METHOD AND APPARATUS FOR THE CONTINUOUS VAPOR DEPOSITION OF SILICON ON SUBSTRATES

Abstract

A method for the continuous vapour deposition of silicon on substrates, including the following steps: a) introducing at least one substrate into a reaction chamber; b) introducing a process gas and at least one gaseous silicon precursor compound into the reaction chamber; c) forming a gaseous mixture of at least one silicon-based intermediate product coexisting with the gaseous silicon precursor compound and the process gas; d) forming a silicon layer by vapour deposition of silicon from the gaseous silicon precursor compound and/or the silicon-based intermediate product on the substrate; e) discharging an excess of the gaseous mixture from the reaction chamber; f) returning at least one of the constituents of the excess of the gaseous mixture, selected from the silicon precursor compound, the silicon-based intermediate product and/or the process gas into the reaction chamber, wherein introducing the gaseous silicon precursor compound into the reaction chamber is regulated such that the molar ratio of the silicon-based intermediate product to the silicon precursor compound has a value of 0.2:0.8 to 0.5:0.5.

Claims

1. A process for the continuous vapor deposition of silicon on substrates, comprising the following steps: (a) introducing at least one substrate into a reaction chamber (2); (b) introducing a process gas and also at least one gaseous silicon precursor compound into the reaction chamber (2); (c) forming a gaseous mixture of at least one silicon-based intermediate in coexistence with the gaseous silicon precursor compound and the process gas in the reaction chamber (2); (d) forming a silicon layer by vapor deposition of silicon from at least one of the gaseous silicon precursor compound or from the silicon-based intermediate on the substrate; (e) discharging an excess of the gaseous mixture from the reaction chamber (2); (f) recirculating at least one of the constituents of the excess of the gaseous mixture selected from at least one of the silicon precursor compound, the silicon-based intermediate or the process gas into the reaction chamber (2), and regulating an introduction of the gaseous silicon precursor compound into the reaction chamber (2) in the process such that a molar ratio of the silicon-based intermediate to the silicon precursor compound has a value of from 0.2:0.8 to 0.5:0.5.

2. The process as claimed in claim 1, further comprising determining the molar ratio of the silicon-based intermediate and the silicon precursor compound in the excess of the gaseous mixture in step (f) using a measuring unit.

3. The process as claimed in claim 2, further comprising transmitting the molar ratio of the silicon-based intermediate to the silicon precursor compound determined by the measuring unit to a control unit which regulates the introduction of the silicon precursor compound such that the molar ratio of the silicon-based intermediate to the silicon precursor compound has a value of from 0.2:0.8 to 0.5:0.5 in the process gas.

4. The process as claimed in claim 1, further comprising freeing or partially separating the excess of the gaseous mixture in step (f) of impurities using by a recovery unit (7).

5. The process as claimed in claim 4, wherein at least one of the silicon-based intermediate, the silicon precursor compound, or the process gas are recirculated via the circulation conduit (5) into the reaction chamber (2) in step (f).

6. The process as claimed in claim 1, wherein the silicon precursor compound is a chlorosilane.

7. The process as claimed in claim 1, wherein the process gas is hydrogen.

8. The process as claimed in claim 1, wherein the silicon-based intermediate is a chlorosilane.

9. The process as claimed in claim 1, wherein a total amount of the silicon precursor compound and the silicon-based intermediate in step (c) is present in a molar ratio of from 1 to 10 mol % in the process gas.

10. The process as claimed in claim 1, wherein the formation of a silicon layer by vapor deposition of silicon from at least one of the silicon precursor compound or the silicon-based intermediate on the substrate takes place at a pressure of from 0.8 to 1.2 bar in the reaction chamber (2).

11. The process as claimed in claim 1, further comprising heating at least the substrate in the reaction chamber (2) to a temperature of from 700° C. to 1400° C.

12. An apparatus (1) for the continuous vapor deposition of silicon on substrates configured to carry out the process as claimed in claim 1, the apparatus comprising: a reaction chamber (2) which comprises at least one inlet opening (8) and at least one outlet opening (9) for substrates; a transport device (10) configured to transport the substrates through the reaction chamber (2) from the inlet opening (8) to the outlet opening (9); at least two gas inlets (11, 12) configured to feed a gas into the reaction chamber (2); at least one gas outlet (16) configured to discharge the gas from the reaction chamber (2); at least two fluid feed conduits (13, 14) that are connected to two of the gas inlets (11, 12) of the reaction chamber (2); at least one circulation conduit (5) arranged between the gas outlet (16) and one of the gas inlets (12) of the reaction chamber (2), said circulation conduit (5) is connected to the fluid feed conduit (13) and also to the gas outlet (16) of the reaction chamber (2); at least one measuring unit (3) configured to determine at least one of a molar ratio of the silicon-based intermediate and the silicon precursor compound or a parameter equivalent thereto; and wherein the control unit (4) and the measuring unit (3) are configured to interact such that a flow through the feed conduits (13, 14) is controlled or regulated by the control unit (4) based on a signal transmitted from the measuring unit (3) to the control unit (4).

