH-UHFFFAOYSA-N tritylphosphane Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(P)C1=CC=CC=C1 CGRJOQDFNTYSGH-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the field of electronic precursor purification, in particular to a method for purifying a tantalum source precursor, which comprises the following steps: (S.1) dispersing an adsorbent in an inert liquid medium without volatility to obtain adsorption slurry; (S.2) dissolving the crude tantalum source precursor into the adsorption slurry to enable the crude tantalum source precursor to be in contact with the adsorbent, so that impurities in the crude tantalum source precursor are adsorbed by the adsorbent; (S.3) raising the temperature of the adsorption slurry to the evaporation temperature of the tantalum source precursor, so that the tantalum source precursor is evaporated, and thus forming tantalum source precursor steam; and (S.4) collecting the tantalum source precursor steam and condensing the tantalum source precursor steam to obtain the high-purity tantalum source precursor. According to the method, the purification step is simplified by changing the purification mode of the tantalum source precursor in the purification process of the tantalum source precursor, the purification efficiency and the purification effect are effectively improved, and the energy consumption in the purification process of the tantalum source precursor is effectively reduced in the purification process.
Description
Technical Field
The invention relates to the field of electronic precursor purification, in particular to a method for purifying a tantalum source precursor.
Background
Tantalum nitride is a transition metal nitride, and because of high hardness and controllable conductivity, the tantalum nitride has a diffusion barrier effect on metal elements, and is the most widely researched diffusion barrier layer material in the copper interconnection technology in the field of microelectronic industry. With the reduction of feature size and the increase of trench aspect ratio of integrated circuits, early Physical Vapor Deposition (PVD) processes have difficulty meeting future fabrication requirements, and thus Atomic Layer Deposition (ALD) techniques are crucial for the preparation of ultra-thin tantalum nitride barrier layers.
For atomic layer deposition of tantalum nitride, organometallic tantalum is often used in the industry as a tantalum source precursor. However, researchers have found that the purity of the tantalum source precursor has a significant effect on the final deposited tantalum nitride film. The organometallic tantalum is usually prepared from tantalum halide in the preparation process, so that a certain amount of tantalum halide and other halogen-containing impurities are often left in the prepared organometallic tantalum, and the halogen-containing impurities can generate corrosive byproducts in the atomic deposition process, thereby being not beneficial to industrial application. In addition, a certain amount of oxygen impurity is often present in the organometallic tantalum, which results in a high oxygen residue in the deposited tantalum nitride, and thus the tantalum nitride is more easily oxidized, which leads to other problems such as poor stability.
The patent with the application number of 201710492823.4 discloses a synthesis method of pentakis (dimethylamino) tantalum, which comprises the steps of adding an organic lithium reagent and a hydrocarbon solvent into a reactor under the protection of inert atmosphere, and then introducing dimethylamine gas into the system to prepare dimethylamino lithium; adding tantalum pentachloride into the system, and stirring for reaction under the protection of inert atmosphere after the tantalum pentachloride is added; filtering after the reaction is finished, and distilling the obtained filtrate to remove the hydrocarbon solvent; after the solvent is completely removed, the solid is sublimated to obtain the pentakis (dimethylamino) tantalum product. Although the synthesis cost and the reaction toxicity are reduced in the process of preparing the pentakis (dimethylamino) tantalum, the pentakis (dimethylamino) tantalum is purified only by adopting a sublimation step, and a certain amount of impurities are still doped in the pentakis (dimethylamino) tantalum.
Patent No. 201911061946.8 discloses a pentakis (dimethylamino) tantalum refining method, which comprises heating pentakis (dimethylamino) tantalum to sublimate the pentakis (dimethylamino) tantalum, and then enabling vapor of the pentakis (dimethylamino) tantalum to pass through metal-organic framework ceramic, so that impurities in the pentakis (dimethylamino) tantalum vapor are adsorbed, and the content of a product is further improved. Although the method can further improve the purity of the pentakis (dimethylamino) tantalum, the contact time of pentakis (dimethylamino) tantalum steam and the metal organic framework ceramic is short, so that the impurities in the pentakis (dimethylamino) tantalum steam are difficult to adsorb completely, and the purity of the pentakis (dimethylamino) tantalum prepared is still difficult to improve. Meanwhile, the speed of the pentakis (dimethylamino) tantalum steam is lower when the pentakis (dimethylamino) tantalum steam passes through the metal organic framework ceramic, so that the purification efficiency of the pentakis (dimethylamino) tantalum is difficult to improve.
Disclosure of Invention
The invention provides a method for purifying a tantalum source precursor, aiming at overcoming the defects that impurities doped in the tantalum source precursor are difficult to remove in the purification process of the tantalum source precursor in the prior art and the purification efficiency of the tantalum source precursor is low.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for purifying a tantalum source precursor, comprising the steps of:
(S.1) dispersing an adsorbent in an inert liquid medium without volatility to obtain adsorption slurry;
(S.2) dissolving the crude tantalum source precursor into the adsorption slurry, and enabling the crude tantalum source precursor to be in contact with an adsorbent, so that impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
(S.3) raising the temperature of the adsorption slurry to the evaporation temperature of the tantalum source precursor, so that the tantalum source precursor is evaporated, and thus forming tantalum source precursor steam;
and (S.4) collecting the tantalum source precursor vapor and condensing the tantalum source precursor vapor to obtain the high-purity tantalum source precursor.
Tantalum source precursors are typically in solid form at room temperature, and because of their rapid sublimation upon heating, prior art tantalum source precursors typically rely on sublimation to reduce impurities incorporated in the tantalum source precursor, as described in the background section. However, the tantalum source precursor is also doped with impurities to sublimate together in the sublimation process, so that the tantalum source precursor obtained by sublimation and condensation is difficult to remove all the impurities.
