Multi-sensor gas sampling detection system for radical gases and short-lived molecules and method of use - Patents.com

Abstract

To provide a multi-sensor gas sampling detection system and a method for detecting and measuring a radical in a radical gas stream.SOLUTION: In a processing system 10, an analysis circuit 66 reacts at least one reagent with a radical within defined volume of a radical gas stream, thereby forming at least one chemical species within at least one compound stream. At least one sensor module 36 within the analysis circuit 66 measures concentration of a chemical species within the compound stream, and one or more flow measurement modules 40 are in fluid communication with a sensor module 36 to measure the volume of at least one of the compound stream and the radical gas stream during use.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. patent application Ser. No. 62 / 593,721, filed December 1, 2017, and entitled "Multi-Sensor Gas Sampling Detection System for Radical Gases and Short-Lived Molecules and Method of Use," and U.S. patent application Ser. No. 62 / 646,867, filed March 22, 2018, and entitled "Multi-Sensor Gas Sampling Detection System for Radical Gases and Short-Lived Molecules and Method of Use," the contents of both of which are hereby incorporated by reference in their entireties. [Background technology]

[0002] Electronic devices and systems are being integrated into an ever-increasing number of devices, systems, and applications. As a result, the market demand for low-cost integrated circuits with high complexity and small scale continues to grow. Various microfabrication processes, such as radical-based semiconductor wafer processing, have been developed to address the scaling issues. To cost-effectively design and manufacture high-performance integrated circuits, the parameters of radical-based semiconductor wafer fabrication processes need to be carefully controlled.

[0003] Currently, several radical-based semiconductor wafer processing methods are in use. The radical gases used in processing are H, O, N, F, Cl, Br, NH, NH 2 , N.F., C.H., C.H. 2Radical species include atoms not normally present in gases such as COFs, excited molecules, and many short-lived molecules. Currently available radical-based semiconductor wafer processes have proven somewhat useful in the past, but several drawbacks have been identified. For example, radical species generated during wafer processing are short-lived, thereby making accurate measurement and analysis difficult. As a result, rather than relying on quantitative analysis, currently available radical-based semiconductor wafer fabrication methods involve precise recipes and virtual metrology to achieve the desired wafer architecture. Any variation in the recipe and / or control process can greatly affect production yield. In addition to this, the highly reactive radical species generated during wafer processing have a tendency to rapidly degrade analytical devices and sensors, optical windows and components, and other systems or devices positioned within the radical stream and processing chamber. Summary of the Invention [Problem to be solved by the invention]

[0004] In view of the above, therefore, there is a continuing need for a multi-sensor gas sampling and detection system useful in radical-based semiconductor wafer processing. [Means for solving the problem]

[0005] The present application relates to a multi-sensor gas sampling detection system and method for detecting and measuring atomic radicals, molecular radicals, and / or short-lived molecules in a radical gas stream or similar gas stream. The detection and measurement system may include at least one radical gas generator in communication with at least one gas source. The radical gas generator may be configured to generate at least one radical gas stream that may be used in a process chamber. The process chamber is thus in fluid communication with the radical gas generator. At least one analytical circuit may be in fluid communication with the radical gas, and the radical gas generator may be used in a detection and measurement system. The analytical circuit may be configured to receive a defined volume and / or flow rate of the radical gas stream. In one embodiment, the analytical circuit may be configured to react at least one reagent with the radical gas in the defined volume of the radical gas stream. The reaction produces at least one compound stream (or reaction product) from the radical gas and at least one reagent that may be in the form of a chemical species, charged particle, photon emission, or thermal energy emission that may be measured by at least one sensor module in the analytical circuit. One or more flow measurement modules may be in fluid communication with the sensor module. During use, the flow measurement modules may be configured to measure a volume and / or flow rate of at least one of the compound stream and the radical gas stream. Based on the measured amount of reaction product and the volume and / or flow rate of the compound stream and the radical gas stream, a concentration or amount of radical gas in the radical gas stream may be obtained.