13. The apparatus as claimed in claim 12, wherein the measuring unit (3) is arranged on the circulation conduit (5).

14. The apparatus as claimed in claim 12, wherein the measuring unit (3) is configured as spectrometer, as mass flow meter or as volume flow meter.

15. The apparatus as claimed in claim 12, wherein the at least one of the fluid feed conduits (13, 14) has a vaporizer (15) which serves to bring at least one of the silicon precursor compound or the silicon-based intermediate into the gaseous state.

16. The apparatus as claimed in claim 12, wherein the circulation conduit (5) has at least one of a gas scrubber (6) or a recovery unit (7), and the recovery unit (7) is at least one of configured as distillative separation apparatus or comprises a dry absorber or adsorber.

17. The apparatus as claimed in claim 12, wherein the circulation conduit (5) between the recirculation unit (7) and the fluid feed conduit (13, 14) has a plurality of subconduits (51, 52, 53) configured for separate recirculation of the process gas, of at least one of the silicon-based intermediate or of the silicon precursor compound, and each said subconduit (51, 52, 53) has a separate measuring unit (31, 32, 33) for determining at least one of the mass flow or volume flow of the process gas, of at least one of the silicon-based intermediate or of the silicon precursor compound.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Further advantageous properties of the invention can be derived from the following description of working examples with the aid of the drawing. The drawings show:

[0052] FIG. 1 a schematic depiction of a first working example of an apparatus according to the invention for the continuous vapor deposition of silicon on substrates,

[0053] FIG. 2 a schematic depiction of a second working example of an apparatus according to the invention for the continuous vapor deposition of silicon on substrates, and

[0054] FIG. 3 a schematic depiction of a third working example of an apparatus according to the invention for the continuous vapor deposition of silicon on substrates.

DETAILED DESCRIPTION

[0055] FIG. 1 shows a first working example of an apparatus 1 according to the invention for the continuous vapor deposition of silicon on substrates. This apparatus 1 comprises a reaction chamber 2, a measuring unit 3, a control unit 4, a circulation conduit 5, a gas scrubber 6 and a recovery unit 7.

[0056] The reaction chamber 2 has an inlet opening 8 through which substrates to be coated can be introduced into the reaction chamber 2. Furthermore, there is an outlet opening 9 on the side of the reaction chamber 2 opposite the inlet opening 8, via which outlet opening 9 silicon-coated substrates can be discharged from the reaction chamber 2. Transport of the substrates into the reaction chamber 2 and out again is effected by a transport device 10. As indicated by an arrow in FIG. 1, the transport device 10 has a transport direction for the substrates from the inlet opening 8 to the outlet opening 9. The transport device 10 can be configured as a conveyor belt. As an alternative, the transport device 10 can also have a plurality of transport rollers, or be configured as sliding rail transport.

[0057] As shown in FIG. 1, two substrates can in each case be introduced in an upright position into the reaction chamber 2 by the transport device 10. Here, the substrates are arranged parallel to one another, so that the sides to be coated of the substrates are opposite one another. Furthermore, the reaction chamber 2 has a temperature of 1100° C. in the present working example.

[0058] To introduce a gaseous silicon precursor compound and a process gas, two gas inlets 11, 12, via which the gaseous silicon precursor compound and the process gas can be introduced separately from one another into the reaction chamber, are arranged on the reaction chamber 2 in the region of the inlet opening 8. In the present working example, high-purity hydrogen is used as process gas. The formation of parasitic deposits in the gas inlets 11, 12 can be prevented by separate introduction of the gaseous silicon precursor compound and the process gas.

[0059] Furthermore, the gas inlets 11, 12 are each connected to a fluid feed conduit 13, 14 through which the silicon precursor compound and the process gas can be fed to the gas inlets 11, 12. In the present working example, silicon tetrachloride is used as silicon precursor compound. Since silicon tetrachloride has a boiling point of 57.6° C. and is thus liquid at room temperature, a vaporizer 15 is arranged on the fluid feed conduit 13. Liquid silicon tetrachloride is brought into the gaseous state by the vaporizer 15 before it is introduced into the reaction chamber 2.

[0060] In order to be able to discharge the excess of the gas mixture composed of the excess silicon precursor compound, the silicon-based intermediate and the process gas from the reaction chamber 2 after the substrates have been coated with silicon, the reaction chamber 2 has a gas outlet 16 in the region of the outlet opening 9. The gas outlet 16 is connected to the circulation conduit 5 which serves for recirculation of at least one of the constituents of the excess of the gaseous mixture, selected from among the silicon precursor compound, the silicon-based intermediate and/or the process gas, into the reaction chamber 2. Furthermore, the circulation conduit 5 is connected to the fluid feed conduit 13.

[0061] In the present working example, the gas scrubber 6, the recovery unit 7 and the measuring unit 3 are arranged on the circulation conduit 5 and are connected to one another via the continuous circulation conduit 5, in fact from the side of the gas outlet 16 to the side of the fluid feed conduit 13.