The invention innovatively provides a novel purification method for a tantalum source precursor, and the method comprises the steps of firstly dissolving a crude tantalum source precursor into adsorption slurry containing an adsorbent, so that impurities in the crude tantalum source precursor can be adsorbed by the adsorbent in the contact process of the crude tantalum source precursor and the adsorbent. After impurities in the crude tantalum source precursor are completely adsorbed by the adsorbent, the temperature of the whole system is raised, at the moment, the tantalum source precursor can form steam, and the tantalum source precursor steam with ultra-high purity can be formed after being collected and condensed, so that the performance of the tantalum nitride film can be improved in the process of preparing the ultra-thin tantalum nitride barrier layer.
Compared with the simple sublimation condensation or adsorption of the vapor of the tantalum source precursor in the prior art, the purification method of the tantalum source precursor can obviously improve the purification efficiency and the purification effect.
Firstly, the method breaks through the limitation of the form of the tantalum source precursor, the solid tantalum source precursor which is not suitable for direct purification originally is dissolved in the liquid medium and then purified, the solid tantalum source precursor is not required to be firstly converted into the gaseous tantalum source precursor and then the vapor of the gaseous tantalum source precursor is absorbed and purified as in the prior art, and the purification steps are simplified.
Secondly, because the purification step of the method is carried out in the liquid medium, the contact time between the purification step and the adsorbent can be regulated and controlled at any time according to the adsorption effect, thereby ensuring the adsorption effect on the impurities in the tantalum source precursor. However, the contact time between the vapor of the tantalum source precursor and the adsorbent in the prior art cannot be maintained for a long time, so that the purification effect of the tantalum source precursor cannot be maintained at a high level.
Thirdly, in the invention, the system temperature is only required to be increased when the tantalum source precursor is sublimated, and the heat preservation and heating effect on the tantalum source precursor steam is not required. In order to ensure that the tantalum source precursor vapor is not condensed when contacting the adsorbent so as to block the adsorbent in the prior art, the tantalum source precursor vapor needs to be heated at the same time. Therefore, the purification method greatly reduces energy consumption and is more environment-friendly.
Finally, the inert liquid medium adopted in the invention is an inert liquid medium without volatility, so that when the tantalum source precursor reaches the evaporation temperature, the liquid media cannot be evaporated along with the tantalum source precursor, thereby reducing the purity of the tantalum source precursor.
Preferably, the adsorbent in step (s.1) comprises any one of activated carbon, porous alumina, silica gel powder, zeolite or molecular sieve.
The adsorbent adopted in the invention is an adsorbent with a porous structure, and impurities in the tantalum source precursor can be adsorbed and captured by the adsorbent in a physical form after entering the porous structure of the adsorbent, so that the purity of the tantalum source precursor is effectively improved.
Preferably, the surface of the adsorbent is also loaded with simple substance iron and manganese monoxide;
the outer surface of the adsorbent is also coated with a carbon layer with a porous structure.
The adsorption principle of the adsorbent (such as activated carbon, porous alumina, silica gel powder and the like) provided by the invention is that the adsorbent plays a good adsorption role on impurities in the tantalum source precursor in a physical adsorption mode. However, the physical adsorption method has a low adsorption capacity and also has a desorption problem, and thus although the purity of the tantalum source precursor can be improved, the upper limit of the purification effect is low, and it is difficult to achieve a higher purity level. Therefore, the invention carries out certain modification aiming at the adsorbents, thereby leading the adsorbents to have the effect of chemical adsorption, overcoming the problem of desorption and improving the upper limit of the purification effect.
Firstly, the surface of the adsorbent in the invention is loaded with simple substance iron and manganese oxide.
Wherein elemental iron is capable of reacting with small amounts of halogen-containing impurities remaining in the tantalum source precursor (e.g., it may react with hydrogen chloride, as well as hydrogen bromide), thereby immobilizing the halogen-containing impurities as well as the iron salt on the sorbent surface. Meanwhile, the elemental iron particles have extremely strong reducibility and can react with oxygen molecules doped in the tantalum source precursor, so that the oxygen content in the tantalum source precursor is reduced.
Correspondingly, the manganese oxide is loaded on the surface of the adsorbent, the adsorbent can have a good reaction effect with halogen-containing impurities, and meanwhile, when the manganese oxide is low-valence manganese monoxide, the adsorbent has a strong adsorption effect on oxygen, and when the manganese oxide reacts with the oxygen to form high-valence manganese oxide, the adsorbent still has a good absorption effect on the halogen-containing impurities.
In addition, after practical tests, when the reactants are simultaneously loaded with the oxides of the simple substance iron and the manganese, the adsorption effect of the reactants on the halogen-containing impurities and the oxygen is obvious because the reactants are independently loaded with the oxides of the simple substance iron and the manganese, and the collocation of the two reactants can play an obvious synergistic effect.
Preferably, the preparation method of the adsorbent is as follows:
(1) Soaking the adsorbent in a solution containing ferric salt and manganese salt to obtain the adsorbent loaded with ferric salt and manganese salt;
(2) Heating the adsorbent loaded with ferric salt and manganese salt in an air atmosphere to convert the ferric salt and the manganese salt into ferric oxide and manganese oxide;
(3) Then reducing the oxide of the iron into simple substance iron in the hydrogen atmosphere, and reducing the oxide of the manganese into manganese monoxide;
(4) Loading a layer of carbon precursor on the surface of the adsorbent loaded with the elemental iron and the manganese monoxide, and then converting the carbon precursor into a carbon layer with a porous structure under the protection of inert gas to obtain the adsorbent.
According to the invention, the simple substance iron and manganese monoxide are loaded by adopting an impregnation method, then the iron salt and manganese salt are finally converted into iron and manganese oxides through an oxidation reaction of air, and finally the iron oxide can be reduced into the simple substance iron through selective reduction of hydrogen, and the manganese oxide can only be reduced to the state of manganese monoxide at most under the reduction action of the hydrogen, so that the finally obtained adsorbent only can contain the simple substance iron and the manganese monoxide.
