CN113842658B - Refining method of liquid ALD precursor - Google Patents
Refining method of liquid ALD precursor Download PDFInfo
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- CN113842658B CN113842658B CN202111117166.8A CN202111117166A CN113842658B CN 113842658 B CN113842658 B CN 113842658B CN 202111117166 A CN202111117166 A CN 202111117166A CN 113842658 B CN113842658 B CN 113842658B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
- B01D3/148—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step in combination with at least one evaporator
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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Abstract
The invention discloses a refining method of a liquid ALD precursor, which comprises the following steps: rectifying the low-purity crude product of the liquid ALD precursor; pretreating the polyethylene porous particles of the purification material, and filling the purification tower with the pretreated purification material; flowing the rectified components into a purifying tower filled with a purifying material, and purifying at the boiling point temperature to obtain a high-purity product. The purification method is simple to operate and wide in application range, can be used for carrying out purification treatment on various ALD precursors, and in addition, the polyethylene porous purification particles are polymer materials, can not release metal ions to pollute raw materials, can lock impurity ions, and the purity of the ALD precursor compound purified by the polyethylene porous purification particles is up to 99.9999%, so that the purity requirement of the ALD precursor material is met.
Description
Technical Field
The invention relates to a purification method of a liquid compound, in particular to a purification method of a liquid ALD precursor.
Background
In a Complementary Metal Oxide Semiconductor (CMOS) process, the feature size is typically represented by the width of the "gate", i.e., the channel length of a Metal Oxide Semiconductor (MOS) device. In general, the smaller the feature size, the higher the integration of the chip, the better the performance and the lower the power consumption. The traditional gate dielectric material is SiO 2 With the development of the integrated circuit industry, as the thickness of the silicon dioxide gate approaches 2-3nm, direct electron tunneling and high leakage current seriously hamper the reliability of the device. These problems can be overcome by replacing SiO with a high dielectric constant (high K) material 2 Solving the problem.
The high-K gate dielectric can increase the physical thickness of the gate dielectric while keeping the gate capacitance unchanged, thereby achieving the dual purposes of reducing the gate leakage current and improving the reliability of the device, wherein the high-K material of nitride and metal oxide is the most promising substitute for SiO 2 As gate dielectric material.
Typical metal oxide high-K materials are TiO 2 、ZrO 2 、HfO 2 ALD precursor sources such as tetrakis (dimethylamino) titanium, tetrakis (dimethylamino) hafnium, tetrakis (methylethylamino) titanium, tetrakis (methylethylamino) zirconium, tetrakis (methylethylamino) hafnium, tetrakis (diethylamino) titanium, tetrakis (diethylamino) zirconium, tetrakis (diethylamino) hafnium, etc., all of which correspond to each otherIs in the liquid phase. Since the purity of the precursor is critical to the performance of the thin film in the atomic layer deposition process, the purity requirement of the precursor in the semiconductor industry is very severe, but the purity of the ALD precursor prepared at present is difficult to reach 99.9999%, and a purification method is urgently needed to improve the purity of the ALD precursor.
Disclosure of Invention
In order to solve the technical problems, the invention provides a refining method of a liquid ALD precursor, which is characterized in that the liquid ALD precursor with low purity is rectified and purified by special purification materials to obtain a product with purity as high as 99.9999 percent.
The invention provides the following technical scheme:
the invention provides a refining method of a liquid ALD precursor, which comprises the following steps:
rectifying the crude product of the liquid ALD precursor;
pretreating the purified material, and filling the pretreated purified material into a purifying tower;
flowing the rectified components into a purification tower filled with a purification material, purifying at the boiling point temperature, and discharging after purification to obtain a high-purity ALD precursor;
the purification material is porous particles, the porous particles are provided with through pore passages with hollow bending structures, and the pore passages are provided with a plurality of U-shaped bends; the boiling point temperature is the boiling point temperature of the liquid ALD precursor in a reduced pressure state, and the boiling point temperature interval is 50-120 ℃; the high purity is higher than 99.9999%.
Further, the boiling temperature is preferably the boiling temperature of the ALD precursor at 0.1 mmHg.
Further, the liquid ALD precursor is one of tetra (dimethylamino) titanium, tetra (dimethylamino) hafnium, tetra (methylethylamino) titanium, tetra (methylethylamino) zirconium, tetra (methylethylamino) hafnium, tetra (diethylamino) titanium, tetra (diethylamino) zirconium, tetra (diethylamino) hafnium.
Further, the mesh number of the purified material is 100-200.
