Purification device for liquid semiconductor precursor material

Abstract

The utility model discloses a purification device for a liquid semiconductor precursor material. The purification device comprises a tower kettle, a rectifying tower, a tower top condenser, a reflux ratio controller, a low-water low-oxygen manual operation box, a raw material bottle, a heavy component bottle, a sampling bottle, a light component bottle, a product bottle, a gas filter, a cold trap and a vacuum pump, on one hand, a tower kettle, a rectifying tower, a tower top condenser and a reflux ratio controller are connected with a raw material bottle, a heavy component bottle, a sampling bottle, a light component bottle and a product bottle in a low-water low-oxygen manual operation box through pipelines to form a material passage; on the other hand, the tower top condenser, the sampling bottle, the light component bottle and the product bottle are connected with the vacuum pump through a pipeline via the cold trap to form a vacuum and tail gas passage. The purification device disclosed by the utility model solves the problems that the existing purification device is complex in pipeline system, troublesome in operation and high in manufacturing cost when being used for purifying water-oxygen sensitive materials, and can be used for obtaining liquid semiconductor precursor materials with high purity and low granularity.

Description

TECHNICAL FIELD

[0001] The utility model belongs to the separation and purification equipment technical field of liquid material especially relates to a kind of purification device for liquid semiconductor precursor material. BACKGROUND

[0002] Precursor is a kind of existence form before obtaining target product, in semiconductor, it is with target element, in gaseous state, solid state or liquid state, with reactive activity, chemical thermal stability, a kind of substance, mainly used in thin film deposition in semiconductor manufacturing process. Thin film is mainly prepared by chemical vapor deposition (CVD, Chemical Vapor Deposition) and atomic layer deposition (ALD, Atomic Layer Deposition). Precursor material for CVD, ALD, according to material classification, there are silicon-based, metal-based, at room temperature, common silicon-based precursor material in liquid state has bis (diethylamino) silane (BDEAS), bis (tert-butyl amino) silane (BTBAS), di (isopropyl amino) silane (DIPAS) and so on, common metal-based precursor material in liquid state, for example, trimethylaluminum (TMA), tetra (dimethylamino) titanium (TDMAT), tetra (methyl ethyl amino) hafnium (TEMAHf), tris (dimethylamine) cyclopentadienyl zirconium (CpTDMAZr) and so on. The purity of precursor material used in semiconductor chip device manufacturing will directly affect the quality and performance of chip device. In high-end chip device preparation process, electronic grade precursor material purity requirement is greater than 5N (99.999%), so the purification process and device of precursor material are particularly critical. And most of precursor materials are sensitive to water and oxygen, and will react with water and oxygen, which will reduce the purity of product and greatly increase the difficulty of purification process. Therefore, water and oxygen content must be strictly controlled during purification process to avoid the contact between material and water and oxygen.

[0003] The separation and purification process of liquid compound usually has distillation, rectification, special rectification mode, rectification is a separation process using the volatility of each component in mixture to separate each component, and high-purity target product can be obtained. At present, existing rectification purification device technology is mainly in petrochemical, pharmaceutical, food industry and other fields, and is relatively mature. The liquid material required to be purified in these fields is not sensitive to water and oxygen at room temperature, and the water and oxygen control requirement is not high during operation. In the field of semiconductor materials, especially for the purification of high-purity semiconductor precursor material sensitive to water and oxygen, there are few purification devices, and the device pipeline system is complex, operation is troublesome, and the price is expensive. Therefore, a practical purification device for liquid semiconductor precursor material is needed. UTILITY MODEL CONTENT

[0004] The utility model provides a kind of for liquid semiconductor precursor material's utility model purification device.