In addition, the outer surface of the adsorbent is coated with a layer of porous carbon, and the porous structure can effectively improve the adsorption effect on impurities. Meanwhile, the carbon layer has a good electron conduction effect, so that the electron transfer activity of elemental iron and manganese monoxide in the conversion process can be effectively improved, and the adsorption effect of the adsorbent on impurities is improved.
Meanwhile, in the coating process of the porous carbon, the adsorbent can be coated on the surface by adopting carbon-containing resin or other carbon-containing monomers. The carbon-containing resin may be polyethylene oxide, polypyrrolidone, polyacrylic acid resin, etc., and the carbon-containing simple substance may include dopamine or tannic acid, etc. to coat, so as to form polydopamine or polytannic acid on the surface of the adsorbent, and after the carbon-containing resin and the carbon-containing simple substance are subjected to heat treatment under inert conditions, the carbon layer with a porous structure can be obtained.
Preferably, the inert liquid medium in step (s.1) comprises any one of an ionic liquid or a silicone oil.
The inert liquid medium in the invention can adopt ionic liquid or silicon oil, and the ionic liquid or the silicon oil has good dissolving performance and extremely low saturated vapor pressure for the tantalum source precursor, so that impurities can not be brought into a final finished product in the sublimation process of the tantalum source precursor.
Preferably, the ionic liquid comprises one or more of imidazole ionic liquid, quaternary ammonium ionic liquid, quaternary phosphonium ionic liquid, pyrrolidine ionic liquid and piperidine ionic liquid.
Preferably, the cation of the ionic liquid is any one of N-hexylpyridine, N-butylpyridine, N-octylpyridine, N-butyl-N-methylpyrrolidine, 1-butyl-3-methylimidazole, 1-propyl-3-methylimidazole, 1-ethyl-3-methylimidazole, 1-hexyl-3-methylimidazole, 1-octyl-3-methylimidazole, 1-allyl-3-methylimidazole, 1-butyl-2, 3-dimethylimidazole, 1-butyl-3-methylimidazole, tributylmethylphosphine, tributylethylphosphine, tetrabutylphosphine, tributylhexylphosphine, tributyloctylphosphine, tributyldecylphosphine, tributyldodecylphosphine, tributyltetradecylphosphine, triphenylethylphosphine, triphenylbutylphosphine, triphenylmethylphosphine, triphenylpropylphosphine, triphenylpentylphosphine, triphenylacetonylphosphine, triphenylbenzylphosphine, triphenyl (3-bromopropyl) phosphine, triphenylbromomethylphosphine, triphenylmethoxyphosphine, triphenylethoxycarbonylmethylphosphine, triphenyl3-bromopropylphosphine, triphenylvinylphosphine, and tetraphenylphosphine.
Preferably, the anion of the ionic liquid is BF 4 - 、PF 6 - 、CF 3 SO 3 - 、(CF 3 SO 2 ) 2 N - 、C 3 F 7 COO - 、C 4 F 9 SO 3 、CF 3 COO - 、(CF 3 SO 2 ) 3 C - 、(C 2 F 5 SO 2 ) 3 C - 、(C 2 F 5 SO 2 ) 2 N - 、SbF 6 - Any one of them.
Preferably, the ionic liquid includes 1-butyl-3-methylimidazole trifluoromethanesulfonate, 1-butyl-3-methylimidazole dicyanamine salt, 1-ethyl-3-methylimidazole trifluoroacetate, 1-ethyl-3-methylimidazole chloroaluminate, 1-ethyl-2, 3-dimethylimidazole tetrafluoroborate, 1-hexyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-allyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-ethyl-3-methylimidazole chloride salt, 1-ethyl-3-methylimidazole bistrifluoromethylsulfonyl imide salt, 1-sulfonic acid butyl-2-methyl-3-hexadecylimidazole hydrogen sulfate salt, 1-ethyl-3-methylimidazole tetrafluoroborate, 1-ethyl-3-methylimidazole carbonate, 1-ethyl-3-methylimidazole L-lactate, 1, 3-dimethylimidazole hexafluorophosphate, 1-ethyl-3-methylimidazole hexafluorophosphate, 1-propyl-3-methylimidazole hexafluorophosphate, 1-butyl-3-methylimidazole hexafluorophosphate, 1-hexyl-3-methylimidazole hexafluorophosphate, 1-methyloctylmethyl-3-methylimidazole hexafluorophosphate, 1-tetradecyl-methylimidazole hexafluorophosphate, 1-benzylhexafluorophosphate, 1-methyl imidazole hexafluorophosphate, 1-3-methyl imidazole hexafluorophosphate, 1-decylmethylimidazole hexafluorophosphate, 1-3-methyl imidazole hexafluorophosphate, 1-methyl imidazole benzylhexafluorophosphate, 1-3-methyl imidazole hexafluorophosphate, 1-methyl imidazole, 1-allyl-3-methylimidazole hexafluorophosphate, 1-vinyl-3-ethylimidazole hexafluorophosphate, 1-vinyl-3-butylimidazole hexafluorophosphate, 1-hexadecyl-2, 3-dimethylimidazole hexafluorophosphate, 1-octyl-2, 3-dimethylimidazole hexafluorophosphate, 1, 3-dimethylimidazole tetrafluoroborate, 1-butyl-3-methylimidazole tetrafluoroborate, 1-decyl-3-methylimidazole tetrafluoroborate, 1-benzyl-3-methylimidazole tetrafluoroborate, 1-ethyl-2, 3-dimethylimidazole tetrafluoroborate, 1-propyl-2, 3-dimethylimidazole tetrafluoroborate, 1-octyl-2, 3-dimethylimidazole tetrafluoroborate.
