TWI504774B - Preparing method of high purity pdmat precursor vapor - Google Patents

Description

High-purity PDMAT precursor vapor manufacturing method

The present invention relates to a method for purifying a solid precursor, which is particularly directed to a method for producing a high purity PDMAT precursor vapor for use in atomic layer deposition or chemical vapor deposition.

A tantalum nitride (TaN) film used to fabricate integrated circuits is usually formed by using Atomic Layer Deposition (ALD)/Chemical Vapor Deposition (CVD) methods, and current ALD/CVD methods are common. A tantalum nitride (TaN) film was formed using the precursor penta-dimethyl-amino tantalum = Ta(NMe ₂ ) ₅ (hereinafter referred to as "PDMAT"). However, such precursors are required to have high purity, high volatility, good reactivity, and good thermal stability.

The way in which 钽 precursors are made has been widely proposed. DCBradley and IMThomas, "Metallo-organic compounds containing metal-nitrogen bonds", Can . J. Chem ., 40, 1962, 1355, proposed to react TaCl ₅ with five equivalents of lithium dimethylamine to prepare Ta (NMe). ₂ ) ₅ precursors. The impure Ta(NMe ₂ ) ₅ precursor was distilled at a pressure of 0.1 torr and a temperature of 100 °C. However, the yield is only 73%, and the obtained precursors are not used in the current semiconductor process. The main reason is that the precursors prepared by the method have excessive impurity metal ions and impurities, and are calculated by weight percentage. Ta: 44.8%, NMe ₂ 53.5%, so the overall impurity content is about 1.7%, which is easy to cause metal ion contamination and defects in the process; and if heated under vacuum for 180 ° C for one hour, Ta (NMe ₂ ) ₅ precursor is heated Decomposition, the yield is only about 60%, and its thermal stability is not good.

The following three purification methods are commonly used: recrystallization, distillation, and chromatography. Among them, the recrystallization method and the chromatography method tend to have solvent residues, resulting in low purity, and the chromatography method is complicated and the production cost is high. And because PDMAT itself is a solid that is sensitive to air and moisture, it is also an active substance. Any alcohol, acid, amine, ester, aldehyde, ether, metal alkane, etc. do not require any energy. The reaction can naturally occur in contact with PDMAT. Therefore, PDMAT is not easily purified by recrystallization and chromatography, and therefore is usually purified by distillation. Conventional distillation purification directly heats the solid precursor, which is sublimed and collected. Since PDMAT is a dimethylamine with five single bonds bonded to Ta, its structure itself is not thermally stable. However, direct heating of the solid precursor tends to cause decomposition of the precursor, reducing the yield and purity. In addition, the PDMAT precursor is a solid at room temperature and has a low vapor pressure. The PDMAT precursor must be fed into the deposition chamber in a gaseous form to deposit a film, and the vapor pressure of the precursor must be sufficient to obtain a uniform and dense film.

Today, most of the PDMAT solid precursors are directly ground into a solid, and then poured directly into a cylinder and heated to increase its vapor pressure. When the carrier gas is introduced into a cylinder containing the PDMAT solid precursor, the vaporized PDMAT solid precursor is collected by the PDMAT solid precursor to form a new gas stream, which is then introduced into the thin film deposition system. However, its current technology is due to solids The heat conduction between the two is not easy, and it is easy to be affected by the heating time variation, resulting in uneven heating of the PDMAT solid precursor, formation of agglomeration, or its vapor pressure stability and poor reproducibility, which makes the film defects easily caused by film deposition. In addition, the use of PDMAT solid precursors is also generally low.

Referring to "Low decomposition storage of a tantalum precursor" as taught in U.S. Patent No. 8,088,938, a solid-state precursor container is provided which has an inner and outer double layer structure. The outer layer structure is made of stainless steel, and the inner layer structure is made of glass, tantalum, cerium oxide, tantalum carbide, quartz, titanium oxide, titanium nitride (PFTE), tantalum oxide and tantalum nitride, which can reduce the decomposition rate of the solid precursor of the tantalum. To improve the quality of the deposited film.

