CN117362357A - High purity La (iPrCp) 3 Preparation method and application thereof - Google Patents
High purity La (iPrCp) 3 Preparation method and application thereof Download PDFInfo
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- CN117362357A CN117362357A CN202311481935.1A CN202311481935A CN117362357A CN 117362357 A CN117362357 A CN 117362357A CN 202311481935 A CN202311481935 A CN 202311481935A CN 117362357 A CN117362357 A CN 117362357A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 26
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 239000004065 semiconductor Substances 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 92
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 21
- 239000012043 crude product Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000007792 addition Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 18
- 239000000243 solution Substances 0.000 description 29
- 239000011734 sodium Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011261 inert gas Substances 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000010408 film Substances 0.000 description 7
- 238000005292 vacuum distillation Methods 0.000 description 7
- BHWFVSOAOOHARF-UHFFFAOYSA-N C(C)(C)C1(C=CC=C1)[La](C1(C=CC=C1)C(C)C)C1(C=CC=C1)C(C)C Chemical compound C(C)(C)C1(C=CC=C1)[La](C1(C=CC=C1)C(C)C)C1(C=CC=C1)C(C)C BHWFVSOAOOHARF-UHFFFAOYSA-N 0.000 description 6
- 230000003247 decreasing effect Effects 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- JPOCYXBYTNUETJ-UHFFFAOYSA-N 1-propan-2-ylcyclopenta-1,3-diene;sodium Chemical compound [Na].CC(C)C1=CC=CC1 JPOCYXBYTNUETJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MWQKURVBJZAOSC-UHFFFAOYSA-N 1-propan-2-ylcyclopenta-1,3-diene Chemical compound CC(C)C1=CC=CC1 MWQKURVBJZAOSC-UHFFFAOYSA-N 0.000 description 1
- NAMYKGVDVNBCFQ-UHFFFAOYSA-N 2-bromopropane Chemical compound CC(C)Br NAMYKGVDVNBCFQ-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- NUUNDIOOYFEMQN-UHFFFAOYSA-N cyclopenta-1,3-diene;sodium Chemical compound [Na].C1C=CC=C1 NUUNDIOOYFEMQN-UHFFFAOYSA-N 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- 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
- C23C16/40—Oxides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a high-purity La (iPrCp) 3 And a preparation method and application thereof. The preparation method comprises the following steps: will contain LaCl 3 Heating and refluxing the liquid phase reaction system of xTHF and Na (iPrCp), and then carrying out post-treatment on the obtained reaction product to obtain high-purity La (iPrCp) 3 . La (iPrCp) obtained by the preparation method 3 The organic purity in the product can reach more than 99.99%, the inorganic impurity content is less than 1ppm, the lanthanum metal purity reaches more than 99.9999%, and the method is suitable for preparing the lanthanum oxide film for semiconductors.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and in particular relates to a high-purity La (iPrCp) 3 And a preparation method and application thereof.
Background
Lanthanum is a metal rare earth element, and has active chemical property and is easy to oxidize in air. At present, lanthanum oxide is lanthanum oxide (La 2 O 3 ) Is widely used in semiconductor processes because of La 2 O 3 The dielectric constant of the dielectric layer is high, the band gap is wide (-5.5 eV), and the dielectric layer can be singly used for the thin gate oxideFilms, also with HfO 2 、Y 2 O 3 Doping forms a high dielectric constant (high-k) layer in the DRAM memory chip. At the same time La 2 O 3 Also used for HfO 2 Capping layer of gate oxide film layer, la/La 2 O 3 As a passivation layer of germanium (Ge). La (La) 2 O 3 Is "transparent" over a wide range of wavelengths and is therefore also a good optical film.
