CN112552321A - Lanthanum-containing organic compound and application thereof - Google Patents
Lanthanum-containing organic compound and application thereof Download PDFInfo
- Publication number
- CN112552321A CN112552321A CN202011457623.3A CN202011457623A CN112552321A CN 112552321 A CN112552321 A CN 112552321A CN 202011457623 A CN202011457623 A CN 202011457623A CN 112552321 A CN112552321 A CN 112552321A
- Authority
- CN
- China
- Prior art keywords
- lanthanum
- organic compound
- containing organic
- lacl
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 52
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910002249 LaCl3 Inorganic materials 0.000 claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 11
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 239000012065 filter cake Substances 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 4
- -1 R' is one of H Chemical group 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 7
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000012266 salt solution Substances 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BDNKZNFMNDZQMI-UHFFFAOYSA-N 1,3-diisopropylcarbodiimide Chemical compound CC(C)N=C=NC(C)C BDNKZNFMNDZQMI-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N deuterated benzene Substances [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 2
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000706 filtrate Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C267/00—Carbodiimides
-
- 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
Abstract
The invention discloses a lanthanum-containing organic compound and application thereof, wherein the chemical formula of the organic compound is LaCl31.5THF, the organic compound is prepared from lanthanum powder, trimethylchlorosilane and ethanol by reflux reaction in a THF solution; the application of the lanthanum-containing organic compound is that LaCl is added31.5 reaction of THF with lithium amidinate to prepare La (R)2‑R’AMD)3Adding LaCl31.5 reaction of THF with M (RCp), lithium diisopropylacetamidinate (RCp)2La(iPr2-MeAMD). The lanthanum-containing organic compound LaCl is prepared by the reflux reaction of lanthanum powder, trimethylchlorosilane and ethanol in a THF solution31.5THF, high yield of the lanthanum containing organic compound prepared, high reactivity, preparation of lanthanum precursor La (R) using the lanthanum containing organic compound2‑R’AMD)3And (RCp)2La(iPr2MeAMD) can greatly reduce the production time and also increase the yield of the product.
Description
Technical Field
The invention relates to the field of semiconductor materials, in particular to a lanthanum-containing organic compound and application thereof.
Background
Lanthanum is a metal rare earth element, which is chemically active and easily oxidized in air. Lanthanum oxide (La)2O3) Is an oxide of lanthanum, widely used in semiconductor technology due to its high dielectric constant (hexagonal phase La)2O3Has a dielectric constant of 27) and a wide band gap of (-5.5eV), and thus can be used alone for a gate oxide thin film or with HfO2、Y2O3The doping forms a high dielectric constant (high-k) layer in the DRAM memory chip. While La2O3Is also used for HfO2Capping layer of gate oxide film, La/La2O3As a passivation layer for germanium (Ge). La2O3Is "transparent" over a wide range of wavelengths and is also a good optical film.
For depositing high quality La2O3Thin films, La precursor materials have been extensively studied, and conventional La precursors include: la (thd)3，La(Cp)3，La(iPrCp)3And La [ N (SiMe)3)2]3. Wherein: la (thd)3The deposition rate of (A) is low, and is only 0.36A/cycle; la (Cp)3And La (iPrCp)3The thermal stability of the film is poor, the film is not suitable for film deposition at the temperature of more than 250 ℃, and carbon residue often exists in the film; la [ N (SiMe)3)2]3There is no stable ALD saturation curve and there is Si remaining in the film. Therefore, a La precursor material with high thermal stability and high vapor pressure: la (iPr2-MeAMD)3、La(iPr2-FMD)3And (RCp)2La(iPr2MeAMD) gradually replaced the conventional La precursor.