[0006] The present application further discloses a method for measuring radical gases in a radical gas stream. More specifically, the method for measuring radicals in a gas stream includes providing at least one radical gas stream having radicals therein. The sampling gas stream can be generated by directing a defined volume and / or flow rate of the radical gas stream to at least one sampling module. At least one reagent can be combined with the radicals in the sampling gas stream to form at least one compound stream having at least one chemical species therein. The concentration of the chemical species in the compound stream can then be measured using at least one sensor module. Furthermore, the remaining volume of the radical gas stream can be directed into at least one processing chamber. The flow of the radical gas stream and / or the compound gas stream can be measured using at least one flow measurement module in fluid communication with the sensor module. Finally, the concentration of radicals in the processing chamber can be calculated by comparing the ratio of the concentration of the chemical species in the compound stream per defined volume of the radical gas stream forming the sampling gas stream to the remaining volume of the radical gas stream.

[0007] In another embodiment, the present application discloses a method for measuring radicals in a radical gas stream. The method includes providing at least one radical gas stream having radicals therein. The at least one upstream gas stream can be formed by directing a defined volume of the radical gas stream to at least one upstream sampling module, while simultaneously directing a remaining volume of the radical gas stream into at least one processing chamber. The at least one chamber sampling gas stream can be formed by directing a defined volume of the radical gas stream from the processing chamber to at least one chamber sampling module, while simultaneously a volume of the radical gas stream remaining in the processing chamber is exhausted from the processing chamber, thereby forming at least one exhaust gas stream. The at least one exhaust sampling gas stream can be formed by directing a defined volume and / or flow rate of the exhaust gas stream to at least one exhaust sampling module. Thereafter, at least one reagent can react with the radicals in the radical gas stream in at least one of the upstream sampling module, the chamber sampling module, and the exhaust sampling module to form at least one of an upstream compound stream, a chamber compound stream, and an exhaust compound stream, at least one of which has at least one chemical species therein. The amount of the chemical species in at least one of the upstream compound stream, the chamber compound stream, and the exhaust compound stream can be measured, and the concentration of the radicals in the process chamber can be calculated by comparing the ratio of the concentration of the chemical species in at least one of the upstream compound stream, the chamber compound stream, and the exhaust compound stream for a defined volume of the radical gas stream forming the upstream sampling gas stream, the chamber sampling gas stream, and the exhaust sampling gas stream to the remaining volume of the radical gas stream.

[0008] In addition, the present application discloses a multi-sensor gas detection system for use in a wafer processing system. The wafer processing system includes an upstream sampling module in fluid communication with a radical gas stream emitted from at least one of the radical gas sources. The upstream sampling module can be configured to receive a controlled volume and / or flow rate of the radical gas stream from the radical gas source. At least one reagent reacts with the controlled volume and / or flow rate of the radical gas stream to generate an upstream compound stream. Furthermore, at least one chamber sampling module can be in fluid communication with at least one radical gas stream present in at least one processing chamber. The chamber sampling module can be configured to receive a controlled volume and / or flow rate of the radical gas stream and react the controlled volume and / or flow rate of the radical gas stream with the at least one reagent to generate a chamber compound stream. In addition, at least one exhaust sampling module can be in fluid communication with a radical gas stream exhausted from the processing chamber. The exhaust sampling module may be configured to receive a controlled volume and / or flow rate of the radical gas stream and react the controlled volume and / or flow rate of the radical gas stream with at least one reagent to generate an exhaust compound stream. The at least one sensor module may be in communication with at least one of the upstream sampling module, the chamber sampling module, and the exhaust sampling module. The sensor module may be configured to measure a concentration of at least one of the upstream compound stream, the chamber compound stream, and the exhaust compound stream. The at least one flow module may be in communication with at least one of the upstream sampling module, the chamber sampling module, the exhaust sampling module, and the sensor module. The flow module may be configured to control a flow rate of at least one of the upstream compound stream, the chamber compound stream, and the exhaust compound stream.

[0009] The present application also discloses a sampling reaction module for use in a reactive gas processing system. The sampling reaction module can include at least one analytical accessory having an analytical accessory body. The analytical accessory body defines at least one fluid channel therein. At least one fluid inlet port and a fluid outlet port can be formed in the analytical accessory body. The inlet port and the outlet port can be in fluid communication with the fluid channel formed in the analytical accessory body. At least one coupling body extends from the analytical accessory body. In one embodiment, the coupling body includes at least one coupling passage formed therein. At least one sampling tube traversing through the analytical accessory body can be positioned within the coupling passage of the coupling body. Additionally, at least one module body defining at least one vacuum passage configured to receive the at least one analytical accessory body thereon can be included in the sampling reaction module. The module body can have at least one sampling tube receiver formed therein, such that the sampling tube receiver can be in fluid communication with the vacuum passage.