[0005] To achieve the above object, the technical scheme of the utility model is:

[0006] A kind of for liquid semiconductor precursor material's purification device, including tower cauldron, rectifying column, overhead condenser, reflux ratio controller, low water low oxygen hand operation box, raw material bottle, heavy component bottle, sampling bottle, light component bottle, product bottle, cold trap and vacuum pump;Raw material bottle, heavy component bottle, sampling bottle, light component bottle, product bottle are all set in low water low oxygen hand operation box;Low water low oxygen hand operation box is closed and filled with high-purity inert gas;Raw material bottle connects tower cauldron material import, and heavy component bottle connects tower cauldron material export;Tower cauldron upper mouth is communicated with rectifying column, and rectifying column is loaded with filler, and the upper mouth of rectifying column is communicated with overhead condenser, and overhead condenser is communicated with reflux ratio controller, and the liquid outlet pipe line of reflux ratio controller forms branch pipe line, and is communicated with the upper side mouth of rectifying column, sampling bottle, light component bottle, product bottle respectively to form material passage;Overhead condenser, sampling bottle, light component bottle and product bottle are connected with vacuum pump through cold trap respectively by pipeline, and form vacuum and tail gas passage.

[0007] Preferably, raw material bottle is connected with tower cauldron by first transition pipe L1;Heavy component bottle is connected with tower cauldron material export by second transition pipe L2;Tower cauldron upper mouth is connected with rectifying column by third transition pipe L3, and rectifying column is loaded with filler, and the upper mouth of rectifying column is connected with overhead condenser by fourth transition pipe L4, and overhead condenser is connected with reflux ratio controller by fifth transition pipe L5, and the liquid outlet of reflux ratio controller forms two branches: sixth transition pipe L6 is connected with the upper side mouth of rectifying column, and seventh transition pipe L7 is connected with first three-way valve F31, and first three-way valve F31 is connected with product bottle by eighth transition pipe L8 respectively, and is connected with second three-way valve F32 by ninth transition pipe L9;Second three-way valve F32 is connected with light component bottle by tenth transition pipe L10 respectively, and is connected with sampling bottle by eleventh transition pipe L11.

[0008] Preferably, the end of overhead condenser is connected with first gas path pipe G1, the bottle mouth of product bottle is connected with first gas path branch pipe G21, the bottle mouth of light component bottle is connected with second gas path branch pipe G22, the bottle mouth of sampling bottle is connected with third gas path branch pipe G23, first, second, third gas path branch pipe G21, G22, G23 are gathered into second gas path pipe G2, first gas path pipe G1 and second gas path pipe G2 are communicated, and the end of second gas path pipe G2 is connected with vacuum pump through cold trap.

[0009] More preferably, the second gas path pipe G2 is connected with the gas filter through the fourth gas path branch pipe G24, the gas filter is arranged in the low-water and low-oxygen manual operation box, air can be supplied to the purification device through the gas filter, and the inert gas in the low-water and low-oxygen manual operation box can be used to supply air to the purification device, so that the low-water and low-oxygen state in the device is ensured.

[0010] Preferably, the height-to-diameter ratio of the rectifying tower is 150-300:5-10, and the size of the filler is 2-10 mm.

[0011] Preferably, the filler in the rectifying tower is one or more of triangular spiral ring fillers, Ceta ring fillers and pressed hole ring fillers, and the particle size of the filler is 2-10 mm.

[0012] Preferably, the inert gas is one or more of nitrogen, argon and helium, the water content in the manual operation box is less than 0.1 ppm, and the oxygen content in the manual operation box is less than 0.1 ppm.

[0013] More preferably, the connection mode between the tower kettle, the rectifying tower, the overhead condenser, the reflux ratio controller, the low-water and low-oxygen manual operation box, the raw material bottle, the heavy component bottle, the sampling bottle, the light component bottle, the product bottle, the gas filter, the cold trap, the vacuum pump and the transition pipe, the valve and the gas path pipe is selected from VCR type connection or sleeve type connection; the tower kettle is provided with a first thermometer T1 and a first pressure gauge P1; the rectifying tower is provided with a second thermometer T2 and a second pressure gauge P2, and one end of the first gas path branch pipe G21 connected with the bottle mouth of the product bottle is provided with a third pressure gauge P3.

