WO2024087339A1 - Method for purifying tantalum source precursor - Google Patents
Method for purifying tantalum source precursor Download PDFInfo
- Publication number
- WO2024087339A1 WO2024087339A1 PCT/CN2022/138261 CN2022138261W WO2024087339A1 WO 2024087339 A1 WO2024087339 A1 WO 2024087339A1 CN 2022138261 W CN2022138261 W CN 2022138261W WO 2024087339 A1 WO2024087339 A1 WO 2024087339A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- source precursor
- tantalum
- tantalum source
- adsorbent
- purification
- Prior art date
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- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 184
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 239000002243 precursor Substances 0.000 title claims abstract description 148
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000000746 purification Methods 0.000 claims abstract description 119
- 239000003463 adsorbent Substances 0.000 claims abstract description 98
- 238000001179 sorption measurement Methods 0.000 claims abstract description 62
- 239000012535 impurity Substances 0.000 claims abstract description 39
- 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 4
- 230000008020 evaporation Effects 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 44
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 36
- 238000009833 condensation Methods 0.000 claims description 33
- 230000005494 condensation Effects 0.000 claims description 33
- 239000007789 gas Substances 0.000 claims description 33
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 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 25
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 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 19
- 238000010438 heat treatment Methods 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
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- 150000002505 iron Chemical class 0.000 claims description 10
- 150000002696 manganese Chemical class 0.000 claims description 10
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- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007833 carbon precursor Substances 0.000 claims description 4
- 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
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 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
- 239000002808 molecular sieve Substances 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
- 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 description 2
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- 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
- 238000000859 sublimation Methods 0.000 description 8
- 230000008022 sublimation Effects 0.000 description 8
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- 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
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
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- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/12—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the preparation of the feed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
- B01D5/006—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes with evaporation or distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
- B01J20/3204—Inorganic carriers, supports or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/324—Inorganic material layers containing free carbon, e.g. activated carbon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- the invention relates to the field of electronic precursor purification, and in particular to a method for purifying a tantalum source precursor.
- Tantalum nitride is a transition metal nitride. Due to its high hardness, controllable conductivity, and diffusion barrier effect on metal elements, tantalum nitride is the most widely studied diffusion barrier material in copper interconnect technology in the field of microelectronics industry. With the reduction of integrated circuit feature size and the increase of trench aspect ratio, the early physical vapor deposition (PVD) process is difficult to meet its future production needs, so atomic layer deposition (ALD) technology plays a vital role in the preparation of ultra-thin tantalum nitride barrier layer.
- PVD physical vapor deposition
- ALD atomic layer deposition
- organic metal tantalum is often used as a tantalum source precursor in the industry.
- the purity of the tantalum source precursor has a significant impact on the final deposited tantalum nitride film.
- Organic metal tantalum is usually prepared from tantalum halide during the preparation process. Therefore, a certain amount of tantalum halide and other halogen-containing impurities often remain in the prepared organic metal tantalum. These halogen-containing impurities will produce corrosive by-products during the atomic deposition process, so they are not conducive to industrial applications.
- Patent No. 201710492823.4 discloses a method for synthesizing tantalum penta(dimethylamino). Under the protection of an inert atmosphere, an organic lithium reagent and a hydrocarbon solvent are added to a reactor, and then dimethylamine gas is introduced into the system to obtain dimethylamino lithium; tantalum pentachloride is added to the system, and after the addition, the reaction is stirred under the protection of an inert atmosphere; after the reaction is completed, the reaction is filtered, and the filtrate is distilled to remove the hydrocarbon solvent; after all the solvents are removed, the solid is sublimated to obtain a tantalum penta(dimethylamino) product.
- the patent with application number 201911061946.8 discloses a method for refining tantalum penta(dimethylamino), which heats tantalum penta(dimethylamino) to make it sublime, and then passes the vapor of tantalum penta(dimethylamino) through metal organic framework ceramics, thereby adsorbing impurities in the vapor of tantalum penta(dimethylamino) to further increase the content of the product.
- this method can further improve the purity of tantalum penta(dimethylamino), it is difficult to adsorb all the impurities in it due to the short contact time between tantalum penta(dimethylamino) vapor and metal organic framework ceramics, resulting in the purity of the prepared tantalum penta(dimethylamino) still being difficult to improve.
- the speed of tantalum penta(dimethylamino) vapor passing through metal organic framework ceramics is slow, so it is difficult to improve the purification efficiency of tantalum penta(dimethylamino).
- the present invention aims to overcome the defects in the prior art that it is difficult to remove impurities doped in the tantalum source precursor during the purification process and the purification efficiency of the tantalum source precursor is low, and provides a purification method for a tantalum source precursor to overcome the above shortcomings.
- the present invention provides a method for purifying a tantalum source precursor, comprising the following steps:
- Tantalum source precursors are usually in solid form at room temperature. As they sublimate quickly when heated, as described in the background art, tantalum source precursors in the prior art usually rely on sublimation methods to reduce impurities doped in the tantalum source precursors. However, since the tantalum source precursors will also sublime with impurities during the sublimation process, it is difficult to remove all impurities from the tantalum source precursors obtained by sublimation and condensation.
- the present invention innovatively proposes a new purification method for tantalum source precursors.
- the crude tantalum source precursor is first dissolved in an adsorption slurry containing an adsorbent, so that in the process of the crude tantalum source precursor and the adsorbent contacting, the impurities in the crude tantalum source precursor can be adsorbed by the adsorbent.
- the temperature of the entire system is increased, and the tantalum source precursor can form steam.
- a tantalum source precursor with ultra-high purity can be formed, which can be beneficial to improve the performance of the tantalum nitride film in the process of preparing an ultra-thin tantalum nitride barrier layer.
- the purification method of the tantalum source precursor in the present invention can effectively improve both the purification efficiency and the purification effect compared with the simple sublimation condensation or adsorption of the vapor of the tantalum source precursor in the prior art.
- the present invention breaks through the limitation of the form of tantalum source precursor.
- the solid tantalum source precursor which is not suitable for direct purification is dissolved in a liquid medium and then purified. There is no need to convert the solid tantalum source precursor into a gaseous state and then purify the gaseous tantalum source precursor vapor by adsorption as in the prior art, thereby simplifying the purification steps.
- the contact time between the vapor and the adsorbent can be adjusted at any time according to the adsorption effect, thereby ensuring the adsorption effect of impurities in the tantalum source precursor.
- the contact time between the tantalum source precursor vapor and the adsorbent cannot be maintained for a long time, so the purification effect of the tantalum source precursor cannot be maintained at a high level.
- the present invention it is only necessary to increase the system temperature when the tantalum source precursor is sublimated, and it is not necessary to heat the tantalum source precursor vapor.
- the purification method in the present invention greatly reduces energy consumption and is more environmentally friendly.
- the inert liquid medium used in the present invention is a non-volatile inert liquid medium. Therefore, when the tantalum source precursor reaches the evaporation temperature, these liquid media will not evaporate together with the tantalum source precursor, thereby causing a decrease in the purity of the tantalum source precursor.
- the adsorbent in step (S.1) comprises any one of activated carbon, porous alumina, silica gel powder, zeolite or molecular sieve.
- the adsorbent used in the present invention is an adsorbent with a porous structure.
- the impurities in the tantalum source precursor enter the porous structure of these adsorbents, they can be physically adsorbed and captured by the adsorbent, thereby effectively improving the purity of the tantalum source precursor.
- the surface of the adsorbent is also loaded with elemental iron and manganese monoxide;
- the outer surface of the adsorbent is also coated with a carbon layer with a porous structure.
- the adsorbents described above in the present invention (such as activated carbon, porous alumina, silica gel powder, etc.) all have a good adsorption effect on impurities in the tantalum source precursor by physical adsorption.
- the physical adsorption method has a low adsorption capacity and also has the problem of desorption. Therefore, 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 reach a higher purity level. Therefore, the present invention has made certain modifications to these adsorbents so that they have the effect of chemical adsorption, thus overcoming the problem of desorption and improving the upper limit of the purification effect.
- the adsorbent in the present invention has oxides of elemental iron and manganese loaded on its surface.
- elemental iron can react with a small amount of halogen-containing impurities remaining in the tantalum source precursor (for example, it can react with hydrogen chloride and hydrogen bromide), thereby fixing the halogen-containing impurities and iron salts on the surface of the adsorbent.
- elemental iron particles have extremely strong reducibility and can react with oxygen molecules doped in the tantalum source precursor, thereby reducing the oxygen content in the tantalum source precursor.
- manganese oxide is also loaded on the surface of the adsorbent, which can also have a good reaction effect with halogen-containing impurities.
- the manganese oxide when the manganese oxide is low-valent manganese monoxide, it also has a strong adsorption effect on oxygen, and when it reacts with oxygen to form high-valent manganese oxide, it still has a good absorption effect on halogen-containing impurities.
- the preparation method of the adsorbent is as follows:
- a layer of carbon precursor is loaded on the surface of the adsorbent loaded with elemental iron and manganese monoxide, and then the carbon precursor is converted into a carbon layer with a porous structure under the protection of an inert gas, thereby obtaining the adsorbent.
- elemental iron and manganese monoxide are loaded with iron salt and manganese salt by impregnation method, and then these iron salt and manganese salt are finally converted into iron and manganese oxides through oxidation reaction in air, and finally the iron oxide is reduced to elemental iron through selective reduction by hydrogen. Since manganese oxide can only be reduced to the state of manganese monoxide at most under the reducing action of hydrogen, the finally obtained adsorbent can only contain elemental iron and manganese monoxide.
- the present invention also coats a layer of porous carbon on the outer surface of the adsorbent.
- its porous structure can effectively improve the adsorption of impurities.
- the carbon layer has a good electron conduction effect, it can effectively improve the electron transfer activity of elemental iron and manganese monoxide during the transformation process, thereby improving the adsorption effect of the adsorbent on impurities.
- the adsorbent in the coating process of porous carbon, can be coated with a carbon-containing resin or other carbon-containing single substance.
- the carbon-containing resin can be, for example, polyethylene oxide, polypyrrolidone or polyacrylic resin, and the carbon-containing single substance can be coated with, for example, dopamine or tannic acid, so as to form polydopamine or polytannic acid on the surface of the adsorbent.
- the inert liquid medium in step (S.1) comprises any one of ionic liquid and silicone oil.
- the inert liquid medium in the present invention can be ionic liquid or silicone oil, both of which have good solubility and extremely low saturated vapor pressure for the tantalum source precursor, thereby ensuring that the tantalum source precursor will not bring impurities into the final product during the sublimation process.
- the ionic liquid includes one or more combinations of imidazole ionic liquids, quaternary ammonium ionic liquids, quaternary phosphonium ionic liquids, pyrrolidine ionic liquids, and piperidine ionic liquids.
- the cation of the ionic liquid is 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, Any one of tetrabutylphosphine, tributylhexylphosphine, tributyloctylphosphine, tributyldecylphosphine, tributyldodecylphosphine,
- the anion of the ionic liquid is any one of BF4- , PF6- , CF3SO3- , ( CF3SO2 ) 2N- , C3F7COO- , C4F9SO3 , CF3COO- , ( CF3SO2 ) 3C- , ( C2F5SO2 ) 3C- , ( C2F5SO2 ) 2N- , and SbF6- .
- the ionic liquid includes 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium chloroaluminate, 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium bis-trifluoromethanesulfonyl imide, 1-allyl-3-methylimidazolium bis-trifluoromethanesulfonyl imide, 1-ethyl-3-methylimidazolium chloride, 1-ethyl -3-Methylimidazolium bistrifluoromethanesulfonyl imide salt, 1-sulfonic acid butyl-2-methyl-3-hexadecyl imidazolium hydrogen sulf
- the tantalum source precursor includes any one of penta(dimethylamino)tantalum, penta(diethylamino)tantalum, pentaethoxytantalum, and tri(diethylamino)tantalum-tert-butyramide.
- the step (S.2) further comprises the step of introducing an inert gas into the adsorption slurry under reduced pressure.
- an inert gas is introduced into the adsorption slurry under reduced pressure, the purpose of which is to remove a portion of gaseous impurities doped in the tantalum source precursor from the system through the inert gas, thereby effectively improving the purity of the final tantalum source precursor.
- the present invention further provides a purification system for purifying a tantalum source precursor, which at least comprises:
- a purification unit comprising a purification tank for containing materials, a stirring device for stirring the materials inside the purification tank, and a heating device for heating the purification tank;
- a gas supply unit which is connected to the bottom pipeline of the purification tank, so as to be used to introduce inert gas into the purification tank;
- a collecting unit which includes a condensing device connected to the top pipeline of the purification tank, so as to condense and collect the tantalum source precursor vapor evaporated in the cavity;
- the capture unit comprises a capture bottle connected to a condensation device pipeline, wherein a cold trap is provided on the outside of the capture bottle;
- the pressure control unit is connected to the capture bottle pipeline and is used to control the internal pressure of the entire system.
