CN117986126A - Tetrakis (methyl ethylamino) hafnium product and preparation method thereof - Google Patents
Tetrakis (methyl ethylamino) hafnium product and preparation method thereof Download PDFInfo
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- NPEOKFBCHNGLJD-UHFFFAOYSA-N ethyl(methyl)azanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C NPEOKFBCHNGLJD-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 38
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims description 30
- PDPJQWYGJJBYLF-UHFFFAOYSA-J hafnium tetrachloride Chemical compound Cl[Hf](Cl)(Cl)Cl PDPJQWYGJJBYLF-UHFFFAOYSA-J 0.000 claims description 20
- 238000001179 sorption measurement Methods 0.000 claims description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- 239000003463 adsorbent Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 12
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 7
- 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 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052744 lithium Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 238000007344 nucleophilic reaction Methods 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 238000010668 complexation reaction Methods 0.000 claims description 2
- SMQFETZVGKJCSL-UHFFFAOYSA-N ethylazanide;hafnium(4+) Chemical compound [Hf+4].CC[NH-].CC[NH-].CC[NH-].CC[NH-] SMQFETZVGKJCSL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003456 ion exchange resin Substances 0.000 claims description 2
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 2
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 26
- 238000000746 purification Methods 0.000 abstract description 10
- 230000035484 reaction time Effects 0.000 abstract description 9
- 239000004065 semiconductor Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- -1 crown ether modified silica gel Chemical class 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 239000003729 cation exchange resin Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910021655 trace metal ion Inorganic materials 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000000231 atomic layer deposition Methods 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 239000012264 purified product Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- CRHIBFCNJROORF-UHFFFAOYSA-N hafnium(4+);methylazanide Chemical compound [Hf+4].[NH-]C.[NH-]C.[NH-]C.[NH-]C CRHIBFCNJROORF-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000003949 trap density measurement Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- NYQDCVLCJXRDSK-UHFFFAOYSA-N Bromofos Chemical compound COP(=S)(OC)OC1=CC(Cl)=C(Br)C=C1Cl NYQDCVLCJXRDSK-UHFFFAOYSA-N 0.000 description 1
- 108091006149 Electron carriers Proteins 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000005527 interface trap Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YXFVVABEGXRONW-JGUCLWPXSA-N toluene-d8 Chemical compound [2H]C1=C([2H])C([2H])=C(C([2H])([2H])[2H])C([2H])=C1[2H] YXFVVABEGXRONW-JGUCLWPXSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a tetra (methyl ethylamino) hafnium product and a preparation method thereof; the method is a purification method for preparing high-purity tetra (methyl ethylamino) hafnium and removing metal ions under specific anhydrous, oxygen-free and dust-free conditions; the method has the advantages of short reaction time, good safety, high product yield, simple post-treatment operation, capability of effectively controlling and removing the content of metal ions with the strictest product quality requirement, no more than 0.76ppm of total metal ions in the final product, high purity (more than or equal to 99.99992 percent), high yield (more than or equal to 50 percent) and complete satisfaction of the current requirements of advanced integrated circuit manufacturing; not only solves the key problem of improving the purity in the production process of tetra (methyl ethylamino) hafnium, but also greatly improves the feasibility and economic benefit of the industrialized production. This is critical to meeting the rapid development demands of the integrated circuit industry, and also brings great practical significance to the promotion of the technological progress of the semiconductor industry.
Description
Technical Field
The invention relates to the field of electronic chemicals of high-end fine chemicals, in particular to an important precursor tetra (methyl ethylamino) hafnium (TEMAH) product required for depositing an HfO 2 film and a preparation method thereof.
Background
HfO 2 has recently received much attention as a dielectric material due to its high dielectric constant and excellent leakage characteristics resulting from its wide bandgap, and in particular, hfO 2 thin film has been widely studied as a high- κ gate dielectric in Metal Oxide Semiconductor Field Effect Transistors (MOSFETs) because HfO 2 is thermodynamically stable in contact with Si and exhibits a lower trap density at the HfO 2/Si interface. The thermal stability of HfO 2 allows for effective suppression of low k SiOx interfacial layer formation even at high temperatures and its low interface trap density allows for high field effect mobility of electron carriers in the MOSFET.