In addition, the solid precursor transport mode described above, when applied in actual chemical vapor deposition, causes a gas flow when the carrier gas enters the solid precursor container loaded, which facilitates suspending the un-sublimated solid precursor on the load. The particles in the solid precursor container are carried into the vapor deposition reaction chamber, so that the deposited film is contaminated with dust and the film quality is lowered.

"Method and apparatus of generating PDMAT precursor" as proposed in U.S. Patent No. 7,270,709, which further comprises a plurality of separators in a cylinder loaded with a PDMAT precursor, the separators providing a larger heated area of the PDMAT precursor and heating The source transfers heat uniformly to the PDMAT precursor via the separators, which effectively increases the yield and reduces the generation of impurities after deposition. However, this method will cause the cylinder to be difficult to clean when it is repeatedly used, thereby causing pollution, and the structure of the cylinder is complicated. Increase the production cost of cylinders.

In view of this, the inventors of the present invention have carefully studied and proposed a method for preparing a high-purity PDMAT precursor vapor, which mainly comprises the following steps: grinding and mixing a PDMAT solid together with a viscous carrier liquid to form a uniform The PDMAT solid precursor particles are dispersed in the viscous carrier liquid in a nanometer diameter manner; after a heating process, the PDMAT vapor formed by the PDMAT solid precursor particles is carried out by a carrier gas to form a high purity PDMAT. Precursor vapor. The high purity PDMAT precursor vapor has a metal ion purity of less than 1 PPM and an impurity content of less than 0.2%.

The invention mainly provides a method for preparing a high-purity PDMAT precursor vapor, which is mainly for the purpose of the present invention, which comprises the following steps: (1) placing a plurality of PDMAT solids and a viscous carrier liquid together in a grinding process. Uniform grinding in the apparatus to form a plurality of PDMAT solid precursor particles dispersed in the viscous carrier liquid in a nanometer diameter manner. The PDMAT solid precursor particles have a nanometer particle size range of 10 nm to 10 μm. The viscous carrier liquid has a viscosity of between 1 cp and 1000 cp; (2) the PDMAT solid precursor particles and the viscous carrier liquid are placed together in a container, the entire length of the container having a substantially fixed a cross section, and a top closure portion and a bottom closure portion defining the interior of the container; (3) heating the container by a heating process to vaporize the PDMAT solid precursor particles to form a PDMAT vapor; (4) providing a carrier Gas is introduced into the viscous carrier liquid through an inlet pipe to form a plurality of bubbles, and the carrier gas is a flow rate of 3 sccm to 1000 sccm, the intake pipe being disposed at a top closure of the container and extending into the interior of the container and below the viscous liquid-carrying liquid surface; and (5) mixing the bubbles with the PDMAT The vapor is passed out through an vent to form the high purity PDMAT precursor vapor. Wherein the mixing weight ratio of the viscous carrier liquid to the PDMAT solid precursor particles is between 4:1 and 1:12.

According to a feature of the manufacturing method of the present invention, the viscous carrier liquid system is selected from the group consisting of an alkane, an aromatic, an alkenyl group, an alkynyl group, and the viscous carrier liquid has a hydrogen number of 34 to 84. The viscosity of the viscous carrier liquid is between 120 ° C and 300 ° C under a vacuum pressure of 0.1 torr, and the viscosity of the viscous carrier liquid is preferably between 5 cp and 50 cp.

According to a feature of the manufacturing method of the present invention, the carrier gas system is selected from one of nitrogen, ammonia, hydrogen, helium and argon, and the flow rate of the carrier gas is preferably between 5 sccm and 100 sccm.

The method for producing high-purity PDMAT precursor vapor of the present invention has the following effects:

1. Different from the traditional heat transfer between solid and solid, the viscous carrier liquid can make the PDMAT solid precursor dispersed and suspended in the container in the nanometer particle size, so it has a larger contact surface area and increases the heat transfer rate. And it is evenly heated, thus shortening the heating temperature and heating time.

2. Due to the pulling property of the viscous carrier liquid, the PDMAT solid precursor particles are not easy to reduce the PDMAT precursor with the carrier gas entering the collection bottle. The purity of the material, or entering the deposition chamber, causes particle contamination problems.

3. Since the viscous carrier liquid does not participate in the PDMAT reaction, and because the viscosity of the viscous carrier liquid is high, it is not easily decomposed by thermal decomposition to cause the organic carbide to contaminate the high purity PDMAT precursor vapor.