In the preparation of La precursor La (iPr2-MeAMD)3、La(iPr2-FMD)3And (RCp)2La(iPr2MeAMD), LaCl due to the steric nature of the metal La and its ability to bind very easily to oxygen3Is easy to be hydrolyzed completely or partially, generates La-O bond with high stability, and cannot further form coordinate bond. Therefore, when the above molecules are prepared, it is not easy to prepareWith LaCl3While tetrahydrofuran-coordinated LaCl is generally used3THFx. There are generally two methods reported in the literature: 1. directly using LaCl3Stirring with THF to form LaCl3THFx; 2. lanthanum powder and hexachloroethane react to prepare LaCl3THFx. LaCl prepared by the first route3THFx has low reactivity and low yield of La complex. For example, La (La) (prepared in the document ALD of Lanthanumaluminum Using Lanthanumformamidate Precursor, mater.Res.Soc.Symp.Proc.Vol.1036iPr2-FMD)3The final yield was only less than 60%. Prepared in the document US9099301-Preparation of lantana-stabilizing primers and position of lantana-stabilizing films: (iPrCp)2La(iPr2MeAMD) yield of only 36%. LaCl prepared by the second route3Improved yield of the product obtained from THFx as starting material, La (f)iPr2-MeAMD)3The yield can reach 77%. However in the preparation of LaCl3THFx, it is necessary to sonicate La powder with hexachloroethane in THF solution for 3-5 days to achieve 84-90% yield in the Synthesis and Characterization of zeolites, thermal Stable, Reactive transfer metals, organic Chemistry,2003,42,7951 and 7958. Low efficiency and is not suitable for production application.
Therefore, it is necessary to develop a new LaCl3The preparation method of the THFx raw material is used for preparing the La-based precursor material, shortens the time, improves the efficiency and can improve the yield.
Disclosure of Invention
In order to solve the defects mentioned in the background technology, the invention aims to provide a lanthanum-containing organic compound and application thereof, wherein lanthanum powder, trimethylchlorosilane and ethanol are subjected to reflux reaction in a THF solution to prepare the lanthanum-containing organic compound LaCl31.5THF, high yield of the lanthanum containing organic compound prepared, high reactivity, preparation of lanthanum precursor La (R) using the lanthanum containing organic compound2-R’AMD)3And (RCp)2La(iPr2MeAMD) can greatly reduce production time and alsoThe yield of the product is improved.
The purpose of the invention can be realized by the following technical scheme:
a lanthanum-containing organic compound, the chemical formula of which is LaCl31.5THF, the organic compound is prepared by the reflux reaction of lanthanum powder, trimethylchlorosilane and ethanol in a THF solution, and the chemical reaction equation is as follows:
the preparation method of the lanthanum-containing organic compound specifically comprises the following steps:
s1, weighing lanthanum powder, adding tetrahydrofuran, quickly stirring and uniformly mixing, adding trimethylchlorosilane while stirring, and uniformly mixing to obtain a mixed solution A;
s2, slowly adding absolute ethyl alcohol into the mixed solution A, enabling small bubbles to overflow from the liquid surface, slightly raising the temperature of the system, heating, refluxing and stirring for 4-6 hours after adding, gradually changing the system from black turbid liquid to gray until the system becomes white turbid liquid, and stopping reaction;
s3, filtering the reacted turbid liquid to obtain a filter cake, washing the filter cake for 2-4 times by using normal hexane, and finally drying the filter cake in vacuum to obtain white powder LaCl3·1.5THF。
Further preferably, the particle size of the lanthanum powder is 50 to 200 mesh.
Further preferably, the molar ratio of lanthanum powder, trimethylchlorosilane to ethanol is 1: 3-4: 3-4.
Further preferably, the temperature of the heating reflux in step S3 is 70-90 ℃.
An application of the lanthanum-contained organic compound LaCl31.5 reaction of THF with lithium amidinate to prepare La (R)2-R’AMD)3R is one of methyl, ethyl, isopropyl, n-butyl and tert-butyl, R' is one of H, methyl, ethyl, isopropyl, n-butyl and tert-butyl, and the chemical reaction formula is as follows:
an application of the lanthanum-containing organic compound LaCl31.5 reaction of THF with M (RCp), lithium diisopropylacetamidinate (RCp)2La(iPr2MeAMD), M is one of Li, Na and K, R is one of H, methyl, ethyl and isopropyl, and the chemical reaction formula is as follows:
the invention has the beneficial effects that:
the lanthanum-containing organic compound LaCl is prepared by the reflux reaction of lanthanum powder, trimethylchlorosilane and ethanol in a THF solution31.5THF, high yield of the lanthanum containing organic compound prepared, high reactivity, preparation of lanthanum precursor La (R) using the lanthanum containing organic compound2-R’AMD)3And (RCp)2La(iPr2MeAMD) can greatly shorten the production time from more than 5 days to less than 3 days, and simultaneously improve the yield of the product from about 77 percent to 85 percent at present.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "opening," "upper," "lower," "thickness," "top," "middle," "length," "inner," "peripheral," and the like are used in an orientation or positional relationship that is merely for convenience in describing and simplifying the description, and do not indicate or imply that the referenced component or element must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be considered as limiting the present invention.