In the scaling down of devices, the physical thickness of HfO 2 thin films should be reduced to less than 10nm, which can be used in various growth techniques for growing such HfO 2 thin films, atomic Layer Deposition (ALD) being one of the most promising approaches. ALD processes based on self-limiting growth, allowing excellent thickness control on an atomic scale, uniform film growth over a large area, and excellent conformality on three-dimensional structures, therefore, ALD processes for HfO 2 thin films have been widely studied.
Tetra (ethylamino) hafnium (TEMAH) is an important precursor for depositing HfO 2 thin films by Atomic Layer Deposition (ALD) process, and with the rapid development of the integrated circuit industry, the demand for semiconductor precursor materials will continue to increase, and has a good market prospect.
However, there are some significant problems with the existing methods of producing hafnium tetra (methylamino). For example, CN106916178a discloses a method for producing tetra (methyl ethylamino) hafnium, which adopts the method that n-BuLi and methyl ethylamine are reacted and then hafnium tetrachloride is added in batches, the hafnium tetrachloride is very sensitive to air, water and oxygen, the operation difficulty is high after the reaction, the danger is high, the optimal feeding mode is that hafnium tetrachloride is put into a reaction kettle in advance and then is subjected to subsequent reaction, and the solid-liquid separator described in the method disclosed by the method separates and removes LiCl, but LiCl is thin and light, centrifugal separation is a better treatment method, and the method disclosed in CN103601750a is similar to the method described above. The purification method of tetra (methyl ethylamino) hafnium has not been reported, but as an important precursor material in the field of integrated circuits, the requirement on purity is extremely strict, and the existing technology obviously cannot meet the requirement, so that a new technology is urgently needed to solve the problem, and a new, efficient and safe tetra (methyl ethylamino) hafnium production method is urgently needed to be developed, and in particular, the problem of how to improve the purity in the production process is needed to be solved. This is not only critical to meet the rapidly evolving needs of the integrated circuit industry, but also of great practical significance to drive the technological advancement of the semiconductor industry.
Disclosure of Invention
Aiming at the problems that the purity of the product is low, the reaction time is long, the operation is complicated, the safety is poor in the existing preparation process of tetra (methyl ethyl amino) hafnium (TEMAH) technical route, the obtained product cannot meet the requirements of the current advanced integrated circuit manufacturing and the like, the invention provides the preparation method of tetra (methyl ethyl amino) hafnium, which has the advantages of short reaction time, good safety, high product yield and simple post-treatment operation, and simultaneously develops a purification method for removing metal ions by an adsorption method, the purity of the product is high, and the obtained product can meet the requirements of practical application.
The preparation method of tetra (methyl ethylamino) hafnium comprises the following specific process routes:
Under the anhydrous, anaerobic and dust-free conditions, carrying out complexation reaction on hafnium tetrachloride and N-ethylmethylamine in an organic solvent for 1-5 h, wherein the molar ratio of the N-ethylmethylamine to the hafnium tetrachloride is 4.4-5.8:1, then slowly adding N-BuLi solution and the N-ethylmethylamine to carry out hydrogen lithium exchange reaction to generate lithium dimethylamino, the molar ratio of the N-BuLi to the hafnium tetrachloride is 4.4-5.8:1, carrying out reaction for 2-12 h, raising the reaction temperature, carrying out nucleophilic reaction on the lithium methylamino and the hafnium tetrachloride, carrying out reaction for 16-72 h, centrifuging to remove solids, concentrating, removing the solvent, and carrying out reduced pressure distillation to obtain the product hafnium tetra (methylamino), wherein the product content is more than 99%, and the yield is more than 50% (calculated by hafnium tetrachloride).
For the above-described technical solutions, the molar ratio of N-ethylmethylamine to hafnium tetrachloride is preferably 4.4 to 5.4:1, more preferably 4.8 to 5.2:1.