4. Because of the dispersion of the viscous carrier liquid, the PDMAT solid precursor particles are not easy to agglomerate with each other, and the heat transfer stability is good, which can shorten the heating time required to obtain the vapor pressure, increase the PDMAT yield and lower the purification temperature and Purification time.

5. When the container is heated, by using the viscous carrier liquid as a heat transfer medium, the difference in temperature caused by the formation of bubbles by the carrier gas can be avoided, and a stable high-purity PDMAT precursor vapor can be obtained.

6. When the carrier gas enters the viscous carrier liquid, bubbles are generated, which can be uniformly mixed with the PDMAT precursor vapor and exported, and further the turbid flow of the viscous carrier liquid can be increased to increase the heat transfer rate. , heat uniformity and PDMAT are not easy to agglomerate.

7. The high purity PDMAT precursor has a metal ion purity of less than 1 PPM and an impurity content of less than 0.2% by weight.

The above and other objects, features, and advantages of the present invention will become more apparent and understood.

The present invention may be embodied in various forms, and the embodiments shown in the drawings and the following description are preferred embodiments of the present invention, and This is an example of the invention and is not intended to limit the invention to the particular embodiments illustrated and/or described.

The present invention will disclose a method of making a high purity PDMAT precursor vapor. Please refer to FIG. 1 , which is a schematic diagram of a transport device 20 for a PDMAT precursor of the present invention, which mainly includes a container 200 , an air inlet tube 230 , an air outlet 240 , and a temperature sensor 250 . 200 is generally a cylindrical cylinder having a generally fixed cross section and a top closure and bottom closure defining the interior of the container 200 for carrying a viscous carrier liquid 210, and a plurality of PDMAT solid precursors. Particles 220.

Referring now to Figure 2, there is shown a method for producing a high purity PDMAT precursor vapor of the present invention, the steps comprising: (1) placing a plurality of PDMAT solids and the viscous carrier liquid 210 together in a grinding apparatus. The PDMAT solid precursor particles 220 are uniformly ground to form the PDMAT solid precursor particles 220, and are dispersed in the viscous carrier liquid 210 by a nanometer diameter. The particle size of the PDMAT individual precursor particles 220 is between 10 nm and 10 μm. Preferably, the system is between 20 nm and 500 nm; (2) the PDMAT solid precursor particles 220 and the viscous carrier liquid 210 are placed together in the container 200; (3) using a heating process The container 200 is heated to vaporize the PDMAT solid precursor particles 220 to form a PDMAT vapor, the temperature of the heating process is between 20 ° C and 60 ° C; (4) providing a carrier gas to be introduced into the container via the inlet pipe 230 200 to In the viscous carrier liquid 210, a plurality of bubbles 260 are formed, wherein the distance between the bottom of the inlet pipe 230 and the bottom closed portion of the container 200 is between 0.2 cm and 3.0 cm; (5) the bubbles 260 The PDMAT vapor is mixed and the vessel 200 is led through the vent 240 to form the high purity PDMAT precursor vapor.

In the step (1), the viscous carrier liquid 210 is selected from the group consisting of alkanes, aromatics, alkenyls, and alkynyl groups. The viscous carrier liquid 210 does not react with PDMAT to form other compounds which can be suspended in the viscous carrier liquid 210 by milling. The viscosity of the viscous carrier liquid 210 is between 120 ° C and 300 ° C at a pressure of 0.1 torr. In actual deposition, the excessive heating temperature tends to cause the PDMAT to be thermally decomposed. Therefore, the PDMAT is usually heated in a negative pressure environment to reduce the sublimation point of the PDMAT and accelerate the vaporization rate of the PDMAT. If the boiling point of the viscous carrier liquid 210 is too low, the viscous carrier liquid 210 is vaporized by the actual deposition process, thereby contaminating the reaction chamber or the substrate to be deposited. The viscous carrier liquid 210 is selected from the group consisting of 34 to 84 hydrogen atoms. The viscous carrier liquid 210 is selected from the group consisting of Tetradecylbenzene, Pentadecylcyclohexane, Pentadecylbenzene, and Cetylbenzene ( Hexadecylbenzene), Squalane, and Squaleane.