A lanthanum-containing organic compound with the chemical formula of LaCl31.5THF, organic compounds from lanthanum powder, trimethylchlorosilane, ethanol in THF solution reflux reaction, its chemical reaction equation as follows:
the preparation method of the lanthanum-containing organic compound specifically comprises the following steps:
s1, weighing lanthanum powder (45g, 0.3mol), adding 1L tetrahydrofuran, quickly stirring and uniformly mixing, adding trimethylchlorosilane (212g, 1.9mol) while stirring, and uniformly mixing to obtain a mixed solution A;
s2, slowly adding absolute ethyl alcohol (53g, 1.1mol) dropwise into the mixed solution A, enabling small bubbles to overflow from the liquid surface, slightly raising the temperature of the system, heating, refluxing and stirring for 4-6 hours after the dropwise addition is finished, gradually changing the system from black turbid liquid to gray until the system becomes white turbid liquid, and stopping the reaction;
s3, filtering the reacted turbid solution to obtain a filter cake, washing the filter cake for 2-4 times by using 150mL of n-hexane, and finally drying the filter cake in vacuum to obtain 106g of white powder LaCl31.5THF, 93% yield.
An application of a lanthanum-containing organic compound is that the lanthanum-containing organic compound LaCl3 & 1.5THF is reacted with lithium amidinate to prepare La (R)2-R’AMD)3Wherein R is one of methyl, ethyl, isopropyl, n-butyl or tert-butyl, R' is one of H, methyl, ethyl, isopropyl, n-butyl or tert-butyl, and the chemical reaction formula is as follows:
with La (iPr2-MeAMD)3For example, the preparation method specifically comprises the following steps:
(1) sequentially adding N, N' -diisopropylcarbodiimide (75.7g, 0.6mol) and 300mL of tetrahydrofuran into a 1L three-necked bottle in a glove box, slowly dropwise adding an ether solution of methyl lithium (477mL, 0.6mol and 1.6M/L) when the temperature of the system is reduced to-30 ℃, after dropwise adding, the system is a white turbid solution, gradually returning to the room temperature, changing the system into a light yellow solution, and stirring overnight;
(2) sequentially adding LaCl into a 2L three-neck flask31.5THF (70g, 0.2mol), 400mL tetrahydrofuran, quickly dropping the lithium salt solution of step (1) into the system, raising the temperature of the system from 30 ℃ to 40 ℃, changing from white to yellow, stirring overnight after dropping;
(3) the volatile components were removed in vacuo, 200mL of n-hexane was added to the residue, filtered to give a brown filtrate, which was concentrated in vacuo to supersaturation and placed in a refrigerator at-30 ℃ overnight to precipitate a large amount of a yellow solid 91 g.
The nmr spectrum of the resulting yellow solid product was:1HNMR(C6D61.18(d, 12H), 1.66(s, 3H), 3.42(m, 2H) at 25 ℃, and the yellow solid product is La (iPr2-MeAMD)3The yield was 80%.
An application of the lanthanum-containing organic compound LaCl31.5 reaction of THF with M (RCp), lithium diisopropylacetamidinate (RCp)2La(iPr2MeAMD), M is one of Li, Na and K, R is one of H, methyl, ethyl and isopropyl, and the chemical reaction formula is as follows:
in order (EtCp)2La(iPr2MeAMD), the preparation method of which comprises the following steps:
(1) sequentially adding NaH (8.0g, 0.2mol) and 100mL of tetrahydrofuran into a 250mL three-neck flask, slowly dropwise adding a tetrahydrofuran solution of EtCp (0.2mol, 18.8g) while stirring, keeping the temperature of the system at about 15 ℃, keeping bubbles on the liquid surface to overflow in the dropwise adding process, gradually changing the system into a red solution, and stirring at room temperature overnight;
(2) sequentially adding N, N' -diisopropylcarbodiimide (12.6g, 0.1mol) and 100mL of tetrahydrofuran into a 250mL three-neck flask, cooling the temperature of the system to-30 ℃, slowly dropwise adding an ether solution of methyl lithium (62.5mL, 0.1mol, 1.6M/L), and stirring at room temperature overnight after dropwise adding to obtain a light yellow lithium salt solution;
(3) sequentially adding LaCl into a 1L three-neck flask31.5THF (35.3g, 0.1mol), 250mL tetrahydrofuran, and with stirring, the sodium salt solution from (1) was slowly added dropwise, the temperature of the system was increased from 25 ℃ to 31 ℃. Stirring overnight at room temperature;
(4) and (3) dripping the lithium salt solution obtained in the step (2) into the mixed solution, raising the temperature of the system from 25 ℃ to 30 ℃, refluxing and heating overnight after dripping is finished, stopping heating, filtering after the system is recovered to room temperature, removing volatile components in vacuum to obtain brown sticky substances, and distilling under reduced pressure (150 ℃/0.50mbar) to obtain 37.6g of yellow oily liquid.