Further, the purification material is ultra-high molecular weight polyethylene porous particles.
Polyethylene particles with porous structure, its pore structure is similar to the crooked pipeline of cavity, and the material flows into the purification tower bottom through the feed valve, and bottom heating device heats the tower bottom material, and temperature control is at the boiling point temperature of target product, and the material is heated and evaporates, and impurity can be taken to the purification layer by the material from the tower bottom, and material steam shuttles in the pore of each purification particle, takes place the phase transition in pore U-shaped crooked department, forms the hydrops, forms the liquid seal gradually, and impurity metal ion can be locked in the pore bottom to reach purification effect.
The polyethylene porous material is easy to age and even degrade at high temperature, so that the pressure is reduced to reduce the boiling point in the purification process, on one hand, the polyethylene porous material can be prevented from polluting the purified material due to aging, and on the other hand, the service life of the purified material can be prolonged.
Further, the ultra-high molecular weight polyethylene porous particles have a molecular weight of 1500000-3000000.
Because the purified material has certain corrosiveness, the ultra-high molecular weight polyethylene has excellent chemical resistance in the organic high molecular porous material meeting the purification requirement, the secondary pollution of the purified material to the purified material in the purification process can be avoided, the polyethylene has low price, the polymer with the molecular weight of more than 150W is easy to prepare, and the high molecular weight polyethylene porous material is used as the purification material, so that the cost is low and the effect is good.
Further, the ultra-high molecular weight polyethylene porous particles have a molecular weight distribution index of 1.1 to 1.7.
Further, the pore diameter of the ultra-high molecular weight polyethylene porous particles is 0.5-1 mu m.
Further, the particle size of the ultra-high molecular weight polyethylene porous particles is 3-5mm.
The pore diameter and the particle diameter of the polyethylene porous material are controlled in a proper range as the purification material, if the pore diameter is too large, the flow quantity of the material among the pores is increased, impurities are easily carried out in the flow process, the impurities cannot be locked by liquid seal, and if the pore diameter is too small, pore channels are easily blocked, so that the purification effect is poor; in addition, the particle size cannot be too large, the specific surface area of the porous particles is reduced along with the increase of the particle size, and further the purification efficiency is reduced, but the particle size cannot be too small, and the purification is stopped because the liquid seal is formed by the pressure drop to block the filling column easily, so that the particle size and the pore size of the polyethylene porous particles need to be controlled in a proper interval to improve the purification efficiency and the purification effect.
Further, the polyethylene porous particles have a melting point of 200-220 ℃.
Further, the pretreatment of the purified material is specifically: washing the purified material with ultrapure water, and drying the washed purified material to obtain a pretreated purified material; the temperature of the drying treatment is 110-150 ℃, and the time of the drying treatment is 12-36h.
Further, the purifying tower sequentially comprises a heating device, a feeding valve, a tower body and a discharging valve from bottom to top; the tower body is used for containing purified materials, and the heating device is used for heating materials at the bottom of the tower body; the tower body is provided with an insulation layer.
Further, the purification treatment time is 3-9h.
Further, after purification is finished, the recovered purification material is rinsed by an alkane solvent, and then is washed by alkali washing, acid washing and ultrapure water washing, and is dried for standby.
By means of the scheme, the beneficial effects of the invention are as follows: according to the invention, polyethylene porous particles are used as a purification material, and impurity metal ions are locked in the material evaporation process to achieve the purification effect, and the polyethylene is a high polymer material, so that metal ions cannot be released to pollute the raw material; the method is simple to operate, no harmful waste liquid is generated, various liquid-phase ALD precursors can be purified, the purity of the processed compound is up to 99.9999%, the purified material can be recycled, the purification cost is reduced, and the method has good application prospect in the aspect of industrial production and purification.
Drawings
FIG. 1 is a schematic diagram of a purification column apparatus;
FIG. 2 is a schematic cross-sectional view of a porous polyethylene particle;
FIG. 3 is a schematic illustration of the internal single cell structure of a porous polyethylene particle.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified, and materials, reagents, etc. used, unless otherwise specified, are commercially available.
Example 1: purification of tetra (dimethylamino) titanium
Rectifying the low-purity tetra (dimethylamino) titanium, and collecting a fraction of 50 ℃/0.1 mmHg; washing polyethylene porous particles with ultrapure water, drying at 120 ℃ for 24 hours, filling the purification tower with the dried polyethylene porous particles, and detailing each parameter of the polyethylene porous particles in table 1; and (3) flowing the fraction collected in the step (1) into a purifying tower filled with a purifying material, maintaining for 6 hours at 50 ℃/0.1mmHg, and discharging to obtain the high-purity tetra (dimethylamino) titanium.