In addition, the viscosity of the viscous carrier liquid 210 affects the dispersion of the PDMAT solid precursor particles 220 in the viscous carrier liquid 210. The viscosity of the viscous carrier liquid 210 is between 1 cp and 1000 cp. The viscous carrier liquid 210 having a too high viscosity coefficient tends to agglomerate the PDMAT solid precursor particles 220, disperse unevenly, and the traction force for the PDMAT solid precursor particles 220 is too large, so that the PDMAT solid precursor particles 220 It is not easy to sublimate after heating, so that the heating time required to obtain the PDMAT vapor pressure becomes longer. The viscous carrier liquid 210 having a too low viscosity coefficient tends to cause sedimentation of the PDMAT solid precursor particles 220, reducing the usage rate of the PDMAT solid precursor particles 220, and the viscous carrier liquid 210 is easily vaporized and lowered. The purity of the high purity PDMAT precursor vapor. The viscosity of the viscous carrier liquid 210 is preferably between 10 cp and 100 cp, and more preferably between 20 cp and 30 cp.

The PDMAT solids are poured into the grinding apparatus together with the viscous carrier liquid 210, and the PDMAT solids are formed into a particulate state by the high speed operation of the grinding apparatus and the hardness and shearing force of the grinding surface, and the viscous The properties of the liquid 210 itself are highly viscous and do not participate in the reaction, so that the PDMAT solids are allowed to be suspended in the liquid. In the preparation of the PDMAT solid precursor particles 220, the viscous carrier liquid 210 and the PDMAT solid precursors The mixing ratio of the particles 220 is between 4:1 and 1:12. When the ratio of PDMAT solid precursor particles 220 in the liquid is too low, it will cause the PDMAT vapor pressure to be difficult to reach the required pressure during the actual deposition process; and when the concentration of PDMAT solid precursor particles 220 is too high, the PDMAT solid precursor The particles are easily agglomerated, but the heat is not uniform, and the vapor pressure stability is lowered, thereby destroying the theoretical number of plates required for purification in the purification process, which is not conducive to the improvement of purity. Preferably, the viscous carrier liquid 210 and the The mixing weight ratio of PDMAT solid precursor particles 220 is between 2:1 and 1:6. Optimally, the mixing weight ratio of the viscous carrier liquid 210 to the PDMAT solid precursor particles 220 is between Between 1:1 and 1:3.

High purity PDMAT solids are the source of vapor required for the Ta and TaN processes used in CVD or ALD, and any solid precursor suitable for use in purification systems or vapor deposition systems can be used in the present invention. Previous inventors used PDMAT solids to directly grind directly into a cylinder and heat it to increase its vapor pressure, or simultaneously use a carrier gas to bring its vapor pressure into the reaction chamber for a film formation process. Therefore, the PDMAT solid is usually a non-uniform bulk solid. In the heating process, the heat conduction between the solids is not easy and the surface area is not uniform, so that the PDMAT vapor pressure stability reproducibility is not easy to cause defects of the membrane, and it is easy to cause PDMAT. The solids usage is low and the PDMAT solids are brought to the reaction chamber due to the gas stream formed by the carrier gas causing particle size contamination.

Therefore, the present invention proposes to convert the PDMAT solid into a uniform size of PDMAT solid precursor particles 220, which can effectively solve the above problems. The viscous carrier liquid 210 is coated on the outside of the PDMAT solid precursor particles 220 to form a structure as shown in FIG. The viscous carrier liquid 210 separates the PDMAT solid precursor particles 220 from each other, thereby avoiding agglomeration of the PDMAT solid precursor particles 220 and reducing the heated surface area, thereby causing instability of the PDMAT vapor pressure. On the other hand, the viscous carrier liquid 210 can be used as a heat transfer medium to improve the uneven heating of the PDMAT solids, thereby increasing the vapor pressure generation efficiency and solving the viscosity of the viscous carrier liquid 210. because The resulting gas stream caused by the carrier gas carries the PDMAT solid precursor particles 220 to the reaction chamber causing particle size contamination problems.