For the above-described technical scheme, preferably, the solvent of the n-BuLi solution is at least one selected from n-hexane, n-heptane and cyclohexane, and further preferably the n-hexane solution of n-BuLi is preferably at a concentration of 1.5 to 3mol/L, and more preferably 2.5mol/L.
For the above-described technical solutions, the molar ratio of n-BuLi to hafnium tetrachloride is preferably 4.0 to 5.6:1, more preferably 4.4 to 5.2:1, and even more preferably 4.8 to 5.2:1.
For the above-described technical scheme, the addition rate of the n-BuLi solution is preferably 0.5 to 5mL/min, and more preferably 1 to 3mL/min.
For the above-described technical solution, preferably, the organic solvent is alkane C nH2n+2 and/or ether, and n is selected from any integer of 5 to 8, more preferably at least one of n-pentane, n-hexane and diethyl ether, still more preferably n-hexane.
For the technical scheme, the reaction temperature of the hydrogen lithium exchange is preferably-30 to-10 ℃, and the reaction temperature is preferably-20 to-10 ℃.
For the above-described technical scheme, the time of the lithium hydride exchange reaction is preferably 2 to 12 hours, more preferably 2 to 10 hours.
For the above-described technical scheme, preferably, the reaction temperature of the nucleophilic reaction is 50 to 65 ℃.
For the above-described technical scheme, the reaction time of the nucleophilic reaction is preferably 16 to 72 hours, more preferably 16 to 30 hours.
For the technical scheme, the solid LiCl is preferably subjected to high-speed centrifugal separation at a rotating speed of 1000-4000 rpm for 10-20 minutes.
For the above-described technical scheme, it is preferable that, after concentrating to remove the solvent, distillation under reduced pressure (0.02 to 0.05mmHg,50 to 60 ℃ C.) gives a colorless to pale yellow liquid.
For the technical scheme, the method also comprises the steps of removing metal ion impurities by using an adsorbent, adsorbing, and obtaining a purified product by simple filtration, wherein the total metal ion content in the product is not more than 0.03ppm; the adsorbent is at least one selected from activated carbon, silica gel, molecular sieve and ion exchange resin, and the embodiment specifically selects and uses the crown ether modified silica gel (3) and C107E acrylic weak acid cation exchange resin (Purolite) described in the section 2 of the literature for experiments in 10.3969/j.issn.1007-9629.2001.01.011, so that ideal technical effects are obtained.
For the technical scheme, the adsorption temperature is preferably 0-50 ℃, and the product is obtained after adsorption and then filtration yield, and the adsorption temperature is preferably 20-50 ℃, and more preferably 20-40 ℃; further, the adsorption residence time is 10 to 24 hours, more preferably 12 to 24 hours.
For the above-described technical solutions, the amount of adsorbent is preferably 0.2 to 0.6g per ml of TEMAH, more preferably 0.2 to 0.4g per ml of TEMAH.
Another aspect of the invention is to protect the tetra (methylamino) hafnium product obtained by the above process in yields higher than 50.0%; more preferably, the yield is higher than 90.0% (calculated as TEMAH), the purity is not lower than 99.99992%, more preferably not lower than 99.999997%, and the total metal ion content is not higher than 0.76ppm, more preferably not higher than 0.03ppm.
The beneficial effects of the invention are as follows:
(1) The method has short reaction time, simple post-treatment operation and good industrialization prospect;
(2) The invention develops a purification method of tetra (methyl ethylamino) hafnium, and effectively removes and controls the content of metal ions with the strictest product quality requirements; and detecting; the total metal ion content in the final product is not more than 0.03ppm;
(3) The yield of tetra (methyl ethylamino) hafnium is high (more than or equal to 50%), the purity is high (more than or equal to 99.99992%), and the requirements of current practical application can be met.
Drawings
FIG. 1 is a block diagram of TEMAH;
FIG. 2 is a nuclear magnetic structure spectrum 1H NMR(400Hz,toluene-d8 of TEMAH);
fig. 3 is a process flow diagram of TEMAH.
Detailed Description
The present invention will be further illustrated by the following examples, which are not intended to limit the scope of the invention, but are used by conventional means known to those skilled in the art, in order to better understand the present invention.