Preferably, the tantalum source precursor includes any one of pentakis (dimethylamino) tantalum, pentakis (diethylamino) tantalum, pentaethyoxyl tantalum, and tris (diethylamino) tert-butylamido tantalum.
Preferably, the step (s.2) further comprises a step of introducing an inert gas into the adsorption slurry under reduced pressure.
In the invention, inert gas is introduced into the adsorption slurry under the condition of reduced pressure, and the aim is that a part of gaseous impurities doped in the tantalum source precursor are taken out of the system through the inert gas, so that the purity of the finally obtained tantalum source precursor can be effectively improved.
In a second aspect, the present invention also provides a purification system for purifying a tantalum source precursor, comprising:
the purification unit comprises a purification tank for containing materials, a stirring device for stirring the materials in the purification tank, and a heating device for heating the purification tank;
a gas supply unit communicated with a bottom pipeline of the purification tank so as to introduce inert gas into the purification tank;
the collecting unit comprises a condensing device communicated with a top pipeline of the purifying tank, so that the condensing device is used for condensing and collecting tantalum source precursor vapor obtained by evaporation in the cavity;
the trapping unit comprises a trapping bottle communicated with a pipeline of the condensing device, and a cold trap is sleeved outside the trapping bottle;
and the pressure control unit is communicated with the collecting bottle pipeline and is used for controlling the internal pressure of the whole system.
Preferably, the gas supply unit includes a gas tank for storing an inert gas; and (c) a second step of,
a pressure control valve for controlling the flow rate of the gas stream delivered to the purification unit.
Preferably, the condensing device comprises a product collecting tank and a condensing pipe arranged at the upper end of the collecting tank;
a plurality of condensation baffles are alternately arranged in the condensation pipe;
the top end of the condensing pipe is communicated with the purification tank pipeline, and the bottom end of the condensing pipe is communicated with the trapping bottle pipeline.
Therefore, the invention has the following beneficial effects:
(1) In the purification process of the tantalum source precursor, the purification step is simplified by changing the purification mode of the tantalum source precursor;
(2) According to the method, the purification efficiency and the purification effect are effectively improved in the purification process of the tantalum source precursor;
(3) And the energy consumption in the purification process of the tantalum source precursor is effectively reduced in the purification process.
Drawings
FIG. 1 is a schematic diagram of a purification system for purifying a tantalum source precursor according to the present invention.
Fig. 2 is a schematic view of a structure of a conventional purification apparatus.
Fig. 3 is an electron micrograph of the surface-modified adsorbent a.
Wherein: the device comprises a purification unit 100, a purification tank 110, a stirring device 120, a driving motor 121, a transmission rod 122, a stirring paddle 123, a heating device 130, a gas transmission pipe 140, a gas outlet pipe 150, a gas supply unit 200, a gas tank 210, a pressure control valve 220, a condensing device 300, a product collecting tank 310, a condensing pipe 320, a condensation baffle 321, a trapping unit 400, a trapping bottle 410, a cold trap 420, a pressure control unit 500, a distiller 600, a first heating unit 610, an adsorption unit 700, a second heating unit 710, a condensation unit 800 and a vacuum control unit 900.
Detailed Description
The invention is further described with reference to the drawings and the specific embodiments. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
[ PREPARATION OF SURFACE-LOADED MODIFIED ADSORBENT ]
Surface-supported modified adsorbent a:
(1) Soaking 100g of silica gel powder in a solution containing 0.1mol/L ferric chloride and 0.05mol/L manganese chloride for 30min, and filtering and drying to obtain an adsorbent loaded with ferric chloride and manganese chloride;
(2) Heating silica gel powder loaded with ferric chloride and manganese chloride to 350 ℃ in the air atmosphere, and maintaining for 2 hours to convert the ferric chloride and the manganese chloride into iron oxide and manganese oxide;
(3) Then heating silica gel powder carrying iron oxide and manganese oxide to 650 ℃ in a hydrogen atmosphere, and keeping for 3 hours to reduce the iron oxide into simple substance iron and reduce the manganese oxide into manganese monoxide;
(4) Dispersing 100g of the adsorbent loaded with the simple substance iron and the manganese monoxide into 1000ml of water, adding 300ml of ethanol and 80g of resorcinol, stirring for 30min at 40 ℃, then dropwise adding 40ml of formaldehyde, stirring for reacting for 6h to form a layer of phenolic resin on the surface of the adsorbent, centrifugally collecting silica gel powder loaded with the simple substance iron and the manganese monoxide and containing the phenolic resin on the surface, and heating to 700 ℃ at a speed of 2 ℃/min under the condition, so that the phenolic resin is converted into a carbon layer with a porous structure, and finally obtaining the adsorbent A with the modified surface loading.
Surface-supported modified adsorbent B:
the difference between the adsorbent C and the adsorbent A is that only 0.15mol/L ferric chloride is added in the step (1), the other conditions are not changed, and only elemental iron and a carbon layer with a porous structure are loaded in the finally obtained adsorbent B.
Surface-supported modified adsorbent C:
the difference between the adsorbent C and the adsorbent A is that only 0.15mol/L manganese chloride is added in the step (1), the other conditions are not changed, and only manganese monoxide and a carbon layer with a porous structure are loaded in the finally obtained adsorbent B.
Surface-supported modified adsorbent D:
the adsorbent D is different from the adsorbent a in that the step (4) is omitted, i.e., no porous-structure-coated carbon layer is coated outside the adsorbent loaded with elemental iron and manganese monoxide.
[ purifying system for purifying tantalum source precursor ]
As shown in fig. 1, the present invention provides a purification system for purifying a tantalum source precursor, comprising:
a purification unit 100 comprising a purification tank 110 for holding a material comprising a crude tantalum source precursor, an adsorbent, an inert liquid medium having no volatility, etc., so that the crude tantalum source precursor can be contacted with the adsorbent dispersed in the inert liquid medium inside the purification tank 110, thereby enabling the adsorption purification of halogen-containing impurities and oxygen in the crude tantalum source precursor by the adsorbent.