[0010] Finally, the present application further discloses a calorimetry system. More specifically, the calorimetry system includes at least one reactant gas conduit defining at least one gas passage therein. In use, the gas passage is configured to flow at least one reactant gas therethrough. Furthermore, at least a first sensor body can be positioned within the gas passage of the reactant gas conduit. In one embodiment, the sensor body is configured to measure a temperature of the reactant gas flowed through the gas passage. In addition, at least one sensor device can be in communication with the sensor body. In use, the sensor device can be configured to receive temperature data associated with the reactant gas flow from the sensor body. At least one processor can be in communication with the first sensor device and can be configured to calculate a harvesting power of the reactant gas flowing through the reactant gas conduit.

[0011] Other features and advantages of the multi-sensor gas sampling detection systems and methods for detecting and measuring radicals in a radical gas stream as described herein will become more apparent from consideration of the following detailed description.

[0012] The novel aspects of the multi-sensor gas sampling detection systems and methods for detecting and measuring radicals in a radical gas stream as disclosed herein will become more apparent upon inspection of the following figures. [Brief description of the drawings]

[0013] [Figure 1] 1 is a schematic diagram of an embodiment of a multi-sensor gas sampling detection system. [Diagram 2] FIG. 2 is a schematic diagram of another embodiment of a dual-sensor gas sampling detection system for taking gas samples from a radical gas stream upstream from and within a process chamber. [Diagram 3] FIG. 2 is a schematic diagram of another embodiment of a dual-sensor gas sampling detection system for taking gas samples from a radical gas stream upstream from, from within, and downstream of a process chamber. [Figure 4] FIG. 13 is a schematic diagram of an alternative embodiment of a dual-sensor gas sampling detection system. [Diagram 5] FIG. 13 is a schematic diagram of an alternative embodiment of a multi-sensor gas sampling detection system with an associated reagent source. [Figure 6] FIG. 13 is a schematic diagram of another alternative embodiment of a dual-sensor gas sampling detection system. [Figure 7] FIG. 13 is a schematic diagram of another alternative embodiment of a dual-sensor gas sampling detection system. [Figure 8] 1 is an elevated perspective view of an embodiment of a sampling reaction module for use in a multi-sensor gas sampling detection system; FIG. [Figure 9]2 is an alternative elevated perspective view of an embodiment of a sampling reaction module for use in the multi-sensor gas sampling detection system shown in FIG. 1. [Figure 10] 2 is an elevated front perspective view of an embodiment of an analytical accessory for use with the sampling reaction module shown in FIG. 1. [Figure 11] 2 is an elevated front exploded view of this embodiment of an analytical accessory for use with the sampling and reaction module shown in FIG. 1. [Figure 12] 2 is an elevated rear perspective view of an embodiment of an analytical accessory for use with the sampling reaction module shown in FIG. 1. [Figure 13] 2 is an elevated rear exploded view of an embodiment of an analytical accessory for use with the sampling reaction module shown in FIG. 1. [Figure 14] FIG. 2 is an elevated perspective view of an embodiment of a sampling reaction module body. [Figure 15] 15 is an elevational cross-sectional perspective view of the embodiment of the sampling reaction module body shown in FIG. 14 taken along line 15-15. [Figure 16] 8 is a flow chart illustrating a method of using the multi-sensor gas sampling detection system illustrated in FIGS. 1-7. [Figure 17] 8 is a flow chart illustrating a method of using the multi-sensor gas sampling detection system illustrated in FIGS. 1-7. [Figure 18] 8 is a flow chart illustrating an alternative method of using the multi-sensor gas sampling detection system illustrated in FIGS. 1-7. [Figure 19] 8 is a flow chart illustrating another method of using the multi-sensor gas sampling detection system illustrated in FIGS. 1-7. [Figure 20] FIG. 20 is a graphical illustration of how the multi-sensor