The trace metal ion content detection method described in the examples: taking 5-50mg of purified product, precisely weighing, adding 0.5mL of concentrated sulfuric acid (high-grade pure) into each 10mg of sample, heating to 90 ℃, adding nitric acid (99.999%) into each 10mg of product after the liquid turns black, volatilizing acid as much as possible in the sample preparation process, carrying out digestion, fixing the volume of the sample liquid to 100mL by deionized water, synchronously configuring a reference sample, determining the ion concentration by an inductively coupled plasma mass spectrometer (Nexion G), and calculating the metal impurity content in the tetra (methyl ethylamino) hafnium product according to a test result.
Example 1
Hafnium tetrachloride (0.32 g,1 mmol) was added to a 10mL reaction flask under anhydrous, anaerobic and dust-free conditions, 3.0mL of N-hexane was added, followed by slow addition of N-ethylmethylamine (0.296 g) in a cold bath at-10℃for 1h, 2.5M N-BuLi (2.0 mL) was slowly added for 2h, the temperature was slowly raised to 55℃for 24h, solids were removed by centrifugation, the separated liquid was concentrated to remove the solvent N-hexane, and the remaining liquid was distilled under reduced pressure to give a colorless to pale yellow liquid which was tetra (methylamino) hafnium (TEMAH) in a yield of 78.6%.
Examples 2 to 31
Considering the preparation method of TEMAH, on the basis of the method steps provided in example 1, five aspects of the solvent type of the n-BuLi solution, the reaction temperature of the slow lifting stage, the equivalent of the reactant, the concentration of the substrate and the reaction time are respectively changed, and under the condition that a single factor is changed, the product yields are respectively detected, and the results are shown in the following table 1:
TABLE 1
Conclusion: examples 5, 6, 7, 8 resulted in lower yields due to lower reaction temperatures; at lower temperatures, the reaction may not proceed sufficiently or the reaction rate may slow down such that the amount of the target product produced is reduced. Therefore, it is recommended to appropriately increase the reaction temperature to obtain a higher yield.
Example 20 results in lower yields due to higher solvent levels and too low substrate concentrations; the proper increase of the substrate concentration is beneficial to the improvement of the reaction yield.
Examples 27 and 28 resulted in lower yields due to shorter reaction times with incomplete conversion of hafnium tetrachloride. During the reaction, if the reaction time is insufficient, the reactants may not sufficiently react, resulting in a decrease in yield. Therefore, it is recommended to suitably lengthen the reaction time to promote complete conversion of hafnium tetrachloride and to obtain higher yields.
Example 32
Hafnium tetrachloride (6 g,18.73 mmol) was added to a 10mL reaction flask under anhydrous, oxygen-free and dust-free conditions, 35mL of N-hexane was added, followed by a slow addition of N-ethylmethylamine (5.54 g) in a cold bath at-10℃for 1h, 2.5M N-BuLi (37.46 mL) was slowly added for 2h, the temperature was slowly raised to 55℃for 24h, the solids were removed by centrifugation, the separated liquid was concentrated to remove the solvent N-hexane, and the remaining liquid was distilled under reduced pressure to give a colorless to pale yellow liquid, which was tetra (methylamino) hafnium (TEMAH), yield 76.7%, the amplified synthesis of the product was excellent, and the yield was within the expected range.
Example 33
Under anhydrous, oxygen-free and dust-free conditions, 0.5mL of tetra (methyl ethylamino) hafnium (TEMAH) obtained by distillation in example 1 is taken and placed in a reaction bottle with a stirrer, 0.1g of crown ether modified silica gel (10.3969/j.issn.1007-9629.2001.01.011.) is added for adsorption purification, the adsorption temperature is 35 ℃, the stirring rotation speed is 300rpm, the adsorption is 10 hours, and the vacuum distillation (0.02 mmHg,55 ℃) is carried out to obtain a product, 13.3mgTEMAH is taken, the method is adopted, after the content of trace metal ions is detected, the total metal ion content is 0.03ppm, the purity is 99.999997 percent, and the content of each metal element of the purified product is as follows:
| metallic element | Concentration (ug/L) | Content (ppm) |
| Zn | 0.004 | 0.03 |
| Ni | 0.000 | 0.00 |
| Al | ＜DL | ND |
| K | ＜DL | ND |
| Fe | 0.000 | 0.00 |
| Mn | 0.000 | 0.00 |
| Cr | ＜DL | 0.00 |
| Mg | ＜DL | ND |
| Cu | 0.000 | 0.00 |
| Ca | ＜DL | ND |
| Na | ＜DL | ND |
Trace metal ion content detection results demonstrate that: the crown ether modified silica gel is an effective adsorbent, and can effectively remove impurity metal ions in the TEMAH and improve the purity of the product.
