Concentration measurement and control of hydrogen peroxide and acid/base component in a semiconductor bath

• US 5,439,569 A
• Filed: 07/20/1994
• Issued: 08/08/1995
• Est. Priority Date: 02/12/1993
• Status: Expired due to Fees

• Current Assignee: Sematech, Inc.
• Original Assignee: Sematech, Inc.
• Inventors: Carpio, Ronald A.
• Primary Examiner(s): Niebling, John
• Assistant Examiner(s): Bell, Bruce F.
• Application Number:
  US08/277,688
• Time in Patent Office: 384 Days
• Field of Search: 204/409, 204/406, 204/434, 204/412, 204/153.12, 204/153.1, 422/68.1, 422/81, 422/82.01, 422/82.02
• US Class Current: 134/1.3
• CPC Class Codes: G05D 21/02 characterised by the use of electric means

Abstract

A feedback control system for providing automated control of multi-component chemical concentrations in a hydrogen peroxide/ammonia (SC-1) aqueous bath or in a hydrogen peroxide/hydrochloric (SC-2) aqueous bath used for semiconductor processing. A sample from the liquid bath is routed to two sensors. Three separate schemes for determining concentrations of the two chemicals in the bath are provided by the selection of one of three separate pairs of sensors. A processor is used to monitor and control the chemical makeup of the bath.

Claims

1. A method for monitoring concentration levels of a first chemical specie, which is hydrogen peroxide (H₂ O₂), and a second chemical specie, which is either an acid or a base, in a multi-component aqueous bath utilized in semiconductor processing, in order to provide feedback to control an amount of said H₂ O₂ and said second chemical specie present in said bath comprising the steps of:

sampling said bath to obtain a solution sample;

performing a potentiometric detection of said sample to measure concentration of said second chemical specie in said sample;

performing an amperometric detection of said sample to measure concentration of said H₂ O₂ in said sample;

analyzing concentration measurements of said sample to determine if said H₂ O₂ and said chemical specie in said bath are within set concentration levels;

introducing additional H₂ O₂, said second chemical specie, other compensating chemical or diluting agent into said bath to adjust said bath to within said set concentration levels, if adjustment is needed;

wherein said bath is monitored and compensated to maintain said set concentration levels of H₂ O₂ and said second chemical specie in said bath.

2. The method of claim 1 wherein said second chemical specie is ammonium hydroxide (NH₄ OH).

3. The method of claim 1 wherein said bath is comprised of a H₂ O₂ --NH₄ OH--H₂ O solution which is utilized for wafer cleaning.

4. A method for monitoring concentration levels of a first chemical specie, which is hydrogen peroxide (H₂ O₂), and a second chemical specie, which is either an acid or a base, in a multi-component aqueous bath utilized in semiconductor processing, in order to provide feedback to control an amount of said H₂ O₂ and said second chemical specie present in said bath comprising the steps of:

sampling said bath to obtain a solution sample;

performing a potentiometric detection of said sample to measure concentration of said second chemical specie in said sample;

performing a conductivity detection of said sample to measure total ionic conductivity in said sample;

calculating a difference of ionic conductivity attributable to measured concentration of said second chemical by said potentiometric detection from said total ionic conductivity to determine concentration of said H₂ O₂ in said sample;

analyzing concentration measurements of said sample to determine if said H₂ O₂ and said second chemical specie in said bath are within set concentration levels;

introducing additional H₂ O₂, said second chemical specie, other compensating chemical or diluting agent into said bath to adjust said bath to within said set concentration levels, if adjustment is needed;

wherein said bath is monitored and compensated to maintain said set concentration levels of H₂ O₂ and said second chemical specie in said bath.

5. The method of claim 4 wherein said second chemical specie is ammonium hydroxide (NH₄ OH).

6. The method of claim 4 wherein said bath is comprised of a H₂ O₂ --NH₄ OH--H₂ O solution which is utilized for wafer cleaning.

7. A method for monitoring concentration levels of a first chemical specie, which is hydrogen peroxide (H₂ O₂), and a second chemical specie, which is either an acid or a base, in a multi-component aqueous bath utilized in semiconductor processing, in order to provide feedback to control an amount of said H₂ O₂ and said second chemical specie present in said bath comprising the steps of:

sampling said bath to obtain a solution sample;

performing an amperometric detection of said sample to measure concentration of said H₂ O₂ in said sample;

performing a conductivity detection of said sample to measure total ionic conductivity in said solution;

calculating a difference of ionic conductivity attributable to measured concentration of said H₂ O₂ by said amperometric detection from said total ionic conductivity to determine concentration of said H₂ O₂ in said sample;

analyzing concentration measurements of said sample to determine if said H₂ O₂ and said second chemical specie in said bath are within set concentration levels;

introducing additional H₂ O₂, said second chemical specie, other compensating chemical or diluting agent into said bath to adjust said bath to within said set concentration levels, if adjustment is needed;

wherein said bath is monitored and compensated to maintain said set concentration levels of H₂ O₂ and said second chemical specie in said bath.

8. The method of claim 7 wherein said second chemical specie is ammonium hydroxide (NH₄ OH).

9. The method of claim 7 wherein said bath is comprised of a H₂ O--NH₄ OH--H₂ O solution which is utilized for wafer cleaning.