In order to improve the contact effect of the crude tantalum source precursor and the adsorbent, a stirring device 120 for stirring the materials in the purification tank 110 is specially arranged on the purification tank 110, the stirring device 120 comprises a driving motor 121 arranged at the top of the purification tank 110 and a transmission rod 122 connected with the driving motor and extending into the purification tank 110, a stirring paddle 123 for stirring the materials is arranged on the transmission rod 122, and after the driving motor 121 is started, the driving motor 121 can drive the transmission rod 122 to rotate, so that the stirring paddle 123 plays a role in shearing the materials, and the stirring effect on the materials is improved.
In order to facilitate the temperature control of the materials inside the purification tank 110, the invention further provides a heating device 130 at the periphery of the purification tank 110, so as to facilitate the heating of the materials inside the purification tank 110.
The purification tank 110 is further provided at the top thereof with a gas pipe 140 extending through the purification tank 110 toward the bottom of the purification tank 110 for connecting with a gas supply unit 200 provided outside the purification tank 110. The gas supply unit 200 comprises a gas tank 210 for storing inert gas, which is connected to a pressure control valve 220 and is communicated with the gas pipe 140 through a pipeline, when the pressure control valve 220 is opened, the inert gas in the gas tank 210 can enter the purification tank 110 through the pipeline, so as to take out a part of the gaseous impurities doped in the tantalum source precursor from the system through the part of the introduced inert gas.
The top of the purification tank 110 is further provided with an outlet pipe 150 communicated with the outside, so that the inert gas or the tantalum source precursor vapor can flow along the outlet pipe 150 to the outside of the purification tank 110, and is connected to the outlet pipe 150, the outside of the purification tank 110 is further provided with a condensing device 300 communicated with the outlet pipe 150, the condensing device 300 comprises a collecting tank 310 and a condensing pipe 320 arranged at the upper end of the collecting tank 310, and a plurality of condensing baffles 321 are alternately arranged inside the condensing pipe 320. When the inert gas comes out from the interior of the purification tank 110 together with the non-condensable gas such as oxygen, the inert gas enters the top of the condensation pipe 320 along the gas outlet pipe 150, and then flows to the outside of the condensation device 300 through the bottom of the condensation pipe 320. When the tantalum source precursor vapor exits the purification tank 110, it can enter the interior of the condensation tube 320 through the gas outlet tube 150, and then can condense on the surface of the condensation baffle 321 after contacting the condensation baffle 321, and then fall into the bottom product collection tank 310. In order to ensure that the tantalum source precursor can smoothly drop off the condensation baffle 321, the condensation baffles 321 can be alternately arranged in a left-right inclined manner, so that the falling resistance of the tantalum source precursor is reduced.
In addition, because of the pressure setting, a part of the tantalum source precursor vapor directly flows out from the condensing device 300 without being condensed, at this time, a trap unit 400 can be connected to the outside of the condensing device 300, the trap unit 400 includes a trap bottle 410 communicated with the pipeline of the condensing device 120, a cold trap 420 is sleeved outside the trap bottle 410, and a condensing medium such as liquid nitrogen can be added into the cold trap 420, so that the escaped tantalum source precursor vapor can be condensed, and prevented from entering the subsequent pressure control unit 500.
Finally, the present invention is also provided with a pressure control unit 500, which may be constituted by a vacuum pump, which is in communication with the trap bottle 410 in a piping manner, so that when it is operated, it can perform a vacuum work for the inside of the entire system, thereby serving to control the pressure inside the entire system.
[ conventional purification apparatus ]
The conventional purification apparatus includes a distiller 600 and an adsorption unit 700 located at the top of the distiller 600, wherein a first heating unit 610 for heating the distiller 600 is arranged outside the distiller 600, the adsorption unit 700 is filled with an adsorbent, and the adsorption unit 700 is also covered with a second heating unit 710 for heating the adsorption unit 700, the top of the adsorption unit 700 is connected with a condensation unit 800, so that tantalum source precursor vapor flowing out from the top of the adsorption unit 700 can be condensed in the condensation unit 800, and a vacuum control unit 900 for controlling the pressure of the whole system is connected to the adsorption unit 700.
Example 1
The purification method of pentakis (dimethylamino) tantalum comprises the following steps:
s.1, adding 10L 1-ethyl-3-methylimidazole chlorine salt and 100g of activated carbon into a purification tank 110, uniformly stirring, and obtaining adsorption slurry inside the purification tank 110;
s.2, 100g of crude pentakis (dimethylamino) tantalum is dissolved in the purification tank 110, the temperature in the purification tank 110 is controlled to 40 ℃, and the crude pentakis (dimethylamino) tantalum is dissolved in the adsorption slurry by stirring. Then, the system pressure is controlled to 1 kPa by a pressure control unit 500, argon is introduced into the purification tank 110 at a rate of 10L/h under the stirring condition, so that the crude pentakis (dimethylamino) tantalum is contacted with the adsorbent, and impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
s.3, after stirring and adsorbing for 3 hours, stopping introducing argon, reducing the system pressure to 0.1 kPa, continuing stirring for 0.5 hour, and then raising the temperature of the adsorption slurry to 65 ℃ so as to evaporate the tantalum source precursor, thereby forming tantalum source precursor steam;
s.4 the tantalum source precursor vapor enters the condenser tube 122 along the outlet tube 150, is condensed in the condenser tube 122, and collects the high purity pentakis (dimethylamino) tantalum that falls into the collection tank 121.