Example 34
Under anhydrous, oxygen-free and dust-free conditions, 0.5mL of tetra (methyl ethylamino) hafnium (TEMAH) obtained by distillation obtained in the initial distillation of the example 1 is taken and placed in a reaction bottle with a stirrer, 0.15g of C107E type acrylic weak acid cation exchange resin (Purolite) is added for adsorption purification, the adsorption temperature is 10 ℃, the stirring rotation speed is 300rpm, the adsorption is carried out for 16 hours, the vacuum distillation is carried out to obtain a product, 13.3mgTEMAH is obtained, the sample is prepared according to the method, after the content of trace metal ions is detected, the total metal ion content is 0.58ppm, the purity is more than 99.99994%, and the content of each metal element of the purified product is as follows:
| Metal | Concentration (ug/L) | Content (ppm) |
| Zn | 0.000 | 0.00 |
| Ni | 0.002 | 0.02 |
| Al | ＜DL | ND |
| K | ＜DL | ND |
| Fe | 0.029 | 0.28 |
| Mn | ＜DL | ND |
| Cr | 0.000 | 0.00 |
| Mg | 0.011 | 0.10 |
| Cu | 0.017 | 0.16 |
| Ca | ＜DL | ND |
| Na | ＜DL | ND |
The trace metal ion content detection result shows that the total metal ion content is 0.58ppm, and the purity is more than 99.99994%. Although the purity was slightly lower than when crown ether modified silica gel was used, it was still very high and the content of each metal element was also low. This suggests that the C107E type acrylic weakly acidic cation exchange resin is also a viable adsorbent option, which can effectively increase the purity of TEMAH.
Example 35
Under anhydrous, oxygen-free and dust-free conditions, 0.5mL of tetra (methyl ethylamino) hafnium (TEMAH) obtained in the embodiment 1 through initial distillation is taken and placed in a reaction bottle with a stirrer, 0.2g of C107E type acrylic weak acid cation exchange resin (Purolite) is added for adsorption purification, the adsorption temperature is 50 ℃, the stirring rotation speed is 300rpm, the adsorption is carried out for 10 hours, the product is obtained through reduced pressure distillation, 9.5mg of TEMAH is taken, the sample is prepared according to the method, after trace metal ion content detection, the total metal ion content is 0.76ppm, the purity is higher than 99.99992%, and the content of each metal element of the purified product is as follows:
In this example, the same type C107E acrylic weakly acidic cation exchange resin as in example 34 was used as the adsorbent, but the adsorption conditions were changed, including increasing the adsorption temperature to 50 ℃ and shortening the adsorption time to 10 hours. The purity was maintained at a higher level despite the increased total metal ion content of the purified product of 0.76ppm, purity > 99.99992 ppm, as compared to 0.58ppm of example 34.
Examples 36 to 37
According to the experimental conditions of example 33, silica gel, ZSM-5 molecular sieve and activated carbon are used as adsorbents for purification respectively, and the specific steps are as follows:
| Examples | Adsorbent and process for producing the same | Total ion content/ppm |
| 33 | ZSM-5 molecular sieve | 20.84 |
| 34 | Activated carbon | 26.77 |
In both examples, purification was performed using silica gel and ZSM-5 molecular sieve as adsorbents, respectively, and the results showed that the total ion content using ZSM-5 molecular sieve was 20.84ppm and the total ion content using activated carbon was 26.77ppm. Both of these results were higher than the purification effect using crown ether modified silica gel (example 33) and C107E acrylic weak acid cation exchange resin (examples 34 and 35). This indicates that crown ether modified silica gel and C107E type acrylic weak acid cation exchange resin, silica gel, ZSM-5 molecular sieve and activated carbon are all effective in removing impurity metal ions in TEMAH.