- the gas supply unit comprises a gas tank for storing inert gas; and,
- a pressure control valve is used to control the flow rate of a gas stream delivered to a purification unit.
- 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 inside the condensation tube;
- the top end of the condenser is connected to the purification tank pipeline, and the bottom end is connected to the capture bottle pipeline.
- the present invention has the following beneficial effects:
- the present invention simplifies the purification steps by changing the purification method of the tantalum source precursor during the purification process of the tantalum source precursor;
- the present invention effectively improves the purification efficiency and purification effect in the purification process of tantalum source precursor
- FIG. 1 is a schematic diagram of a structure of a purification system for purifying a tantalum source precursor according to the present invention.
- FIG2 is a schematic diagram of the structure of a conventional purification device.
- Figure 3 is an electron microscope photograph of adsorbent A after surface loading modification.
- purification unit 100 purification tank 110, stirring device 120, driving motor 121, transmission rod 122, stirring paddle 123, heating device 130, gas transmission pipe 140, gas outlet pipe 150, gas supply unit 200, gas tank 210, pressure control valve 220, condensation device 300, product collection tank 310, condensation pipe 320, condensation baffle 321, capture unit 400, capture bottle 410, cold trap 420, pressure control unit 500, distiller 600, first heating unit 610, adsorption unit 700, second heating unit 710, condensation unit 800, vacuum control unit 900.
- the silica gel powder loaded with iron oxide and manganese oxide is heated to 650 degrees Celsius in a hydrogen atmosphere and maintained for 3 hours to reduce the iron oxide to elemental iron and the manganese oxide to manganese monoxide;
- the silica gel powder loaded with elemental iron and manganese monoxide containing phenolic resin on the surface was collected by centrifugation, and then the temperature was raised to 700°C at a rate of 2°C/min under the same conditions, so that the phenolic resin was converted into a carbon layer with a porous structure, and finally the adsorbent A modified by the surface loading was obtained.
- Adsorbent B modified by surface loading :
- adsorbent C and adsorbent A The difference between adsorbent C and adsorbent A is that only 0.15 mol/L of ferric chloride is added in step (1), and the other conditions remain unchanged.
- the final adsorbent B is only loaded with elemental iron and a porous carbon layer.
- Adsorbent C modified by surface loading :
- adsorbent C and adsorbent A The difference between adsorbent C and adsorbent A is that only 0.15 mol/L manganese chloride is added in step (1), and the other conditions remain unchanged.
- the final adsorbent B only carries manganese monoxide and a porous carbon layer.
- Adsorbent D modified by surface loading :
- step (4) is omitted, that is, there is no porous carbon layer coating the outside of the adsorbent loaded with elemental iron and manganese monoxide.
- the present invention provides a purification system for purifying a tantalum source precursor, which at least comprises:
- the purification unit 100 includes a purification tank 110 for containing materials, wherein the materials include a crude tantalum source precursor, an adsorbent, a non-volatile inert liquid medium, etc. Therefore, the crude tantalum source precursor can be in contact with the adsorbent dispersed in the inert liquid medium inside the purification tank 110, so that the halogen-containing impurities and oxygen in the crude tantalum source precursor can be adsorbed and purified by the adsorbent.
- the materials include a crude tantalum source precursor, an adsorbent, a non-volatile inert liquid medium, etc. Therefore, the crude tantalum source precursor can be in contact with the adsorbent dispersed in the inert liquid medium inside the purification tank 110, so that the halogen-containing impurities and oxygen in the crude tantalum source precursor can be adsorbed and purified by the adsorbent.
- the present invention deliberately arranges a stirring device 120 on the purification tank 110 for stirring the material inside the purification tank 110.
- the stirring device 120 includes a driving motor 121 arranged on the top of the purification tank 110 and a transmission rod 122 connected thereto and extending into the purification tank 110.
- the transmission rod 122 is provided with a stirring paddle 123 for stirring the material.
- the present invention further provides a heating device 130 on the periphery of the purification tank 110 , thereby facilitating the heating of the material inside the purification tank 110 .
- a gas delivery pipe 140 is also provided on the top of the purification tank 110, which penetrates the purification tank 110 and extends to the bottom of the purification tank 110, and is used to connect with a gas supply unit 200 provided outside the purification tank 110.
- the gas supply unit 200 includes a gas tank 210 for storing inert gas, which is connected to a pressure control valve 220 and communicates with the gas delivery pipe 140 through a pipeline. When the pressure control valve 220 is opened, the inert gas inside the gas tank 210 can enter the purification tank 110 along the pipeline, so that a part of the gaseous impurities doped in the tantalum source precursor are taken out of the system through this part of the inert gas introduced.
- the top of the purification tank 110 is also provided with an air outlet pipe 150 connected to the outside, so that the inert gas or tantalum source precursor vapor can flow along the air outlet pipe 150 to the outside of the purification tank 110.
- the outside of the purification tank 110 is also provided with a condensation device 300 connected to the air outlet pipe 150.
- the condensation device 300 includes a collection tank 310 and a condensation pipe 320 disposed at the upper end of the collection tank 310.
- a plurality of condensation baffles 321 are alternately disposed inside the condensation pipe 320.
- the inert gas mixed with non-condensable gases such as oxygen comes out from the inside of the purification tank 110, it can enter the top of the condensation pipe 320 along the air outlet pipe 150, and then flow to the outside of the condensation device 300 through the bottom of the condensation pipe 320.
- the tantalum source precursor vapor comes out from the purification tank 110, it can enter the condenser tube 320 along the gas outlet pipe 150.
- the tantalum source precursor vapor contacts the condensation baffle 321, it can condense on the surface of the condensation baffle 321 and then fall into the product collection tank 310 at the bottom.
- the condensation baffle 321 can be tilted alternately left and right to reduce the resistance of the tantalum source precursor falling.
- a capture unit 400 can be connected to the outside of the condensation device 300, which includes a capture bottle 410 connected to the condensation device 120 pipeline.
- a cold trap 420 is provided on the outside of the capture bottle 410.
- a condensation medium such as liquid nitrogen can be added to the inside of the cold trap 420, which is conducive to the condensation of the escaped tantalum source precursor vapor and prevents it from entering the subsequent pressure control unit 500.
- a pressure control unit 500 which can be composed of a vacuum pump, which is connected to the collection bottle 410 pipeline, so when it is working, it can evacuate the inside of the entire system, thereby being used to control the internal pressure of the entire system.
- Conventional purification equipment 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 disposed outside the distiller 600, the adsorption unit 700 is filled with an adsorbent, and the outside of 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 to a condensation unit 800, so that the tantalum source precursor vapor flowing out from the top of the adsorption unit 700 can be condensed in the condensation unit 800, and the adsorption unit 700 is connected to a vacuum control unit 900 for controlling the overall system pressure.
- the method for purifying penta(dimethylamino)tantalum comprises the following steps:
- the tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino) tantalum that falls into the collection tank 121 is collected.
- the method for purifying penta(dimethylamino)tantalum comprises the following steps:
- the tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino) tantalum that falls into the collection tank 121 is collected.
- the method for purifying penta(dimethylamino)tantalum comprises the following steps:
- the tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino)tantalum that falls into the collection tank 121 is collected.
- the method for purifying penta(dimethylamino)tantalum comprises the following steps:
- the tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino) tantalum that falls into the collection tank 121 is collected.
- the method for purifying penta(dimethylamino)tantalum comprises the following steps:
- the tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino) tantalum that falls into the collection tank 121 is collected.
- the method for purifying penta(dimethylamino)tantalum comprises the following steps:
- the tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino) tantalum that falls into the collection tank 121 is collected.
- Example 7 The steps of Example 7 are basically the same as those of Comparative Example 3, except that penta(dimethylamino)tantalum is replaced with penta(diethylamino)tantalum, and the distillation temperature is increased to 75°C.
- Crude penta(dimethylamino)tantalum is placed inside the distiller 600 of a conventional horizontal sublimation refining tower, silica gel powder is placed in the adsorption unit 700, and then the system pressure is reduced to 0.1 kPa to remove the air inside the horizontal sublimation refining tower, and the temperature of the distiller 600 and the adsorption unit 700 is increased to 65°C to form penta(dimethylamino)tantalum vapor, which enters the condensation unit 800 after passing through the adsorption unit 700, so that the penta(dimethylamino)tantalum is condensed into a solid again to obtain purified penta(dimethylamino)tantalum.
- Crude penta(dimethylamino)tantalum is placed inside the distiller 600 of a conventional horizontal sublimation refining tower, and adsorbent A modified by surface loading is placed in the adsorption unit 700.
- the system pressure is then reduced to 0.1 kPa to remove the air inside the horizontal sublimation refining tower, and the temperature of the distiller 600 and the adsorption unit 700 is increased to 65°C to form penta(dimethylamino)tantalum vapor.
- the condensation unit 800 After passing through the adsorption unit 700, it enters the condensation unit 800, whereby the penta(dimethylamino)tantalum is condensed into a solid again to obtain purified penta(dimethylamino)tantalum.
- the preparation method of the present invention can achieve a good purification effect on the tantalum source precursor, which is effective compared with the simple sublimation condensation or adsorption of the vapor of the tantalum source precursor in the prior art, and has obvious improvements in both purification efficiency and purification effect.
- the present invention only needs to use a simple adsorbent to achieve a good adsorption and purification effect on the tantalum source precursor, and the internal impurity content of the purified tantalum source precursor can be reduced to the ppm level.
- it is not limited to the specific form of the tantalum source precursor. Both solid penta(dimethylamino)tantalum and liquid penta(diethylamino)tantalum can be effectively purified, which effectively simplifies the purification steps.
- the present invention only needs to increase the system temperature when the tantalum source precursor is sublimated, and there is no need to heat the tantalum source precursor vapor.
- this purification method in the present invention greatly reduces energy consumption and is more environmentally friendly.
- the present invention also found that after the adsorbent is surface-loaded and modified, the purification effect of the tantalum source precursor can be further improved, so that the internal impurities can reach the ppb level.
- the adsorption effect of halogen-containing impurities and oxygen in the tantalum source precursor can be effectively improved.
- the provision of the carbon layer effectively improves the electronic conduction effect of the adsorbent, so that the electron transfer activity of elemental iron and manganese monoxide during the transformation process can be effectively improved, thereby improving the adsorption effect of the adsorbent on impurities.
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Abstract
The present invention relates to the field of purification of electron precursors, and in particular relates to a method for purifying a tantalum source precursor. The method comprises the following steps: (S.1) dispersing an adsorbent in an inert liquid medium without volatility to obtain an adsorption slurry; (S.2) dissolving a crude product tantalum source precursor in the adsorption slurry, to bring the crude product tantalum source precursor in contact with the adsorbent, such that impurities in the crude product tantalum source precursor are adsorbed by the adsorbent; (S.3) increasing the temperature of the adsorption slurry to the evaporation temperature of the tantalum source precursor to evaporate the tantalum source precursor so as to form a tantalum source precursor steam; and (S.4) collecting the tantalum source precursor steam and condensing same to obtain a high-purity tantalum source precursor. In the present invention, by changing the purification mode of the tantalum source precursor during the purification process of the tantalum source precursor, the purification steps are simplified, the purification efficiency and the purification effect are effectively improved, and the energy consumption during the purification process of the tantalum source precursor is also effectively reduced during the purification process.
Description
本发明涉及电子前驱体纯化领域，尤其涉及钽源前驱体的纯化方法。The invention relates to the field of electronic precursor purification, and in particular to a method for purifying a tantalum source precursor.
氮化钽是一种过渡金属氮化物，由于其硬度高，导电性可控，对金属元素具有扩散阻挡的作用，在微电子工业领域中氮化钽是铜互连技术中研究最为广泛的扩散阻挡层材料。随着集成电路特征尺寸的减小及沟槽深宽比的增加，早期的物理气相沉积( PVD) 工艺难以满足其未来的制作需求，因此原子层沉积( ALD) 技术对制备超薄氮化钽阻挡层起着至关重要的作用。Tantalum nitride is a transition metal nitride. Due to its high hardness, controllable conductivity, and diffusion barrier effect on metal elements, tantalum nitride is the most widely studied diffusion barrier material in copper interconnect technology in the field of microelectronics industry. With the reduction of integrated circuit feature size and the increase of trench aspect ratio, the early physical vapor deposition (PVD) process is difficult to meet its future production needs, so atomic layer deposition (ALD) technology plays a vital role in the preparation of ultra-thin tantalum nitride barrier layer.