[0014] More preferably, the liquid semiconductor precursor material is a monocyclopentadienyl metal complex, and the monocyclopentadienyl metal complex is a tris(dialkylamino) monocyclopentadienyl metal complex, and the structural formula is as follows:

[0015]

[0016] wherein the metal M is selected from Zr and Hf; R1 and R2 are the same or different and are selected from C1-C4 alkyl;

[0017] R3 is selected from hydrogen and C1-C4 alkyl.

[0018] More preferably, the tris(dialkylamino) monocyclopentadienyl metal complex is selected from the following structures:

[0019]

[0020] The utility model has the advantages of:

[0021] A novel purification apparatus for liquid semiconductor precursor materials is disclosed, particularly suitable for purifying water- and oxygen-sensitive liquid semiconductor precursor materials. It avoids contact between water, oxygen, particles, and the material, reducing the possibility of contamination. This invention can yield high-purity, low-particle-size liquid semiconductor precursor materials. The invention features a simple structure and high operability, and can be used for both atmospheric and vacuum distillation operations. It solves the problems of complex piping systems, cumbersome operation, and high costs associated with existing purification devices used for purifying water- and oxygen-sensitive materials. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of the device in Embodiment 1 of this utility model. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of the embodiments of this utility model clearer, the technical solutions of the embodiments of this utility model will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this utility model, not all embodiments. Based on the embodiments of this utility model, all other embodiments obtained by those skilled in the art without creative effort are within the protection scope of this utility model.

[0024] Example 1

[0025] like Figure 1 As shown, this embodiment of a purification device for liquid semiconductor precursor materials includes a reboiler 01, a distillation column 02, a column top condenser 03, a reflux ratio controller 04, a low-water, low-oxygen manual control box 05, a raw material bottle 09, a heavy component bottle 10, a sampling bottle 06, a light component bottle 07, a product bottle 08, a cold trap 12, and a vacuum pump 13. The raw material bottle 09, heavy component bottle 10, sampling bottle 06, light component bottle 07, and product bottle 08 are all housed within the low-water, low-oxygen manual control box 05. The low-water, low-oxygen manual control box 05 is sealed and filled with high-purity inert gas. The raw material bottle 09 is connected to the material inlet of the reboiler 01. The recombining bottle 10 is connected to the material outlet of the column bottom 01; the upper opening of the column bottom 01 is connected to the distillation column 02, which is filled with packing material. The upper opening of the distillation column 02 is connected to the top condenser 03, which is connected to the reflux ratio controller 04. The liquid outlet pipe of the reflux ratio controller 04 forms a branch pipe, which is connected to the upper side opening of the distillation column 02, the sampling bottle 06, the light component bottle 07, and the product bottle 08 to form a material passage. The top condenser 03, the sampling bottle 06, the light component bottle 07, and the product bottle 08 are connected to the vacuum pump 13 through the cold trap 12 via pipes to form a vacuum and exhaust gas passage.

[0026] The raw material bottle 09 is connected to the column still 01 through the first transition pipe L1; the heavy component bottle 10 is connected to the material outlet of the column still 01 through the second transition pipe L2; the upper opening of the column still 01 is connected to the rectifying column 02 through the third transition pipe L3, the rectifying column 02 is provided with packing, the upper opening of the rectifying column 02 is connected to the overhead condenser 03 through the fourth transition pipe L4, the overhead condenser 03 is connected to the reflux ratio controller 04 through the fifth transition pipe L5, the liquid outlet of the reflux ratio controller 04 is branched into two branches: the sixth transition pipe L6 is connected to the upper side opening of the rectifying column 02, and the seventh transition pipe L7 is connected to the first three-way valve F31, the first three-way valve F31 is connected to the product bottle 08 through the eighth transition pipe L8, and connected to the second three-way valve F32 through the ninth transition pipe L9; the second three-way valve F32 is connected to the light component bottle 07 through the tenth transition pipe L10, and connected to the sampling bottle 06 through the eleventh transition pipe L11.