The PDMAT solid may also be first mixed with a liquid, and then the PDMAT solid precursor particles 220 are formed by agitation grinding to be dispersed in the viscous carrier liquid 210 in a nanometer diameter manner. Grinding can be carried out manually (such as with a mortar and pestle) or via a machine (such as with a grinder). Stirring can be carried out by any suitable means, such as tapping, shaking, rotating, shaking, shaking, pressurizing, vibrating via electrostrictive or magnetostrictive transducers, or manually rotating the cylinder to make the PDMAT solid precursors The particles 220 can be uniformly dispersed in the viscous carrier liquid 210.

In step (2), the PDMAT solid precursor particles 220 and the viscous carrier liquid 210 are placed together in the container 200 of the delivery device 20 of the PDMAT precursor. Referring now to FIG. 2, the PDMAT precursor transport device 20 mainly includes a container 200, an air intake tube 230, an air outlet 240, and a temperature sensor 250. The container 200 is typically a cylindrical cylinder having a generally fixed cross-section along the entire length and a top and bottom closure defining the interior of the container 200 for carrying a viscous carrier liquid 210 with a plurality of PDMAT solids. Precursor particles 220. The intake pipe 230 is disposed at a top closure of the vessel 200 and extends into the interior of the vessel 200 below the level of the viscous carrier liquid 210. The air outlet 240 is also disposed in the top closure of the container 200, but does not extend into the interior of the container 200. The top closure of the container 200 includes a temperature sensor 250 that extends into the interior of the container 200. And under the liquid surface of the viscous carrier liquid 210, the temperature of the heating process is detected.

In the step (3), the heating process mainly prevents the viscosity of the viscous carrier liquid 210 from changing due to the temperature drop after the carrier gas is introduced, thereby controlling the viscosity of the viscous carrier liquid 210. At the same time, the viscous carrier liquid 210 in the vessel 200 is subjected to a uniform temperature to heat the PDMAT solid precursor particles 220, thereby obtaining a stable PDMAT vapor, while controlling the desired vapor concentration by temperature adjustment.

In step (3), the heating process is carried out at a decomposition temperature lower than the PDMAT solids. Typically, the heating process is carried out at 30 ° C which is below the thermal decomposition temperature of the PDMAT solids, and more typically at 50 ° C below the decomposition temperature of the PDMAT solids. The temperature of the heating process is between 20 ° C and 60 ° C. The heating may be performed by using a water bath, an oil bath, hot air, a heating pack, or the like to prevent the viscosity of the viscous carrier liquid 210 from changing due to a decrease in temperature after the carrier gas is introduced, so that the viscous carrier liquid 210 is The viscosity is controlled while the viscous carrier liquid 210 in the vessel 200 is subjected to a uniform temperature to heat the PDMAT solid precursor particles 220, thereby obtaining a stable PDMAT vapor, while controlling the desired vapor concentration by temperature adjustment. . When the container is heated by the heating process, the container 200 is evacuated by a pumping system, so that the pressure in the container 200 is between 5 mtorr and 10 torr, preferably between 10 mtorr and 100 mtorr. The better one is between 20mtorr and 50mtorr.

In step (4), when the carrier gas enters the viscous carrier liquid 210 Bubbles 260 are generated, which can be uniformly mixed and exported with the PDMAT vapor, and further cause the turbid flow of the viscous carrier liquid 210 to increase the heat transfer rate and heat uniformity, and the PDMAT solid precursor particles 220 are further Not easy to reunite. The carrier gas is a gas that does not react with the viscous carrier liquid 210 and the PDMAT solid precursor particles 220, and is selected from one of nitrogen, ammonia, hydrogen, helium, argon, and combinations thereof. The flow rate of the carrier gas is between 3 sccm and 1000 sccm, preferably between 5 sccm and 100 sccm, and more preferably between 10 sccm and 20 sccm.

It should be noted that the distance between the bottom of the intake pipe 230 and the bottom closed portion of the container 200 is between 0.2 cm and 3.0 cm. If the distance between the bottom of the intake pipe 230 and the bottom closed portion of the container 200 is too long, that is, the distance between the bottom of the intake pipe 230 and the liquid surface of the viscous carrier liquid 210 is short, the carrier gas cannot be generated. Sufficient bubble 260 is mixed with the PDMAT vapor. The shorter the distance between the bottom of the intake pipe 230 and the bottom closed portion of the container 200, that is, the longer the distance from the intake pipe 230 into the viscous carrier liquid 210, the more bubbles 260 can be generated. It can effectively cause turbulence to the viscous carrier liquid 210 to increase heat transfer speed and heat uniformity.