The nmr hydrogen spectrum of the resulting yellow oily liquid product was:1HNMR(C6D625 ℃): 0.89(d, 12H), 1.19(t, 6H), 1.48(s, 3H), 2.53(m, 4H), 3.15(s, 2H), 6.06(s, 3H), 6.18(s, 3H), the product as a yellow oily liquid (EtCp)2La(iPr2MeAMD), the yield of which is 80%.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed.
Claims (6)
1. A lanthanum-containing organic compound characterized in that the chemical formula of the organic compound is LaCl31.5THF, the organic compound is prepared by the reflux reaction of lanthanum powder, trimethylchlorosilane and ethanol in a THF solution, and the chemical reaction equation is as follows:
the preparation method of the lanthanum-containing organic compound specifically comprises the following steps:
s1, weighing lanthanum powder, adding tetrahydrofuran, quickly stirring and uniformly mixing, adding trimethylchlorosilane while stirring, and uniformly mixing to obtain a mixed solution A;
s2, slowly adding absolute ethyl alcohol into the mixed solution A, enabling small bubbles to overflow from the liquid surface, slightly raising the temperature of the system, heating, refluxing and stirring for 4-6 hours after adding, gradually changing the system from black turbid liquid to gray until the system becomes white turbid liquid, and stopping reaction;
s3, filtering the reacted turbid liquid to obtain a filter cake, washing the filter cake for 2-4 times by using normal hexane, and finally drying the filter cake in vacuum to obtain white powder LaCl3·1.5THF。
2. The lanthanum-containing organic compound according to claim 1, wherein the lanthanum powder has a particle size of 50 to 200 mesh.
3. The lanthanum-containing organic compound of claim 1, wherein the molar ratio of lanthanum powder, chlorotrimethylsilane, and ethanol is 1: 3-4: 3-4.
4. The lanthanum-containing organic compound according to claim 1, wherein the temperature of the heating reflux in step S3 is 70-90 ℃.
5. Use of the lanthanum containing organic compound of claim 1, wherein the lanthanum containing organic compound LaCl is added31.5 reaction of THF with lithium amidinate to prepare La (R)2-R’AMD)3R is one of methyl, ethyl, isopropyl, n-butyl and tert-butyl, R' is one of H, methyl, ethyl, isopropyl, n-butyl and tert-butyl, and the chemical reaction formula is as follows:
6. use of the lanthanum containing organic compound of claim 1, wherein the lanthanum containing organic compound LaCl is added31.5 reaction of THF with M (RCp), lithium diisopropylacetamidinate (RCp)2La(iPr2MeAMD), M is one of Li, Na and K, R is one of H, methyl, ethyl and isopropyl, and the chemical reaction formula is as follows:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011457623.3A CN112552321B (en) | 2020-12-10 | 2020-12-10 | Lanthanum-containing organic compound and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011457623.3A CN112552321B (en) | 2020-12-10 | 2020-12-10 | Lanthanum-containing organic compound and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112552321A true CN112552321A (en) | 2021-03-26 |
| CN112552321B CN112552321B (en) | 2023-12-12 |
Family
ID=75062150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011457623.3A Active CN112552321B (en) | 2020-12-10 | 2020-12-10 | Lanthanum-containing organic compound and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112552321B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113582879A (en) * | 2021-09-02 | 2021-11-02 | 合肥安德科铭半导体科技有限公司 | Organic lanthanum precursor La (iPr)2-FMD)3Preparation method of (1) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471494A (en) * | 2000-10-03 | 2004-01-28 | �ǵ�˹ | Rare earth or gallium additive composition, methods for preparing same and use thereof as catalyst |
-
2020