The purity of the obtained tetra (dimethylamino) titanium was detected by ICP, and the result shows that the purity of the product tetra (dimethylamino) titanium is as high as 99.9999%.
TABLE 1 values of parameters for polyethylene porous particles
| Number of meshes | Molecular weight | Molecular weight distribution index | Pore diameter | Particle size |
| 100 | 1750000 | 1.3 | 0.5μm | 5mm |
Example 2: purification of tetra (methylethylamino) titanium
Rectifying low-purity tetra (methyl ethylamino) titanium, and collecting fraction of 78 ℃/0.1 mmHg; washing polyethylene porous particles with ultrapure water, drying at 120 ℃ for 24 hours, filling the purification tower with the dried polyethylene porous particles, and detailing each parameter of the polyethylene porous particles in table 2; and (3) flowing the fraction collected in the step (1) into a purifying tower filled with a purifying material, maintaining the temperature at 78 ℃ and 0.1mmHg for 6 hours, and discharging to obtain the high-purity tetra (methyl ethylamino) titanium.
The purity of the obtained tetra (methyl ethylamino) titanium was detected by ICP, and the result shows that the purity of the product tetra (methyl ethylamino) titanium is as high as 99.9999%.
TABLE 2 values of parameters for polyethylene porous particles
| Number of meshes | Molecular weight | Molecular weight distribution index | Pore diameter | Particle size |
| 100 | 1980000 | 1.4 | 0.6μm | 5mm |
Example 3: purification of tetra (methyl ethylamino) zirconium
Rectifying low-purity tetra (methyl ethylamino) zirconium, and collecting a fraction of 81 ℃/0.1 mmHg; washing polyethylene porous particles with ultrapure water, drying at 120 ℃ for 24 hours, filling the purification tower with the dried polyethylene porous particles, and detailing the parameters of the polyethylene porous particles in table 3; and (3) flowing the fraction collected in the step (1) into a purifying tower filled with a purifying material, maintaining for 6 hours at 81 ℃ per 0.1mmHg, and discharging to obtain high-purity tetra (methyl ethylamino) zirconium.
The purity of the obtained tetra (methyl ethylamino) zirconium was detected by ICP, and the result shows that the purity of the product tetra (methyl ethylamino) zirconium is as high as 99.9999%.
TABLE 3 values of parameters for polyethylene porous particles
| Number of meshes | Molecular weight | Molecular weightDistribution index | Pore diameter | Particle size |
| 100 | 2200000 | 1.3 | 0.7μm | 4mm |
Example 4: purification of hafnium tetra (diethylamino)
Rectifying the low-purity tetra (diethylamino) hafnium, and collecting a fraction of 130 ℃/0.1 mmHg; washing the polyethylene porous particles with ultrapure water, drying at 120 ℃ for 24 hours, filling the purification tower with the dried polyethylene porous particles, and detailing each parameter of the polyethylene porous particles in table 4; and (3) flowing the fraction collected in the step (1) into a purifying tower filled with a purifying material, maintaining the temperature at 130 ℃ and 0.1mmHg for 6 hours, and discharging to obtain high-purity tetra (diethylamino) hafnium.
The purity of the obtained tetra (diethylamino) hafnium was examined by ICP, and the result showed that the purity of the product tetra (diethylamino) hafnium was as high as 99.9999%.
TABLE 4 values of parameters for ethylene porous particles
| Number of meshes | Molecular weight | Molecular weight distribution index | Pore diameter | Particle size |
| 200 | 2500000 | 1.4 | 0.8μm | 4mm |
Comparative example 1: purifying tetra (dimethylamino) titanium by rectification
The tetra (dimethylamino) titanium with low purity is rectified, the fraction with 50 ℃/0.1mmHg is collected, and the purity of the product is 99.9454 percent through ICP detection.
Comparative example 2: purifying tetra (methyl ethylamino) titanium by rectification
The low-purity tetra (methyl ethylamino) titanium is rectified, the fraction with the speed of 78 ℃/0.1mmHg is collected, and the purity of the product is 99.9689 percent through ICP detection.
Comparative example 3: purifying tetra (methyl ethylamino) zirconium by rectification
The low-purity tetra (methyl ethylamino) zirconium is rectified, the fraction of 81 ℃/0.1mmHg is collected, and the purity of the product is 99.9326% through ICP detection.