In the step (5), after the high-purity PDMAT precursor vapor is led out of the container 200, if it is not immediately used in the thin film deposition process, it can be further introduced into a collection bottle 50 via a purification tube 40, as shown in FIG. Shown to form a high purity PDMAT precursor solid or to maintain a high purity PDMAT precursor vapor. The purity of the resulting high purity PDMAT precursor vapor is greater than 6N. Another implementation of the invention In one example, the high purity PDMAT precursor vapor can be introduced into a deposition system 60 to form a uniform dense TaN or Ta film.

In a preferred embodiment of the present invention, the purification tube 40 can be directly disposed inside the top closed portion of the container 200 and connected to the air outlet 240. The high purity PDMAT precursor vapor can be exported before the container 200 is exported. After purification through the purification tube 40, it is introduced into the deposition system 60 to form a uniform dense TaN or Ta film. The deposition system 60 can be atomic layer deposition or chemical vapor deposition.

Through the above process steps, the high purity PDMAT precursor vapor or the high purity PDMAT precursor has a metal ion purity of less than 1 PPM and an impurity content of less than 0.2% by weight of the total weight.

First embodiment:

20 g of pentylenecyclohexane viscous carrier liquid and PDMAT 20 g were uniformly dispersed by grinding and mixing in a ratio of 1:1 to form uniform PDMAT solid precursor particles 220, and poured into the container 200. And opening the heating system such that the container 200 and the viscous carrier liquid 210 in the container 200 are maintained at 60 degrees, and when the temperature is stabilized and the Vent Valve is opened until the system pressure in the container 200 is stable and below 0.1 torr, then The carrier gas nitrogen gas was introduced into the vessel 200 through the intake pipe 230 at a flow rate of 10 sccm, and bubbles 260 were formed below the liquid surface of the viscous carrier liquid 210 and uniformly mixed with the PDMAT vapor. Finally, the bubble 260 is mixed with the PDMAT vapor and sent to the collection bottle 50 via the vent 240 to obtain a high purity PDMAT precursor having a purity of 6.5N.

Second embodiment:

10 g of Squalane squalane viscous carrier liquid and PDMAT 40 g were uniformly dispersed by grinding and mixing at a ratio of 1:4 to form uniform PDMAT solid precursor particles 220, which were poured into the container 200 and opened. The heating system maintains the viscous carrier liquid 210 in the container 200 and the container 200 at 50 degrees. When the temperature is stabilized and the Vent Valve is opened until the system pressure in the container 200 is stable and below 0.1 torr, the carrier gas is then carried. Nitrogen gas was introduced into the vessel 200 through the intake pipe 230 at a flow rate of 5 sccm, and bubbles 260 were formed below the liquid surface of the viscous carrier liquid 210 and uniformly mixed with the PDMAT vapor. Finally, the bubble 260 is mixed with the PDMAT vapor and is led out through the vent 240, purified by the purification tube 40, and finally sent to the collection bottle 50 to obtain a high purity PDMAT precursor having a purity of 7N (>99.99999%).

The following three purification methods are commonly used: recrystallization, distillation, and chromatography. Among them, recrystallization and chromatography are prone to solvent residues, resulting in low purity, complex chromatography, high production costs, and because PDMAT itself is a solid that is sensitive to air and moisture, it is also an active substance. Any alcohol, acid, amine, ester, aldehyde, ether, metal alkane, etc. can naturally react. Therefore, PDMAT is not easy to be purified by recrystallization and chromatography, so it is usually used. Purification by distillation. Conventional distillation purification directly heats the solid precursor, which is sublimed and collected. Since PDMAT is a dimethylamine with five single bonds bonded to Ta, its structure itself is not thermally stable. However, direct heating of the solid precursor tends to cause decomposition of the precursor, reducing the yield and purity. By using the purification method described in the embodiment of the present invention, by using the viscous carrier liquid 210 as a heat conduction medium, the heating temperature can be effectively reduced. The desired PDMAT vapor pressure is obtained, thereby avoiding thermal decomposition of the PDMAT precursor to reduce yield and increase purity.

