TWI391324B - Process for purifying silicon source material by high gravity rotating packed beds - Google Patents

Description

Method for producing ruthenium raw material by super-gravity rotating packed bed

The present invention relates to a process for producing a purified ruthenium raw material, and more particularly to a process for purifying a mixture of trichloromethane or trichloromethane and ruthenium tetrachloride by a supergravity rotating packed bed.

Electronic grade polysilicon (EGS) can be obtained by removing impurities such as boron and phosphorus trichloromethane or a mixture of trichloromethane and hafnium tetrachloride. Most of the impurities can be removed immediately by fractional distillation. Trace impurities such as boron and phosphorus are typically present in the form of BCl ₃ , PCl ₃ , B ₂ H ₆ or PH ₃ , but fractional distillation to reduce these contaminations to an acceptable low level requires several successive fractionation steps. The main reason is that the bubbles of the impurity gas are not easily removed from the liquid trichloromethane and the antimony tetrachloride, and the impurity gas may be dissolved in the liquid. The other reason is that the boiling point of BCl ₃ (12.5 ° C) and the boiling point of PCl ₃ (74.2 ° C) are not high enough or low enough to run out with trichloromethane when the temperature is higher than 32 ° C.

U.S. Patent No. 5,616,245 to Albrecht et al. teaches a supergravity separator to separate solids. Other processes also recommend removing the oxygen or other gases in the water with a supergravity separator. U.S. Patent No. 4,283,255 to the entire disclosure of the entire disclosure of the entire disclosure of the entire disclosure of the entire disclosure of the entire disclosure of the disclosure of the disclosure of the disclosure of the present disclosure. U.S. Patent Nos. 4,374,110 and 4,409,195, the disclosure of each of which is incorporated herein by reference to the entire entire entire entire entire entire entire entire entire entire entire entire the

Therefore, there is a need for a purification process that can achieve higher purity without requiring time and investment for multiple fractionation and high temperature reactions.

The present invention addresses this need and proposes a purification process that can solve the above disadvantages.

It is an object of the present invention to provide a process for improving the purification of ruthenium raw materials.

A second object of the present invention is to provide a process for improving the purification of trichloromethane.

Another object of the present invention is to provide a process for improving the purification of antimony tetrachloride.

A further object of the present invention is to provide a process for improving the purification of a mixture of trichloromethane and ruthenium tetrachloride.

Still another object of the present invention is to provide a process for improving the removal of gaseous or liquid impurities comprising boron and phosphorus at a lower temperature.

In order to achieve the above and other objects, a first aspect of the present invention teaches a method for purifying a raw material comprising ruthenium chloride, which comprises one or more impurities such as boron, phosphorus, etc., by using two supergravity rotating packed beds. The chloride, hydride or intermediate complex of chlorine and hydrogen containing boron, phosphorus, etc. is removed from the ruthenium raw material, and comprises the following steps: (1) passing the liquid ruthenium raw material into the first super sponge-like metal filler Gravity rotating packed bed, the raw material including trichloromethane and antimony tetrachloride, the first supergravity rotating packed bed is kept below the boiling temperature of the antimony raw material (for example, the boiling point of trichloromethane is 32 ° C, that is, maintained at 20-30 At °C), no gas is introduced into the first supergravity rotating packed bed, and the impurities such as pH ₃ , B ₂ H ₆ vapor and other chlorodecane or decane having a boiling point lower than that of the ruthenium raw material are separated from the liquid ruthenium raw material. The pump is taken out for reuse or discarded, and the output raw material is then introduced into the raw material inlet of the second supergravity rotating packed bed; (2) the liquid raw material is introduced into the second super gravity with the sponge metal filling Rotating packed bed The second supergravity rotating packed bed is maintained at a temperature lower than the boiling point of the helium raw material, and oxygen is also introduced from the upper periphery into the second supergravity rotating packed bed, the second supergravity rotating packed bed of the trichloromethane inlet and the oxygen inlet. The flow rate can be controlled so that the molar ratio of oxygen to trichloromethane to oxygen is 0.005 to 0.5 to form an impurity-free cerium hydroxide complex, and the impurity hydride vapor and other chlorodecane or decane are again separated from the liquid cerium raw material. The pump is pumped out for reuse or disposal; (3) the liquid helium material containing the barium hydroxide complex having a higher boiling point than the raw material is collected; (4) the barium hydroxide step is used to remove the barium hydroxide containing the impurity from the barium material. Complex.