- 2020-12-10 CN CN202011457623.3A patent/CN112552321B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1471494A (en) * | 2000-10-03 | 2004-01-28 | �ǵ�˹ | Rare earth or gallium additive composition, methods for preparing same and use thereof as catalyst |
Non-Patent Citations (4)
| Title |
|---|
| PETRICEK, SASA: "Structural variety of lanthanide halide complexes with tetrahydrofuran", SLOVENSKI KEMIJSKI DNEVI, 10TH, MARIBOR, SLOVENIA, pages 641 - 648 * |
| ROSSMANITH, KURT: "Tetrahydrofuran solvates of rare earth metal chlorides new compounds, solubilities, reactions)", MONATSH. CHEM., vol. 100, pages 1484 - 8 * |
| TATYANA V. BALASHOVA ET AL: "Use of Neodymium Diiodide in the Synthesis of Organosilicon, -Germanium and -Tin Compounds", Z. ANORG. ALLG. CHEM., vol. 633, pages 256 - 260 * |
| 丁宗彪等: "无水稀土氯化物的新制备方法", 化学学报, vol. 55, pages 1004 - 1008 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113582879A (en) * | 2021-09-02 | 2021-11-02 | 合肥安德科铭半导体科技有限公司 | Organic lanthanum precursor La (iPr)2-FMD)3Preparation method of (1) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112552321B (en) | 2023-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5180040B2 (en) | Metal complexes of tridentate beta ketoiminates | |
| KR101120065B1 (en) | Novel germanium complexes with amidine derivative ligand and process for preparing the same | |
| KR20120078025A (en) | Organometallic compounds with silylamine ligand, and method for deposition of a thin-film of metal oxide or silicon-containing metal oxide therefrom | |
| CN112552321A (en) | Lanthanum-containing organic compound and application thereof | |
| JP3698163B1 (en) | Hafnium-containing film forming material and method for producing hafnium-containing thin film produced from the material | |
| JP3227891B2 (en) | Novel organometallic complexes and their ligands | |
| CN115260018B (en) | Preparation method of tris (2,2,6,6-tetramethyl-3,5-pimelic acid) bismuth | |
| CN113582879A (en) | Organic lanthanum precursor La (iPr)2-FMD)3Preparation method of (1) | |
| KR102589267B1 (en) | Metal precursor compound for and deposition method for preparing film using the same | |
| WO2007136186A1 (en) | Synthesis of aluminum compound for forming aluminum films by chemical vapor deposition | |
| JP2024519132A (en) | Novel hafnium-containing compound, hafnium precursor composition containing the same, hafnium-containing thin film using the hafnium precursor composition, and method for producing the same | |
| CN107935823A (en) | The preparation method of cis-jasmone | |
| KR102283752B1 (en) | Novel group iv transition metal compounds and preparation method thereof | |
| JP4120925B2 (en) | Copper complex and method for producing copper-containing thin film using the same | |
| KR20100102545A (en) | Method for preparing metal complexes of polydentate beta-ketoiminates | |
| CN112851697B (en) | Preparation method of series 2, 3-disubstituted succinimide metal mixed complex | |
| JP3947815B2 (en) | Coating liquid and thin film manufacturing method using the same | |
| CN113563390B (en) | Preparation method of bis (triisopropylcyclopentadienyl) strontium | |
| CN117263996B (en) | Cyclopentadienyl magnesium complex and preparation process and application thereof | |
| KR100695571B1 (en) | Novel praseodymium(iii) complexes and preparation method thereof | |
| JPS6086026A (en) | Production of composite perovskite compound | |
| CN117820349A (en) | Mixed type amido zirconium complex, preparation method and application thereof | |
| KR102418179B1 (en) | Novel organo-zirconium compounds as a precursor for ald or cvd and preparation method thereof | |
| KR20230038836A (en) | New Ruthenium organometallic compound, and method for producing same | |
| Chiba et al. | Incubation time free CVD-TiO2 film preparation using novel titanium precursor, Ti-DOT |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |