Systems and methods for monitoring plating and etching baths

• US 8,475,642 B2
• Filed: 10/04/2007
• Issued: 07/02/2013
• Est. Priority Date: 04/08/2005
• Status: Expired due to Fees

• Current Assignee: Trustees Of Columbia University In The City Of New York (Columbia University)
• Original Assignee: Trustees Of Columbia University In The City Of New York (Columbia University)
• Inventors: West, Alan C., Willey, Mark J., von Gutfeld, Robert J.
• Primary Examiner(s): Noguerola, Alex
• Application Number:
  US11/867,399
• Publication Number:
  US 20080264801A1
• Time in Patent Office: 2,098 Days
• Field of Search: 204/400, 204/409, 204/411, 204/434, 205/775, 205/794, 205/81
• US Class Current: 205/81
• CPC Class Codes: G01N 27/42 Measuring deposition or liberation of materials from an electrolyte; Coulometry, i.e. measuring coulomb-equivalent of material in an electrolyte

Abstract

Methods and systems for monitoring electrolyte bath fluids are provided. The electrolyte bath fluids can be electroplating, electroless plating or etching solutions. The monitoring systems employ microfluidic devices, which have built in microfluidic channels and microfabricated thin-film electrodes. The devices are configured with fluid pumps to control the movement and mixing of test fluids through the microfluidic channels. The microfabricated thin-film electrodes are configured so that the plating or etching bath fluid composition can be characterized by electrochemical measurements. The monitoring methods and system provide faster measurement times, generate minimal waste, and occupy dramatically reduced physical space compared to conventional bath-monitor systems. The monitoring systems and method also provide low-cost system and methods for measuring or monitoring electroless plating bath rates.

Claims

1. A microfluidic system for monitoring the composition of electrolyte bath fluids, the microfluidic system comprising:

(a) a sampling probe comprising;

(i) a chip substrate having a measurement microchannel wherein the measurement microchannel has areal dimensions of less than 0.006 sq. mm; and

(ii) a set of electrodes disposed on an inner surface of the measurement microchannel;

(b) monitoring electronics connected to the set of electrodes, wherein the monitoring electronics and set of electrodes are configured to measure one or more electrochemical properties of a predetermined volume of the bath fluids pumped through the measurement microchannel of the microfluidic system; and

an external fluid pumping arrangement connectable to an inlet disposed at an end of the measurement microchannel.

2. The system of claim 1 wherein electrolyte bath fluid comprises one of a plating solution and an etching solution.

3. The system of claim 1 wherein the electrodes are thin film metallic electrodes.

4. The system of claim 1 wherein the external fluid pumping arrangement comprises a mixing manifold, whereby samples of bath fluids and other fluids can be mixed prior to insertion in the measurement microchannel.

5. The system of claim 1 wherein the chip substrate further comprises a micro mixing manifold connected to the measurement microchannel, whereby samples of bath fluids and other fluids can be mixed prior to insertion in the measurement microchannel.

6. The system of claim 1 wherein the chip substrate further comprises a waste reservoir disposed at an end of the microchannel.

7. The system of claim 1 further comprising a waste reservoir, which is disposed external to the chip substrate and adapted for connection to an end of the microchannel.

8. The system of claim 1 wherein

the chip substrate comprises an array of microchannels including at least one measurement microchannel, each microchannel adapted for connection to the external fluid pumping arrangement.

9. The system of claim 8 wherein the array of microchannels comprises a pair of microchannels in fluid communication with the measurement microchannel, whereby the microfluidic system is configured such that a pair of fluids inserted in the pair of microchannels are mixed prior to flow through the measurement microchannel.

10. The system of claim 8 wherein the array of microchannels comprises a set of a number of microchannels in fluid communication with the measurement microchannel, whereby any combination of a corresponding number of fluids can be inserted in the measurement microchannel.

11. The system of claim 8 comprising a plurality of measurement microchannels.

12. A microfluidic system for determining additive concentrations in an etching bath solution, the microfluidic system comprising:

a) a chip substrate having at least one microchannel and a set of thin film electrodes disposed on an interior surface of the microchannel wherein the at least one microchannel has areal dimensions of less than 0.006 sq. mm;

b) at least one pump connected to the microchannel for flowing fluids through the microchannel;

c) at least one of a potentiostat and a power supply that are electrically connected to the electrodes; and

d) means for measuring an electric current when a voltage is applied to said electrodes, wherein the electric current is function of the composition of fluids flowing through the microchannel of the microfluidic system.

13. The system of claim 12 further comprising means for controlling the temperature of the substrate and the microchannel.

14. The system of claim 12 wherein the fluids flowing through the microchannel comprises one of an etching bath sample, a second fluid, a plating fluid, a reference fluid, an electrode cleaning fluid, an electrode conditioning fluid, a calibration fluid, and any combination thereof.

15. The system of claim 12 wherein the thin film electrodes comprises at least one of a working electrode, a reference electrode and a counter electrode.

16. A method of monitoring the composition of plating or etching bath fluids, the method comprising:

(a) providing a microfluidic sampling probe that comprises;

a chip substrate having a measurement microchannel;

a set of electrodes disposed on an inner surface of the measurement microchannel wherein the measurement microchannel has areal dimensions of less than 0.006 sq. mm; and

an external fluid pumping arrangement connectable to an inlet disposed at an end of the measurement microchannel;

(b) flowing a test sample of the bath fluids through the measurement channel; and

(c) applying and measuring electrical voltages and/or currents at the electrodes to determine one or more electrochemical properties of the test sample of the bath fluids flowing through the measurement microchannel, wherein the determined electrochemical properties correspond to a composition of the bath fluids.

17. The method of claim 16, wherein the test sample of the bath fluids comprises a mixture of the bath fluids and another testing fluid.

18. The method of claim 16, wherein the sampling probe comprises a number of microchannels in fluid communication with the measurement microchannel, and wherein differently prepared test samples are sequentially drawn through the number of microchannels and inserted in the measurement microchannel to determine one or more electrochemical properties of the test sample of the bath fluids flowing through the measurement microchannel.

19. The method of claim 16, wherein the sampling probe comprises an additional measurement channel having disposed therein a reference electrode, wherein flowing a test sample of the bath fluids through the measurement channel further comprises flowing a reference fluid through the additional measurement channel.

20. A method of monitoring an etching bath, the method comprising:

providing a microchannel having areal dimensions of less than 0.006 sq. mm;

controlling a flow rate of a test solution of the etching bath through a microfluidic sampling probe comprising a chip substrate having a microchannel having a working electrode comprising an etchable material and a reference electrode disposed in the microchannel;

applying a voltage between the working and reference electrodes;

measuring and recording the current flowing between the working and counter electrodes; and

measuring the dissolution of the etchable material from the working electrode.

21. The method of claim 20 further comprising heating the test solution flowing through the microchannel.