[0027] Preferably, the end of the overhead condenser 03 is connected to the first gas path pipe G1, the bottle opening of the product bottle 08 is connected to the first gas path branch pipe G21, the bottle opening of the light component bottle 07 is connected to the second gas path branch pipe G22, the bottle opening of the sampling bottle 06 is connected to the third gas path branch pipe G23, the first gas path branch pipe G21, the second gas path branch pipe G22 and the third gas path branch pipe G23 are collected into the second gas path pipe G2, the first gas path pipe G1 and the second gas path branch pipe G2 are communicated, and the end of the second gas path pipe G2 is connected to the cold trap 12 and the vacuum pump 13.

[0028] The second gas path pipe G2 is connected to the gas filter 11 through the fourth gas path branch pipe G24, the gas filter 11 is arranged in the low-water and low-oxygen manual box 05, air can be supplied to the purification device through the gas filter 11, and the inert gas in the low-water and low-oxygen manual box 05 can be used to supply air to the purification device, so as to ensure the low-water and low-oxygen state in the device.

[0029] The height to inner diameter ratio of the rectifying column 02 is 150-300:5-10, and the size of the packing is 2-10 mm.

[0030] The packing in the rectifying column 02 is one or more of triangular spiral ring packing, Ceta ring packing and pressed hole ring packing, and the particle size of the packing is 2-10 mm.

[0031] The inert gas is one or more of nitrogen, argon and helium, the water content in the low-water and low-oxygen manual box 05 is less than 0.1 ppm, and the oxygen content in the low-water and low-oxygen manual box 05 is less than 0.1 ppm.

[0032] The tower kettle 01, the rectifying tower 02, the overhead condenser 03, the reflux ratio controller 04, the low water and low oxygen hand-operated box 05, the raw material bottle 09, the heavy component bottle 10, the sampling bottle 06, the light component bottle 07, the product bottle 08, the gas filter 11, the cold trap 12, the vacuum pump 13 and the connection mode between the transition pipe, the valve and the gas path pipe are selected from the VCR type connection or the sleeve type connection; the tower kettle 01 is provided with the first thermometer T1 and the first pressure gauge P1; the rectifying tower 02 is provided with the second thermometer T2 and the second pressure gauge P2; one end of the first gas path branch pipe G21 connected with the bottle mouth of the product bottle 08 is provided with the third pressure gauge P3.

[0033] The liquid semiconductor precursor material is a monocyclopentadienyl metal complex, which is a tris(dialkylamino) monocyclopentadienyl metal complex, and the structural formula is as follows:

[0034]

[0035] wherein the metal M is selected from Zr and Hf; R1 and R2 are the same or different and are selected from C1-C4 alkyl;

[0036] R3 is selected from hydrogen and C1-C4 alkyl.

[0037] The tris(dialkylamino) monocyclopentadienyl metal complex is selected from the following structures:

[0038] The specific use process of the embodiment is as follows:

[0039] The crude raw material is added to the raw material bottle 09 in the low water and low oxygen hand-operated box 05; the intermittent vacuum rectification purification operation is performed, and the feeding, sampling and collection are all operated in the low water and low oxygen hand-operated box 05 filled with high-purity nitrogen, with water oxygen less than 0.1 ppm; the raw material bottle 09 is communicated with the material inlet of the tower kettle 01, and the tower kettle 01 is connected through the transition pipe L1; the tower kettle 01 is heated to form a gas phase which passes through the rectifying tower 02 provided with packing and heat preservation, reaches the overhead condenser 03, and the incondensable gas phase is pumped to the cold trap 12 by the vacuum pump 13; the condensable gas phase is cooled by the overhead condenser 03 to form a liquid phase which flows to the reflux ratio controller 04; the liquid phase in the reflux ratio controller 04 is refluxed to the rectifying tower 02 according to the set reflux ratio, and part of the liquid phase flows to the sampling bottle 06 and the light component (low-boiling-point impurities) bottle in the low water and low oxygen hand-operated box 05; after the product in the sampling bottle 06 is analyzed to reach the electronic grade purity, the liquid phase further flows to the product bottle 08 through the filter to remove microparticles, and finally the liquid semiconductor precursor material with high purity is obtained; when the purification device is restored to normal pressure from vacuum, the gas in the purification device can be supplemented through the gas filter 11, and the gas filter 11 is arranged in the low water and low oxygen hand-operated box 05 to supplement the inert gas in the purification device, so as to ensure the low water and low oxygen state in the device. The purification process is regulated by the pressure control system.

