Process for producing polycrystalline silicon

Abstract

Deposition on a sightglass in a reactor for CVD deposition of silicon is reduced by conducting a first purge gas stream substantially parallel to the reactor end surface of the sightglass, and conducting a second purge gas stream within the sightglass tube at an angle from the sightglass surface toward the interior of the reactor.

Claims

1. A process for producing polycrystalline silicon, comprising: introducing a reaction gas comprising a silicon-containing component and hydrogen into a reactor containing at least one heated filament rod onto which polycrystalline silicon is deposited, wherein the reactor has an interior surrounded by a reactor wall, and at least one sightglass tube having an internal diameter D secured to an orifice in the reactor wall, the sightglass tube having a reactor side end open to the reactor interior, and having an opposing sightglass end containing a sightglass having an inner surface facing the reactor interior and an outer surface facing away from the reactor interior, wherein the sightglass tube has a first plurality of holes arranged in one or more rows in a wall of the sightglass tube proximate the sightglass, the first plurality of holes being holes in the wall of the sightglass tube which run parallel to the inner surface of the sightglass and which are separated from the inner surface of the sightglass by an axial distance S1_n between the sightglass inner surface and a first row of holes of the first plurality of holes, a further plurality of holes located in the sightglass tube wall between the reactor interior and the first plurality of holes, the further plurality of holes being at an angle to a bore axis of the sightglass tube away from the inner surface of the sightglass and toward the reactor interior, wherein a ratio D/S1_n between the sightglass tube internal diameter D and the axial distance S1_n is greater than 1 and less than 40, introducing a first purge gas stream M1 through the first plurality of holes in a direction parallel to the inner surface of the sightglass, and introducing a further purge gas stream M2 through the further plurality of holes in the direction of the reactor interior, the purge gas streams M1 and M2 supplied during the period over which deposits can be deposited on the sightglass.

2. The process of claim 1, wherein the purge gas is selected from the group consisting of noble gases; nitrogen; chlorosilanes of the formula SiH.sub.nCl.sub.n-4 where n=0-4, in conjunction with a chlorosilane-free gas; hydrogen; HCl, and mixtures of said gases.

3. The process of claim 1, wherein a ratio L/D of sightglass tube length L to sightglass tube diameter D is 0.5-4.0.

4. The process of claim 1, wherein the ratio of purge gas mass flow rates of purge gases M1 and M2 is more than ⅓ and less than 20.

5. The process of claim 1, wherein purge gas stream M2 is supplied through one or more holes having geometric axes that form an angular range α of 10°-80° with a geometric axis of the sightglass tube.

6. The process of claim 1, wherein the two purge gas streams M1 and M2 are injected via one or more mutually offset rows of holes, each comprising a plurality of holes in the sightglass tube.

7. The process of claim 6, wherein holes in a row of holes are each arranged within an angular range of 40°-180° with respect to an internal cross section of the sightglass.

8. The process of claim 1, wherein the further plurality of holes comprises two or more rows of holes.

9. The process of claim 1, wherein a ratio D/S2_k between tube diameter D and a maximum axial separation S2_k of the further plurality of holes is greater than 0.4 and less than 40.

10. The process of claim 1, wherein the sightglass comprises an infrared transmitting glass.

11. The process of claim 1, wherein the sightglass comprises a quartz glass.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows, in highly schematic form, a deposition reactor with sightglass.

(2) FIG. 2 shows one embodiment of the invention in longitudinal section.

(3) FIG. 3 shows one embodiment of the invention in cross section through the tube.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(4) The inventors have recognized that, in the solutions proposed in the prior art, it was not possible to reliably prevent contact of the silicon-containing reaction gas with the glass surface of the sightglass because an injector effect was associated with the purge gas jets directed toward the glass surface of the sightglass, and this conveyed silicon-containing reaction gas to the glass surface and led to unwanted formation of deposits at least in some regions.

(5) Therefore, a sightglass having a novel purge gas supply has been developed, which suppresses contact of the glass surfaces on the reactor side with the reaction gas (chlorosilanes) and hence prevents formation of deposits.