Third embodiment:

A viscous carrier liquid of 10 g of Squalane squalane was mixed with PDMAT 60 g in a ratio of 1:6 and uniformly dispersed, and then filled in the container 200, and heated to 40 degrees first, and when the temperature was stabilized, the Vent Valve was opened until The system pressure in the vessel 200 is stable and below 0.1 torr, and then the carrier gas helium gas is introduced into the vessel 200 via the intake pipe 230 at a flow rate of 5 sccm, so that helium gas is mixed with the PDMAT vapor. Finally, the bubble 260 is mixed with the PDMAT vapor and sent to the reaction chamber through the vent 240, and the TaN long film process can be performed. After use, the residual liquid of the container 200 is poured out and can be removed by using toluene under ultrasonic vibration cleaning. Residual solution.

If the PDMAT solid is directly ground and poured into the container 200 by a conventional method, and then the container 200 is placed in a gas cylinder cabinet on the long film machine, the PDMAT solid residual amount will be greater than 15%, and the use The method for preparing high-purity PDMAT precursor vapor proposed by the invention can significantly reduce the residual amount of PDMAT solids to less than 10%, improve the utilization rate of the PDMAT precursor, and reduce the pollution of the deposited film.

Fourth embodiment:

10 g of melamine, viscous carrier liquid and PDMAT 60 g were mixed and uniformly dispersed in a 1:6 ratio, and then filled in the container 200, and heated to 40 degrees first, when the temperature was stabilized and the system was inside the container 200. Stable pressure and less than 0.1torr Hereinafter, the carrier gas helium gas was introduced into the vessel 200 through the intake pipe 230 at a flow rate of 5 sccm, after the helium gas was mixed with the PDMAT vapor. Finally, the bubble 260 is mixed with the PDMAT vapor and sent to the reaction chamber through the vent 240, and the TaN long film process can be performed. After use, the residual liquid of the container 200 is poured out and can be removed by using toluene under ultrasonic vibration cleaning. Residual solution.

In summary, the present invention has the following effects:

1. Different from the traditional heat transfer between solid and solid, the viscous carrier liquid can make the PDMAT solid precursor dispersed and suspended in the container in the nanometer particle size, so it has a larger contact surface area and increases the heat transfer rate. And it is evenly heated, thus shortening the heating temperature and heating time.

2. Due to the pulling property of the viscous carrier liquid, the PDMAT solid precursor particles are not easy to reduce the purity of the PDMAT precursor or enter the deposition chamber to cause particle contamination problems as the carrier gas enters the collection bottle.

3. Since the viscous carrier liquid does not participate in the PDMAT reaction, and because the viscosity of the viscous carrier liquid is high, it is not easily decomposed by thermal decomposition to cause the organic carbide to contaminate the high purity PDMAT precursor vapor.

4. Because of the dispersion of the viscous carrier liquid, the PDMAT solid precursor particles are not easy to agglomerate with each other, and the heat transfer stability is good, which can shorten the heating time required to obtain the vapor pressure and improve the service life of the PDMAT.

5. When the container is heated, by using the viscous carrier liquid as a heat transfer medium, the difference in temperature caused by the formation of bubbles by the carrier gas can be avoided, and a stable high-purity PDMAT precursor vapor can be obtained.

6. When the carrier gas enters the viscous carrier liquid, bubbles are generated, which can be uniformly mixed with the PDMAT precursor vapor and exported, and further the turbid flow of the viscous carrier liquid can be increased to increase the heat transfer rate. , heat uniformity and PDMAT are not easy to agglomerate.

7. The high purity PDMAT precursor has a metal ion purity of less than 1 PPM and an impurity content of less than 0.2% by weight.