gas sampling detection system described in FIG. 19 can be used to establish upper and lower limits. [Figure 21] 8 is a flow chart illustrating a method of calibrating the multi-sensor gas sampling detection system illustrated in FIGS. 1-7. [Figure 22]FIG. 22 graphically illustrates extrapolated power measurements calculated while calibrating the dual-sensor gas sampling detection system described in FIG. 21. [Figure 23] FIG. 2 is a graphical illustration of the measured concentration of oxygen radicals measured using an optical-based measurement system having a multi-sensor gas sampling detection system as described in the present application. [Figure 24] 8 is a flow chart illustrating an optical-based method using the multi-sensor gas sampling detection system illustrated in FIGS. 1-7. [Diagram 25] 8 is a flow chart illustrating a semiconductor-based method for using the multi-sensor gas sampling detection system illustrated in FIGS. 1-7. [Figure 26] FIG. 26 graphically illustrates the result of resistance changes as the radical output stream is activated and deactivated when using the resistance-based sampling architecture shown in FIG. 25. [Figure 27] FIG. 13 is a schematic diagram of another alternative embodiment of a dual-sensor gas sampling detection system. [Figure 28] 28 is an elevated perspective view of an embodiment of a reactive gas conduit having at least one sensor body positioned therein for use in the embodiment of the gas sampling detection system shown in FIG. 27. [Figure 29] 28 is an elevated perspective view of another embodiment of a reactive gas conduit having at least one sensor body positioned therein for use in the embodiment of the gas sampling detection system shown in FIG. 27. [Diagram 30] 28 is an elevated perspective view of another embodiment of a reactive gas conduit having at least one sensor body positioned therein for use in the embodiment of the gas sampling detection system shown in FIG. 27. [Diagram 31] 31 is a flow chart illustrating a method of using the multi-sensor gas sampling detection system illustrated in FIGS. 27, 29, and 30. [Diagram 32] 31 is a flow chart illustrating another method of using the multi-sensor gas sampling detection system illustrated in FIGS. 27, 29, and 30. [Diagram 33] FIG. 31 graphically illustrates the temperature delta of a sensor body positioned within a reactant gas conduit of the multi-sensor gas sampling detection system described in FIGS. 27-30. [Figure 34A] FIG. 31 is a graphical illustration of the performance of a first radical gas generator used in the embodiment of the sensor gas sampling detection system described in FIGS. 27 and 30. [Figure 34B] FIG. 31 is a graphical illustration of the performance of a second radical gas generator used in the embodiment of the sensor gas sampling detection system described in FIGS. 27 and 30. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The present application relates to a multi-sensor gas sampling detection system and method of use for atomic radicals, molecular radicals, and short-lived molecules (hereinafter "radicals"). More specifically, the present application discloses a gas sampling detection system configured to allow a user to easily and accurately measure the concentration of radicals in a gas stream. In one embodiment, the gas sampling detection system disclosed herein can be configured to measure the concentration of radicals in a gas stream before the gas stream is introduced into a process chamber or similar vessel. In another embodiment, the gas sampling detection system disclosed herein can be configured to measure the concentration of radicals in a gas stream in a process chamber or vessel. Optionally, the gas sampling detection system disclosed herein can be used to measure the concentration of radicals in an exhaust stream exhausted from a process chamber or vessel. More specifically, the methods disclosed herein allow for the measurement of the concentration of radicals that have been previously difficult to measure by reacting radicals in a gas sample with selected elements and compounds to produce chemical species that can be easily and accurately detected and measured using a variety of measurement techniques. In some embodiments, the measurement process can be performed in situ. Optionally, the measurement process can be performed at a remote location.