Comparative example 4: purifying tetra (diethylamino) hafnium by rectification
The low-purity tetra (diethylamino) hafnium is rectified, and the fraction with the purity of 99.6651 percent is obtained by collecting the fraction with the purity of 130 ℃/0.1mmHg and detecting by ICP.
The ICP test results of the above examples and comparative examples are shown in table 5 below:
TABLE 5 ICP detection results
From the above, it can be seen that the purity of the crude products of tetra (dimethylamino) titanium, tetra (methylethylamino) zirconium and tetra (diethylamino) hafnium is only 99.9% by rectification; after the rectified product is purified by a purifying tower filled with polyethylene porous particle purifying materials, the purity of the obtained product is up to 99.9999 percent, so that the purity of the product can be greatly improved by the purifying method, and the purity requirement of the product serving as an ALD precursor material can be met.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (6)
1. A method for refining a liquid ALD precursor, comprising the steps of:
rectifying the crude product of the liquid ALD precursor;
pretreating the purified material, and filling the pretreated purified material into a purifying tower;
flowing the rectified components into a purification tower filled with a purification material, purifying at the boiling point temperature, and discharging after purification to obtain a high-purity ALD precursor;
the purification material is porous particles, the porous particles are provided with through pore passages with hollow bending structures, and the pore passages are provided with a plurality of U-shaped bends; the boiling point temperature is the boiling point temperature of the liquid ALD precursor in a reduced pressure state, and the boiling point temperature interval is 50-120 ℃; the high purity is higher than 99.9999%; the purification material is ultra-high molecular weight polyethylene porous particles; the molecular weight of the ultra-high molecular weight polyethylene porous particles is 1500000-3000000, and the molecular weight distribution index is 1.1-1.7; the particle size of the ultra-high molecular weight polyethylene porous particles is 3-5mm, and the pore diameter is 0.5-1 mu m;
in the purification treatment process, material steam shuttles into the pore canal of each purification particle, phase change occurs at the U-shaped bend of the pore canal to form liquid accumulation, liquid seal is gradually formed, and impurity metal ions are locked at the bottom of the pore canal so as to achieve the purification effect.
2. The method of claim 1, wherein the liquid ALD precursor is one of tetra (dimethylamino) titanium, tetra (dimethylamino) hafnium, tetra (methylethylamino) titanium, tetra (methylethylamino) zirconium, tetra (methylethylamino) hafnium, tetra (diethylamino) titanium, tetra (diethylamino) zirconium, tetra (diethylamino) hafnium.
3. A method of refining a liquid ALD precursor according to claim 1, characterized in that the ultra high molecular weight polyethylene porous particles have a melting point of 200-220 ℃.
4. A method for refining a liquid ALD precursor according to claim 1, characterized in that the pretreatment of the purified material is in particular: washing the purified material with ultrapure water, and drying the washed purified material to obtain a pretreated purified material; the temperature of the drying treatment is 110-150 ℃, and the time of the drying treatment is 12-36h.
5. The method for refining a liquid ALD precursor according to claim 1, wherein the purifying column comprises a heating device, a feed valve, a column body and a discharge valve in this order from bottom to top; the tower body is used for containing purified materials, and the heating device is used for heating materials at the bottom of the tower body; the tower body is provided with an insulation layer.
6. A method of refining a liquid ALD precursor according to claim 1, characterized in that the purification treatment takes 3-9 hours.
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| CN106279474A (en) * | 2016-08-19 | 2017-01-04 | 中国科学院化学研究所 | Solubilising type super high molecular weight micronized polyethylene and preparation method thereof |
| JP2019177347A (en) * | 2018-03-30 | 2019-10-17 | 地方独立行政法人神奈川県立産業技術総合研究所 | Purification module and purification unit |
| CN112807724A (en) * | 2020-12-28 | 2021-05-18 | 湖南两山环境科技有限公司 | Distillation device based on sedimentation impurity removal mechanism |
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| CN106279474A (en) * | 2016-08-19 | 2017-01-04 | 中国科学院化学研究所 | Solubilising type super high molecular weight micronized polyethylene and preparation method thereof |
| JP2019177347A (en) * | 2018-03-30 | 2019-10-17 | 地方独立行政法人神奈川県立産業技術総合研究所 | Purification module and purification unit |
| CN112807724A (en) * | 2020-12-28 | 2021-05-18 | 湖南两山环境科技有限公司 | Distillation device based on sedimentation impurity removal mechanism |
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