While the present invention has been described in its preferred embodiments, it is not intended to limit the scope of the invention, and various modifications and changes can be made without departing from the spirit and scope of the invention. As explained above, various modifications and variations can be made without departing from the spirit of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

20‧‧‧PDMAT precursor transport device

200‧‧‧ container

210‧‧‧ viscous carrier liquid

220‧‧‧PDMAT solid precursor particles

230‧‧‧Intake pipe

240‧‧‧ Vents

250‧‧‧temperature sensor

260‧‧‧ bubble

30‧‧‧ heating device

40‧‧‧purification tube

50‧‧‧Collection bottle

60‧‧‧Deposition system

The above and other objects, features, and advantages of the present invention will become more apparent from the aspects of the preferred embodiments of the invention. FIG. 2 is a flow chart showing a method for preparing a high purity PDMAT precursor vapor of the present invention; FIG. 3 is a schematic view showing the structure of the PDMAT solid precursor particles of the present invention; and FIG. 4 is a view showing the structure of the present invention. High purity PDMAT precursor vapor application.

Claims (15)

A method for preparing a high-purity PDMAT precursor vapor comprises the steps of: placing a plurality of PDMAT solids and a viscous carrier liquid together in a grinding apparatus for uniform grinding to form a plurality of PDMAT solid precursor particles, and The micron-sized particle size is dispersed in the viscous carrier liquid, wherein the PDMAT solid precursor particles have a nanometer particle size of between 10 nm and 10 μm, and the viscosity of the viscous carrier liquid is between 1 cp and 1000 cp; Placing the PDMAT solid precursor particles together with the viscous carrier liquid into a container having a substantially fixed cross section throughout the length and defining a top closure portion and a bottom closure portion of the interior of the container; Heating the vessel to heat the vessel to vaporize the PDMAT solid precursor particles to form a PDMAT vapor; providing a carrier gas to the vessel via an inlet tube to the viscous carrier liquid to form a plurality of bubbles, and The flow rate of the carrier gas is from 3 sccm to 1000 sccm, and the intake pipe is disposed at a top closed portion of the container and extends into the interior of the container, and in the viscous carrier liquid Below the surface; and mixing the bubbles with the PDMAT vapor and deriving the vessel via an vent to form the high purity PDMAT precursor vapor; wherein the viscous carrier liquid is mixed with the PDMAT solid precursor particles The weight ratio is between 4:1 and 1:12. The manufacturing method according to claim 1, wherein the viscous carrier liquid The system is selected from the group consisting of alkanes, aromatics, alkenyls, and alkynyl groups, and the viscous carrier liquid has a hydrogen number of 34 to 84. The production method according to claim 2, wherein the viscous carrier liquid system is selected from the group consisting of Tetradecylbenzene, Pentadecylcyclohexane, and pentadecylbenzene ( Pentadecylbenzene), Hexadecylbenzene, Squalane, Squaleane. The production method according to claim 2, wherein the viscosity of the viscous carrier liquid is between 120 ° C and 300 ° C under a vacuum pressure of 0.1 torr. The manufacturing method according to claim 2, wherein the viscosity of the viscous carrier liquid is preferably between 5 cp and 50 cp. The method of claim 1, wherein the PDMAT solid precursor particles preferably have a nanometer particle size of between 20 nm and 500 nm. The production method according to claim 1, wherein the carrier gas system is selected from one of nitrogen, ammonia, hydrogen, helium, and argon. The manufacturing method described in claim 7, wherein the carrier gas flow The preferred amount is between 5 sccm and 100 sccm. The manufacturing method according to claim 1, wherein the temperature of the heating process is between 20 ° C and 60 ° C. The manufacturing method according to claim 1, wherein when the container is heated by the heating process, the pressure in the container is between 5 mtorr and 10 torr. The manufacturing method according to claim 10, wherein when the container is heated by the heating process, the pressure in the container is preferably from 10 mtorr to 100 mtorr. The manufacturing method of claim 1, wherein the top closure portion of the container comprises a temperature sensor extending into the interior of the container and below the viscous liquid carrying liquid level. For detecting the temperature of the heating process. The method of claim 1, wherein the high purity PDMAT precursor vapor can be passed through a purification tube to obtain a higher purity PDMAT precursor. The production method of claim 1, wherein the high purity PDMAT precursor vapor can be introduced into a deposition system to form a TaN or Ta film. The production method according to claim 14, wherein the high purity PDMAT precursor vapor can be purified through the purification tube and then introduced into a deposition system to form a TaN or Ta film.