对于原子层沉积氮化钽，工业上常以有机金属钽作为钽源前驱体。然而研究人员发现，钽源前驱体的纯度对于最终沉积得到的氮化钽薄膜具有重大的影响。有机金属钽在制备过程中通常是由钽卤化物制备得到，因此在制备得到的有机金属钽中往往会残留一定量的钽卤化物以及其他含卤杂质，这些含卤杂质在原子沉积过程中会产生腐蚀性副产物，因此不利于工业应用。此外，有机金属钽中也往往会存在一定的杂质氧，导致在沉积的氮化钽中有较高的氧残留，从而氮化钽更容易被氧化，进而导致稳定性差等其他问题。For atomic layer deposition of tantalum nitride, organic metal tantalum is often used as a tantalum source precursor in the industry. However, researchers have found that the purity of the tantalum source precursor has a significant impact on the final deposited tantalum nitride film. Organic metal tantalum is usually prepared from tantalum halide during the preparation process. Therefore, a certain amount of tantalum halide and other halogen-containing impurities often remain in the prepared organic metal tantalum. These halogen-containing impurities will produce corrosive by-products during the atomic deposition process, so they are not conducive to industrial applications. In addition, there is often a certain amount of impure oxygen in organic metal tantalum, resulting in a higher oxygen residue in the deposited tantalum nitride, so that the tantalum nitride is more easily oxidized, which in turn leads to other problems such as poor stability.
申请号为201710492823 .4的专利，公开了五(二甲胺基)钽的合成方法，在惰性气氛保护下，在反应器中加入有机锂试剂和烃类溶剂，然后向体系中通入二甲胺气体，制得二甲胺基锂；向体系中加入五氯化钽，加完之后惰性气氛保护下搅拌反应；反应结束后进行过滤，得到的滤液进行蒸馏除掉烃类溶剂；等溶剂全部除去后，升华固体得到五(二甲胺基 )钽产品。其在制备五(二甲胺基 )钽的过程中虽然降低了合成成本和反应的毒性，但是其仅仅采用升华的步骤对制备得到的五(二甲胺基 )钽起到提纯作用，但是仍然会在五(二甲胺基 )钽内部掺杂一定量的杂质。Patent No. 201710492823.4 discloses a method for synthesizing tantalum penta(dimethylamino). Under the protection of an inert atmosphere, an organic lithium reagent and a hydrocarbon solvent are added to a reactor, and then dimethylamine gas is introduced into the system to obtain dimethylamino lithium; tantalum pentachloride is added to the system, and after the addition, the reaction is stirred under the protection of an inert atmosphere; after the reaction is completed, the reaction is filtered, and the filtrate is distilled to remove the hydrocarbon solvent; after all the solvents are removed, the solid is sublimated to obtain a tantalum penta(dimethylamino) product. Although the synthesis cost and the toxicity of the reaction are reduced in the process of preparing tantalum penta(dimethylamino), it only uses the sublimation step to purify the prepared tantalum penta(dimethylamino), but a certain amount of impurities will still be doped inside the tantalum penta(dimethylamino).
申请号为201911061946 .8的专利公开了一种五 （二甲胺基）钽的精制方法，其通过对五（二甲胺基）钽加热使得其的升华，然后将五（二甲胺基）钽的蒸汽通过金属有机骨架陶瓷，从而吸附五（二甲胺基）钽蒸汽中的杂质，进一步提升产品的含量。这种方式虽然能够进一步提升五（二甲胺基）钽的纯度，但是由于五（二甲胺基）钽蒸汽与金属有机骨架陶瓷的接触时间较短，因此难以将其中的杂质全部吸附，导致制备得到的五（二甲胺基）钽纯度仍然难以提升。同时五（二甲胺基）钽蒸汽在通过金属有机骨架陶瓷时的速度较慢，因此难以提升五（二甲胺基）钽的纯化效率。The patent with application number 201911061946.8 discloses a method for refining tantalum penta(dimethylamino), which heats tantalum penta(dimethylamino) to make it sublime, and then passes the vapor of tantalum penta(dimethylamino) through metal organic framework ceramics, thereby adsorbing impurities in the vapor of tantalum penta(dimethylamino) to further increase the content of the product. Although this method can further improve the purity of tantalum penta(dimethylamino), it is difficult to adsorb all the impurities in it due to the short contact time between tantalum penta(dimethylamino) vapor and metal organic framework ceramics, resulting in the purity of the prepared tantalum penta(dimethylamino) still being difficult to improve. At the same time, the speed of tantalum penta(dimethylamino) vapor passing through metal organic framework ceramics is slow, so it is difficult to improve the purification efficiency of tantalum penta(dimethylamino).
本发明是为了克服现有技术中的钽源前驱体在纯化过程中难以将掺杂在其中的杂质除净，同时钽源前驱体的纯化效率较低的缺陷，提供了一种钽源前驱体的纯化方法以克服上述不足之处。The present invention aims to overcome the defects in the prior art that it is difficult to remove impurities doped in the tantalum source precursor during the purification process and the purification efficiency of the tantalum source precursor is low, and provides a purification method for a tantalum source precursor to overcome the above shortcomings.
为实现上述发明目的，本发明通过以下技术方案实现：To achieve the above-mentioned purpose, the present invention is implemented by the following technical solutions:
第一方面，本发明提供了钽源前驱体的纯化方法，包括以下步骤：In a first aspect, the present invention provides a method for purifying a tantalum source precursor, comprising the following steps:
（S.1）将吸附剂分散于不具有挥发性的惰性液体介质中，得到吸附浆料；(S.1) dispersing the adsorbent in a non-volatile inert liquid medium to obtain an adsorption slurry;
（S.2）将粗品钽源前驱体溶于吸附浆料中，使得粗品钽源前驱体与吸附剂相接触，从而使得粗品钽源前驱体中的杂质被吸附剂所吸附；(S.2) dissolving the crude tantalum source precursor in the adsorption slurry so that the crude tantalum source precursor contacts the adsorbent, thereby allowing impurities in the crude tantalum source precursor to be adsorbed by the adsorbent;
（S.3）提升吸附浆料的温度至钽源前驱体的蒸发温度，使得钽源前驱体蒸发，从而形成钽源前驱体蒸汽；(S.3) raising the temperature of the adsorption slurry to the evaporation temperature of the tantalum source precursor, so that the tantalum source precursor evaporates, thereby forming tantalum source precursor vapor;
（S.4）收集钽源前驱体蒸汽并将其冷凝，得到高纯钽源前驱体。(S.4) Collecting the tantalum source precursor vapor and condensing it to obtain a high-purity tantalum source precursor.
钽源前驱体在室温下通常是以固体形式存在，由于其受热升华速度较快，因此如背景技术中所述，现有技术中钽源前驱体通常依靠升华的方法以减少掺杂在钽源前驱体中的杂质。但是由于钽源前驱体在升华过程中也会夹杂着杂质一起升华，导致通过升华冷凝得到的钽源前驱体难以将全部杂质除净。Tantalum source precursors are usually in solid form at room temperature. As they sublimate quickly when heated, as described in the background art, tantalum source precursors in the prior art usually rely on sublimation methods to reduce impurities doped in the tantalum source precursors. However, since the tantalum source precursors will also sublime with impurities during the sublimation process, it is difficult to remove all impurities from the tantalum source precursors obtained by sublimation and condensation.
本发明创新性的提出了一种对于钽源前驱体新的纯化方法，本发明中首先将粗品钽源前驱体溶于含有吸附剂的吸附浆料中，从而在粗品钽源前驱体与吸附剂相接触的过程中，粗品钽源前驱体中的杂质能够被吸附剂所吸附。待到粗品钽源前驱体中的杂质被吸附剂完全吸附后，再升高整体体系的温度，此时钽源前驱体便可形成蒸汽，将这些钽源前驱体蒸汽进行收集冷凝之后便可形成具有超高纯度的钽源前驱体，从而能够有利于在制备超薄氮化钽阻挡层的过程中提升氮化钽薄膜的性能。The present invention innovatively proposes a new purification method for tantalum source precursors. In the present invention, the crude tantalum source precursor is first dissolved in an adsorption slurry containing an adsorbent, so that in the process of the crude tantalum source precursor and the adsorbent contacting, the impurities in the crude tantalum source precursor can be adsorbed by the adsorbent. After the impurities in the crude tantalum source precursor are completely adsorbed by the adsorbent, the temperature of the entire system is increased, and the tantalum source precursor can form steam. After the tantalum source precursor steam is collected and condensed, a tantalum source precursor with ultra-high purity can be formed, which can be beneficial to improve the performance of the tantalum nitride film in the process of preparing an ultra-thin tantalum nitride barrier layer.
本发明中的这种钽源前驱体的纯化方法，能够有效相较于现有技术中简单的升华冷凝或者将钽源前驱体的蒸汽通过吸附的方式而言，其无论是在纯化效率以及纯化效果方面均具有明显的提升。The purification method of the tantalum source precursor in the present invention can effectively improve both the purification efficiency and the purification effect compared with the simple sublimation condensation or adsorption of the vapor of the tantalum source precursor in the prior art.
首先，本发明突破了钽源前驱体形态的限制，将原本不适宜直接提纯的固态钽源前驱体溶于液体介质中后再进行纯化，无需如现有技术那样需要先将固态的钽源前驱体先转化为气态，再将气态的钽源前驱体蒸汽进行吸附提纯，简化了提纯的步骤。Firstly, the present invention breaks through the limitation of the form of tantalum source precursor. The solid tantalum source precursor which is not suitable for direct purification is dissolved in a liquid medium and then purified. There is no need to convert the solid tantalum source precursor into a gaseous state and then purify the gaseous tantalum source precursor vapor by adsorption as in the prior art, thereby simplifying the purification steps.
其次，由于本发明的提纯步骤是在液体介质中进行的，其与吸附剂之间的接触时间可根据吸附效果随时调控，从而保证对于钽源前驱体中杂质的吸附效果。而现有技术中钽源前驱体蒸汽与吸附剂之间的接触时间通常无法维持较长时间，因此导致钽源前驱体的纯化效果无法保持在较高的水平。Secondly, since the purification step of the present invention is carried out in a liquid medium, the contact time between the vapor and the adsorbent can be adjusted at any time according to the adsorption effect, thereby ensuring the adsorption effect of impurities in the tantalum source precursor. However, in the prior art, the contact time between the tantalum source precursor vapor and the adsorbent cannot be maintained for a long time, so the purification effect of the tantalum source precursor cannot be maintained at a high level.
第三，本发明中只需要在对钽源前驱体升华时提高体系温度，无需对钽源前驱体蒸汽起到保温加热作用。而现有技术中为了保证钽源前驱体蒸汽在与吸附剂接触时不会冷凝从而堵住吸附剂，需要同时对钽源前驱体蒸汽起到加热。因此本发明中的这一纯化方法大大降低了能耗且更加环保。Third, in the present invention, it is only necessary to increase the system temperature when the tantalum source precursor is sublimated, and it is not necessary to heat the tantalum source precursor vapor. In the prior art, in order to ensure that the tantalum source precursor vapor does not condense when in contact with the adsorbent and thus block the adsorbent, it is necessary to heat the tantalum source precursor vapor at the same time. Therefore, the purification method in the present invention greatly reduces energy consumption and is more environmentally friendly.
最后，本发明中采用的惰性液体介质为不具有挥发性的惰性液体介质，因此在使得钽源前驱体达到蒸发温度时，这些液体介质不会随着钽源前驱体一同蒸发，从而导致钽源前驱体纯度的下降。Finally, the inert liquid medium used in the present invention is a non-volatile inert liquid medium. Therefore, when the tantalum source precursor reaches the evaporation temperature, these liquid media will not evaporate together with the tantalum source precursor, thereby causing a decrease in the purity of the tantalum source precursor.
作为优选，步骤（S.1）中所述吸附剂包括活性炭、多孔氧化铝、硅胶粉、沸石或者分子筛中的任意一种。Preferably, the adsorbent in step (S.1) comprises any one of activated carbon, porous alumina, silica gel powder, zeolite or molecular sieve.
本发明中采用的吸附剂为具有多孔结构的吸附剂，当钽源前驱体中的杂质进入到这些吸附剂的多孔结构中后，便能够被吸附剂以物理形式吸附捕获，从而有效提升了钽源前驱体的纯度。The adsorbent used in the present invention is an adsorbent with a porous structure. When the impurities in the tantalum source precursor enter the porous structure of these adsorbents, they can be physically adsorbed and captured by the adsorbent, thereby effectively improving the purity of the tantalum source precursor.
