CN117396640A

CN117396640A - Non-reagent method and process control for measuring and monitoring halogen concentration in electroplating solutions for ferrous ternary metals and alloys thereof

Info

Publication number: CN117396640A
Application number: CN202280019447.6A
Authority: CN
Inventors: E·沙雷特; 柏传楠; V·帕雷克; B·邓
Original assignee: KLA Tencor Corp
Current assignee: KLA Corp
Priority date: 2021-06-10
Filing date: 2022-03-21
Publication date: 2024-01-12

Abstract

Techniques are provided that include methods and apparatus to selectively measure and monitor halide concentrations in process solutions for ferrous ternary metals and alloys thereof. The method includes monitoring for halide ions, for example, based on a first analysis method, such as conductivity; and the main metal concentration results are compensated, such as a second analytical measurement of the concentration of the iron-based ternary metal, such as nickel (Ni). From such measurements, the concentration of certain halide ions may be selectively determined.

Description

Non-reagent method and process control for measuring and monitoring halogen concentration in electroplating solutions for ferrous ternary metals and alloys thereof

Cross reference to related applications

The priority of U.S. provisional patent application Ser. No. 63/209,128, filed on month 6 and 10 of 2021, and Ser. No. 63/220,052, filed on month 7 and 9 of 2021, each of which is incorporated herein by reference in its entirety, is claimed.

Technical Field

The present disclosure relates to analysis and process control of process solutions (e.g., semiconductor process solutions), and to techniques to selectively measure and monitor halogen concentrations in the process solutions for ferrous ternary metals and alloys thereof.

Background

Processing solutions are used in several industries, including the semiconductor industry, to produce products having desired characteristics. The processing solution may include an iron-based ternary metal, such as nickel (Ni) electrodeposit, which is widely used in electronics, semiconductors, automotive, or other industries due to its suitable characteristics. For example, iron-based ternary metals, such as nickel (Ni) electrodeposits, may have magnetic properties that may be varied by varying the ratio of different metal ions in the processing solution. Such ferrous ternary metals, such as nickel (Ni) electrodeposits, may further have high chemical resistivity due to nickel oxide passivation, tunable pressure levels, and high diffusion layer characteristics.

For nickel (Ni) electrodeposits, the passivation characteristics of nickel (Ni) may reduce or prevent, for example, the passivation characteristics of nickel (Ni) in nickel sulfate (NiSO) ₄ ) Use of nickel (Ni) -based anodes in electrolytes. To counteract the passivation feature, a halide ion (e.g., chloride (Cl), bromide (Br), or iodide (I)) may be used to depassivate the nickel (Ni) surface in order to achieve an anodic reaction (e.g., ni+6halogen (-) →ni halogen 6 (4-) +2e (-)). In addition, halogen ions may be consumed at the anode (e.g., 2 halogen (-) →halogen 2+2e (-)) due to side reactions. Thus, the process performance can be consistentThe halogen ions in the process solution are monitored and replenished.

The measurement and monitoring can be performed by titration methods, for example using silver nitrate (AgNO ₃ ). However, the method may require reagents because of the relatively long processing time required for multiple incremental additions of the titrant, the relatively expensive requirement for a titrant comprising a silver (Ag) salt, and safety issues due to the toxicity of silver (Ag). For example, safety issues may arise with respect to the need to extract samples for analysis and to dispose of waste after analysis. Some methods may have the disadvantage of including potentiometric assays with specific ion-selective electrodes, which require a further dilution step for high concentrations. Other methods, such as ion chromatography and capillary electrophoresis, can be relatively expensive, difficult to automate, and have relatively long analysis times.

Disclosure of Invention

It is therefore desirable to provide processes and apparatus to provide economical, safe, efficient, relatively quick and accurate selective measurement and monitoring of halogen concentrations in process solutions for ferrous ternary metals and alloys thereof. The present disclosure addresses these and other needs by providing techniques for selectively measuring and monitoring halide ions, such as chloride (Cl), bromide (Br), or iodide (I), in a process solution, such as a semiconductor process solution.

The present invention provides an exemplary method for determining the concentration of halogen ions in a processing solution comprising a plurality of halogen ions and one or more plated metals. The method includes performing a first analysis method comprising measuring conductivity of the processing solution to provide a first measurement, performing a second analysis method to provide a second measurement, and determining a concentration of halide ions based on the first and second measurements. The halide ions may be selected from a variety of halide ions. The first analytical method may be different from the second analytical method.

In certain embodiments, the second analysis method may include measuring a concentration of one or more electroplated metals.

In certain embodiments, the concentration of one or more electroplated metals may be measured by ultraviolet-visible spectroscopy (UV-Vis).

In certain embodiments, the second analytical method may include measuring absorbance of the processing solution.

In certain embodiments, the plurality of halide ions may include chloride (Cl), bromide (Br), iodide (I), or a combination thereof.

In certain embodiments, the one or more electroplated metals may include ferrous ternary metals and alloys thereof. In certain embodiments, the one or more electroplated metals may include nickel (Ni), cobalt (Co), or iron (Fe).

In certain embodiments, the processing solution may include a blend of one or more salts.

In certain embodiments, the conductivity of the processing solution may be measured at a fixed temperature.

In certain embodiments, the processing solution may be a semiconductor processing solution.

The present invention provides an exemplary method for determining the concentration of halide ions in a process solution comprising a plurality of halide ions and one or more plated metals at a predetermined concentration. The method includes performing a first analysis method including measuring conductivity of the processing solution to provide a first measurement, and determining a concentration of halide ions based on the first measurement and a predetermined concentration of one or more plated metals. The halide ions are selected from a plurality of halide ions.

The present invention provides an exemplary apparatus for determining the concentration of halogen ions in a processing solution comprising a plurality of halogen ions and one or more plated metals. The apparatus comprises: a reservoir adapted to hold a test solution comprising a processing solution, and a sampling mechanism coupled to the reservoir and adapted to provide a predetermined volume of the test solution from the reservoir to one or more sensors coupled to the sampling mechanism. Each of the one or more sensors is adapted to receive at least a portion of a predetermined volume of test solution and is operable to perform one or more analytical methods. The one or more sensors are selected from the group consisting of conductivity sensors and absorbance sensors.

In certain embodiments, the test solution may comprise one or more samples of the processing solution.

In certain embodiments, the test solution may further comprise one or more standard solutions.

In certain embodiments, the sampling mechanism may comprise a syringe, a measuring flask, a measuring cylinder, an automatic syringe, or a metering pump.

In certain embodiments, the one or more analytical methods may include measuring one or more of the conductivity of the test solution, the concentration of the one or more plated metals, or the absorbance of the test solution.

In certain embodiments, the apparatus may further comprise an absorbance meter coupled to the absorbance sensor, a light source, an optical detector, or a combination thereof.

In some embodiments, the apparatus may further comprise a conductivity meter coupled to the conductivity sensor.

In certain embodiments, the one or more sensors may include a conductivity sensor and an absorbance sensor.

In certain embodiments, the processing solution may include a predetermined concentration of one or more plating metals, and the one or more sensors may include a conductivity meter.

In certain embodiments, the one or more electroplated metals may include ferrous ternary metals and alloys thereof.

In certain embodiments, the one or more electroplated metals may include nickel (Ni), cobalt (Co), or iron (Fe).

Drawings

FIG. 1 schematically depicts an exemplary apparatus of the present disclosure for halogen analysis of a process solution;

FIG. 2 depicts the results of measured concentration (g/L) of chloride ions (Cl) relative to the expected concentration (g/L) of chloride ions (Cl) in a solution sample according to example 1; and

FIG. 3 shows the results of the measured concentration (g/L) of chloride ions (Cl) relative to the expected concentration (g/L) of chloride ions (Cl) in a sample of solution according to example 2.

Detailed Description

The present disclosure provides techniques for selectively measuring and monitoring halide ions (e.g., chloride (Cl), bromide (Br), or iodide (I)) in a process solution (e.g., a semiconductor process solution). In certain embodiments, the present disclosure combines the first analysis method with the second analysis method to accurately determine the concentration of the predetermined halide ion in the solution. The first analytical method may be conductivity measurement and the second analytical method may be absorbance measurement. The present disclosure also provides combining the first analysis method with: the concentration of the plated metal in the processing solution, for example, by having a predetermined concentration of the plated metal (e.g., nickel (Ni)); or a second analytical method, which may be a measurement of the concentration in the processing solution. Thus, the halogen ions present in the process solution can be selectively determined, measured and monitored without reagents.