Example 2
The purification method of the pentakis (dimethylamino) tantalum comprises the following steps:
s.1, adding 10L 1-ethyl-3-methylimidazole chlorine salt and 100g of silica gel powder into a purification tank 110, uniformly stirring, and obtaining adsorption slurry inside the purification tank 110;
s.2, 100g of crude pentakis (dimethylamino) tantalum is dissolved in the purification tank 110, the temperature in the purification tank 110 is controlled to 40 ℃, and the crude pentakis (dimethylamino) tantalum is dissolved in the adsorption slurry by stirring. Then, controlling the system pressure to 1 kPa by a pressure control unit 500, and introducing argon into the purification tank 110 at a rate of 10L/h under a stirring condition to contact the crude pentakis (dimethylamino) tantalum with the adsorbent, so that impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
s.3, after stirring and adsorbing for 3 hours, stopping introducing argon, reducing the system pressure to 0.1 kPa, continuously stirring for 0.5 hour, and raising the temperature of the adsorption slurry to 65 ℃ to evaporate the tantalum source precursor, thereby forming tantalum source precursor steam;
s.4 the tantalum source precursor vapor enters the condenser tube 122 along the outlet tube 150, is condensed in the condenser tube 122, and collects the high purity pentakis (dimethylamino) tantalum that falls into the collection tank 121.
Example 3
The purification method of the pentakis (dimethylamino) tantalum comprises the following steps:
s.1, adding 10L 1-ethyl-3-methylimidazole chlorine salt and 100g of adsorbent A subjected to surface loading modification into a purification tank 110, uniformly stirring, and obtaining adsorption slurry inside the purification tank 110;
s.2, dissolving 100g of crude pentakis (dimethylamino) tantalum in the purification tank 110, controlling the temperature in the purification tank 110 to 40 ℃, and stirring to dissolve the crude pentakis (dimethylamino) tantalum in the adsorption slurry. Then, the system pressure is controlled to 1 kPa by a pressure control unit 500, argon is introduced into the purification tank 110 at a rate of 10L/h under the stirring condition, so that the crude pentakis (dimethylamino) tantalum is contacted with the adsorbent, and impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
s.3, after stirring and adsorbing for 3 hours, stopping introducing argon, reducing the system pressure to 0.1 kPa, continuously stirring for 0.5 hour, and raising the temperature of the adsorption slurry to 65 ℃ to evaporate the tantalum source precursor, thereby forming tantalum source precursor steam;
s.4, the tantalum source precursor vapor enters the condensation pipe 122 along the gas outlet pipe 150, is condensed in the condensation pipe 122, and is collected into the high-purity pentakis (dimethylamino) tantalum falling into the collection tank 121.
Example 4
The purification method of pentakis (dimethylamino) tantalum comprises the following steps:
s.1, adding 10L 1-ethyl-3-methylimidazole chlorine salt and 100g of adsorbent B subjected to surface loading modification into a purification tank 110, uniformly stirring, and obtaining adsorption slurry inside the purification tank 110;
s.2, 100g of crude pentakis (dimethylamino) tantalum is dissolved in the purification tank 110, the temperature in the purification tank 110 is controlled to 40 ℃, and the crude pentakis (dimethylamino) tantalum is dissolved in the adsorption slurry by stirring. Then, the system pressure is controlled to 1 kPa by a pressure control unit 500, argon is introduced into the purification tank 110 at a rate of 10L/h under the stirring condition, so that the crude pentakis (dimethylamino) tantalum is contacted with the adsorbent, and impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
s.3, after stirring and adsorbing for 3 hours, stopping introducing argon, reducing the system pressure to 0.1 kPa, continuing stirring for 0.5 hour, and then raising the temperature of the adsorption slurry to 65 ℃ so as to evaporate the tantalum source precursor, thereby forming tantalum source precursor steam;
s.4 the tantalum source precursor vapor enters the condenser tube 122 along the outlet tube 150, is condensed in the condenser tube 122, and collects the high purity pentakis (dimethylamino) tantalum that falls into the collection tank 121.
Example 5
The purification method of the pentakis (dimethylamino) tantalum comprises the following steps:
s.1, adding 10L 1-ethyl-3-methylimidazole chlorine salt and 100g of adsorbent C subjected to surface loading modification into a purification tank 110, uniformly stirring, and obtaining adsorption slurry inside the purification tank 110;
s.2, dissolving 100g of crude pentakis (dimethylamino) tantalum in the purification tank 110, controlling the temperature in the purification tank 110 to 40 ℃, and stirring to dissolve the crude pentakis (dimethylamino) tantalum in the adsorption slurry. Then, the system pressure is controlled to 1 kPa by a pressure control unit 500, argon is introduced into the purification tank 110 at a rate of 10L/h under the stirring condition, so that the crude pentakis (dimethylamino) tantalum is contacted with the adsorbent, and impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
s.3, after stirring and adsorbing for 3 hours, stopping introducing argon, reducing the system pressure to 0.1 kPa, continuously stirring for 0.5 hour, and raising the temperature of the adsorption slurry to 65 ℃ to evaporate the tantalum source precursor, thereby forming tantalum source precursor steam;
s.4 the tantalum source precursor vapor enters the condenser tube 122 along the outlet tube 150, is condensed in the condenser tube 122, and collects the high purity pentakis (dimethylamino) tantalum that falls into the collection tank 121.