作为优选，所述吸附剂表面还负载有单质铁以及一氧化锰；Preferably, the surface of the adsorbent is also loaded with elemental iron and manganese monoxide;
所述吸附剂的外表面还包覆有一层具有多孔结构的碳层。The outer surface of the adsorbent is also coated with a carbon layer with a porous structure.
本发明上文中所述的吸附剂（如活性炭、多孔氧化铝、硅胶粉等）其吸附原理均是通过物理吸附的方式对钽源前驱体中的杂质起到良好的吸附作用。然而，物理吸附的方式其吸附容量较低，同时还存在解吸附的问题，因此虽然能够提升钽源前驱体的纯度，但是其提纯效果的上限较低，难以达到更高的纯度水平。因此，本发明针对这些吸附剂进行了一定的改性，从而使得其具备了化学吸附的效果，这样克服了解吸附的问题，提高了提纯效果的上限。The adsorbents described above in the present invention (such as activated carbon, porous alumina, silica gel powder, etc.) all have a good adsorption effect on impurities in the tantalum source precursor by physical adsorption. However, the physical adsorption method has a low adsorption capacity and also has the problem of desorption. Therefore, 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 reach a higher purity level. Therefore, the present invention has made certain modifications to these adsorbents so that they have the effect of chemical adsorption, thus overcoming the problem of desorption and improving the upper limit of the purification effect.
首先，本发明中的吸附剂表面负载有单质铁以及锰的氧化物。First, the adsorbent in the present invention has oxides of elemental iron and manganese loaded on its surface.
其中，单质铁能够与钽源前驱体中残余的的少量含卤杂质反应（例如其可以与氯化氢、以及溴化氢反应），从而将含卤杂质以及铁盐的形式固定在吸附剂表面。同时单质铁颗粒的还原性极强，其能够与钽源前驱体中掺杂的氧分子反应，从而降低了钽源前驱体中的氧气含量。Among them, elemental iron can react with a small amount of halogen-containing impurities remaining in the tantalum source precursor (for example, it can react with hydrogen chloride and hydrogen bromide), thereby fixing the halogen-containing impurities and iron salts on the surface of the adsorbent. At the same time, elemental iron particles have extremely strong reducibility and can react with oxygen molecules doped in the tantalum source precursor, thereby reducing the oxygen content in the tantalum source precursor.
与之相对应的，本发明中还在吸附剂的表面负载锰的氧化物，其同样能够与含卤杂质起到良好的反应效果，同时当锰的氧化物为低价态的一氧化锰时，还对氧气有着极强的吸附作用，并且当其与氧气反应形成高价态的锰氧化物后，其仍然对含卤杂质有着良好的吸收效果。Correspondingly, in the present invention, manganese oxide is also loaded on the surface of the adsorbent, which can also have a good reaction effect with halogen-containing impurities. At the same time, when the manganese oxide is low-valent manganese monoxide, it also has a strong adsorption effect on oxygen, and when it reacts with oxygen to form high-valent manganese oxide, it still has a good absorption effect on halogen-containing impurities.
此外，经过实际的测试后发现，当反应物中同时负载单质铁以及锰的氧化物时，其对于含卤杂质以及氧气的吸附效果明显由于单独负载了单质铁以及锰的氧化物时的效果，表明其两者之间的搭配能够起到明显的协同增效的效果。In addition, after actual testing, it was found that when the reactants were loaded with elemental iron and manganese oxides at the same time, the adsorption effect on halogen-containing impurities and oxygen was significantly better than when the elemental iron and manganese oxides were loaded separately, indicating that the combination of the two can achieve a significant synergistic effect.
作为优选，所述吸附剂的制备方法如下：Preferably, the preparation method of the adsorbent is as follows:
（1）将吸附剂浸渍于含有铁盐以及锰盐的溶液中，得到负载有铁盐以及锰盐的吸附剂；(1) immersing the adsorbent in a solution containing an iron salt and a manganese salt to obtain an adsorbent loaded with the iron salt and the manganese salt;
（2）将负载有铁盐以及锰盐的吸附剂在空气氛围下加热，使得铁盐以及锰盐转变为铁的氧化物以及锰的氧化物；(2) heating the adsorbent loaded with iron salt and manganese salt in an air atmosphere so that the iron salt and manganese salt are converted into iron oxide and manganese oxide;
（3）然后再在氢气氛围下将铁的氧化物还原成单质铁，将锰的氧化物还原成一氧化锰；(3) Then, in a hydrogen atmosphere, the iron oxide is reduced to elemental iron, and the manganese oxide is reduced to manganese monoxide;
（4）将负载有单质铁以及一氧化锰的吸附剂表面负载一层碳前驱体，然后在惰性气体保护下将碳前驱体转变成具有多孔结构的碳层，即得所述吸附剂。(4) A layer of carbon precursor is loaded on the surface of the adsorbent loaded with elemental iron and manganese monoxide, and then the carbon precursor is converted into a carbon layer with a porous structure under the protection of an inert gas, thereby obtaining the adsorbent.
本发明中单质铁以及一氧化锰采用浸渍法将铁盐以及锰盐进行负载，然后通过空气的氧化反应，这些铁盐以及锰盐最终转变为铁以及锰的氧化物，最后通过氢气的选择性还原，从而能够将氧化铁还原成单质铁，而由于锰的氧化物在氢气的还原作用下最高只能还原至一氧化锰的状态，因此最终得到的吸附剂中仅仅可以包含单质铁以及一氧化锰。In the present invention, elemental iron and manganese monoxide are loaded with iron salt and manganese salt by impregnation method, and then these iron salt and manganese salt are finally converted into iron and manganese oxides through oxidation reaction in air, and finally the iron oxide is reduced to elemental iron through selective reduction by hydrogen. Since manganese oxide can only be reduced to the state of manganese monoxide at most under the reducing action of hydrogen, the finally obtained adsorbent can only contain elemental iron and manganese monoxide.
此外，本发明在吸附剂的外表面还包覆了一层多孔碳，首先其多孔结构能够有效提升对于杂质的吸附作用。同时由于碳层具有良好的电子传导效果，因此能够有效提升单质铁以及一氧化锰在转变过程中的电子传递活性，从而提升了吸附剂对于杂质的吸附效果。In addition, the present invention also coats a layer of porous carbon on the outer surface of the adsorbent. First, its porous structure can effectively improve the adsorption of impurities. At the same time, since the carbon layer has a good electron conduction effect, it can effectively improve the electron transfer activity of elemental iron and manganese monoxide during the transformation process, thereby improving the adsorption effect of the adsorbent on impurities.
同时，在多孔碳的包覆过程中，可以采用含碳的树脂或者其他的含碳单质对吸附剂进行表面包覆。含碳的树脂可以采用例如聚氧化乙烯，聚吡咯烷酮或者聚丙烯酸树脂等，而含碳单质则可以包含如多巴胺或者单宁酸等进行包覆，从而在吸附剂的表面形成聚多巴胺或者聚单宁酸，将这些含碳的树脂以及含碳的单质在惰性条件下热处理后，便能够得到具有多孔结构的碳层。At the same time, in the coating process of porous carbon, the adsorbent can be coated with a carbon-containing resin or other carbon-containing single substance. The carbon-containing resin can be, for example, polyethylene oxide, polypyrrolidone or polyacrylic resin, and the carbon-containing single substance can be coated with, for example, dopamine or tannic acid, so as to form polydopamine or polytannic acid on the surface of the adsorbent. After heat treatment of these carbon-containing resins and carbon-containing single substances under inert conditions, a carbon layer with a porous structure can be obtained.
作为优选，步骤（S.1）中所述惰性液体介质包括离子液体或者硅油中的任意一种。Preferably, the inert liquid medium in step (S.1) comprises any one of ionic liquid and silicone oil.
本发明中的惰性液体介质可以采用离子液体或者硅油，其两者对于钽源前驱体而言均具有良好的溶解性能以及极低的饱和蒸气压，因而可以保证在钽源前驱体在升华过程中不会将杂质带入到最终的成品中。The inert liquid medium in the present invention can be ionic liquid or silicone oil, both of which have good solubility and extremely low saturated vapor pressure for the tantalum source precursor, thereby ensuring that the tantalum source precursor will not bring impurities into the final product during the sublimation process.
作为优选，所述离子液体包括咪唑类离子液体、季铵类离子液体、季鏻类离子液体、吡咯烷类离子液体、哌啶类离子液体中的一种或多种的组合。Preferably, the ionic liquid includes one or more combinations of imidazole ionic liquids, quaternary ammonium ionic liquids, quaternary phosphonium ionic liquids, pyrrolidine ionic liquids, and piperidine ionic liquids.
作为优选，所述离子液体的阳离子为N-己基吡啶、N-丁基吡啶、N-辛基吡啶、N-丁基-N-甲基吡咯烷、1-丁基-3-甲基咪唑、1-丙基-3-甲基咪唑、1-乙基-3-甲基咪唑、1-己基-3-甲基咪唑、1-辛基-3-甲基咪唑、1-烯丙基-3-甲基咪唑、1-丁基-2，3-二甲基咪唑、1-丁基-3-甲基咪唑、三丁基甲基膦、三丁基乙基膦、四丁基膦、三丁基己基膦、三丁基辛基膦、三丁基癸基膦、三丁基十二烷基膦、三丁基十四烷基膦、三苯基乙基膦、三苯基丁基膦、三苯基甲基膦、三苯基丙基膦、三苯基戊基膦、三苯基丙酮基膦、三苯基苄基膦、三苯基(3-溴丙基)膦、三苯基溴甲基膦、三苯基甲氧基膦、三苯基乙氧羰基甲基膦、三苯基((3-溴丙基)膦、三苯基乙烯基膦、四苯基膦中的任意一种。Preferably, the cation of the ionic liquid is 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, Any one of tetrabutylphosphine, tributylhexylphosphine, tributyloctylphosphine, tributyldecylphosphine, tributyldodecylphosphine, tributyltetradecylphosphine, triphenylethylphosphine, triphenylbutylphosphine, triphenylmethylphosphine, triphenylpropylphosphine, triphenylpentylphosphine, triphenylacetonylphosphine, triphenylbenzylphosphine, triphenyl(3-bromopropyl)phosphine, triphenylbromomethylphosphine, triphenylmethoxyphosphine, triphenylethoxycarbonylmethylphosphine, triphenyl(3-bromopropyl)phosphine, triphenylvinylphosphine, and tetraphenylphosphine.
作为优选，所述离子液体的阴离子为BF
4
-、PF
6
- 、CF
3SO
3
-、(CF
3SO
2)
2N
-、C
3F
7COO
-、C
4F
9SO
3、CF
3COO
- 、(CF
3SO
2)
3C
- 、(C
2F
5SO
2)
3C
-
、(C
2F
5SO
2)
2N
-、SbF
6
-中的任意一种。
Preferably, the anion of the ionic liquid is any one of BF4- , PF6- , CF3SO3- , ( CF3SO2 ) 2N- , C3F7COO- , C4F9SO3 , CF3COO- , ( CF3SO2 ) 3C- , ( C2F5SO2 ) 3C- , ( C2F5SO2 ) 2N- , and SbF6- .
