SIO probe for real-time monitoring and control of oxygen during czochralski growth of single crystal silicon

• US 5,795,381 A
• Filed: 09/09/1996
• Issued: 08/18/1998
• Est. Priority Date: 09/09/1996
• Status: Expired due to Term

• Current Assignee: SunEdison, Inc.
• Original Assignee: SunEdison, Inc.
• Inventors: Holder, John D.
• Primary Examiner(s): STUCKER, JEFFREY J
• Application Number:
  US08/711,085
• Time in Patent Office: 708 Days
• Field of Search: 75/10.5, 423/350, 423/325, 373/22, 117/11-20
• US Class Current: 117/14
• CPC Class Codes: G01N 33/0011 Sample conditioning preparing specimens for investigation G01N1/28
• CPC Class Codes: G01N 33/2025 Gaseous constituents
• CPC Class Codes: G01N 33/205 in liquid state, e.g. molten metals

Abstract

Methods for quantifying, in near real-time, the amount of silicon oxide (SiO) volatilized from a pool of molten silicon such as a Czochralski silicon melt and present in the atmosphere over the melt are disclosed. A preferred method includes reacting a gas sample containing SiO withdrawn from the atmosphere over the molten silicon with a reactant to form a detectable reaction product, determining the amount of reaction product formed, and correlating the determined amount of reaction product to the amount of SiO present in the atmosphere. The quantification of SiO is used for monitoring and/or controlling the amount of oxygen in the molten silicon or the oxygen content in single crystal silicon being drawn from the molten silicon. A SiO reaction probe and a system using the probe for monitoring and/or controlling oxygen are also disclosed.

Claims

1. A method for determining the amount of SiO present in an atmosphere over a pool of molten silicon, the method comprising

withdrawing a sample containing SiO from the atmosphere over the pool of molten silicon, reacting SiO present in the sample with a reactant to form a detectable reaction product,

determining the amount of reaction product formed, and

correlating the determined amount of reaction product to the amount of SiO present in the atmosphere.

2. The method of claim 1 wherein the reaction product is a gaseous reaction product which is detectable at ambient temperature.

3. The method of claim 1 wherein the reactant is a carbon-containing material and at least one reaction product is carbon monoxide gas.

4. The method of claim 1 wherein the SiO present in the atmosphere over the molten silicon is reacted with graphite to form carbon monoxide gas and silicon carbide.

5. The method of claim 1 wherein the time elapsed between the step of withdrawing the sample and the step of determining the amount of reaction product formed is less than about 5 minutes.

6. The method of claim 1 wherein the sample containing SiO is withdrawn into a reaction probe that includes a graphite reactant, the SiO present in the sample is reacted with graphite in the probe to form carbon monoxide gas and silicon carbide, the amount of carbon monoxide formed is determined using a quadrupole gas mass analyzer, and the determined amount of carbon monoxide is correlated to the amount of SiO present in the atmosphere over the pool.

7. A method for determining the amount of oxygen in a pool of molten silicon, the method comprising

quantifying the amount of SiO present in an atmosphere over the pool of molten silicon, and

correlating the quantified amount of SiO to the amount of oxygen in the molten silicon.

8. The method of claim 7 wherein the amount of SiO present in the atmosphere over the pool is quantified by withdrawing a sample containing SiO from the atmosphere, reacting SiO present in the sample with a reactant to form a detectable reaction product, determining the amount of reaction product formed, and correlating the determined amount of reaction product to the amount of SiO present in the atmosphere.

9. A method for determining the amount of oxygen in a pool of molten silicon, the method comprising

withdrawing a sample containing SiO from an atmosphere over the molten silicon,

reacting SiO present in the sample with a reactant to form a detectable reaction product,

determining the amount of reaction product formed, and

correlating the determined amount of reaction product to the amount of oxygen in the pool of molten silicon.

10. A method for determining, in near real-time, the oxygen content in a single crystal silicon ingot being drawn from a pool of molten silicon, the method comprising

quantifying the amount of SiO present in an atmosphere over the pool of molten silicon, and

correlating the quantified amount of SiO to the oxygen content in the single crystal silicon ingot.

11. The method of claim 10 wherein the amount of SiO present in the atmosphere over the pool is quantified by withdrawing a sample containing SiO from the atmosphere, reacting SiO present in the sample with a reactant to form a detectable reaction product, determining the amount of reaction product formed, and correlating the determined amount of reaction product to the amount of SiO present in the atmosphere.

12. A method for determining, in near real-time, the oxygen content in a single crystal silicon ingot being drawn from a pool of molten silicon, the method comprising

withdrawing a sample containing SiO from an atmosphere over the pool of molten silicon,

reacting SiO present in the sample with a reactant to form a detectable reaction product,

determining the amount of reaction product formed, and

correlating the determined amount of reaction product to the oxygen content in the single crystal silicon ingot.

13. A method for controlling, in near real-time, the oxygen content in a single crystal silicon ingot being drawn from a pool of molten silicon under a set of process conditions that affect the oxygen content in the ingot, the method comprising

quantifying the amount of SiO present in an atmosphere over the pool of molten silicon while the silicon ingot is being drawn, and

effecting a change in at least one process condition that affects the oxygen content in the silicon ingot, the sense and magnitude of the change being based on the quantified amount of SiO present in the atmosphere.

14. The method of claim 13 wherein the amount of SiO present in the atmosphere over the pool is quantified by withdrawing a sample containing SiO from the atmosphere, reacting SiO present in the sample with a reactant to form a detectable reaction product, determining the amount of reaction product formed, and correlating the determined amount of reaction product to the amount of SiO present in the atmosphere.