Example 6
The purification method of the pentakis (dimethylamino) tantalum comprises the following steps:
s.1, adding 10L 1-ethyl-3-methylimidazole chlorine salt and 100g of adsorbent D subjected to surface loading modification into a purification tank 110, uniformly stirring, and obtaining adsorption slurry inside the purification tank 110;
s.2, 100g of crude pentakis (dimethylamino) tantalum is dissolved in the purification tank 110, the temperature in the purification tank 110 is controlled to 40 ℃, and the crude pentakis (dimethylamino) tantalum is dissolved in the adsorption slurry by stirring. Then, controlling the system pressure to 1 kPa by a pressure control unit 500, and introducing argon into the purification tank 110 at a rate of 10L/h under a stirring condition to contact the crude pentakis (dimethylamino) tantalum with the adsorbent, so that impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
s.3, after stirring and adsorbing for 3 hours, stopping introducing argon, reducing the system pressure to 0.1 kPa, continuously stirring for 0.5 hour, and raising the temperature of the adsorption slurry to 65 ℃ to evaporate the tantalum source precursor, thereby forming tantalum source precursor steam;
s.4, the tantalum source precursor vapor enters the condensation pipe 122 along the gas outlet pipe 150, is condensed in the condensation pipe 122, and is collected into the high-purity pentakis (dimethylamino) tantalum falling into the collection tank 121.
Example 7
Example 7 is essentially the same as the procedure of comparative example 3, except that pentakis (dimethylamino) tantalum is replaced with pentakis (diethylamino) tantalum and the distillation temperature is raised to 75 ℃.
Comparative example 1
Placing crude pentakis (dimethylamino) tantalum into a distiller 600 of a conventional horizontal sublimation refining tower, placing silica gel powder into an adsorption unit 700, reducing the pressure to 0.1 kPa to extract air in the horizontal sublimation refining tower, raising the temperature of the distiller 600 and the adsorption unit 700 to 65 ℃ to form pentakis (dimethylamino) tantalum vapor, passing through the adsorption unit 700 and entering a condensation unit 800, and condensing the pentakis (dimethylamino) tantalum into a solid again to obtain purified pentakis (dimethylamino) tantalum.
Comparative example 2
Placing crude pentakis (dimethylamino) tantalum into a distiller 600 of a conventional horizontal sublimation refining tower, placing an adsorbent A with modified surface into an adsorption unit 700, reducing the pressure to 0.1 kPa to remove air in the horizontal sublimation refining tower, raising the temperature of the distiller 600 and the adsorption unit 700 to 65 ℃ to form pentakis (dimethylamino) tantalum vapor, passing through the adsorption unit 700 and entering a condensation unit 800, and condensing the pentakis (dimethylamino) tantalum into a solid again to obtain purified pentakis (dimethylamino) tantalum.
[ results of Performance test ]
The impurity contents of pentakis (dimethylamino) tantalum obtained by purification in examples 1 to 6 and comparative application examples 1 to 2 and pentakis (diethylamino) tantalum obtained in example 7 are shown in table 1 below.
TABLE 1
As can be seen from the above data, the preparation method of the present invention can achieve a good purification effect on the tantalum source precursor, and effectively improves the purification efficiency and the purification effect compared to the simple sublimation condensation or adsorption of the vapor of the tantalum source precursor in the prior art.
Meanwhile, the tantalum source precursor can be well adsorbed and purified only by using a simple adsorbent, and the content of impurities in the purified tantalum source precursor can be reduced to ppm level. Meanwhile, the method is not limited to the specific form of the tantalum source precursor, and both solid pentakis (dimethylamino) tantalum and liquid pentakis (diethylamino) tantalum can be effectively purified, so that the purification steps are effectively simplified. Meanwhile, in the invention, the system temperature is only required to be increased when the tantalum source precursor is sublimated, and the heat preservation and heating effect on the vapor of the tantalum source precursor is not required. In order to ensure that the tantalum source precursor vapor is not condensed when contacting the adsorbent so as to block the adsorbent, the tantalum source precursor vapor needs to be heated at the same time in the prior art. Therefore, the purification method greatly reduces energy consumption and is more environment-friendly.
Meanwhile, the invention also finds that after the surface loading modification is carried out on the adsorbent, the purification effect of the tantalum source precursor can be further improved, so that the internal impurities can reach the ppb level. Meanwhile, actual test results show that when elementary iron and manganese monoxide are simultaneously loaded on the surface of the adsorbent, the adsorption effect on halogen-containing impurities and oxygen in the tantalum source precursor can be effectively improved. And the setting up of carbon layer makes the electron conduction effect of adsorbent effectively promote, consequently can effectively promote elementary substance iron and manganese monoxide electron transfer activity at the transition in-process to the adsorption effect of adsorbent to impurity has been promoted.
Claims (6)
1. The method for purifying the tantalum source precursor is characterized by comprising the following steps of:
(S.1) dispersing an adsorbent in an inert liquid medium without volatility to obtain adsorption slurry;
(S.2) dissolving the crude tantalum source precursor into the adsorption slurry to enable the crude tantalum source precursor to be in contact with the adsorbent, so that impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
(S.3) raising the temperature of the adsorption slurry to the evaporation temperature of the tantalum source precursor, so that the tantalum source precursor is evaporated, and thus forming tantalum source precursor steam;
(S.4) collecting tantalum source precursor steam and condensing the tantalum source precursor steam to obtain a high-purity tantalum source precursor;
the adsorbent is subjected to surface loading modification;
the surface of the adsorbent subjected to surface loading modification is also loaded with simple substance iron and manganese monoxide;
the outer surface of the adsorbent subjected to surface loading modification is further coated with a carbon layer with a porous structure.
2. The method of purifying a tantalum source precursor according to claim 1,
in the step (S.1), the adsorbent comprises any one of activated carbon, porous silica alumina, silica gel powder, zeolite or molecular sieve.
3. The method of purifying a tantalum source precursor according to claim 1,
the preparation method of the adsorbent subjected to surface loading modification comprises the following steps:
(1) Soaking the adsorbent in a solution containing ferric salt and manganese salt to obtain the adsorbent loaded with ferric salt and manganese salt;
(2) Heating the adsorbent loaded with ferric salt and manganese salt in an air atmosphere to convert the ferric salt and the manganese salt into ferric oxide and manganese oxide;
(3) Then reducing the oxide of the iron into simple substance iron in the hydrogen atmosphere, and reducing the oxide of the manganese into manganese monoxide;
(4) Loading a layer of carbon precursor on the surface of the adsorbent loaded with the elemental iron and the manganese monoxide, and then converting the carbon precursor into a carbon layer with a porous structure under the protection of inert gas to obtain the adsorbent subjected to surface loading modification.