作为优选，所述离子液体包括1-丁基-3-甲基咪唑三氟甲磺酸盐、1-丁基-3-甲基咪唑二氰胺盐、1-乙基-3-甲基咪唑三氟乙酸盐、1-乙基-3-甲基咪唑氯铝酸盐、1-乙基-2,3-二甲基咪唑四氟硼酸盐、1-己基-3-甲基咪唑双三氟甲磺酰亚胺盐、1-烯丙基-3-甲基咪唑双三氟甲磺酰亚胺盐、1-乙基-3-甲基咪唑氯盐、1-乙基-3-甲基咪唑双三氟甲磺酰亚胺盐、1-磺酸丁基-2-甲基-3-十六烷基咪唑硫酸氢盐、1-乙基-3-甲基咪唑四氟硼酸盐、1-乙基-3-甲基咪唑碳酸盐、1-乙基-3-甲基咪唑L-乳酸盐、1,3-二甲基咪唑六氟磷酸盐、1-乙基-3-甲基咪唑六氟磷酸盐、1-丙基-3-甲基咪唑六氟磷酸盐、1-丁基-3-甲基咪唑六氟磷酸盐、1-己基-3-甲基咪唑六氟磷酸盐、1-辛基-3-甲基咪唑六氟磷酸盐、1-癸基-3-甲基咪唑六氟磷酸盐、1-十四烷基-3-甲基咪唑六氟磷酸盐、1-苄基-3-甲基咪唑六氟磷酸盐、1-烯丙基-3-甲基咪唑六氟磷酸盐、1-乙烯基-3-乙基咪唑六氟磷酸盐、1-乙烯基-3-丁基咪唑六氟磷酸盐、1-十六烷基-2,3-二甲基咪唑六氟磷酸盐、1-辛基-2,3-二甲基咪唑六氟磷酸盐、1,3-二甲基咪唑四氟硼酸盐、1-丁基-3-甲基咪唑四氟硼酸盐、1-癸基-3-甲基咪唑四氟硼酸盐、1-苄基-3-甲基咪唑四氟硼酸盐、1-乙基-2,3-二甲基咪唑四氟硼酸盐、1-丙基-2,3-二甲基咪唑四氟硼酸盐、1-辛基-2,3-二甲基咪唑四氟硼酸盐、1-辛基-2,3-二甲基咪唑四氟硼酸盐。Preferably, the ionic liquid includes 1-butyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium dicyanamide, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium chloroaluminate, 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium bis-trifluoromethanesulfonyl imide, 1-allyl-3-methylimidazolium bis-trifluoromethanesulfonyl imide, 1-ethyl-3-methylimidazolium chloride, 1-ethyl -3-Methylimidazolium bistrifluoromethanesulfonyl imide salt, 1-sulfonic acid butyl-2-methyl-3-hexadecyl imidazolium hydrogen sulfate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium carbonate, 1-ethyl-3-methylimidazolium L-lactate, 1,3-dimethylimidazolium hexafluorophosphate, 1-ethyl-3-methylimidazolium hexafluorophosphate, 1-propyl-3-methylimidazolium hexafluorophosphate, 1-butyl-3-methylimidazolium hexafluorophosphate, 1-hexyl- 3-Methylimidazolium hexafluorophosphate, 1-octyl-3-methylimidazolium hexafluorophosphate, 1-decyl-3-methylimidazolium hexafluorophosphate, 1-tetradecyl-3-methylimidazolium hexafluorophosphate, 1-benzyl-3-methylimidazolium hexafluorophosphate, 1-allyl-3-methylimidazolium hexafluorophosphate, 1-vinyl-3-ethylimidazolium hexafluorophosphate, 1-vinyl-3-butylimidazolium hexafluorophosphate, 1-hexadecyl-2,3-dimethylimidazolium hexafluorophosphate, 1-octyl -2,3-dimethylimidazolium hexafluorophosphate, 1,3-dimethylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-decyl-3-methylimidazolium tetrafluoroborate, 1-benzyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate, 1-propyl-2,3-dimethylimidazolium tetrafluoroborate, 1-octyl-2,3-dimethylimidazolium tetrafluoroborate, 1-octyl-2,3-dimethylimidazolium tetrafluoroborate.
作为优选，所述钽源前驱体包括五（二甲胺基）钽、五（二乙胺基）钽、五乙氧基钽、三(二乙基氨基)叔丁酰胺钽的任意一种。Preferably, the tantalum source precursor includes any one of penta(dimethylamino)tantalum, penta(diethylamino)tantalum, pentaethoxytantalum, and tri(diethylamino)tantalum-tert-butyramide.
作为优选，所述步骤（S.2）中还包括在减压条件下将惰性气体通入到吸附浆料中的步骤。Preferably, the step (S.2) further comprises the step of introducing an inert gas into the adsorption slurry under reduced pressure.
本发明中在减压条件下向吸附浆料中通入惰性气体，其目的在于钽源前驱体中掺杂的一部分气态杂质通过惰性气体从体系中带出，从而可以有效提升最终得到的钽源前驱体的纯度。In the present invention, an inert gas is introduced into the adsorption slurry under reduced pressure, the purpose of which is to remove a portion of gaseous impurities doped in the tantalum source precursor from the system through the inert gas, thereby effectively improving the purity of the final tantalum source precursor.
第二方面，本发明还提供了一种用于纯化钽源前驱体的纯化系统，其至少包含：In a second aspect, the present invention further provides a purification system for purifying a tantalum source precursor, which at least comprises:
纯化单元，其包括用于盛放物料的纯化罐，还包括用于对纯化罐内部物料起到搅拌作用的搅拌装置，以及用于对纯化罐起到加热的加热装置；A purification unit, comprising a purification tank for containing materials, a stirring device for stirring the materials inside the purification tank, and a heating device for heating the purification tank;
供气单元，其与纯化罐的底部管路联通，从而用于向纯化罐内部通入惰性气体；A gas supply unit, which is connected to the bottom pipeline of the purification tank, so as to be used to introduce inert gas into the purification tank;
收集单元，其包括一个与纯化罐的顶部管路联通的冷凝装置，从而用于对腔体内蒸发得到的钽源前驱体蒸汽起到冷凝以及收集作用；A collecting unit, which includes a condensing device connected to the top pipeline of the purification tank, so as to condense and collect the tantalum source precursor vapor evaporated in the cavity;
捕集单元，其包括一个与冷凝装置管路联通的捕集瓶，所述捕集瓶的外部套设有一个冷阱；The capture unit comprises a capture bottle connected to a condensation device pipeline, wherein a cold trap is provided on the outside of the capture bottle;
压力控制单元，其与捕集瓶管路联通，用于控制整个体系内部压力。The pressure control unit is connected to the capture bottle pipeline and is used to control the internal pressure of the entire system.
作为优选，所述供气单元包括用于存储惰性气体的气罐；以及，Preferably, the gas supply unit comprises a gas tank for storing inert gas; and,
用于控制向纯化单元输送的气流的流速的压力控制阀。A pressure control valve is used to control the flow rate of a gas stream delivered to a purification unit.
作为优选，所述冷凝装置包括产品收集罐以及设置在收集罐上端的冷凝管；Preferably, the condensing device comprises a product collecting tank and a condensing pipe arranged at the upper end of the collecting tank;
所述冷凝管内部交替设置有若干冷凝挡板；A plurality of condensation baffles are alternately arranged inside the condensation tube;
所述冷凝管的顶端与纯化罐管路联通，底端与捕集瓶管路联通。The top end of the condenser is connected to the purification tank pipeline, and the bottom end is connected to the capture bottle pipeline.
因此，本发明具有以下有益效果：Therefore, the present invention has the following beneficial effects:
（1）本发明在钽源前驱体的纯化过程中通过改变对于钽源前驱体的纯化方式，简化了提纯步骤；(1) The present invention simplifies the purification steps by changing the purification method of the tantalum source precursor during the purification process of the tantalum source precursor;
（2）本发明在钽源前驱体的纯化过程中有效提高了纯化效率以及纯化效果；(2) The present invention effectively improves the purification efficiency and purification effect in the purification process of tantalum source precursor;
（3）在提纯过程中还有效降低了钽源前驱体纯化过程中能源消耗。(3) The energy consumption during the purification process of tantalum source precursor is effectively reduced.
图1 为本发明用于纯化钽源前驱体的纯化系统的一种结构示意图。FIG. 1 is a schematic diagram of a structure of a purification system for purifying a tantalum source precursor according to the present invention.
图2 为常规提纯设备的一种结构示意图。FIG2 is a schematic diagram of the structure of a conventional purification device.
图3为经过表面负载改性的吸附剂A的电镜照片。Figure 3 is an electron microscope photograph of adsorbent A after surface loading modification.
其中：纯化单元100、纯化罐110、搅拌装置120、驱动电机121、传动杆122、搅拌桨123、加热装置130、输气管140、出气管150、供气单元200、气罐210、压力控制阀220、冷凝装置300、产品收集罐310、冷凝管320、冷凝挡板321、捕集单元400、捕集瓶410、冷阱420、压力控制单元500、蒸馏器600、第一加热单元610、吸附单元700、第二加热单元710、冷凝单元800、真空控制单元900。Wherein: purification unit 100, purification tank 110, stirring device 120, driving motor 121, transmission rod 122, stirring paddle 123, heating device 130, gas transmission pipe 140, gas outlet pipe 150, gas supply unit 200, gas tank 210, pressure control valve 220, condensation device 300, product collection tank 310, condensation pipe 320, condensation baffle 321, capture unit 400, capture bottle 410, cold trap 420, pressure control unit 500, distiller 600, first heating unit 610, adsorption unit 700, second heating unit 710, condensation unit 800, vacuum control unit 900.
下面结合说明书附图以及具体实施例对本发明做进一步描述。本领域普通技术人员在基于这些说明的情况下将能够实现本发明。此外，下述说明中涉及到的本发明的实施例通常仅是本发明一部分的实施例，而不是全部的实施例。因此，基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都应当属于本发明保护的范围。The present invention is further described below in conjunction with the accompanying drawings and specific embodiments of the specification. Those of ordinary skill in the art will be able to implement the present invention based on these descriptions. In addition, the embodiments of the present invention involved in the following description are generally only embodiments of a part of the present invention, rather than all embodiments. Therefore, based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work should fall within the scope of protection of the present invention.
【经过表面负载改性的吸附剂的制备】【Preparation of surface-loaded modified adsorbent】
经过表面负载改性的吸附剂A:Adsorbent A modified by surface loading:
（1）将100g硅胶粉浸渍于含有0.1mol/L的氯化铁以及0.05mol/L的氯化锰的溶液中30min，过滤烘干后得到负载有氯化铁以及氯化锰的吸附剂；(1) 100 g of silica gel powder was immersed in a solution containing 0.1 mol/L ferric chloride and 0.05 mol/L manganese chloride for 30 min, and an adsorbent loaded with ferric chloride and manganese chloride was obtained after filtering and drying;
（2）将载有氯化铁以及氯化锰的硅胶粉在空气氛围下加热至350℃，维持2h，使得氯化铁以及氯化锰转变为铁的氧化物以及锰的氧化物；(2) heating the silica gel powder loaded with ferric chloride and manganese chloride to 350° C. in an air atmosphere and maintaining the temperature for 2 h to convert the ferric chloride and manganese chloride into iron oxide and manganese oxide;
（3）然后再在氢气氛围下将载有铁的氧化物以及锰的氧化物的硅胶粉，加热至650摄氏度，并保持3h，使得铁的氧化物还原成单质铁，将锰的氧化物还原成一氧化锰；(3) Then, the silica gel powder loaded with iron oxide and manganese oxide is heated to 650 degrees Celsius in a hydrogen atmosphere and maintained for 3 hours to reduce the iron oxide to elemental iron and the manganese oxide to manganese monoxide;
（4）将负载有单质铁以及一氧化锰的吸附剂100g分散至1000ml的水中，然后加入300ml乙醇以及80g间苯二酚，40℃搅拌30min，然后滴加40ml甲醛,搅拌反应6h后，使得吸附剂表面形成一层酚醛树脂，离心收集表面含有酚醛树脂的负载有单质铁以及一氧化锰的硅胶粉，然后在但其条件下以2℃/min的速度升温至700℃，从而使得有酚醛树脂转变成具有多孔结构的碳层，最终得到所述经过表面负载改性的吸附剂A。(4) 100 g of the adsorbent loaded with elemental iron and manganese monoxide was dispersed in 1000 ml of water, and then 300 ml of ethanol and 80 g of resorcinol were added. The mixture was stirred at 40°C for 30 min, and then 40 ml of formaldehyde was added dropwise. After stirring for 6 h, a layer of phenolic resin was formed on the surface of the adsorbent. The silica gel powder loaded with elemental iron and manganese monoxide containing phenolic resin on the surface was collected by centrifugation, and then the temperature was raised to 700°C at a rate of 2°C/min under the same conditions, so that the phenolic resin was converted into a carbon layer with a porous structure, and finally the adsorbent A modified by the surface loading was obtained.
经过表面负载改性的吸附剂B:Adsorbent B modified by surface loading:
吸附剂C与吸附剂A的区别在于，仅仅在步骤（1）中添加了0.15mol/L的氯化铁，其余条件不变，最终得到的吸附剂B中仅仅只负载有单质铁以及多孔结构的碳层。The difference between adsorbent C and adsorbent A is that only 0.15 mol/L of ferric chloride is added in step (1), and the other conditions remain unchanged. The final adsorbent B is only loaded with elemental iron and a porous carbon layer.
经过表面负载改性的吸附剂C:Adsorbent C modified by surface loading:
吸附剂C与吸附剂A的区别在于，仅仅在步骤（1）中添加了0.15mol/L的氯化锰，其余条件不变，最终得到的吸附剂B中仅仅只负载有一氧化锰以及多孔结构的碳层。The difference between adsorbent C and adsorbent A is that only 0.15 mol/L manganese chloride is added in step (1), and the other conditions remain unchanged. The final adsorbent B only carries manganese monoxide and a porous carbon layer.