10. An apparatus for monitoring concentration levels of a first chemical specie, which is hydrogen peroxide (H₂ O₂) and a second chemical specie, which is either an acid or a base, present in a multi-component aqueous bath utilized in semiconductor processing, in order to provide feedback and control to adjust an amount of said H₂ O₂ and said second chemical specie present in said bath comprising:

a sampling device for obtaining a sample of said solution from said bath and introducing said sample into a flow path;

a potentiometric sensor coupled to said flow path for receiving said sample and for performing a potentiometric detection of said sample to measure concentration of said second chemical specie in said sample;

an amperometric sensor coupled to said flow path for receiving said sample and for performing an amperometric detection of said sample to measure concentration of H₂ O₂ in said sample;

a processor coupled to said potentiometric and amperometric sensors for obtaining data pertaining to said concentration of said second chemical specie and H₂ O₂, processing said data to determine if said concentration of said second chemical specie and H₂ O₂ is within set concentration levels and introducing compensating chemical or diluting agent into said bath to adjust said bath to within said set concentration levels for said bath;

wherein said bath is monitored and compensated by said processor to maintain control of said set concentration levels of H₂ O₂ and said second chemical specie.

11. The apparatus of claim 10 further including a first pump and a second pump, each coupled to said bath and said processor, wherein said first pump is used to pump H₂ O₂ into said bath under control of said processor and said second pump is used to pump said second chemical specie into said bath under control of said processor, and wherein said second chemical specie is ammonium hydroxide (NH₄ OH).

12. The apparatus of claim 10 further including a first pump and a second pump, each coupled to said bath and said processor, wherein said first pump is used to pump H₂ O₂ into said bath under control of said processor and said second pump is used to pump said second chemical specie into said bath under control of said processor, and wherein said bath is comprised of a H₂ O₂ --NH₄ OH--H₂ O solution which is utilized for wafer cleaning.

13. An apparatus for monitoring concentration levels of a first chemical specie, which is hydrogen peroxide (H₂ O₂) and a second chemical specie, which is either an acid or a base, present in a multi-component aqueous bath utilized in semiconductor processing, in order to provide feedback and control to adjust an amount of said H₂ O₂ and said second chemical specie present in said bath comprising:

a sampling device for obtaining a sample of said solution from said bath and introducing said sample into a flow path;

a potentiometric sensor coupled to said flow path for receiving said sample and for performing a potentiometric detection of said sample to measure concentration of said second chemical specie in said sample;

a conductivity sensor coupled to said flow path for receiving said sample and for performing a conductivity detection of said sample to measure total ionic conductivity in said sample;

a processor coupled to said potentiometric and conductivity sensors for obtaining data pertaining to said concentration of said second chemical specie and total ionic conductivity, computing a difference of ionic conductivity attributable to measured concentration of said second chemical by said potentiometric detection from said total ionic conductivity to determine concentration of said H₂ O₂ in said sample, processing said data to determine if said concentration of said second chemical specie and H₂ O₂ is within set concentration levels, and introducing compensating chemical or diluting agent into said bath to adjust said bath to within said set concentration levels for said bath;

wherein said bath is monitored and compensated by said processor to maintain control of said set concentration levels of H₂ O₂ and said second chemical specie.

14. The apparatus of claim 13 further including a first pump and a second pump, each coupled to said bath and said processor, wherein said first pump is used to pump H₂ O₂ into said bath under control of said processor and said second pump is used to pump said second chemical specie into said bath under control of said processor, and wherein said second chemical specie is ammonium hydroxide (NH₄ OH).

15. The apparatus of claim 13 further including a first pump and a second pump, each coupled to said bath and said processor, wherein said first pump is used to pump H₂ O₂ into said bath under control of said processor and said second pump is used to pump said second chemical specie into said bath under control of said processor, and wherein said bath is comprised of a H₂ O₂ --NH₄ OH--H₂ O solution which is utilized for wafer cleaning.

16. An apparatus for monitoring concentration levels of a first chemical specie, which is hydrogen peroxide (H₂ O₂) and a second chemical specie, which is either an acid or a base, present in a multi-component aqueous bath utilized in semiconductor processing, in order to provide feedback and control to adjust an amount of said H₂ O₂ and said second chemical specie present in said bath comprising:

a sampling device for obtaining a sample of said solution from said bath and introducing said sample into a flow path;

an amperometric sensor coupled to said flow path for receiving said sample and for performing an amperometric detection of said sample to measure concentration of said H₂ O₂ in said sample;

a conductivity sensor coupled to said flow path for receiving said sample and for performing a conductivity detection of said sample to measure total ionic conductivity in said sample;

a processor coupled to said amperometric and conductivity sensors for obtaining data pertaining to said concentration of said H₂ O₂ and total ionic conductivity, computing a difference of ionic conductivity attributable to measured concentration of said H₂ O₂ by said amperometric detection from said total ionic conductivity to determine concentration of said second chemical specie in said sample, processing said data to determine if said concentration of said second chemical specie and H₂ O₂ is within set concentration levels, and introducing compensating chemical or diluting agent into said bath to adjust said bath to within said set concentration levels for said bath;

wherein said bath is monitored and compensated by said processor to maintain control of said set concentration levels of H₂ O₂ and said second chemical specie.

17. The apparatus of claim 16 further including a first pump and a second pump, each coupled to said bath and said processor, wherein said first pump is used to pump H₂ O₂ into said bath under control of said processor and said second pump is used to pump said second chemical specie into said bath under control of said processor, and wherein said second chemical specie is ammonium hydroxide (NH₄ OH).

18. The apparatus of claim 16 further including a first pump and a second pump, each coupled to said bath and said processor, wherein said first pump is used to pump H₂ O₂ into said bath under control of said processor and said second pump is used to pump said second chemical specie into said bath under control of said processor, and wherein said bath is comprised of a H₂ O₂ --NH₄ OH--H₂ O solution which is utilized for wafer cleaning.

19. The apparatus of claim 16 further including a first pump and a second pump, each coupled to said bath and said processor, wherein said first pump is used to pump H₂ O₂ into said bath under control of said processor and said second pump is used to pump said second chemical specie into said bath under control of said processor, and wherein said second chemical specie is hydrochloric acid (HCl).