Comparative example 1 ion content test of the initial product obtained by distillation
The primary distillation of example 1 gave hafnium tetra (methylamino), 25.0mg of TEMAH, which was sampled as described above and tested for trace metal ion content, and the total ion content was 2858ppm, with the following metal element contents:
This comparative example 1 reveals limitations in the prior art for the production of tetra (methylamino) hafnium, particularly in terms of purity control. The ion content in tetra (methyl ethylamino) hafnium obtained by primary distillation is as high as 2858ppm, and the tetra (methyl ethylamino) hafnium contains various metal elements, which can not meet the strict purity requirement of precursor materials in the field of integrated circuits. The existing technical means obviously cannot solve the problem, and a new, efficient and safe tetra (methyl ethylamino) hafnium production method is required to be developed;
The data of the comprehensive examples and the comparative examples show that the invention not only solves the key problem of improving the purity in the production process of tetra (methyl ethylamino) hafnium, but also greatly improves the feasibility and economic benefit of the industrialized production. This is critical to meeting the rapid development demands of the integrated circuit industry, and also brings great practical significance to the promotion of the technological progress of the semiconductor industry.
The foregoing is a further description of the invention in connection with specific preferred embodiments thereof, and is not intended to limit the practice of the invention to such description. It is intended that all such variations and modifications as would be included within the scope of the invention are within the scope of the following claims.
Claims (10)
1. A method for preparing tetra (methyl ethylamino) hafnium, which is characterized by comprising the following steps:
Under the anhydrous, anaerobic and dust-free conditions, carrying out complexation reaction on hafnium tetrachloride and N-ethylmethyl amine in an organic solvent for 1-5 h, wherein the molar ratio of the N-ethylmethyl amine to the hafnium tetrachloride is 4.4-5.8:1, then slowly adding N-BuLi solution and the N-ethylmethyl amine to carry out hydrogen-lithium exchange reaction, wherein the molar ratio of the N-BuLi to the hafnium tetrachloride is 4.4-5.8:1, carrying out reaction for 2-12 h, raising the reaction temperature, carrying out nucleophilic reaction on the lithium methylamino and the hafnium tetrachloride, carrying out reaction for 16-72 h, centrifuging to remove solids, concentrating and removing the solvent.
2. The method according to claim 1, wherein the molar ratio of N-ethylmethylamine to hafnium tetrachloride is 4.4 to 5.4:1.
3. The method according to claim 1, wherein the solvent of the n-BuLi solution is selected from at least one of n-hexane, n-heptane, cyclohexane; the concentration of the n-BuLi solution is 1.5-3 mol/L.
4. The method according to claim 1, wherein the molar ratio of n-BuLi to hafnium tetrachloride is 4.0 to 5.6:1.
5. The method according to claim 1, wherein the n-BuLi is added at a rate of 0.5 to 5mL/min.
6. The method according to claim 1, wherein the organic solvent is alkanes C nH2n+2 and/or ethers, and n is selected from any integer from 5 to 8.
7. The method according to claim 1, wherein the reaction temperature of the lithium hydride exchange is-30 to-10 ℃; the nucleophilic reaction temperature is 50-65 ℃.
8. The method of claim 1, further comprising the step of removing metal ion impurities with an adsorbent; the adsorbent is at least one selected from activated carbon, silica gel, molecular sieve and ion exchange resin.
9. The method of claim 8, wherein the adsorption temperature is 20 to 50 ℃ and the adsorption residence time is 10 to 24 hours; the amount of the adsorbent is 0.2-0.6 g of the adsorbent added per milliliter of TEMAH.
10. A tetrakis (ethylamino) hafnium product obtained by the process of claim 8; the purity of the product is more than or equal to 99.99992 percent; the total metal ion content is not more than 0.76ppm.
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