经过表面负载改性的吸附剂D:Adsorbent D modified by surface loading:
吸附剂D与吸附剂A的区别在于，省略了步骤（4），即在负载有单质铁以及一氧化锰的吸附剂外部没有包覆多孔结构的碳层。The difference between adsorbent D and adsorbent A is that step (4) is omitted, that is, there is no porous carbon layer coating the outside of the adsorbent loaded with elemental iron and manganese monoxide.
【纯化钽源前驱体的纯化系统】[Purification system for purifying tantalum source precursor]
如图1所示，本发明提供了一种用于纯化钽源前驱体的纯化系统，其至少包含：As shown in FIG. 1 , the present invention provides a purification system for purifying a tantalum source precursor, which at least comprises:
纯化单元100，其包括用于盛放物料的纯化罐110，所述物料包括粗品钽源前驱体、吸附剂、不具有挥发性的惰性液体介质等，因此粗品钽源前驱体可以在纯化罐110的内部与分散于惰性液体介质中的吸附剂相接触，从而使得粗品钽源前驱体中的含卤杂质以及氧气能够被吸附剂所吸附净化。The purification unit 100 includes a purification tank 110 for containing materials, wherein the materials include a crude tantalum source precursor, an adsorbent, a non-volatile inert liquid medium, etc. Therefore, the crude tantalum source precursor can be in contact with the adsorbent dispersed in the inert liquid medium inside the purification tank 110, so that the halogen-containing impurities and oxygen in the crude tantalum source precursor can be adsorbed and purified by the adsorbent.
为了提升与此粗品钽源前驱体与吸附剂相接触的接触效果，本发明特意在纯化罐110上设置用于对纯化罐110内部物料起到搅拌作用的搅拌装置120，该搅拌装置120包括设置在纯化罐110顶部的驱动电机121以及与之与之相连接并且深入到纯化罐110内部的传动杆122，传动杆122上设置有用于对物料起到搅拌作用的搅拌桨123，当启动驱动电机121后驱动电机121即可带动传动杆122转动，从而使得搅拌桨123对物料起到剪切作用，从而增加了对于物料的搅拌效果。In order to improve the contact effect between the crude tantalum source precursor and the adsorbent, the present invention deliberately arranges a stirring device 120 on the purification tank 110 for stirring the material inside the purification tank 110. The stirring device 120 includes a driving motor 121 arranged on the top of the purification tank 110 and a transmission rod 122 connected thereto and extending into the purification tank 110. The transmission rod 122 is provided with a stirring paddle 123 for stirring the material. When the driving motor 121 is started, the driving motor 121 can drive the driving rod 122 to rotate, so that the stirring paddle 123 shears the material, thereby increasing the stirring effect on the material.
为了方便对纯化罐110内部物料起到控温作用，本发明还在纯化罐110的外围设置有加热装置130，从而方便对于纯化罐110内部的物料起到加热作用。In order to facilitate the temperature control of the material inside the purification tank 110 , the present invention further provides a heating device 130 on the periphery of the purification tank 110 , thereby facilitating the heating of the material inside the purification tank 110 .
纯化罐110的顶部还设置有一根贯穿纯化罐110且向纯化罐110底部延伸的输气管140，其用于与设置在纯化罐110外部的供气单元200相连接。所述供气单元200包括一个用于存储惰性气体的气罐210，其与一个压力控制阀220相连接，并且通过管路与输气管140联通，当打开压力控制阀220后，气罐210内部的惰性气体便能够沿着管路进入到纯化罐110内部，从而将钽源前驱体中掺杂的一部分气态杂质通过这部分通入的惰性气体从体系中带出。A gas delivery pipe 140 is also provided on the top of the purification tank 110, which penetrates the purification tank 110 and extends to the bottom of the purification tank 110, and is used to connect with a gas supply unit 200 provided outside the purification tank 110. The gas supply unit 200 includes a gas tank 210 for storing inert gas, which is connected to a pressure control valve 220 and communicates with the gas delivery pipe 140 through a pipeline. When the pressure control valve 220 is opened, the inert gas inside the gas tank 210 can enter the purification tank 110 along the pipeline, so that a part of the gaseous impurities doped in the tantalum source precursor are taken out of the system through this part of the inert gas introduced.
纯化罐110的顶部还设置有一根与外界相连通的出气管150，从而使得惰性气体或者钽源前驱体蒸汽能够沿着出气管150流动至纯化罐110的外部，与之相连接的，所述纯化罐110的外部还设置有一个与出气管150管路联通的冷凝装置300，该冷凝装置300包括收集罐310以及设置在收集罐310上端的冷凝管320，所述冷凝管320内部交替设置有若干冷凝挡板321。当惰性气体夹杂着氧气等不凝气体从纯化罐110内部出来时，便可沿着出气管150进入到冷凝管320的顶部，然后再通过冷凝管320的底部流动至冷凝装置300的外部。当钽源前驱体蒸汽从纯化罐110内部出来时，其可沿着出气管150进入到冷凝管320内部，当钽源前驱体蒸汽接触到冷凝挡板321后即可在冷凝挡板321的表面冷凝，随后掉落至底部的产品收集罐310中。为了保证钽源前驱体能够在冷凝挡板321顺利掉落，冷凝挡板321可左右交替倾斜设置，减少了钽源前驱体下落的阻力。The top of the purification tank 110 is also provided with an air outlet pipe 150 connected to the outside, so that the inert gas or tantalum source precursor vapor can flow along the air outlet pipe 150 to the outside of the purification tank 110. Connected thereto, the outside of the purification tank 110 is also provided with a condensation device 300 connected to the air outlet pipe 150. The condensation device 300 includes a collection tank 310 and a condensation pipe 320 disposed at the upper end of the collection tank 310. A plurality of condensation baffles 321 are alternately disposed inside the condensation pipe 320. When the inert gas mixed with non-condensable gases such as oxygen comes out from the inside of the purification tank 110, it can enter the top of the condensation pipe 320 along the air outlet pipe 150, and then flow to the outside of the condensation device 300 through the bottom of the condensation pipe 320. When the tantalum source precursor vapor comes out from the purification tank 110, it can enter the condenser tube 320 along the gas outlet pipe 150. When the tantalum source precursor vapor contacts the condensation baffle 321, it can condense on the surface of the condensation baffle 321 and then fall into the product collection tank 310 at the bottom. In order to ensure that the tantalum source precursor can fall smoothly on the condensation baffle 321, the condensation baffle 321 can be tilted alternately left and right to reduce the resistance of the tantalum source precursor falling.
此外，由于压力设置的原因，有一部分的钽源前驱体蒸汽还未被冷凝即直接从冷凝装置300中流出，此时可在冷凝装置300的外部连接一个捕集单元400，其包括一个与冷凝装置120管路联通的捕集瓶410，所述捕集瓶410的外部套设有一个冷阱420，在冷阱420的内部可添加液氮等冷凝介质，从而有利于逃逸的钽源前驱体蒸汽冷凝，防止进入到后续的压力控制单元500中。In addition, due to the pressure setting, a portion of the tantalum source precursor vapor has not been condensed and directly flows out of the condensation device 300. At this time, a capture unit 400 can be connected to the outside of the condensation device 300, which includes a capture bottle 410 connected to the condensation device 120 pipeline. A cold trap 420 is provided on the outside of the capture bottle 410. A condensation medium such as liquid nitrogen can be added to the inside of the cold trap 420, which is conducive to the condensation of the escaped tantalum source precursor vapor and prevents it from entering the subsequent pressure control unit 500.
最后，本发明还设置有一个压力控制单元500，其可由真空泵构成，其与捕集瓶410管路联通，因此当其工作时，其可对整个体系内部进行抽真空工作，从而用于控制整个体系内部压力。Finally, the present invention is also provided with a pressure control unit 500, which can be composed of a vacuum pump, which is connected to the collection bottle 410 pipeline, so when it is working, it can evacuate the inside of the entire system, thereby being used to control the internal pressure of the entire system.
【常规提纯设备】【Conventional purification equipment】
常规提纯设备包括蒸馏器600以及位于蒸馏器600顶部的吸附单元700，所述蒸馏器600外部设置有用于对其加热的第一加热单元610，所述吸附单元700内部填充有吸附剂，且其外部同样包覆有用于对吸附单元700加热的第二加热单元710，吸附单元700的顶部与一个冷凝单元800相连接，从而从吸附单元700的顶部流出的钽源前驱体蒸汽能够在冷凝单元800冷凝，吸附单元700处连接有一个用于控制整体体系压力的真空控制单元900。Conventional purification equipment 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 disposed outside the distiller 600, the adsorption unit 700 is filled with an adsorbent, and the outside of 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 to a condensation unit 800, so that the tantalum source precursor vapor flowing out from the top of the adsorption unit 700 can be condensed in the condensation unit 800, and the adsorption unit 700 is connected to a vacuum control unit 900 for controlling the overall system pressure.
实施例1Example 1
五（二甲胺基）钽的纯化方法，包括以下步骤：The method for purifying penta(dimethylamino)tantalum comprises the following steps:
S.1向纯化罐110中加入10L
1-乙基-3-甲基咪唑氯盐以及100g活性炭，搅拌均匀后，在纯化罐110内部得到吸附浆料；S.1 Add 10L 1-ethyl-3-methylimidazolium chloride and 100g activated carbon into the purification tank 110, stir evenly, and obtain adsorption slurry inside the purification tank 110;
S.2将100g粗品五（二甲胺基）钽溶于加入纯化罐110内部中，控制纯化罐110内部温度至40℃，搅拌使得粗品五（二甲胺基）钽溶于吸附浆料中。然后通过压力控制单元500控制体系压力至1 kPa，并在搅拌条件下向纯化罐110内部以10L/h的速率通入氩气，使得粗品五（二甲胺基）钽与吸附剂相接触，从而使得粗品钽源前驱体中的杂质被吸附剂所吸附；S.2 Dissolve 100g of crude tantalum penta(dimethylamino) in the purification tank 110, control the temperature inside the purification tank 110 to 40°C, and stir to dissolve the crude tantalum penta(dimethylamino) in the adsorption slurry. Then control the system pressure to 1 kPa through the pressure control unit 500, and introduce argon gas into the purification tank 110 at a rate of 10L/h under stirring conditions, so that the crude tantalum penta(dimethylamino) is in contact with the adsorbent, so that the impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
S.3搅拌吸附3h后，停止通入氩气，并且降低体系压力至0.1 kPa，继续搅拌0.5h后提升吸附浆料的温度至65℃，使得钽源前驱体蒸发，从而形成钽源前驱体蒸汽；S.3 After stirring and adsorbing for 3 hours, stop introducing argon gas and reduce the system pressure to 0.1 kPa. Continue stirring for 0.5 hours and then raise the temperature of the adsorption slurry to 65°C to evaporate the tantalum source precursor, thereby forming tantalum source precursor vapor.
S.4钽源前驱体蒸汽沿着出气管150进入到冷凝管122中，并在冷凝管122中冷凝，收集掉落至收集罐121中的高纯五（二甲胺基）钽。S.4 The tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino) tantalum that falls into the collection tank 121 is collected.
实施例2Example 2
五（二甲胺基）钽的纯化方法，包括以下步骤：The method for purifying penta(dimethylamino)tantalum comprises the following steps:
S.1向纯化罐110中加入10L
1-乙基-3-甲基咪唑氯盐以及100g硅胶粉，搅拌均匀后，在纯化罐110内部得到吸附浆料；S.1 Add 10L 1-ethyl-3-methylimidazolium chloride and 100g silica gel powder into the purification tank 110, stir evenly, and obtain adsorption slurry inside the purification tank 110;
S.2将100g粗品五（二甲胺基）钽溶于加入纯化罐110内部中，控制纯化罐110内部温度至40℃，搅拌使得粗品五（二甲胺基）钽溶于吸附浆料中。然后通过压力控制单元500控制体系压力至1 kPa，并在搅拌条件下向纯化罐110内部以10L/h的速率通入氩气，使得粗品五（二甲胺基）钽与吸附剂相接触，从而使得粗品钽源前驱体中的杂质被吸附剂所吸附；S.2 Dissolve 100g of crude tantalum penta(dimethylamino) in the purification tank 110, control the temperature inside the purification tank 110 to 40°C, and stir to dissolve the crude tantalum penta(dimethylamino) in the adsorption slurry. Then control the system pressure to 1 kPa through the pressure control unit 500, and introduce argon gas into the purification tank 110 at a rate of 10L/h under stirring conditions, so that the crude tantalum penta(dimethylamino) is in contact with the adsorbent, so that the impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
S.3搅拌吸附3h后，停止通入氩气，并且降低体系压力至0.1 kPa，继续搅拌0.5h后提升吸附浆料的温度至65℃，使得钽源前驱体蒸发，从而形成钽源前驱体蒸汽；S.3 After stirring and adsorbing for 3 hours, stop introducing argon gas and reduce the system pressure to 0.1 kPa. Continue stirring for 0.5 hours and then raise the temperature of the adsorption slurry to 65°C to evaporate the tantalum source precursor, thereby forming tantalum source precursor vapor.