(6) In contrast to the prior art, the purge gas is injected here into the sightglass tube at several positions.

(7) A purge gas stream is introduced close to the glass surface of the tube. This runs essentially parallel to the glass surface.

(8) For this purpose, offset rows of holes aligned parallel to the glass surface are preferably provided in the immediate proximity of the glass surface. This effectively produces a “curtain” of purge gas that can keep the reaction gas away from the glass surface.

(9) Without further measures, however, this can only be achieved when the purge gas rate supplied is suitably selected.

(10) In order to be independent of the purge gas rate supplied, in accordance with the invention, at least one second purge gas stream is provided, spaced apart from the first purge gas stream in the direction of the reactor end of the tube.

(11) This second purge gas stream does not, or the further purge gas streams do not, run parallel to the glass surface of the sightglass, but at an oblique angle, namely inclined with respect to the plane of the glass surface of the sightglass, specifically in the direction of the reactor end of the sightglass. The reactor end means that end of the tube mounted at an orifice in the reactor wall.

(12) In order to introduce the second purge gas stream into the tube of the sightglass, holes aligned preferably at an oblique angle to the middle of the reactor are present in the tube.

(13) The introduction of the further purge gas stream gives rise to a flow regime independent of the purge gas rate supplied in the sightglass tube.

(14) This enables process-matched regulation of the purge gas rate required for sightglass purging, without worsening the quality of the sightglass purging.

(15) Suitable purge gas is the following gases or any desired combinations as a gas mixture: noble gases (e.g. Ar, He), nitrogen, chlorosilanes of the SiH.sub.nCl.sub.n-4 form, n=0-4, in conjunction with a chlorosilane-free gas (e.g. SiCl.sub.4 with hydrogen), hydrogen, HCl gas.

(16) Particular preference is given to using hydrogen.

LIST OF REFERENCE NUMERALS USED

(17) 1 deposition reactor

(18) 2 sightglass

(19) 3 glass pane

(20) 4 hole(s) for purge mass flow M1

(21) 5 hole(s) for purge mass flow M2

(22) FIG. 1 shows a deposition reactor 1 and a sightglass 2 secured to the reactor wall.

(23) FIG. 2 shows a deposition reactor 1 and a sightglass 2 secured to the reactor wall and having a glass pane 3. The sightglass 2 comprises two rows of holes 4 for purge mass flow M1 and one row of holes 5 for purge mass flow M2.

(24) FIG. 3 shows section A-A through a row of holes 4 of FIG. 2. It becomes apparent that several holes parallel to one another are present.

(25) The invention enables the use of sightglasses having comparatively small tube/construction lengths. Thus, preference is given to a ratio L/D of tube length L to tube diameter D of 0.5-4.0. More preferably, the ratio L/D=0.7-3.0, most preferably 1.0-2.0.

(26) Preference is given to injecting a first portion M1 of the purge gas through one or more mutually offset rows of holes.

(27) These rows of holes are arranged on one side of the tube, preferably the upper side, within an angle range β1_n (n=index for row of holes) of 40°-180°, preferably 50°-130°, more preferably 60°-120°, about the vertical. Rotation of the angle range β1_n including the holes by 0-180° about the tube axis (deviation from the vertical) is possible.

(28) The distance of the holes within a row from the respective neighboring hole may be different or equal within a row, and is preferably equal.

(29) Holes are preferably positioned such that their exit orifices in the sightglass tube are within the angle range β1_n. The rows of holes are preferably aligned parallel to one another and to the glass surface. All the holes are preferably likewise aligned parallel to one another and to the opposite tube wall. In this way, a broad purge gas curtain is placed in front of the glass surface.

(30) According to the invention, the purge gas is divided into two substreams (M1 and M2). M1 corresponds to the gas stream running parallel to the glass surface, M2 to the gas stream that runs at an oblique angle; see also FIG. 2. The ratio of the purge mass flow rates is preferably set as follows: ⅓<M1/M2<20. More preferably, 1<M1/M2<15; most preferably, 2<M1/M2<10.