The above and other objects and advantages of the present invention will be more fully understood from the description and appended claims appended claims.

Please refer to FIG. 1. FIG. 1 is a cross-sectional view showing a supergravity rotating packed bed according to a preferred embodiment of the present invention. Figure 2 is a plan view showing a supergravity rotating packed bed in accordance with a preferred embodiment of the present invention. The first supergravity rotating packed bed 100 has a chamber 112 for feeding a liquid helium material such as trichloromethane, hafnium tetrachloride or a mixture of trichloromethane and hafnium tetrachloride. The flow rate of the feedstock inlet 101 is controlled by a controller (not shown). The gas outlet 102 is connected to a pump (not shown) for extracting gaseous impurities. The oxygen inlet 103 is closed. When the turntable 113 is driven at a rotational speed of about 1500 rpm in the shaft seals 109, 110, the input liquid helium material enters the turntable 113 from the distributor 108 and is outwardly smashed by supergravity. On the way, the liquid is turned by the turntable 113. The spongy metal filler 107 is blocked to form droplets or films, so that the gaseous impurities are easily separated from the liquid and extracted through the gas outlet 102. The liquid helium raw material has no bubbles or gas dissolved therein, and the purified liquid helium raw material 105 flows out through the helium raw material outlet 106.

The second supergravity rotating packed bed 200 has a chamber 212 for inputting liquid helium raw material from the crucible raw material outlet 106, and an oxygen inlet 203 for inputting oxygen 204, mounted on the upper edge of the chamber 212, and an oxygen inlet. The flow rate of 203 is controlled by a controller (not shown). The gas outlet 202 is connected to a pump (not shown) for extracting gaseous impurities. When the turntable 213 is driven at a rotational speed of about 1500 rpm in the shaft seals 209, 210, the input liquid helium material enters the turntable 213 from the distributor 208 and is outwardly smashed by supergravity. On the way, the liquid is turned by the turntable 213. The spongy metal filler 207 is blocked to form droplets or films, so that the gaseous impurities are separated from the liquid again and are withdrawn through the gas outlet 202. The liquid helium material is free of bubbles and no gas therein. Oxygen reacts with the Si-H bond in the trichloromethane at a lower temperature in the spongy metal filler 207 to form SiOH particles and combines with the impurities present in the trichloromethane to form Impurity yttrium hydroxide complex. Purified liquid scorpion Feed 205 flows out through the crucible feed outlet 206.

The process for purifying the ruthenium raw material is as follows: First, the ruthenium raw material such as trichloromethane is cooled to a temperature lower than the boiling point of the ruthenium raw material, such as trichloromethane at 32 ° C, and then passed to the first raw material inlet 101 of the first supergravity rotary packed bed 100. The flow rate is controlled, for example, to produce 1,250 tons of trichloromethane per year at 195 g/sec, and the rotation speed of the turntable 113 is about 1500 rpm. When the liquid trichloromethane passes through the sponge-like metal filler 107, the liquid becomes a droplet or a film and the gaseous impurity such as PH ₃ , B ₂ H ₆ or SiH ₄ is separated from the liquid helium raw material and is withdrawn from the gas outlet 102. In this process, no oxygen is used to avoid the reaction of oxygen with PH ₃ , B ₂ H ₆ or SiH _{4 ,} etc. Secondly, the liquid helium raw material is discharged from the raw material outlet 106 and then input into the second supergravity rotating packed bed 200, and oxygen is also introduced. The oxygen inlet 203 controls the flow rate of trichloromethane and oxygen to a molar ratio of trichloromethane to oxygen of from 0.005 to 0.5, for example, 1,250 tons of trichloromethane per year is 195 g/sec, and 0.01 mole of oxygen is 0.375 g/sec. Thus, oxygen reacts with the Si-H bond in the trichloromethane at a lower temperature in the spongy metal filler 107 to form SiOH particles and is combined with the impurities present in the trichloromethane. A cerium hydroxide complex which forms an impurity which is less volatile than trichloromethane. The purified trichloromethane is then separated from the less volatile impurities such as boron and phosphorus lanthanum hydroxide complexes in a subsequent fractionation step.