S.4钽源前驱体蒸汽沿着出气管150进入到冷凝管122中，并在冷凝管122中冷凝，收集掉落至收集罐121中的高纯五（二甲胺基）钽。S.4 The tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino) tantalum that falls into the collection tank 121 is collected.
实施例3Example 3
五（二甲胺基）钽的纯化方法，包括以下步骤：The method for purifying penta(dimethylamino)tantalum comprises the following steps:
S.1向纯化罐110中加入10L
1-乙基-3-甲基咪唑氯盐以及100g经过表面负载改性的吸附剂A，搅拌均匀后，在纯化罐110内部得到吸附浆料；S.1 Add 10L of 1-ethyl-3-methylimidazolium chloride and 100g of surface-loaded modified adsorbent A into the purification tank 110, stir evenly, and obtain an adsorption slurry inside the purification tank 110;
S.2将100g粗品五（二甲胺基）钽溶于加入纯化罐110内部中，控制纯化罐110内部温度至40℃，搅拌使得粗品五（二甲胺基）钽溶于吸附浆料中。然后通过压力控制单元500控制体系压力至1 kPa，并在搅拌条件下向纯化罐110内部以10L/h的速率通入氩气，使得粗品五（二甲胺基）钽与吸附剂相接触，从而使得粗品钽源前驱体中的杂质被吸附剂所吸附；S.2 Dissolve 100g of crude tantalum penta(dimethylamino) in the purification tank 110, control the temperature inside the purification tank 110 to 40°C, and stir to dissolve the crude tantalum penta(dimethylamino) in the adsorption slurry. Then control the system pressure to 1 kPa through the pressure control unit 500, and introduce argon gas into the purification tank 110 at a rate of 10L/h under stirring conditions, so that the crude tantalum penta(dimethylamino) is in contact with the adsorbent, so that the impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
S.3搅拌吸附3h后，停止通入氩气，并且降低体系压力至0.1 kPa，继续搅拌0.5h后提升吸附浆料的温度至65℃，使得钽源前驱体蒸发，从而形成钽源前驱体蒸汽；S.3 After stirring and adsorbing for 3 hours, stop introducing argon gas and reduce the system pressure to 0.1 kPa. Continue stirring for 0.5 hours and then raise the temperature of the adsorption slurry to 65°C to evaporate the tantalum source precursor, thereby forming tantalum source precursor vapor.
S.4钽源前驱体蒸汽沿着出气管150进入到冷凝管122中，并在冷凝管122中冷凝，收集掉落至收集罐121中的高纯五（二甲胺基）钽。S.4 The tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino)tantalum that falls into the collection tank 121 is collected.
实施例4Example 4
五（二甲胺基）钽的纯化方法，包括以下步骤：The method for purifying penta(dimethylamino)tantalum comprises the following steps:
S.1向纯化罐110中加入10L
1-乙基-3-甲基咪唑氯盐以及100g经过表面负载改性的吸附剂B，搅拌均匀后，在纯化罐110内部得到吸附浆料；S.1 Add 10L of 1-ethyl-3-methylimidazolium chloride and 100g of surface-loaded modified adsorbent B into the purification tank 110, stir evenly, and obtain an adsorption slurry inside the purification tank 110;
S.2将100g粗品五（二甲胺基）钽溶于加入纯化罐110内部中，控制纯化罐110内部温度至40℃，搅拌使得粗品五（二甲胺基）钽溶于吸附浆料中。然后通过压力控制单元500控制体系压力至1 kPa，并在搅拌条件下向纯化罐110内部以10L/h的速率通入氩气，使得粗品五（二甲胺基）钽与吸附剂相接触，从而使得粗品钽源前驱体中的杂质被吸附剂所吸附；S.2 Dissolve 100g of crude tantalum penta(dimethylamino) in the purification tank 110, control the temperature inside the purification tank 110 to 40°C, and stir to dissolve the crude tantalum penta(dimethylamino) in the adsorption slurry. Then control the system pressure to 1 kPa through the pressure control unit 500, and introduce argon gas into the purification tank 110 at a rate of 10L/h under stirring conditions, so that the crude tantalum penta(dimethylamino) is in contact with the adsorbent, so that the impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
S.3搅拌吸附3h后，停止通入氩气，并且降低体系压力至0.1 kPa，继续搅拌0.5h后提升吸附浆料的温度至65℃，使得钽源前驱体蒸发，从而形成钽源前驱体蒸汽；S.3 After stirring and adsorbing for 3 hours, stop introducing argon gas and reduce the system pressure to 0.1 kPa. Continue stirring for 0.5 hours and then raise the temperature of the adsorption slurry to 65°C to evaporate the tantalum source precursor, thereby forming tantalum source precursor vapor.
S.4钽源前驱体蒸汽沿着出气管150进入到冷凝管122中，并在冷凝管122中冷凝，收集掉落至收集罐121中的高纯五（二甲胺基）钽。S.4 The tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino) tantalum that falls into the collection tank 121 is collected.
实施例5Example 5
五（二甲胺基）钽的纯化方法，包括以下步骤：The method for purifying penta(dimethylamino)tantalum comprises the following steps:
S.1向纯化罐110中加入10L
1-乙基-3-甲基咪唑氯盐以及100g经过表面负载改性的吸附剂C，搅拌均匀后，在纯化罐110内部得到吸附浆料；S.1 Add 10L of 1-ethyl-3-methylimidazolium chloride and 100g of surface-loaded modified adsorbent C into the purification tank 110, stir evenly, and obtain an adsorption slurry inside the purification tank 110;
S.2将100g粗品五（二甲胺基）钽溶于加入纯化罐110内部中，控制纯化罐110内部温度至40℃，搅拌使得粗品五（二甲胺基）钽溶于吸附浆料中。然后通过压力控制单元500控制体系压力至1 kPa，并在搅拌条件下向纯化罐110内部以10L/h的速率通入氩气，使得粗品五（二甲胺基）钽与吸附剂相接触，从而使得粗品钽源前驱体中的杂质被吸附剂所吸附；S.2 Dissolve 100g of crude tantalum penta(dimethylamino) in the purification tank 110, control the temperature inside the purification tank 110 to 40°C, and stir to dissolve the crude tantalum penta(dimethylamino) in the adsorption slurry. Then control the system pressure to 1 kPa through the pressure control unit 500, and introduce argon gas into the purification tank 110 at a rate of 10L/h under stirring conditions, so that the crude tantalum penta(dimethylamino) is in contact with the adsorbent, so that the impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
S.3搅拌吸附3h后，停止通入氩气，并且降低体系压力至0.1 kPa，继续搅拌0.5h后提升吸附浆料的温度至65℃，使得钽源前驱体蒸发，从而形成钽源前驱体蒸汽；S.3 After stirring and adsorbing for 3 hours, stop introducing argon gas and reduce the system pressure to 0.1 kPa. Continue stirring for 0.5 hours and then raise the temperature of the adsorption slurry to 65°C to evaporate the tantalum source precursor, thereby forming tantalum source precursor vapor.
S.4钽源前驱体蒸汽沿着出气管150进入到冷凝管122中，并在冷凝管122中冷凝，收集掉落至收集罐121中的高纯五（二甲胺基）钽。S.4 The tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino) tantalum that falls into the collection tank 121 is collected.
实施例6Example 6
五（二甲胺基）钽的纯化方法，包括以下步骤：The method for purifying penta(dimethylamino)tantalum comprises the following steps:
S.1向纯化罐110中加入10L
1-乙基-3-甲基咪唑氯盐以及100g经过表面负载改性的吸附剂D，搅拌均匀后，在纯化罐110内部得到吸附浆料；S.1 Add 10L of 1-ethyl-3-methylimidazolium chloride and 100g of surface-loaded modified adsorbent D into the purification tank 110, stir evenly, and obtain an adsorption slurry inside the purification tank 110;
S.2将100g粗品五（二甲胺基）钽溶于加入纯化罐110内部中，控制纯化罐110内部温度至40℃，搅拌使得粗品五（二甲胺基）钽溶于吸附浆料中。然后通过压力控制单元500控制体系压力至1 kPa，并在搅拌条件下向纯化罐110内部以10L/h的速率通入氩气，使得粗品五（二甲胺基）钽与吸附剂相接触，从而使得粗品钽源前驱体中的杂质被吸附剂所吸附；S.2 Dissolve 100g of crude tantalum penta(dimethylamino) in the purification tank 110, control the temperature inside the purification tank 110 to 40°C, and stir to dissolve the crude tantalum penta(dimethylamino) in the adsorption slurry. Then control the system pressure to 1 kPa through the pressure control unit 500, and introduce argon gas into the purification tank 110 at a rate of 10L/h under stirring conditions, so that the crude tantalum penta(dimethylamino) contacts the adsorbent, so that the impurities in the crude tantalum source precursor are adsorbed by the adsorbent;
S.3搅拌吸附3h后，停止通入氩气，并且降低体系压力至0.1 kPa，继续搅拌0.5h后提升吸附浆料的温度至65℃，使得钽源前驱体蒸发，从而形成钽源前驱体蒸汽；S.3 After stirring and adsorbing for 3 hours, stop introducing argon gas and reduce the system pressure to 0.1 kPa. Continue stirring for 0.5 hours and then raise the temperature of the adsorption slurry to 65°C to evaporate the tantalum source precursor, thereby forming tantalum source precursor vapor.
S.4钽源前驱体蒸汽沿着出气管150进入到冷凝管122中，并在冷凝管122中冷凝，收集掉落至收集罐121中的高纯五（二甲胺基）钽。S.4 The tantalum source precursor vapor enters the condenser 122 along the outlet pipe 150 and condenses in the condenser 122 , and the high-purity tantalum penta(dimethylamino) tantalum that falls into the collection tank 121 is collected.
实施例7Example 7
实施例7与对比例3步骤基本相同，区别在于，将五（二甲胺基）钽替换成为五（二乙胺基）钽，且蒸馏温度提升至75℃。The steps of Example 7 are basically the same as those of Comparative Example 3, except that penta(dimethylamino)tantalum is replaced with penta(diethylamino)tantalum, and the distillation temperature is increased to 75°C.
对比例1Comparative Example 1
向常规的卧式升华精制塔的蒸馏器600内部放置粗品五（二甲胺基）钽，向吸附单元700中放入硅胶粉，然后减压至体系压力为0.1 kPa，以抽除卧式升华精制塔内部空气，将蒸馏器600以及吸附单元700的温度提升至65℃，从而形成五（二甲胺基）钽蒸汽，经过吸附单元700后进入到冷凝单元800，从而五（二甲胺基）钽再次冷凝成固体，即得纯化后的五（二甲胺基）钽。Crude penta(dimethylamino)tantalum is placed inside the distiller 600 of a conventional horizontal sublimation refining tower, silica gel powder is placed in the adsorption unit 700, and then the system pressure is reduced to 0.1 kPa to remove the air inside the horizontal sublimation refining tower, and the temperature of the distiller 600 and the adsorption unit 700 is increased to 65°C to form penta(dimethylamino)tantalum vapor, which enters the condensation unit 800 after passing through the adsorption unit 700, so that the penta(dimethylamino)tantalum is condensed into a solid again to obtain purified penta(dimethylamino)tantalum.
对比例2Comparative Example 2
向常规的卧式升华精制塔的蒸馏器600内部放置粗品五（二甲胺基）钽，向吸附单元700中放入经过表面负载改性的吸附剂A，然后减压至体系压力为0.1 kPa，以抽除卧式升华精制塔内部空气，将蒸馏器600以及吸附单元700的温度提升至65℃，从而形成五（二甲胺基）钽蒸汽，经过吸附单元700后进入到冷凝单元800，从而五（二甲胺基）钽再次冷凝成固体，即得纯化后的五（二甲胺基）钽。Crude penta(dimethylamino)tantalum is placed inside the distiller 600 of a conventional horizontal sublimation refining tower, and adsorbent A modified by surface loading is placed in the adsorption unit 700. The system pressure is then reduced to 0.1 kPa to remove the air inside the horizontal sublimation refining tower, and the temperature of the distiller 600 and the adsorption unit 700 is increased to 65°C to form penta(dimethylamino)tantalum vapor. After passing through the adsorption unit 700, it enters the condensation unit 800, whereby the penta(dimethylamino)tantalum is condensed into a solid again to obtain purified penta(dimethylamino)tantalum.
【性能测试结果】【Performance test results】
实施例1~6以及对比应用例1~2中的提纯得到的五（二甲胺基）钽以及实施例7得到的五（二乙胺基）钽中杂质含量如下表1所示。The impurity contents in the penta(dimethylamino)tantalum obtained by purification in Examples 1 to 6 and Comparative Application Examples 1 to 2 and the penta(diethylamino)tantalum obtained in Example 7 are shown in Table 1 below.
表1Table 1
从上表数据中可知，通过本发明的制备方法，能够对钽源前驱体起到良好的纯化效果，有效相较于现有技术中简单的升华冷凝或者将钽源前驱体的蒸汽通过吸附的方式而言，其无论是在纯化效率以及纯化效果方面均具有明显的提升。It can be seen from the data in the above table that the preparation method of the present invention can achieve a good purification effect on the tantalum source precursor, which is effective compared with the simple sublimation condensation or adsorption of the vapor of the tantalum source precursor in the prior art, and has obvious improvements in both purification efficiency and purification effect.
同时，本发明中只需要使用简单的吸附剂即可对钽源前驱体起到良好的吸附提纯作用，经过提纯后的钽源前驱体其内部杂质含量能够降低至ppm级。同时不限于钽源前驱体的具体形式，无论是固态的五（二甲胺基）钽以及液态的五（二乙胺基）钽均可以有效提纯，有效简化了提纯步骤。同时，本发明中只需要在对钽源前驱体升华时提高体系温度，无需对钽源前驱体蒸汽起到保温加热作用。而现有技术中为了保证钽源前驱体蒸汽在于吸附剂接触时不会冷凝从而堵住吸附剂，需要同时对钽源前驱体蒸汽起到加热。因此本发明中的这一纯化方法大大降低了能耗且更加环保。At the same time, the present invention only needs to use a simple adsorbent to achieve a good adsorption and purification effect on the tantalum source precursor, and the internal impurity content of the purified tantalum source precursor can be reduced to the ppm level. At the same time, it is not limited to the specific form of the tantalum source precursor. Both solid penta(dimethylamino)tantalum and liquid penta(diethylamino)tantalum can be effectively purified, which effectively simplifies the purification steps. At the same time, the present invention only needs to increase the system temperature when the tantalum source precursor is sublimated, and there is no need to heat the tantalum source precursor vapor. In the prior art, in order to ensure that the tantalum source precursor vapor will not condense when in contact with the adsorbent and thus block the adsorbent, it is necessary to heat the tantalum source precursor vapor at the same time. Therefore, this purification method in the present invention greatly reduces energy consumption and is more environmentally friendly.
同时，本发明还发现，将吸附剂进行表面负载改性后，能够进一步提升对于钽源前驱体的提纯效果，从而能够使得其内部杂质达到ppb级别。同时，从实际测试结果可以看出，将单质铁与一氧化锰同时负载在吸附剂表面时，能够有效提升对于钽源前驱体中的含卤杂质以及氧气的吸附效果。而碳层的设置使得吸附剂的电子传导效果有效提升，因此能够有效提升单质铁以及一氧化锰在转变过程中的电子传递活性，从而提升了吸附剂对于杂质的吸附效果。At the same time, the present invention also found that after the adsorbent is surface-loaded and modified, the purification effect of the tantalum source precursor can be further improved, so that the internal impurities can reach the ppb level. At the same time, it can be seen from the actual test results that when elemental iron and manganese monoxide are simultaneously loaded on the surface of the adsorbent, the adsorption effect of halogen-containing impurities and oxygen in the tantalum source precursor can be effectively improved. The provision of the carbon layer effectively improves the electronic conduction effect of the adsorbent, so that the electron transfer activity of elemental iron and manganese monoxide during the transformation process can be effectively improved, thereby improving the adsorption effect of the adsorbent on impurities.
Claims (10)
- 钽源前驱体的纯化方法，其特征在于，包括以下步骤：A method for purifying a tantalum source precursor, characterized in that it comprises the following steps:（S.1）将吸附剂分散于不具有挥发性的惰性液体介质中，得到吸附浆料；(S.1) dispersing the adsorbent in a non-volatile inert liquid medium to obtain an adsorption slurry;（S.2）将粗品钽源前驱体溶于吸附浆料中，使得粗品钽源前驱体与吸附剂相接触，从而使得粗品钽源前驱体中的杂质被吸附剂所吸附；(S.2) dissolving the crude tantalum source precursor in the adsorption slurry so that the crude tantalum source precursor contacts the adsorbent, thereby allowing impurities in the crude tantalum source precursor to be adsorbed by the adsorbent;（S.3）提升吸附浆料的温度至钽源前驱体的蒸发温度，使得钽源前驱体蒸发，从而形成钽源前驱体蒸汽；(S.3) raising the temperature of the adsorption slurry to the evaporation temperature of the tantalum source precursor, so that the tantalum source precursor evaporates, thereby forming tantalum source precursor vapor;（S.4）收集钽源前驱体蒸汽并将其冷凝，得到高纯钽源前驱体。(S.4) Collecting the tantalum source precursor vapor and condensing it to obtain a high-purity tantalum source precursor.
- 根据权利要求1所述的钽源前驱体的纯化方法，其特征在于，The method for purifying a tantalum source precursor according to claim 1, characterized in that:步骤（S.1）中所述吸附剂包括活性炭、多孔硅氧化铝、硅胶粉、沸石或者分子筛中的任意一种。The adsorbent in step (S.1) includes any one of activated carbon, porous silicon alumina, silica gel powder, zeolite or molecular sieve.
- 根据权利要求1或2钽源前驱体的纯化方法，其特征在于，The method for purifying a tantalum source precursor according to claim 1 or 2, characterized in that:所述吸附剂经过表面负载改性；The adsorbent is surface-loaded and modified;经过表面负载改性的吸附剂表面还负载有单质铁以及一氧化锰；The surface of the adsorbent modified by surface loading is also loaded with elemental iron and manganese monoxide;所述经过表面负载改性的吸附剂的外表面还包覆有一层具有多孔结构的碳层。The outer surface of the surface-load-modified adsorbent is also coated with a carbon layer with a porous structure.
- 根据权利要求3钽源前驱体的纯化方法，其特征在于，The method for purifying a tantalum source precursor according to claim 3 is characterized in that:所述经过表面负载改性的吸附剂的制备方法如下：The preparation method of the surface-loaded modified adsorbent is as follows:（1）将吸附剂浸渍于含有铁盐以及锰盐的溶液中，得到负载有铁盐以及锰盐的吸附剂；(1) immersing the adsorbent in a solution containing an iron salt and a manganese salt to obtain an adsorbent loaded with the iron salt and the manganese salt;（2）将负载有铁盐以及锰盐的吸附剂在空气氛围下加热，使得铁盐以及锰盐转变为铁的氧化物以及锰的氧化物；(2) heating the adsorbent loaded with iron salt and manganese salt in an air atmosphere so that the iron salt and manganese salt are converted into iron oxide and manganese oxide;（3）然后再在氢气氛围下将铁的氧化物还原成单质铁，将锰的氧化物还原成一氧化锰；(3) Then, in a hydrogen atmosphere, the iron oxide is reduced to elemental iron, and the manganese oxide is reduced to manganese monoxide;（4）将负载有单质铁以及一氧化锰的吸附剂表面负载一层碳前驱体，然后在惰性气体保护下将碳前驱体转变成具有多孔结构的碳层，即得所述经过表面负载改性的吸附剂。(4) A layer of carbon precursor is loaded on the surface of the adsorbent loaded with elemental iron and manganese monoxide, and then the carbon precursor is converted into a carbon layer with a porous structure under the protection of an inert gas, thereby obtaining the adsorbent modified by the surface loading.
- 根据权利要求1或2所述的钽源前驱体的纯化方法，其特征在于，The method for purifying a tantalum source precursor according to claim 1 or 2, characterized in that:步骤（S.1）中所述惰性液体介质包括离子液体或者硅油中的任意一种。The inert liquid medium in step (S.1) includes any one of ionic liquid and silicone oil.
- 根据权利要求1所述的钽源前驱体的纯化方法，其特征在于，The method for purifying a tantalum source precursor according to claim 1, characterized in that:所述钽源前驱体包括五（二甲胺基）钽、五（二乙胺基）钽、五乙氧基钽、三(二乙基氨基)叔丁酰胺钽的任意一种。The tantalum source precursor includes any one of penta(dimethylamino)tantalum, penta(diethylamino)tantalum, pentaethoxytantalum, and tri(diethylamino)t-butyramidetantalum.
- 根据权利要求1所述的钽源前驱体的纯化方法，其特征在于，The method for purifying a tantalum source precursor according to claim 1, characterized in that:所述步骤（S.2）中还包括在减压条件下将惰性气体通入到吸附浆料中的步骤。The step (S.2) further comprises the step of introducing an inert gas into the adsorption slurry under reduced pressure.
- 一种用于纯化钽源前驱体的纯化系统，其特征在于，其至少包含：A purification system for purifying a tantalum source precursor, characterized in that it at least comprises:纯化单元（100），其包括用于盛放物料的纯化罐（110），还包括用于对纯化罐（110）内部物料起到搅拌作用的搅拌装置（120），以及用于对纯化罐（110）起到加热的加热装置（130）；A purification unit (100), comprising a purification tank (110) for containing materials, a stirring device (120) for stirring the materials inside the purification tank (110), and a heating device (130) for heating the purification tank (110);供气单元（200），其与纯化罐（110）的底部管路联通，从而用于向纯化罐（110）内部通入惰性气体；A gas supply unit (200) is connected to the bottom pipeline of the purification tank (110) so as to be used to introduce inert gas into the purification tank (110);收集单元（300），其包括一个与纯化罐（110）的顶部管路联通的冷凝装置（310），从而用于对腔体（110）内蒸发得到的钽源前驱体蒸汽起到冷凝以及收集作用；The collecting unit (300) comprises a condensing device (310) connected to the top pipeline of the purification tank (110), so as to condense and collect the tantalum source precursor vapor evaporated in the cavity (110);捕集单元（400），其包括一个与冷凝装置（120）管路联通的捕集瓶（410），所述捕集瓶（410）的外部套设有一个冷阱（420）；A capture unit (400) comprising a capture bottle (410) connected to a pipeline of a condensing device (120), wherein a cold trap (420) is disposed on the outside of the capture bottle (410);压力控制单元（500），其与捕集瓶（410）管路联通，用于控制整个体系内部压力。The pressure control unit (500) is connected to the pipeline of the capture bottle (410) and is used to control the internal pressure of the entire system.
- 根据权利要求8所述的一种用于纯化钽源前驱体的纯化系统，其特征在于，The purification system for purifying a tantalum source precursor according to claim 8, characterized in that:所述供气单元（200）包括用于存储惰性气体的气罐（210）；以及，The gas supply unit (200) comprises a gas tank (210) for storing an inert gas; and,用于控制向纯化单元（100）输送的气流的流速的压力控制阀（220）。A pressure control valve (220) is provided for controlling the flow rate of a gas stream delivered to the purification unit (100).
- 根据权利要求8所述的一种用于纯化钽源前驱体的纯化系统，其特征在于，The purification system for purifying a tantalum source precursor according to claim 8, characterized in that:所述冷凝装置（310）包括产品收集罐（311）以及设置在收集罐（311）上端的冷凝管（312）；The condensing device (310) comprises a product collecting tank (311) and a condensing pipe (312) arranged at the upper end of the collecting tank (311);所述冷凝管（312）内部交替设置有若干冷凝挡板（313）；A plurality of condensation baffles (313) are alternately arranged inside the condensation tube (312);所述冷凝管（312）的顶端与纯化罐（110）管路联通，底端与捕集瓶（410）管路联通。The top end of the condenser tube (312) is connected to the pipeline of the purification tank (110), and the bottom end is connected to the pipeline of the capture bottle (410).
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- 2022-10-27 CN CN202211324335.XA patent/CN115584482B/en active Active
- 2022-12-11 WO PCT/CN2022/138261 patent/WO2024087339A1/en unknown
- 2022-12-11 KR KR1020237038065A patent/KR20240060517A/en unknown
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| CN109110742A (en) * | 2017-06-23 | 2019-01-01 | 四川大学 | Utilize the mesoporous carbon and preparation method of manganese compound preparation |
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| Publication number | Publication date |
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| CN115584482A (en) | 2023-01-10 |
| CN115584482B (en) | 2023-04-11 |
| KR20240060517A (en) | 2024-05-08 |
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