4. The method of purifying a tantalum source precursor according to claim 1 or 2,
the inert liquid medium in step (s.1) comprises any one of an ionic liquid or a silicone oil.
5. The method of purifying a tantalum source precursor according to claim 1,
the tantalum source precursor comprises any one of pentakis (dimethylamino) tantalum, pentakis (diethylamino) tantalum, pentaethoxy tantalum and tri (diethylamino) tert-butanamide tantalum.
6. The method of purifying a tantalum source precursor according to claim 1,
the step (s.2) further includes a step of introducing an inert gas into the adsorption slurry under a reduced pressure.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1281630A (en) * | 1961-02-13 | 1962-01-12 | Monsanto Chemicals | Purification process, in particular of metallic or semi-metallic substances |
| GB1173015A (en) * | 1966-11-01 | 1969-12-03 | Air Reduction | Improvements in or relating to the Production of Metals |
| US5536302A (en) * | 1994-03-23 | 1996-07-16 | Air Products And Chemicals, Inc. | Adsorbent for removal of trace oxygen from inert gases |
| US5538598A (en) * | 1992-03-23 | 1996-07-23 | Fsr Patented Technologies, Ltd. | Liquid purifying/distillation device |
| US6579509B1 (en) * | 1999-11-30 | 2003-06-17 | Japan Pionics Co., Ltd. | Method of cleaning of harmful gas and cleaning apparatus |
| CN102244231A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
| RU2533491C1 (en) * | 2013-08-08 | 2014-11-20 | Федеральное государственное унитарное предприятие "Государственный ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП "ГНИИХТЭОС") | Method of obtaining chemisorbent for purification of inert gases and reducing gases from admixtures |
| CN104975269A (en) * | 2014-04-04 | 2015-10-14 | 广东丹邦科技有限公司 | Tantalum-sourced precursor, preparation method of tantalum-sourced precursor and preparation method of TaN film resistance |
| CN113235056A (en) * | 2021-05-19 | 2021-08-10 | 宁波江丰电子材料股份有限公司 | Preparation method of high-purity tantalum target material |
Family Cites Families (9)
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| JP4162366B2 (en) * | 2000-03-31 | 2008-10-08 | 田中貴金属工業株式会社 | CVD thin film forming process and CVD thin film manufacturing apparatus |
| AU5254801A (en) * | 2000-04-19 | 2001-10-30 | Saes Getters S.P.A. | A process for the purification of organometallic compounds or heteroatomic organic compounds with a catalyst based on iron and manganese supported on zeolites |
| US20020043501A1 (en) * | 2000-08-22 | 2002-04-18 | Irvine Robert L. | Process for treating liquid streams to remove unwanted impurities |
| US7160360B2 (en) * | 2003-12-08 | 2007-01-09 | Air Products And Chemicals, Inc. | Purification of hydride gases |
| JP4949960B2 (en) * | 2007-07-27 | 2012-06-13 | Ｄｏｗａホールディングス株式会社 | Method for producing tantalum oxide |
| CN102517460B (en) * | 2011-12-31 | 2014-02-05 | 宁波江丰电子材料有限公司 | Method for purifying tantalum powder and tantalum target |
| CN109110742B (en) * | 2017-06-23 | 2021-12-24 | 四川大学 | Mesoporous carbon prepared by manganese compound and preparation method thereof |
| CN110790671B (en) * | 2019-11-01 | 2022-05-20 | 浙江博瑞电子科技有限公司 | Method for refining pentakis (dimethylamino) tantalum |
| CN114870804B (en) * | 2022-06-10 | 2022-12-09 | 大连科利德光电子材料有限公司 | Impurity gas adsorbent and preparation method and application thereof |
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- 2022-12-11 WO PCT/CN2022/138261 patent/WO2024087339A1/en not_active Ceased
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Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1281630A (en) * | 1961-02-13 | 1962-01-12 | Monsanto Chemicals | Purification process, in particular of metallic or semi-metallic substances |
| GB1173015A (en) * | 1966-11-01 | 1969-12-03 | Air Reduction | Improvements in or relating to the Production of Metals |
| US5538598A (en) * | 1992-03-23 | 1996-07-23 | Fsr Patented Technologies, Ltd. | Liquid purifying/distillation device |
| US5536302A (en) * | 1994-03-23 | 1996-07-16 | Air Products And Chemicals, Inc. | Adsorbent for removal of trace oxygen from inert gases |
| US6579509B1 (en) * | 1999-11-30 | 2003-06-17 | Japan Pionics Co., Ltd. | Method of cleaning of harmful gas and cleaning apparatus |
| CN102244231A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
| RU2533491C1 (en) * | 2013-08-08 | 2014-11-20 | Федеральное государственное унитарное предприятие "Государственный ордена Трудового Красного Знамени научно-исследовательский институт химии и технологии элементоорганических соединений" (ФГУП "ГНИИХТЭОС") | Method of obtaining chemisorbent for purification of inert gases and reducing gases from admixtures |
| CN104975269A (en) * | 2014-04-04 | 2015-10-14 | 广东丹邦科技有限公司 | Tantalum-sourced precursor, preparation method of tantalum-sourced precursor and preparation method of TaN film resistance |
| CN113235056A (en) * | 2021-05-19 | 2021-08-10 | 宁波江丰电子材料股份有限公司 | Preparation method of high-purity tantalum target material |
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| WO2024087339A1 (en) | 2024-05-02 |
| KR20240060517A (en) | 2024-05-08 |
| CN115584482A (en) | 2023-01-10 |
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