The features and spirit of the present invention are more clearly described in the detailed description of the preferred embodiments of the present invention, and are not intended to limit the scope of the invention. On the contrary, the intention is to cover various modifications and equivalent arrangements within the scope of the invention as claimed.

100‧‧‧First supergravity rotating packed bed

101‧‧‧矽Material entry

102‧‧‧ gas export

103‧‧‧Oxygen inlet

105‧‧‧purified liquid helium raw materials

106‧‧‧矽 Raw material exports

107‧‧‧Sponge metal filler

108‧‧‧Distributor

109, 110‧‧‧ shaft seal

111‧‧‧ shaft

112‧‧‧ chamber

113‧‧‧ Turntable

200‧‧‧Second supergravity rotating packed bed

201‧‧‧矽 Raw material entrance

202‧‧‧ gas export

203‧‧‧Oxygen inlet

204‧‧‧Oxygen

205‧‧‧purified liquid helium raw materials

206‧‧‧矽 Raw material exports

207‧‧‧Sponge metal filler

208‧‧‧Distributor

209, 210‧‧‧ shaft seal

211‧‧‧ shaft

212‧‧‧ chamber

213‧‧‧ Turntable

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a cross-sectional view showing a supergravity rotating packed bed in accordance with a preferred embodiment of the present invention.

Figure 2 is a plan view showing a supergravity rotating packed bed in accordance with a preferred embodiment of the present invention.

100‧‧‧First supergravity rotating packed bed

101‧‧‧矽Material entry

102‧‧‧ gas export

103‧‧‧Oxygen inlet

105‧‧‧purified liquid helium raw materials

106‧‧‧矽 Raw material exports

107‧‧‧Sponge metal filler

108‧‧‧Distributor

110‧‧‧ shaft seal

111‧‧‧ shaft

112‧‧‧ chamber

113‧‧‧ Turntable

200‧‧‧Second supergravity rotating packed bed

201‧‧‧矽 Raw material entrance

202‧‧‧ gas export

203‧‧‧Oxygen inlet

204‧‧‧Oxygen

205‧‧‧purified liquid helium raw materials

206‧‧‧矽 Raw material exports

207‧‧‧Sponge metal filler

208‧‧‧Distributor

210‧‧‧ shaft seal

211‧‧‧ shaft

212‧‧‧ chamber

213‧‧‧ Turntable

Claims (4)

The invention relates to a method for preparing a raw material for purifying trichloromethane by two super-gravity rotating packed bed, wherein the impurity comprises one or more impurities such as boron and phosphorus, and is chloride, hydride or chlorine and hydrogen containing boron, phosphorus and the like. The intermediate complex is removed from the trichloromethane and comprises at least the step of passing the liquid trichloromethane into a first supergravity rotating packed bed having a sponge-like metal filler, the first supergravity rotating packed bed remaining At a temperature lower than the boiling point of the trichloromethane (the boiling point of the trichloromethane is 32 ° C, that is, maintained at 20-30 ° C), no gas is introduced into the first supergravity rotating packed bed, and the boiling point is lower than the three The chloromethane impurity hydride vapor (PH ₃ , B ₂ H ₆ ) and other chlorodecane or decane vapor are separated from the liquid trichlorosilane, pumped out for reuse or discarded, and the output of the chloroform is recanalized. Entering the trichloromethane inlet of the second supergravity rotating packed bed; passing the liquid trichloromethane into a second supergravity rotating packed bed filled with a sponge metal, the second supergravity rotating packed bed being kept below Trichlorodecane At the boiling temperature, oxygen is also passed from the upper edge to the second supergravity rotating packed bed to form the cerium hydroxide (SiOH) complex of impurities (BCl3, PCl3), and the impurities hydride and other chlorodecane vapor or decane vapor are again Dissolving the liquid trichloromethane, pumping it for reuse or disposal; collecting liquid trichloromethane containing a cerium hydroxide complex having a higher boiling point than the trichloromethane; using a fractionation step from the trichloromethane The cerium hydroxide complex containing impurities is removed. The manufacturing method of claim 1, wherein the bismuth raw material comprises trichloromethane and ruthenium tetrachloride. The manufacturing method of claim 1, wherein the amount of oxygen and the molar ratio of trichloromethane to oxygen are from 0.005 to 0.5. The manufacturing method of claim 1, wherein the flow rate of the trichloromethane inlet and the oxygen inlet of the second supergravity rotating packed bed can be controlled.