At present, the lanthanum oxide film is generally obtained by adopting ALD technology, and the La precursor material adopted in the deposition process has the characteristics of variety, quality and La 2 O 3 The quality of the film has a large influence. Tris (isopropylcyclopentadienyl) lanthanum (La (iPrCp) 3 ) Because of its lower melting point (38 ℃) compared to other typical lanthanum precursors, it is widely used in ALD to deposit lanthanum oxide films. However, the prior art processes for preparing tris (isopropylcyclopentadienyl) lanthanum are generally complex, for example, in the case of lanthanum powder to obtain the reaction precursor LaCl 3 In the case of xTHF, the procedure is complicated and requires titration of the x value, which is inefficient and unsuitable for scale-up. In addition, some preparation methods have low purity of the obtained tri (isopropyl cyclopentadienyl) lanthanum, and can not meet the requirement of the semiconductor industry on the purity of the product.
Disclosure of Invention
In order to solve all or part of the technical problems, the invention provides the following technical scheme:
one of the objects of the present invention is to provide La (iPrCp) of high purity 3 The preparation method of (2) comprises the following steps: will contain LaCl 3 Heating and refluxing the liquid phase reaction system of xTHF and Na (iPrCp), and then carrying out post-treatment on the obtained reaction product to obtain high-purity La (iPrCp) 3 。
In some embodiments, the liquid phase reaction system comprises LaCl 3 The molar ratio of the catalyst to Na (iPrCp) is 1-1.1:3-3.5.
In some embodiments, the reflux reaction is at a temperature of 75-80 ℃.
In some embodiments, the reflux reaction is for a period of time ranging from 10 to 12 hours.
In some embodiments, the LaCl 3 In xTHF, the value of x is in the range of 0.6 to 2.
In some embodiments, the method of making comprises: adding the tetrahydrofuran solution of Na (iPrCp) into LaCl in portions 3 In xTHF solution, the liquid phase reaction system was obtained.
Further, the concentration of the tetrahydrofuran solution of Na (iPrCp) is L-2mol/L.
Further, the LaCl 3 The concentration of the xTHF solution is 0.5-1mol/L.
In some embodiments, the post-processing specifically includes: subjecting the reaction product to reduced pressure distillation to isolate La (iPrCp) 3 Crude products; for La (iPrCp) 3 The crude product is subjected to vacuum rectification treatment to obtain high-purity La (iPrCp) 3 。
In some embodiments, the reduced pressure distillation process comprises: continuously heating the reaction product under the vacuum degree of 60-70 KPa to separate tetrahydrofuran solvent from the reaction product, and ending the separation of tetrahydrofuran when the temperature is raised to 80-85 ℃; then, the vacuum degree was adjusted to 10-20KPa, and La (iPrCp) was collected while maintaining the continuous temperature rise and the continuous vacuum degree decrease 3 Stopping collecting the crude product when the temperature is raised to 145-150deg.C and the vacuum degree is reduced to 0-10KPa, to obtain the La (iPrCp) 3 Crude product.
In some embodiments, the reduced pressure distillation treatment specifically includes: and continuously heating the reaction product at a heating rate of 1-5 ℃ per minute under the vacuum degree condition of 60-70 KPa until the temperature is raised to 80-85 ℃.
In some embodiments, the reduced pressure distillation treatment specifically includes: after the separation of tetrahydrofuran is finished, the vacuum degree is continuously reduced to 0-10KPa at the speed of 5-10 KPa/min, and the temperature is continuously increased at the heating speed of 1-5 ℃/min until the temperature is increased to 145-150 ℃.
In some embodiments, the reduced pressure rectification process comprises: under the vacuum condition of inert atmosphere and 10-15KPa, the La (iPrCp) is treated 3 Temperature control of crude productThe vacuum rectification is carried out at 120-125 ℃ to obtain the La (iPrCp) with high purity 3 . Under the condition of reduced pressure distillation, the method is favorable for obtaining high-purity products under the conditions of high efficiency and energy conservation.
In some embodiments, during the vacuum distillation, 20% of the front fraction and 20% of the rear fraction are removed, and only 60% of the middle fraction is collected to obtain the high purity La (iPrCp) 3 。
In some embodiments, the LaCl 3 The preparation method of xTHF comprises the following steps: at 120-125 deg.C for LaCl 3 Vacuum drying to obtain high-purity LaCl 3 Carrying out water removal treatment on tetrahydrofuran to obtain anhydrous tetrahydrofuran; under the inert atmosphere condition, the high-purity LaCl 3 Dissolving in anhydrous tetrahydrofuran to obtain LaCl 3 xTHF solution. And the tetrahydrofuran is subjected to water removal treatment, for example, a pumped and baked 4A molecular sieve is adopted for water removal. For LaCl 3 Vacuum drying and water removal treatment are carried out on tetrahydrofuran, so that a product with higher purity is obtained.
In some examples, the Na (iPrCp) tetrahydrofuran solution was added to LaCl in portions 3 Specifically included in the xTHF solution are: dropwise adding the tetrahydrofuran solution of Na (iPrCp) to LaCl at an adding speed of 10-20 drops/s under the inert atmosphere condition 3 In xTHF solution, and maintaining stirring during the addition.
Another object of the present invention is to provide La (iPrCp) of high purity obtained by the above-mentioned production method 3 Said high purity La (iPrCp) 3 The organic purity of (2) is more than 99.99 percent, and the inorganic impurity content<1ppm。
In some embodiments, the high purity La (iPrCp) 3 The purity of lanthanum metal in the alloy is more than 99.999 percent. More preferably 99.9999% or more.
It is a third object of the present invention to provide La (iPrCp) having a high purity as defined in any one of the above-mentioned aspects 3 The application in preparing lanthanum oxide film.
Applications include the preparation of lanthanum oxide films for semiconductors using chemical vapor deposition techniques, such as ALD processes.
Compared with the prior art, the invention has at least the following beneficial effects: la (iPrCp) obtained by the preparation method 3 The organic purity in the product can reach more than 99.99%, the content of inorganic impurities is less than 1ppm, the content of Na and K in the product is low, and the purity of lanthanum metal reaches more than 99.999%, even 99.9999%; la (iPrCp) of the high purity 3 The method is suitable for preparing lanthanum oxide films for semiconductors; the preparation method provided by the invention realizes a one-pot method, directly rectifies and purifies to obtain a high-purity product, has simple operation and high reaction efficiency, uses fewer reaction vessels, and is suitable for large-scale production.
Drawings
FIG. 1 shows a high purity La (iPrCp) obtained in example 1 of the present invention 3 Is a NMR test spectrum of (2);
FIG. 2 shows a high purity La (iPrCp) obtained in example 1 of the present invention 3 Is a spectrogram of ICP-MS test.
Detailed Description
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention. Specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
Unless otherwise indicated, all materials and reagents used in the present invention are commercially available.
Example 1
This example provides a high purity La (iPrCp) 3 The preparation method of (2) has the following reaction formula:
removing water from tetrahydrofuran by using a pumped and baked 4A molecular sieve to obtainTo anhydrous tetrahydrofuran solvent; at 120 ℃ for LaCl 3 Vacuum heating to remove LaCl 3 Organic impurities and low boiling point impurities in the obtained product to obtain high-purity LaCl 3 。
Under the protection of inert gas nitrogen, the LaCl which is subjected to the vacuum pumping and drying treatment is processed 3 (186 g,0.5 mol) and 1L of the dehydrated tetrahydrofuran solvent were put into a 5L four-necked flask equipped with a stirring and cooling reflux apparatus, and dissolved by mechanical stirring to give LaCl 3 xTHF solution; na (iPrCp) (196 g,1.5 mol) was dissolved in tetrahydrofuran (1L) to give a tetrahydrofuran solution of Na (iPrCp);
dropwise adding a tetrahydrofuran solution of Na (iPrCp) into LaCl under the protection of inert gas nitrogen 3 In xTHF solution, obtaining a reaction system, and maintaining stirring treatment in the dripping process; after the dripping is finished, the temperature of the reaction system is raised to 80 ℃, and the reaction system is heated and refluxed for 12 hours to obtain a reaction product;
heating the reaction product in a reaction kettle at a heating rate of 1 ℃/min, adjusting the vacuum degree to 70KPa, distilling under reduced pressure to separate tetrahydrofuran solvent in the reaction product, and finishing the separation of tetrahydrofuran solvent when the temperature is raised to 85 ℃, and maintaining stirring treatment in the process; then, the temperature of the reaction vessel was continuously increased at a heating rate of 1℃per minute while stirring was maintained, and the vacuum was continuously decreased at a rate of 5KPa/min to receive La (iPrCp) 3 The crude product is stopped collecting when the temperature is raised to 150 ℃ and the vacuum degree is reduced to 0 KPa;
la (iPrCp) obtained by rectifying column pair with 0 type stainless steel mixed filler in inert gas glove box 3 The crude product is subjected to vacuum distillation, the vacuum degree in the vacuum distillation process is controlled to be 10-15KPa, the temperature is controlled to be 120-125 ℃, 20 percent of distillate which is distilled off firstly is removed in the process of collecting the distillate, then the middle-section distillate (accounting for 60 percent) is collected, and finally 20 percent of distillate which is distilled off is also removed, and the collected middle-section distillate is La (iPrCp) with high purity 3 The present example gives La (iPrCp) of high purity 3 170g, 75% yield.
The organic purity of the organic material is over 99.99 percent by NMR measurement, and the content of all inorganic impurities detected by ICP-MS total elements is less than 1ppm, thereby meeting the product purity requirement of the semiconductor industry.
Example 2
Removing water from tetrahydrofuran by using a dried 4A molecular sieve to obtain an anhydrous tetrahydrofuran solvent; at 120 ℃ for LaCl 3 Vacuum heating to remove LaCl 3 Organic impurities and low boiling point impurities in the obtained product to obtain high-purity LaCl 3 。
Under the protection of inert gas nitrogen, the LaCl which is subjected to the vacuum pumping and drying treatment is processed 3 (186 g,0.5 mol) and 1L of the dehydrated tetrahydrofuran solvent were put into a 5L four-necked flask equipped with a stirring and cooling reflux apparatus, and dissolved by mechanical stirring to give LaCl 3 xTHF solution; na (iPrCp) (196 g,1.5 mol) was dissolved in tetrahydrofuran (1L) to give a tetrahydrofuran solution of Na (iPrCp);
dropwise adding a tetrahydrofuran solution of Na (iPrCp) into LaCl under the protection of inert gas nitrogen 3 In xTHF solution, obtaining a reaction system, and maintaining stirring treatment in the dripping process; after the dripping is finished, the reaction system is heated to 75 ℃, and the mixture is heated and refluxed for 10 hours to obtain a reaction product;
heating the reaction product in a reaction kettle at a heating rate of 5 ℃/min, adjusting the vacuum degree to 60KPa, distilling under reduced pressure to separate tetrahydrofuran solvent in the reaction product, and finishing the separation of tetrahydrofuran solvent when the temperature is raised to 80 ℃, and maintaining stirring treatment in the process; then, the temperature of the reaction vessel was continuously increased at a heating rate of 5℃per minute while stirring was maintained, and the vacuum was continuously decreased at a rate of 10KPa/min to receive La (iPrCp) 3 Stopping collecting the crude product when the temperature is raised to 145 ℃ and the vacuum degree is reduced to 10 KPa;
la (iPrCp) obtained by rectifying column pair with 0 type stainless steel mixed filler in inert gas glove box 3 The crude product is subjected to vacuum distillation, the vacuum degree in the vacuum distillation process is controlled to be 10-15KPa, the temperature is 120-125 ℃, 20 percent of the fraction distilled first is removed in the process of collecting the fraction, and then the middle-stage fraction (accounting for60%) and the final 20% fraction was removed, and the middle fraction obtained was collected as high purity La (iPrCp) 3 。
The organic purity obtained by the method is more than 99.99%, the content of all inorganic impurities detected by ICP-MS (inductively coupled plasma-mass spectrometry) is less than 1ppm, and the product purity requirement of the semiconductor industry is met.
Example 3
Removing water from tetrahydrofuran by using a dried 4A molecular sieve to obtain an anhydrous tetrahydrofuran solvent; at 120 ℃ for LaCl 3 Vacuum heating to remove LaCl 3 Organic impurities and low boiling point impurities in the obtained product to obtain high-purity LaCl 3 。
Under the protection of inert gas nitrogen, the LaCl which is subjected to the vacuum pumping and drying treatment is processed 3 (186 g,0.5mo 1) and 1L of the tetrahydrofuran solvent subjected to the water removal treatment were put into a 5L four-necked flask equipped with a stirring and cooling reflux apparatus, and dissolved by mechanical stirring to give LaCl 3 xTHF solution; na (iPrCp) (196 g,1.5 mol) was dissolved in tetrahydrofuran (1L) to give a tetrahydrofuran solution of Na (iPrCp);
dropwise adding a tetrahydrofuran solution of Na (iPrCp) into LaCl under the protection of inert gas nitrogen 3 In xTHF solution, obtaining a reaction system, and maintaining stirring treatment in the dripping process; after the dripping is finished, the temperature of the reaction system is raised to 78 ℃, and the reaction system is heated and refluxed for 11 hours to obtain a reaction product;
heating the reaction product in a reaction kettle at a heating rate of 3 ℃/min, adjusting the vacuum degree to 65KPa, distilling under reduced pressure to separate tetrahydrofuran solvent in the reaction product, and ending the separation of tetrahydrofuran solvent when the temperature is raised to 83 ℃, and maintaining stirring treatment in the process; then, the temperature of the reaction vessel was continuously increased at a heating rate of 3℃per minute while stirring was maintained, and the vacuum was continuously decreased at a rate of 8KPa/min to receive La (iPrCp) 3 Stopping collecting the crude product when the temperature is raised to 147 ℃ and the vacuum degree is reduced to 5 KPa;
la (iPrCp) obtained by rectifying column pair with 0 type stainless steel mixed filler in inert gas glove box 3 The crude product is subjected to vacuum distillation, the vacuum degree in the vacuum distillation process is controlled to be 10-15KPa, the temperature is controlled to be 120-125 ℃, 20 percent of distillate which is distilled off firstly is removed in the process of collecting the distillate, then the middle-section distillate (accounting for 60 percent) is collected, and finally 20 percent of distillate which is distilled off is also removed, and the collected middle-section distillate is La (iPrCp) with high purity 3 。
The organic purity obtained by the method is more than 99.99%, the content of all inorganic impurities detected by ICP-MS (inductively coupled plasma-mass spectrometry) is less than 1ppm, and the product purity requirement of the semiconductor industry is met.
Example 4
This example differs from example 1 only in that no 4A molecular sieve was used to remove water from tetrahydrofuran, and no LaCl 3 Vacuum heating treatment was performed, and the rest was performed in the same manner as in example. The obtained product has an organic purity of 90% or higher as determined by NMR, and all inorganic impurity contents are detected by ICP-MS>100ppm, yield 30%.
Comparative example 1
Comparative example 1 differs from example 1 only in that a tetrahydrofuran solution of Na (iPrCp) was added dropwise into LaCl under the protection of inert gas nitrogen 3 In xTHF solution, obtaining a reaction system, and maintaining stirring treatment in the dripping process; after the dripping is finished, the reaction system is heated to 70 ℃, and the mixture is heated and refluxed for 8 hours to obtain a reaction product.
The remainder was carried out in the same manner as in example 1, with a yield of 70%.
Comparative example 2
Comparative example 1 differs from example 1 only in that a tetrahydrofuran solution of Na (iPrCp) was added dropwise into LaCl under the protection of inert gas nitrogen 3 In xTHF solution, obtaining a reaction system, and maintaining stirring treatment in the dripping process; after the dripping is finished, the reaction system is heated to 85 ℃, and the mixture is heated and refluxed for 14 hours to obtain a reaction product.
The remainder was carried out in the same manner as in example 1, with a yield of 75%.
Comparative example 3
Comparative example 3 differs from example 1 only in that the reaction product was placed in a reaction vessel toHeating at a heating rate of 1 ℃/min, adjusting the vacuum degree to 55KPa, distilling under reduced pressure to separate tetrahydrofuran solvent in the reaction product, and ending the separation of tetrahydrofuran solvent when the temperature is raised to 75 ℃, and maintaining stirring treatment in the process; then, the temperature of the reaction vessel was continuously increased at a heating rate of 1℃per minute while stirring was maintained, and the vacuum was continuously decreased at a rate of 5KPa/min to receive La (iPrCp) 3 The crude product is stopped when the temperature is raised to 140 ℃ and the vacuum degree is reduced to 20 KPa.
The remainder was carried out in the same manner as in example 1, and the organic purity of the obtained product was 99.99%, and the content of all inorganic impurities was <1ppm by ICP-MS total element detection, with a yield of 50%.
Comparative example 4
Comparative example 4 differs from example 1 only in that the reaction product was heated in a reaction vessel at a heating rate of 1 to 5 ℃/min, the vacuum degree was adjusted to 80KPa, the tetrahydrofuran solvent in the reaction product was separated by distillation under reduced pressure, and when the temperature was raised to 90 ℃, the separation of the tetrahydrofuran solvent was ended, and the stirring treatment was maintained during the process; then, the temperature of the reaction vessel was continuously increased at a heating rate of 1℃per minute while stirring was maintained, and the vacuum was continuously decreased at a rate of 5KPa/min to receive La (iPrCp) 3 And stopping collecting the crude product when the temperature is raised to 155 ℃ and the vacuum degree is reduced to-5 KPa.
The remainder was carried out in the same manner as in example 1, and the organic purity of the obtained product was 99%, and the content of all inorganic impurities was <10ppm by ICP-MS total element detection, with a yield of 60%.
Comparative example 5
Comparative example 5 differs from example 1 only in that no vacuum rectification treatment, la (iPrCp), was performed 3 The organic purity of the crude product is 90%, and the content of all inorganic impurities is detected by ICP-MS (inductively coupled plasma-mass spectrometry) all elements>100ppm。
Comparative example 6
Sodium cyclopentadiene was prepared from 30 g of fine sodium beads (twice the excess) and 50 ml of monomeric cyclopentadiene in 500ml of Tetrahydrofuran (THF); then transferring the obtained product into another container and stirring, simultaneously adding 60ml of isopropyl bromide from a dropping funnel, and precipitating NaBr after completion; the resulting yellowish solution containing isopropylcyclopentadiene was then transferred to another vessel containing excess fresh sodium beads; the solution was heated to 40 ℃ and stirred overnight to ensure complete reaction to give sodium isopropylcyclopentadiene;
the solution containing sodium isopropylcyclopentadiene obtained above was transferred to another flask, added to 50g of anhydrous lanthanum chloride, and stirred at 60℃for 3 hours to allow excess LaCl 3 And NaCl to obtain tri (isopropylcyclopentadienyl) lanthanum, transferring the solution containing tri (isopropylcyclopentadienyl) lanthanum into another flask, vacuum removing solvent at room temperature or below, vacuum distilling at temperature range of 10-minus 2torr and 180-195 deg.C to obtain viscous yellowish liquid tri (isopropylcyclopentadienyl) lanthanum with yield of 70%, obtaining product with organic purity of 90%, and detecting all inorganic impurity content by ICP-MS total element>100ppm。
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. High purity La (iPrCp) 3 Is characterized by comprising the following steps: will contain LaCl 3 Heating and refluxing the liquid phase reaction system of xTHF and Na (iPrCp), and then carrying out post-treatment on the obtained reaction product to obtain high-purity La (iPrCp) 3 。
2. The method of manufacturing according to claim 1, characterized in that: laCl contained in the liquid phase reaction system 3 The molar ratio of the catalyst to Na (iPrCp) is 1-1.1:3-3.5;
and/or, the temperature of the reflux reaction is 75-80 ℃;
and/or the reflux reaction time is 10-12 hours;
and/or the LaCl 3 In xTHF, the value of x is in the range of 0.6 to 2.
3. The method of manufacturing according to claim 1, comprising: adding the tetrahydrofuran solution of Na (iPrCp) into LaCl in portions 3 Obtaining said liquid phase reaction system in an xTHF solution;
preferably, the concentration of the tetrahydrofuran solution of Na (iPrCp) is 1-2mol/L;
preferably, the LaCl 3 The concentration of the xTHF solution is 0.5-1mol/L.
4. A method according to claim 3, wherein the post-treatment comprises: subjecting the reaction product to reduced pressure distillation to isolate La (iPrCp) 3 Crude products; for La (iPrCp) 3 The crude product is subjected to vacuum rectification treatment to obtain high-purity La (iPrCp) 3 。
5. According to claim 4Is characterized in that the reduced pressure distillation treatment comprises: continuously heating the reaction product under the vacuum degree of 60-70 KPa to separate tetrahydrofuran solvent from the reaction product, and ending the separation of tetrahydrofuran when the temperature is raised to 80-85 ℃; then, the vacuum was adjusted to 10-20KPa and maintained at a constant temperature, and La (iPrCp) was collected 3 Stopping collecting the crude product when the temperature is raised to 145-150deg.C and the vacuum degree is reduced to 0-10KPa, to obtain the La (iPrCp) 3 Crude products;
preferably, the reduced pressure distillation treatment specifically includes: continuously heating the reaction product at a heating rate of 1-5 ℃/min under the vacuum degree condition of 60-70 KPa until the temperature is raised to 80-85 ℃; and/or after the separation of tetrahydrofuran is finished, continuously reducing the vacuum degree to 0-10KPa at a speed of 5-10 KPa/min, and continuously heating at a heating speed of 1-5 ℃/min until the temperature is raised to 145-150 ℃.
6. The method according to claim 4, wherein the vacuum rectification treatment comprises: under the vacuum condition of inert atmosphere and 10-15KPa, the La (iPrCp) is treated 3 The temperature of the crude product is controlled between 120 ℃ and 125 ℃ to carry out the vacuum rectification, and the La (iPrCp) with high purity is obtained 3 ；
Preferably, in the vacuum rectification process, a front fraction accounting for 20% and a rear fraction accounting for 20% are removed, and a middle fraction accounting for 60% is collected to obtain the La (iPrCp) with high purity 3 。
7. The method of claim 1, wherein the LaCl 3 The preparation method of xTHF comprises the following steps: at 120-125 deg.C for LaCl 3 Vacuum drying to obtain high-purity LaCl 3 Carrying out water removal treatment on tetrahydrofuran to obtain anhydrous tetrahydrofuran; under the inert atmosphere condition, the high-purity LaCl 3 Dissolving in anhydrous tetrahydrofuran to obtain LaCl 3 xTHF solution.
8. The process according to claim 3, wherein the tetrahydrofuran solution of Na (iPrCp) is added to LaCl in portions 3 Specifically included in the xTHF solution are: adding the tetrahydrofuran solution of Na (iPrCp) to LaCl at an adding speed of 10-20 drops/s under the inert atmosphere condition 3 In xTHF solution, and maintaining stirring during the addition.
9. The La (iPrCp) of high purity obtained by the production process according to claim 1 to 8 3 Said high purity La (iPrCp) 3 The organic purity of (2) is more than 99.99 percent, and the inorganic impurity content is less than 1ppm; preferably, the high purity La (iPrCp) 3 The lanthanum metal purity is 99.999% or more, more preferably 99.9999% or more.
10. The high purity La (iPrCp) of claim 9 3 Application in preparing lanthanum oxide film; preferably, the application comprises: the lanthanum oxide film for the semiconductor is prepared by adopting a chemical vapor deposition technology.
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