15. A method for controlling, in near real-time, the oxygen content in a single crystal silicon ingot being drawn from a pool of molten silicon under a set of process conditions that affect the oxygen content in the ingot, the method comprising

withdrawing a sample containing SiO from an atmosphere over the pool of molten silicon,

reacting SiO present in the sample with a reactant to form a detectable reaction product,

determining the amount of reaction product formed, and

effecting a change in at least one process condition that affects the oxygen content in the silicon ingot, the sense and magnitude of the change being based on the determined amount of reaction product.

16. The method of claim 15 wherein the change in at least one process condition affecting the oxygen content is effected by communicating the determined amount of reaction product to an automated control system capable of controlling at least one process condition that affects the oxygen content in the ingot and using the control system to effect the change, the sense and magnitude of the change being based on the determined amount of reaction product communicated to the control system.

17. The method of claim 15 wherein the reaction product is a gaseous reaction product which is detectable at ambient temperature.

18. The method of claim 15 wherein the reactant is a carbon-containing material and at least one reaction product is carbon monoxide gas.

19. The method of claim 15 wherein the SiO present in the atmosphere over the molten silicon is reacted with graphite to form carbon monoxide gas and silicon carbide.

20. The method of claim 15 wherein the time elapsed between the step of withdrawing the sample and the step of using the control system to effect a change in at least one process condition that affects the oxygen content is less than about 10 minutes.

21. The method of claim 15 wherein the control system is used to effect a change in a process condition selected from the group consisting of crucible rotation rate, crucible rotation rate modulation, magnetic field strength and magnetic field location.

22. A probe for use in reacting SiO present in a gas sample withdrawn from an atmosphere over a pool of molten silicon with a reactant to form a detectable reaction product, the probe being suitable for use in a system for determining or controlling, in near-real time, the amount of SiO present in the atmosphere over the molten silicon, the amount of oxygen in the molten silicon or the oxygen content of a single crystal silicon ingot drawn from the molten silicon, the probe comprising

a reaction chamber defined in a body of the probe, the probe body being made of a material having a melting point greater than about 1500°

C. and being non-contaminating to the molten silicon when positioned over the pool of molten silicon,

an inlet port in fluid communication with the chamber and adapted for fluid communication with the atmosphere for withdrawing a sample containing SiO from the atmosphere into the chamber, and

an outlet port in fluid communication with the chamber and adapted for fluid communication with a detector for determining the amount of reaction product formed.

23. The SiO probe of claim 22 further comprising a reactant material contained within the chamber, the reactant material being capable of reacting with SiO present in the sample drawn into the chamber through the inlet port to form a detectable reaction product.

24. The SiO probe of claim 23 wherein the reactant material is graphite.

25. The SiO probe of claim 22 further comprising means for supplying a reactant in the chamber to react with SiO to form a reaction product.

26. A system for use in determining or controlling, in near-real time, the amount of SiO present in an atmosphere over a pool of molten silicon contained within a quartz crucible, the amount of oxygen in the molten silicon or the oxygen content of a single crystal silicon ingot drawn from the molten silicon according to the Czochraski method, the system comprising

a SiO reaction probe located within a Czochraski crystal puller in the atmosphere over the pool of molten silicon for reacting SiO present in a gas sample withdrawn from the atmosphere with a reactant to form a detectable reaction product, the probe comprising a reaction chamber defined in a body of the probe, the probe body being made of a material having a melting point greater than about 1500°

C. and being non-contaminating to the molten silicon, an inlet port in fluid communication with the chamber and adapted for fluid communication with the atmosphere for withdrawing a sample containing SiO from the atmosphere into the chamber, an outlet port in fluid communication with the chamber and adapted for fluid communication with a detector for determining the amount of reaction product formed, and a reactant material contained within the chamber, the reactant material being capable of reacting with SiO present in the sample drawn into the chamber through the inlet port to form a detectable reaction product, and

a detector for determining the amount of reaction product formed.

27. The system of claim 26 wherein the reaction product formed is a gas detectable at ambient temperature, the system further comprising a conduit in fluid communication with the probe and adapted for fluid communication with the detector to pass the gaseous reaction product from the probe to the detector, the detector being located outside of the crystal puller.

28. The system of claim 26 further comprising

a controller for receiving a signal generated by the detector, the signal being representative of the determined amount of reaction product and being received by the controller directly from the detector or indirectly therefrom via a microprocessor, the controller generating a control signal based on the signal received, and

a process control element for receiving the control signal, the control signal being received directly from the controller or indirectly therefrom via a microprocessor, the process control element effecting a change in at least one process condition that affects the oxygen content in the silicon ingot, the sense and magnitude of the change being based on the control signal.

29. A method for determining, in near real-time, the oxygen content in a single crystal silicon ingot being drawn from a pool of molten silicon, the method comprising

withdrawing a sample containing SiO from an atmosphere over the pool of molten silicon,

reacting SiO present in the sample with graphite to form gaseous carbon monoxide and SiC,

determining the amount of carbon monoxide formed, and

correlating the determined amount of carbon monoxide to the oxygen content in the single crystal silicon ingot.

30. The method of claim 29 wherein the sample containing SiO is withdrawn into a reaction probe that includes the graphite reactant, the amount of carbon monoxide formed is determined using a quadrupole gas mass analyzer, and the time elapsed between the step of withdrawing the sample and the step of determining the amount of carbon monoxide formed is less than about 1 minute.