(31) The cross-sectional area of the tube (A.sub.T) based on the total area (A.sub.M1) of all the holes in the first portion of the purge gas (M1) is preferably within the range of 8<A.sub.T/A.sub.M1<300, more preferably 12<A.sub.T/A.sub.M1<150 and most preferably 15<A.sub.T/A.sub.M1<80.

(32) The number (N) of rows of holes through which the first portion of the purge gas is introduced is 1<=N<=5, preferably 1<=N<=3.

(33) The ratio between the tube diameter (D) and the axial separations S1_n of the rows of holes from the sightglass surface is preferably within the range of 1<D/S1_n<40, more preferably 1.5<D/S1_n<20 and most preferably 1.5<D/S1_n<10.

(34) If separations of holes or rows of holes are specified, these are each specified proceeding from the geometric axis of the holes.

(35) For injection of the second portion of the purge gas (M2) at an oblique angle to the tube axis, preference is given to using rows of holes which are likewise preferably arranged on the upper side of the tube within an angle range β2_n (n=index for row of holes) of 40°-180°, more preferably 50°-130°, most preferably 60°-120°, about the vertical. Rotation of the angle range β2_n including the holes by 0-180° about the tube axis (deviation from the vertical) is possible.

(36) The distance of the holes within a row from the respective neighboring hole may be different or equal within a row, and is preferably equal.

(37) The holes are preferably positioned such that the exit orifices thereof in the sightglass tube are within the angle range β2_n.

(38) All the holes for the second portion of the purge gas (M2) are preferably aligned parallel to one another and within an angle range α of 10°-80°, more preferably 20°-70°, most preferably 30°-60°, to the tube axis, in the direction of the reactor end of the tube.

(39) The cross-sectional area of the tube (A.sub.T) based on the total area (A.sub.M2) of all the holes aligned at an oblique angle to the tube axis is preferably 5<A.sub.T/A.sub.M2<500, more preferably 20<A.sub.T/A.sub.M2<300 and most preferably 40<A.sub.T/A.sub.M2<150.

(40) The number (K) of rows of holes for the second portion of the purge hydrogen is 1<=K<=5, preferably 1<=K<=3.

(41) The ratio between the tube diameter (D) and the axial separation (S2_k,) of the hole exits (at oblique angles to the tube axis) or rows of holes from the sightglass surface is preferably in the range of 0.4<D/S2_k<40, more preferably 0.6<D/S2_k<20 and most preferably (0.8<D/S2_k<10). Since the holes run at oblique angles, the distances relative to the geometric axis of the holes at the holes drilled on the inner surface of the tube are specified, cf. FIG. 2.

(42) The process according to the invention with its preferred embodiments virtually completely suppresses contact between reaction gas from the reactor and the internal glass surface of the sightglass at the reactor end. This completely prevents deposits on the glass surface of the sightglass.

(43) The flow field in the sightglass is independent of the purge gas rate. Therefore, if required, very different purge gas rates can be used without deterioration in the quality of the purging through varying flow conditions.

EXAMPLES

(44) In the tests of the different sightglass types, a standard process with a chlorosilane concentration of 20% (mole fraction) in H.sub.2 was used.

(45) In this process, marked deposits normally form on the reactor walls.

(46) The target diameter of the silicon rods to be deposited was 150 mm.

Comparative Example

(47) Tube: L/D=2 and D=50 mm

(48) The sightglass had a row of holes at a distance S1_1 of 10 mm from the glass surface.

(49) The holes were arranged parallel to the glass surface in the upper half of the sightglass tube and aligned in the direction of the tube axis.

(50) Every 30°, there was a hole of hole diameter 4 mm (7 holes in total). No further purge gas injections were present.

(51) The sightglass was purged with 30 m.sup.3 (STP)/h of H.sub.2 through the holes.

(52) During the deposition process, distinctly visible deposits formed on the glass surface at the reactor end in all the batches. These deposits were composed of amorphous compounds consisting of: chlorine, silicon and hydrogen.

(53) The deposits distorted the temperature measurements.