[0062] The gas scrubber 6 serves to concentrate the discharged excess of the gaseous mixture from the reaction chamber by bringing the discharged gaseous excess into contact with a scrubbing liquid in the gas scrubber 6, as a result of which valuable constituents of the excess can be taken up in the scrubbing liquid. The constituents going over can be solid, liquid or gaseous materials. As scrubbing liquid, it is possible to use, for example, chlorosilane.

[0063] The purified excess of the gaseous mixture can be conveyed via the circulation conduit 5 into the recovery unit 7. In the present working example, the recovery unit 7 is configured as distillative separation apparatus. It serves to separate the silicon precursor compound and/or the silicon-based intermediate from the process gas. In addition, the recovery unit 7 makes it possible to separate undesirable by-products of the chemical vapor deposition from the circulation conduit 5.

[0064] The measuring unit 3 is arranged on the circulation conduit 5 in order to determine a molar ratio of the silicon-based intermediate and the silicon precursor compound. In the present example, the measuring unit 3 is configured as infrared spectrometer which measures a concentration of the silicon-based intermediate and the silicon precursor compound in the gas stream of the circulation conduit 5 and in this way determines the molar ratio of the silicon-based intermediate and the silicon precursor compound. However, as an alternative, the measuring unit 3 can also be configured as Coriolis mass flow meter. However, the invention is not restricted thereto.

[0065] In order to regulate the introduction of the silicon precursor compound into the reaction chamber 2, a control unit 4, which can be configured, for example, as gas flow regulator, is arranged on the fluid feed conduit 13. The control unit 4 additionally serves to control the molar ratio of the silicon-based intermediate to the silicon precursor compound in the reaction chamber 2 during introduction. For this purpose, the control unit 4 is connected to the measuring unit 3.

[0066] A molar ratio of the silicon-based intermediate to the silicon precursor compound in the excess of the gaseous mixture in the circulation conduit 5 as determined by the measuring unit 3 is transmitted to the control unit 4. In order to maintain a desired molar ratio of the silicon-based intermediate to the silicon precursor compound of from 0.2:0.8 to 0.5:0.5, preferably from 0.3:0.7 to 0.5:0.5, particularly preferably 0.5:0.5, in the process gas in the reaction chamber 2, the control unit 4 controls the amount of silicon precursor compound fed via the fluid feed conduit 13 and the gas inlet 12 into the reaction chamber on the basis of the molar ratio of the silicon-based intermediate to the silicon precursor compound in the excess of the gaseous mixture in the circulation conduit 5 determined by the measuring unit 3. In the present working example, the control unit 4 and the measuring unit 3 are electrically conductively connected to one another, as a result of which the values measured by the measuring unit 3 are automatically transmitted to the control unit 4. However, it is also within the scope of the invention for a user of the apparatus 1 to read off the molar ratio determined by the measuring unit 3 and provide it manually to the control unit 4.

[0067] FIG. 2 shows a second working example of an apparatus 1 according to the invention for the continuous vapor deposition of silicon on substrates. The apparatus 1 has a structure which is largely identical to the configuration described in FIG. 1, for which reason further details will not be discussed first.

[0068] In order to regulate the introduction of the silicon precursor compound and of the process gas into the reaction chamber 2, the control unit 4 is arranged on the fluid feed conduit 13, 14. The control unit 4 serves firstly to control the molar ratio of the silicon-based intermediate to the silicon precursor compound in the reaction camber 2 during introduction and secondly to set a total amount of the silicon precursor compound and the silicon-based intermediate in step (c) in a molar ratio of from 1 to 10 mol %, preferably from 2 to 7 mol %, particularly preferably from 3 to 6 mol %, in the process gas. In this working example, too, the control unit 4 is connected to the measuring unit 3.

[0069] It is also within the scope of the invention for the excess process gas and/or the silicon-based intermediate and/or the silicon precursor compound to be discharged from the apparatus. In this present working example, the gas scrubber has, for this purpose, a gas outlet 17 with a discharge conduit 18 through which the excess process gas is discharged. However, the invention is not restricted thereto. Furthermore, the distillative separation apparatus can also have a gas outlet with a discharge conduit.

[0070] FIG. 3 shows a third working example of an apparatus 1 according to the invention for the continuous vapor deposition of silicon on substrates. This apparatus 1, too, has a structure which is largely identical to the configuration described in FIG. 1, for which reason further details will not be discussed first.

[0071] Downstream of the recovery unit 7, the circulation conduit 5 is split up into three separate subconduits 51, 52, 53 for the process gas, the silicon-based intermediate and the silicon precursor compound. It is within the scope of the invention for more than three separate subconduits to be located downstream of the recovery unit, especially in order to recirculate other gases, for example hydrogen chloride, separately. The respective mass or volume flows are determined by separate measuring units 31, 32, 33 which are arranged on the subconduits 51, 52, 53 downstream of the recovery unit 7. The molar ratio of the silicon-based intermediate to the silicon precursor compound can be derived therefrom. As can be seen from FIG. 3, the recovered process gas is then fed to the fluid feed conduit 14, the silicon-based intermediate and the silicon precursor compound are the fluid feed conduit 13.