Technical terms used in the present disclosure are generally known to those of skill in the art. As used herein, the phrase "predetermined concentration" refers to a known, target or optimal concentration of a component in a solution.

As used herein, the term "selectively" or "selectively" refers to, for example, monitoring, measuring or determining characteristics of a particular or specific component. For example, the selective measurement of halide ions refers to measuring a specific or predetermined target halide ion of a plurality of halide ions present in a solution.

As used herein, the term "accurate" or "accurately" refers to, for example, a measurement or determination that is relatively close to or approximates the existence of a value or true value, standard or known measurement or value.

As used herein, the term "about" or "approximately" means within an acceptable error range for the particular value being measured by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, "about" may mean a range of up to 20%, up to 10%, up to 5%, and or up to 1% of a given value.

As used herein, the term "coupled" or "operatively coupled" refers to one or more components being combined with each other, and as used herein, is intended to mean either an indirect connection or a direct connection. Thus, if one device couples to a second device, that connection may be through a direct connection, or through an indirect mechanical or other connection via other devices or connections.

The methods of the present disclosure may be applied to various types of solutions, including processing solutions. In certain embodiments, the processing solution may be a semiconductor processing solution.

In certain embodiments, the processing solution may include one or more halide ions. Those skilled in the art will appreciate that a wide variety of halide ions are suitable for use in the present disclosure. In certain embodiments, the one or more halide ions may include chloride (Cl), bromide (Br), iodide (I), or a combination thereof.

In certain embodiments, the processing solution may include one or more electroplated metals. Those skilled in the art will appreciate that a wide variety of electroplated metals are suitable for use in the present disclosure. In certain embodiments, the one or more electroplated metals may include ferrous ternary metals and alloys thereof. The iron-based ternary metal may include nickel (Ni), cobalt (Co), and iron (Fe). In certain embodiments, the one or more electroplated metals may include nickel (Ni).

The methods of the present disclosure provide for a variety of analytical methods and measurement of the process solution, for example, to advantageously selectively measure and monitor halogen ions in the process solution. The concentration of one or more halide ions in the process solution may be monitored by performing a first analysis method, such as by measuring the conductivity of the process solution. In certain aspects, the processing solution may include a blend of one or more salts (e.g., nickel sulfate and nickel chloride or nickel bromide, nickel sulfamate and nickel chloride or nickel bromide, or nickel chloride or nickel bromide and sodium chloride or sodium bromide). Those skilled in the art will appreciate that a wide variety of salts are suitable for use in the present disclosure.

In such an embodiment, measurement of the conductivity of the processing solution will result in the total concentration of the various salts. In order to provide selective measurement and monitoring of halide ions, such as chloride (Cl) or bromide (Br), in the process solution, a second analytical measurement may be performed. In certain embodiments, the second analysis method may include measuring a plating metal concentration of the processing solution, such as one or more ferrous ternary metals and alloys thereof, such as nickel (Ni) concentration. Those skilled in the art will appreciate that a wide variety of methods for measuring the concentration of electroplated metal are suitable for use in this disclosure.

In certain embodiments, the second analytical method may comprise ultraviolet-visible spectroscopy (UV-Vis). Thus, information about the halogen and plated metal concentrations of the process solution can be determined by an economical, safe, efficient, relatively rapid and accurate method. Such measurements may be used to selectively determine the concentration of halide ions in the processing solution. In certain embodiments, a first analysis method (e.g., conductivity measurement of a process solution) may be combined with a second analysis method (e.g., metal concentration measurement of a process solution). In certain aspects, the calculation may be performed by an intermediate process of calculating the metal ion concentration.

For example, in certain embodiments, the halide ion concentration of the processing solution may be determined as follows: [ halogen ] =a1× [ conductivity ] +b1× [ metal ] +c1. Coefficients (a), (b) and (c) can be determined by conductivity and spectral measurements of several standard solutions with known metal and halogen concentrations.

In certain embodiments, the concentration of halide ions in the processing solution may be based on the raw analytical signal. For example, the concentration of one or more halogens in the processing solution may be monitored by performing a first analysis method, such as by measuring the conductivity of the processing solution. A second analytical method may also be performed, for example, the absorbance of the processing solution may be measured. Such measurements may be advantageously used to selectively determine the concentration of halide ions in the processing solution.

For example, in certain embodiments, the halide ion concentration of the processing solution may be determined as follows: [ halogen ] =a2× [ conductivity ] +b2× [ absorbance ] +c2. Coefficients (a), (b) and (c) can be determined by conductivity and spectral measurements of solutions having known metal and halogen concentrations.

Such measurements may be used to selectively determine the concentration of halide ions in the processing solution. In certain embodiments, a first analysis method (e.g., conductivity measurement of a process solution) may be combined with a second analysis method (e.g., metal concentration measurement of a process solution). Additionally, in certain embodiments, a first analysis method (e.g., conductivity measurement of a processing solution) may be combined with a second analysis method (e.g., absorbance measurement of a processing solution).

In certain embodiments, the conductivity of the processing solution may be measured. For example, in certain embodiments, the conductivity of the processing solution may be measured with a conductivity meter. Those skilled in the art will appreciate that a wide variety of methods for measuring conductivity are suitable for use in the present disclosure. In certain embodiments, conductivity measurements may be made at a fixed temperature or temperature compensation. In certain embodiments, the conductivity measurements may be normalized to a particular temperature.

In certain embodiments, the absorbance of the processing solution may be measured. Those skilled in the art will appreciate that a wide variety of methods for measuring absorbance are suitable for use in the present disclosure.

The method of the present disclosure provides for selectively determining the concentration of a predetermined halogen in a process solution. In certain embodiments, the method may include providing a processing solution. The processing solution may include a plurality of halogens and an electroplated metal. In certain embodiments, a first analysis of the processing solution may be performed to provide a first measurement. The first analysis method may include measuring the conductivity of the processing solution. In certain embodiments, the method may include performing a second analysis method on the processing solution to provide a second measurement. The second analysis method may include measuring a concentration of the electroplated metal. The method may further include determining a concentration of a predetermined halogen of the plurality of halogens based on the first and second measurements.

The method of the present disclosure provides for selectively determining the concentration of a predetermined halogen in a process solution. In certain embodiments, the method may include providing a processing solution. The processing solution may include a plurality of halogens and an electroplated metal. In certain embodiments, a first analysis of the processing solution may be performed to provide a first measurement. The first analysis method may include measuring the conductivity of the processing solution. In certain embodiments, the method may include performing a second analysis of the processing solution to provide a second measurement. The second analytical method may comprise measuring the absorbance of the processing solution. The method may further include determining a concentration of a predetermined halogen of the plurality of halogens based on the first and second measurements.

Fig. 1 schematically depicts an exemplary apparatus of the present disclosure. In certain aspects, exemplary apparatus may be directed to measuring and monitoring halogen concentrations in process solutions, for example, for ferrous ternary metals and alloys thereof. The apparatus may include, for example, one or more sensors operable to perform one or more analysis methods. In certain embodiments, the one or more sensors may include a conductivity sensor 310, an optical sensor 320 (e.g., an absorbance sensor), or a combination thereof. In certain embodiments, the apparatus may further comprise conductivity meter 311, absorbance meter 321, light source 322, optical detector 323, or a combination thereof.

In some embodiments, conductivity meter 311 may be connected to conductivity sensor 310. In certain embodiments, an absorbance meter 321, a light source 322, and/or an optical detector 323 may be connected to the optical sensor 320. In certain embodiments, the light source 322 and/or the optical detector 323 can be connected to an absorbance meter 321. The apparatus may further comprise a selector device 100, a sample introducer device 200, or a combination thereof. In certain embodiments, the apparatus may further comprise a selector device 100 and a sample introducer device 200.

In certain embodiments, the selector device 100 may comprise a solution, such as one or more standard solutions, one or more process samples, or a combination thereof. The selector device 100 may be coupled to a sample introducer device 200. In certain embodiments, the sample introducer device 200 can provide a predetermined volume of solution contained in the selector device 100 to one or more sensors. In certain embodiments, the sample introducer device 200 can provide about 5mL to about 45mL, about 5mL to about 40mL, about 5mL to about 35mL, about 5mL to about 30mL, about 5mL to about 25mL, about 5mL to about 20mL, about 5mL to about 10mL, or about 10mL to about 30mL of solution to one or more sensors. For example, the sample introducer device may provide about 5mL, about 10mL, about 15mL, about 20mL, about 25mL, about 30mL, about 35mL, about 40mL, or about 45mL of solution to the one or more sensors. Suitable sample introducer devices 200 for providing a predetermined volume of solution contained in the selector device 100 may include, for example, a syringe or a measuring cylinder for manual delivery, or an automatic syringe or metering pump with associated tubing and wiring, for example, for automatic delivery. Delivery of the predetermined volume of solution may also be performed up to a default level detected by the automatic level sensor. The selector device 100 may be a sump or reservoir. To automatically deliver a solution, the sample introducer device 200 may be connected to, for example, a tubing laid between the selector device 100 and one or more sensors (e.g., conductivity sensor 310, optical sensor 320, or a combination thereof).

In certain aspects, a first portion of the predetermined volume of solution may be delivered to a first sensor, such as conductivity sensor 310, and a second portion of the predetermined volume of solution may be delivered to a second sensor, such as optical sensor 320. In certain embodiments, a predetermined volume of solution may be delivered to one or more sensors arranged in series in any order, such as a first sensor and then a second sensor. In certain embodiments, the predetermined solution portions may be delivered to one or more sensors arranged in combination with each other.

The one or more sensors are operable to perform one or more analysis methods. In certain embodiments, one or more analytical methods may include measuring conductivity (e.g., of a solution), measuring concentration (e.g., of plated metal in a solution), measuring absorbance (e.g., of a solution), or a combination thereof. The one or more sensors may include conductivity sensors 310, optical sensors 320, or a combination thereof. In certain embodiments, the device may include a conductivity sensor 310 and an optical sensor 320. Conductivity sensor 310 may measure, for example, the conductivity of a solution. The optical sensor 320 may measure, for example, the absorbance of a solution. In certain aspects, the apparatus may include a device or sensor for measuring, for example, the concentration of the electroplated metal in the solution. One or more sensors may be connected in parallel, connected in series in any order, or combined. For example, and not by way of limitation, in certain embodiments, an apparatus may include a conductivity sensor 310 and an optical sensor 320 in parallel, in series, or in any order. In some embodiments, the conductivity sensor 310 and the optical sensor 320 may be connected in parallel.

In some embodiments, the apparatus may further comprise conductivity meter 311. Conductivity meter 311 may be operatively coupled to conductivity sensor 310. In some embodiments, conductivity meter 311 may be coupled to conductivity sensor 310 by a cable (e.g., an electrical cable). The apparatus may further comprise an absorbance meter 321, such as a spectrophotometer. In certain embodiments, the absorbance meter 321 may be operatively coupled to the optical sensor 320. In certain aspects, the apparatus may further comprise a light source 322, an optical detector 323, or a combination thereof. In some embodiments, the apparatus may include a light source 322 and an optical detector 323. The light source 322 may be operatively coupled to the absorbance meter 321 and/or the optical sensor 320, for example, by an optical fiber. The optical detector 323 can be operatively coupled to the absorbance meter 321 and/or the optical sensor 320, for example, by an optical fiber.

After the analytical measurement of the solution is completed, the solution may be returned to the process via flow or discarded as waste.

Examples

The subject matter of the present disclosure will be better understood with reference to the following examples. The following examples are merely illustrative of the presently disclosed subject matter and should not be construed as limiting the scope of the subject matter in any way.

Example 1: selective measurement of halide ions using conductivity measurements and predetermined nickel (Ni) concentrations

This example provides for the selective measurement of halide ions, such as chloride ions (Cl), in a process solution having a predetermined concentration of nickel (Ni) using conductivity measurements and a predetermined concentration of electroplated metal. The conductivity of six (6) samples of the processing solution including the electroplated metal (i.e., nickel (Ni)) and the halide ions (i.e., chloride ions (Cl)) was measured at a predetermined nickel (Ni) concentration. The conductivity measurements for each sample are provided in table 1 below.

Table 1.

Sample of	Cl (g/L) is expected	Ni (g/L) is expected	Conductivity (mS/cm)
				1	78.0	56.16	103.7
2	130.0	93.6	129.9
				3	146.3	105.3	133.3
4	86.9	56.16	113.2
				5	137.4	105.3	128.1
6	132.6	56.16	150.1

The concentration of halide chloride (Cl) in each of the processing solution samples was selectively determined based on the conductivity measurements provided in table 1 and the predetermined concentration of nickel (Ni) plating metal.

The results are provided in table 2 and fig. 2.

Table 2.

Sample of	Cl (g/L) is expected	Measurement Cl (g/L)	Accuracy (%)
				1	78	76.66	-1.7
2	130	132.34	1.8
				3	146.25	144.01	-1.5
4	86.89	88.03	1.3
				5	137.36	137.79	0.3
6	132.59	132.21	-0.3
				Average accuracy			1.15

Calculating parameters

The following calculation parameters (equations 1 and 3) are used to selectively determine the measured concentration of halide ions (i.e., chloride ions (Cl)) in the process solution.

[ halogen ] =a1× [ conductivity ] +b1× [ metal ] +c1 (1)

Table 3.

Calculating parameters	Value of
		A1:g×cm/(lx mS)	1.1972
B1	0.6495
		C1:g/l	83.965

Example 2: selective measurement of halide ions using conductivity and absorbance measurements

This example provides for the selective measurement of halide ions, such as chloride (Cl), in a process solution using conductivity and absorbance measurements. The conductivity and absorbance of five (5) samples of the processing solution including electroplated metal (i.e., nickel (Ni)) and halide ions (i.e., chloride ions (Cl)) were measured. The expected nickel (Ni) and chloride (Cl) concentrations for each sample are provided in table 4 below.

Table 4.

Sample of	Ni (g/L) is expected	Cl (g/L) is expected
			7	56	78
8	93	130
			9	105	147
10	117	162.5
			11	56	147

The conductivity and absorbance measurements for each sample are provided in table 5 below. The concentration of halide chloride (Cl) in each processing solution sample was selectively determined as shown in table 5 and fig. 3 based on the conductivity and absorbance measurements provided in table 5.

Table 5.

Sample of	Absorbance of light	Conductivity (mS/cm)	Measurement Ni (g/L)	Measurement Cl (g/L)	Cl accuracy (%)
						7	0.396	157.5	55.41	76.70	-1.7
8	0.713	197.3	92.15	134.49	3.5
						9	0.810	202.1	103.39	146.46	-0.4
10	0.942	205	118.68	159.93	-1.6
						11	0.413	246	57.38	146.65	-0.2
Average accuracy					1.48

Calculating parameters

The following calculated parameters (equation 2 and table 6) were used to selectively determine the measured concentrations of various alkaline chemicals in the solution blend.

[ halogen ] =a2× [ conductivity ] +b2× [ absorbance ] +c2 (2)

Table 6.

Calculating parameters	Value of
		A2:g×cm/(lx mS)	0.774
B2:g/L	85.1
		C2:g/L	-78.9

Example 3: selective measurement-qualitative analysis of halogen ions (chloride ions)

The methods disclosed herein are evaluated by qualitative analysis. 30 continuous runs were performed and 3 runs per day were continued for five (5) days. The results of the 30-point continuous operation test are provided in table 7 below.

Table 7.

The results of the 3-point-per-day test for five (5) days are provided in table 8 below.

Table 8.

***

The description herein is merely illustrative of the principles of the disclosed subject matter. Various modifications and alterations to the described embodiments will be apparent to those skilled in the art in view of the teachings herein. Accordingly, the disclosure herein is intended to be illustrative, but not limiting, of the scope of the disclosed subject matter. Furthermore, the principles of the disclosed subject matter may be implemented in various configurations and are not intended to be in any way limited to the specific embodiments presented herein.

In addition to the various embodiments depicted and claimed, the disclosed subject matter is also directed to other embodiments having other combinations of features disclosed and claimed herein. Thus, the specific features presented herein may be combined with each other in other ways within the scope of the disclosed subject matter such that the disclosed subject matter includes any suitable combination of features disclosed herein. The foregoing descriptions of specific embodiments of the disclosed subject matter have been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosed subject matter to those embodiments disclosed.

It will be apparent to those skilled in the art that various modifications and variations can be made in the systems and methods of the disclosed subject matter without departing from the spirit or scope of the disclosed subject matter. Accordingly, it is intended that the disclosed subject matter encompass modifications and variations that are within the scope of the appended claims and their equivalents.

Claims

1. A method for determining the concentration of halide ions in a processing solution comprising a plurality of halide ions and one or more plated metals, comprising:

performing a first analysis method comprising measuring conductivity of the processing solution to provide a first measurement value;

performing a second analysis method to provide a second measurement value; and

determining the concentration of the halide ions based on the first measurement and the second measurement,

wherein the halide ion is selected from a plurality of halide ions, and

wherein the first analytical method is different from the second analytical method.

2. The method of claim 1, wherein the second analysis method comprises measuring a concentration of the one or more electroplated metals.

3. The method of claim 2, wherein the concentration of the one or more electroplated metals is measured by ultraviolet-visible spectroscopy (UV-Vis).

4. The method of claim 1, wherein the second analytical method comprises measuring absorbance of the processing solution.

5. The method of claim 1, wherein the plurality of halide ions comprises chloride (Cl), bromide (Br), iodide (I), or a combination thereof.

6. The method of claim 1, wherein the one or more electroplated metals comprise ferrous ternary metals and alloys thereof.

7. The method of claim 6, wherein the one or more electroplated metals comprise nickel (Ni), cobalt (Co), or iron (Fe).

8. The method of claim 6, wherein the processing solution comprises a blend of one or more salts.

9. The method of claim 1, wherein the conductivity of the processing solution is measured at a fixed temperature.

10. The method of claim 1, wherein the processing solution is a semiconductor processing solution.

11. A method for determining the concentration of halogen ions in a processing solution comprising a plurality of halogen ions and a predetermined concentration of one or more electroplated metals, comprising:

performing a first analysis method comprising measuring conductivity of the processing solution to provide a first measurement value; and

determining a concentration of the halogen ions based on the first measurement and the predetermined concentration of the one or more plated metals,

wherein the halide ion is selected from a plurality of halide ions.

12. The method of claim 11, wherein the plurality of halide ions comprises chloride (Cl), bromide (Br), iodide (I), or a combination thereof.

13. The method of claim 11, wherein the one or more electroplated metals comprise ferrous ternary metals and alloys thereof.

14. The method of claim 13, wherein the one or more electroplated metals comprise nickel (Ni), cobalt (Co), or iron (Fe).

15. The method of claim 13, wherein the processing solution comprises a blend of one or more salts.

16. The method of claim 11, wherein the conductivity of the processing solution is measured at a fixed temperature.

17. The method of claim 11, wherein the processing solution is a semiconductor processing solution.

18. An apparatus for determining the concentration of halide ions in a processing solution comprising a plurality of halide ions and one or more plated metals, comprising:

a reservoir adapted to hold a test solution comprising the processing solution;

a sampling mechanism coupled to the reservoir and adapted to provide a predetermined volume of the test solution from the reservoir to one or more sensors coupled to the sampling mechanism;

wherein each of the one or more sensors is adapted to receive at least a portion of the predetermined volume of the test solution and is operative to perform one or more analytical methods;

wherein the one or more sensors are selected from the group consisting of conductivity sensors and absorbance sensors.

19. The apparatus of claim 18, wherein the test solution comprises one or more samples of the processing solution.

20. The apparatus of claim 18, wherein the test solution further comprises one or more standard solutions.

21. The apparatus of claim 18, wherein the sampling mechanism comprises a syringe, a measuring flask, a measuring cylinder, an auto-injector, or a metering pump.

22. The apparatus of claim 18, wherein the one or more analysis methods comprise measuring one or more of conductivity of the test solution, concentration of the one or more plated metals, or absorbance of the test solution.

23. The apparatus of claim 18, further comprising an absorbance meter, a light source, an optical detector, or a combination thereof coupled to the absorbance sensor.

24. The apparatus of claim 18, further comprising a conductivity meter coupled to the conductivity sensor.

25. The apparatus of claim 18, wherein the one or more sensors include the conductivity sensor and the absorbance sensor.

26. The apparatus of claim 18, wherein the processing solution comprises a predetermined concentration of the one or more plated metals and the one or more sensors comprise the conductivity meter.

27. The apparatus of claim 18, wherein the one or more electroplated metals comprise ferrous ternary metals and alloys thereof.

28. The apparatus of claim 27, wherein the one or more electroplated metals comprise nickel (Ni), cobalt (Co), or iron (Fe).