(54) The deposition process had to be ended prematurely for all the batches within the rod diameter range of 110-130 mm because of an excessively high electrical power consumption.

(55) On the basis of the resultant high rod temperatures, increased formation of popcorn was detected.

Example 1

(56) Tube: L/D=2 and D=50 mm.

(57) The sightglass had two mutually offset rows of holes at a distance of S1_1=15 mm and S1_2=25 mm from the glass surface.

(58) The purge gas mass flow was split into two substreams. The first substream M1 was supplied close to the sightglass, parallel to the sightglass surface.

(59) For this purpose, holes were arranged on the top of the sightglass tube within an angle range of β1_1=119° about the zero line (vertical). The holes were parallel to the glass surface and aligned vertically downward. The first row consists of 5 holes each with hole diameters of 2 mm. The middle hole was on the vertical. Every two further holes were arranged symmetrically to the vertical at a distance of ±10.3 mm or ±20.5 mm from the vertical. The second row of holes consisted of four holes each having hole diameters of 2 [mm], which were arranged offset from the first row of holes at horizontal separations (every two at ±5.1 mm and ±15.4 mm) symmetrically to the vertical.

(60) The second portion of the purge gas stream was injected obliquely to the tube axis at an angle of α=30° (angle relative to the tube axis) in the direction of the reactor through holes parallel to one another. A row of four holes was arranged on the top of the sightglass tube within an angle range of β2_1=108° about the zero line (vertical). The holes had a diameter of 2 mm. Every two holes were arranged symmetrically to the vertical at a distance of ±9.6 mm or ±19.2 mm from the vertical. The exit orifices of the holes were at a distance of S2_1=55 mm from the glass surface.

(61) The sightglass was purged with 20 m.sup.3 (STP)/h of H.sub.2 through the holes. The ratio of the purge mass flows M1/M2 was 3.

(62) Over the course of the deposition process, no visible deposits formed on the glass surface at the reactor end in any of the batches.

(63) The deposition process reached the rod diameter of 150 mm in all the batches. The batches did not have an elevated proportion of popcorn.

Example 2

(64) Tube: L/D=1.3 and D=75 mm

(65) The sightglass had two mutually offset rows of holes at a distance of S1_1=15 mm and S1_2=25 mm from the glass surface.

(66) The purge gas mass flow was split into two substreams. The first substream M1 was supplied close to the sightglass, parallel to the sightglass surface.

(67) For this purpose, holes were arranged on the top of the sightglass tube within an angle range of β1_1=119° about the zero line (vertical). The holes were parallel to the glass surface and aligned vertically downward. The first row consists of 7 holes each with hole diameters of 3 mm. The middle hole was on the vertical. Every two further holes were arranged symmetrically to the vertical at a distance of ±10.3 mm, ±20.5 mm or ±30.8 mm from the vertical. The second row of holes consisted of six holes each having hole diameters of 3 [mm], which were arranged offset from the first row of holes. Every 2 holes were arranged at a distance of ±5.1 mm, ±15.4 mm and ±25.6 mm symmetrically to the vertical.

(68) The second portion of the purge gas stream was injected obliquely to the tube axis at an angle of α=60° (angle relative to the tube axis) in the direction of the reactor through holes parallel to one another. A row of four holes was arranged on the top of the sightglass tube within an angle range of β2_1=65° about the zero line (vertical). The holes had a diameter of 2 mm. Every two holes were arranged symmetrically to the vertical at a distance of ±9.6 mm or ±19.2 mm from the vertical. The exit orifices of the holes were at a distance of S2_1=65 mm from the glass surface.

(69) The sightglass was purged with 30 m.sup.3 (STP)/h of H.sub.2 through the holes. All the purge gas ducts (M1 and M2) were supplied by a common space that was fed centrally. The ratio of the purge mass flow rates was calculated from the cross-sectional ratio A.sub.M1/A.sub.M2 and was 7.

(70) Over the course of the deposition process, no visible deposits formed on the glass surface at the reactor end in any of the batches.

(71) The deposition process reached the rod diameter of 150-160 mm in all the batches. The morphology of the batches corresponded to the specification.