[0040] Example 2 utilizes the device to purify monocyclopentadienyl zirconium complex Z01 according to the application:

[0041] Utilize Figure 1 The purification device is used to add 5 kg of crude Z01 (ICP-MS / OES test purity 99.9%) into the kettle 01 to perform the vacuum rectification purification operation, and the feeding, sampling and collection are all operated in the low water and low oxygen hand-operated box 05 filled with high-purity nitrogen with water oxygen less than 0.1 ppm.

[0042] The purification method parameters are as follows: the heating temperature of the kettle 01 is 130 DEG C; the height of the rectification tower 02 is 180 cm, and the inner diameter is 50 mm (the height to inner diameter ratio is 180:5); the filler is selected from stainless steel triangular spiral ring filler, and the filler size is 3 mm; the temperature of the overhead condenser 03 is -10 DEG C; the reflux ratio is 1:5; and the overhead pressure is 350 pa. After purification, the electronic grade Z01 is obtained, the yield is 50% (mass fraction), the light component bottle 07 collects 40% (mass fraction), and the heavy component bottle 10 collects 10% (mass fraction). The product after purification is tested by hydrogen spectrum 1HNMR (C6D6), and the hydrogen spectrum purity is 99.9% grade; the purity tested by ICP-MS / OES is 99.9999% (6N) grade, and the specific data are shown in Table 1.

[0043] Example 3 utilizes the device to purify monocyclopentadienyl hafnium complex H01 according to the application

[0044] Utilize Figure 1 The purification device is used to add 5 kg of crude H01 (ICP-MS / OES test purity 99.9%) into the kettle 01 to perform the vacuum rectification purification operation, and the feeding, sampling and collection are all operated in the low water and low oxygen hand-operated box 05 filled with high-purity nitrogen with water oxygen less than 0.1 ppm.

[0045] The purification method parameters are as follows: the heating temperature of the kettle 01 is 125 DEG C; the height of the rectification tower 02 is 200 cm, and the inner diameter is 80 mm (the height to inner diameter ratio is 200:8); the filler is selected from stainless steel Westinghouse ring filler, and the filler size is 6 mm; the temperature of the overhead condenser 03 is -5 DEG C; the reflux ratio is 1:6; and the overhead pressure of the rectification tower 02 is 260 pa. After purification, the electronic grade H01 is obtained, the yield is 45% (mass fraction), the light component bottle 07 collects 45% (mass fraction), and the heavy component bottle 10 collects 10% (mass fraction). The product after purification is tested by hydrogen spectrum 1HNMR (C6D6), and the hydrogen spectrum purity is 99.9%; the purity tested by ICP-MS / OES is 99.9999%, and the specific data are shown in Table 1.

[0046] Table 1 ICP-MS / OES test data

[0047]

[0048]

[0049] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not limited thereto; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that the technical solutions recorded in the foregoing embodiments can still be modified, or some or all of the technical features can be replaced by equivalents; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A purification apparatus for a liquid semiconductor precursor material, characterized by, The application relates to a distillation device, which comprises a tower kettle (01), a rectifying tower (02), a tower top condenser (03), a reflux ratio controller (04), a low-water low-oxygen hand-operated box (05), a raw material bottle (09), a heavy component bottle (10), a sampling bottle (06), a light component bottle (07), a product bottle (08), a cold trap (12) and a vacuum pump (13); the raw material bottle (09), the heavy component bottle (10), the sampling bottle (06), the light component bottle (07) and the product bottle (08) are arranged in the low-water low-oxygen hand-operated box (05); the low-water low-oxygen hand-operated box (05) is filled with high-purity inert gas; the raw material bottle (09) is connected with the material inlet of the tower kettle (01), and the heavy component bottle (10) is connected with the material outlet of the tower kettle (01); the upper opening of the tower kettle (01) is communicated with the rectifying tower (02), the rectifying tower (02) is internally provided with a filler, the upper opening of the rectifying tower (02) is communicated with the tower top condenser (03), the tower top condenser (03) is communicated with the reflux ratio controller (04), the liquid outlet pipeline of the reflux ratio controller (04) forms branch pipelines which are respectively communicated with the upper side opening of the rectifying tower (02), the sampling bottle (06), the light component bottle (07) and the product bottle (08) to form material passages; the tower top condenser (03), the sampling bottle (06), the light component bottle (07) and the product bottle (08) are respectively connected with the vacuum pump (13) through the cold trap (12) by pipelines to form vacuum and tail gas passages.

2. The purification device of claim 1, wherein, The raw material bottle (09) is connected with the tower kettle (01) through a first transition pipe (L1); the heavy component bottle (10) is connected with the material outlet of the tower kettle (01) through a second transition pipe (L2); the upper opening of the tower kettle (01) is connected with the rectifying tower (02) through a third transition pipe (L3); the rectifying tower (02) is internally provided with a filler, the upper opening of the rectifying tower (02) is connected with the tower top condenser (03) through a fourth transition pipe (L4), the tower top condenser (03) is connected with the reflux ratio controller (04) through a fifth transition pipe (L5), and the liquid outlet of the reflux ratio controller (04) forms two branches; a sixth transition pipe (L6) is connected with the upper side opening of the rectifying tower (02), a seventh transition pipe (L7) is connected with a first three-way valve (F31), the first three-way valve (F31) is respectively connected with the product bottle (08) through an eighth transition pipe (L8) and connected with a second three-way valve (F32) through a ninth transition pipe (L9); the second three-way valve (F32) is respectively connected with the light component bottle (07) through a tenth transition pipe (L10) and connected with the sampling bottle (06) through an eleventh transition pipe (L11).

3. The purification device of claim 1, wherein, The end of the tower top condenser (03) is connected with a first gas pipeline (G1), the bottle opening of the product bottle (08) is connected with a first gas branch pipeline (G21), the bottle opening of the light component bottle (07) is connected with a second gas branch pipeline (G22), the bottle opening of the sampling bottle (06) is connected with a third gas branch pipeline (G23), the first, second and third gas branch pipelines (G21), (G22) and (G23) are gathered into a second gas pipeline (G2), the first gas pipeline (G1) and the second gas pipeline (G2) are communicated, and the end of the second gas pipeline (G2) is connected with the vacuum pump (13) through the cold trap (12).

4. The purification device of claim 3, wherein, The second gas path pipe (G2) is connected with the gas filter (11) through the fourth gas path branch pipe (G24), and the gas filter (11) is arranged in the low-water and low-oxygen manual operation box (05).

5. The purification device of claim 1, wherein, The height-to-diameter ratio of the rectifying tower (02) is 150-300:5-10; and the size of the filler is 2-10 mm.

6. The purification device of claim 1, wherein, The filler in the rectifying tower (02) is one or more of triangular spiral ring fillers, Ceta ring fillers and pressed hole ring fillers, and the particle size of the filler is 2-10 mm.

7. The purification device of claim 1, wherein, The inert gas is one or more of nitrogen, argon and helium, the water content in the manual operation box is less than 0.1 ppm, and the oxygen content in the manual operation box is less than 0.1 ppm.

8. The purification device according to any one of claims 1 to 7, characterized in that The tower kettle (01), the rectifying tower (02), the overhead condenser (03), the reflux ratio controller (04), the low-water and low-oxygen manual operation box (05), the raw material bottle (09), the heavy component bottle (10), the sampling bottle (06), the light component bottle (07), the product bottle (08), the gas filter (11), the cold trap (12), the vacuum pump (13) and the transition pipe, the valve and the gas path pipe are connected in a VCR type or a clamping sleeve type; the tower kettle (01) is provided with a first thermometer (T1) and a first pressure gauge (P1); the rectifying tower (02) is provided with a second thermometer (T2) and a second pressure gauge (P2); and one end of the first gas path branch pipe (G21) connected with the bottle opening of the product bottle (08) is provided with a third pressure gauge (P3).

Images