[0015] FIG. 1 illustrates an embodiment of a gas sampling detection system useful for detecting the concentration of radicals in a gas stream. As illustrated, the gas sampling detection system 10 includes at least one plasma generator and / or radical gas generator 12 in fluid communication with at least one process chamber 16 through at least one gas passage 14. In one embodiment, the radical gas generator 12 may include or be in communication with at least one sample gas source and at least one plasma source. During use, the radical gas generator 12 may be configured to excite and dissociate a sample gas to generate at least one reactive gas stream. In one particular embodiment, the radical gas generator 12 includes an RF toroidal plasma source, although one skilled in the art will recognize that any type of plasma source or radical gas source may be used with the system of the present invention. In one embodiment, the radical gas generator 12 includes a hydrogen (H 2 ) to generate atomic hydrogen. 2 In another embodiment, the radical gas generator 12 uses an oxygen (O ) plasma to generate atomic oxygen. 2 Optionally, the radical gas generator 12 utilizes nitrogen trifluoride (NF ) plasma to generate a reactive plasma containing one or more radicals in the gas stream. 3 ), fluorine (F 2 ), Chlorine (Cl 2), or any type of other material may be utilized. Alternatively, the radical gas may be generated by other gas excitation methods, including electron beam excitation, laser excitation, or hot filament excitation. Additionally, while the above description discloses various embodiments of RF-based plasma generation systems, one skilled in the art will recognize that any type of alternative radical gas generation system may be used with the systems of the present invention. Exemplary alternative radical gas generation systems include, but are not limited to, glow discharge plasma systems, capacitively coupled plasma systems, cascaded arc plasma systems, inductively coupled plasma systems, wave heated plasma systems, arc discharge plasma systems, corona discharge plasma systems, dielectric barrier discharge systems, capacitive discharge systems, and piezoelectric direct discharge plasma systems.

[0016] 1, at least one processing chamber 16 can be in fluid communication with the radical gas generator 12 through at least one reactive gas conduit 14. In some applications, the reactive gas conduit 14 is fabricated from a chemically inert material or a material having only low chemical reactivity. Exemplary materials include, but are not limited to, quartz, sapphire, stainless steel, reinforced steel, aluminum, ceramic materials, glass, brass, nickel, YBCO, and the like. 2 O 3 , YAlO x, various alloys, and coated metals such as anodized aluminum. In one embodiment, a single reactive gas conduit 14 is in fluid communication with a single radical gas generator 12. In another embodiment, multiple reactive gas conduits 14 are in fluid communication with a single reactive gas generator 12. In yet another embodiment, a single reactive gas conduit 14 is in fluid communication with multiple radical gas generators 12. Thus, any number of reactive gas conduits 14 can be in communication with any number of radical gas generators 12. Optionally, the reactive gas conduit 14 can include one or more valve devices or systems, sensors or similar devices 22 coupled thereto or in communication therewith. For example, one or more valve devices 22 can be coupled to the reactive gas conduit 14, thereby allowing a user to selectively allow and / or restrict the flow of at least one reactive gas stream through the reactive gas conduit 14.

[0017] As shown in FIG. 1, the process chamber 16 may be coupled to or in communication with the radical gas generator 12 through a reactive gas conduit 14. In one embodiment, the process chamber 16 includes one or more vacuum chambers or vessels configured to have one or more substrates, semiconductor wafers, or similar materials positioned therein. For example, the process chamber 16 may be used for atomic layer processing of semiconductor substrates or semiconductor wafers. Optionally, the process chamber 16 may be used to process any type of substrate or material using any type of processing method and / or system. Exemplary processing methods include, but are not limited to, physical vapor deposition (PVD), chemical vapor deposition (CVD), rapid thermal chemical vapor deposition (RTCVD), atomic layer deposition (ALD), and atomic layer etching (ALE), among others. Those skilled in the art will appreciate that the process chamber 16 may be fabricated from any type of material, including, but are not limited to, stainless steel, aluminum, mild steel, brass, high density ceramics, glass, acrylic, and the like. For example, at least one interior surface of the processing chamber 16 may include at least one coating, anodized material, sacrificial material, physical features or elements, etc., intended to selectively alter reactivity, durability, and / or fill microporosity thereon. At least one exhaust conduit 18 may be coupled to the processing chamber 16 and configured to exhaust one or more gases or materials therefrom. Optionally, one or more control sensors, valves, gas scrubbers, or similar devices 24 may be coupled to or positioned proximate to the exhaust conduit 18, thereby allowing a user to selectively exhaust one or more gases or other materials from the processing chamber 16.

[0018] 1 , at least one chamber processor module 20 may be coupled to or otherwise in communication with the processing chambers 16 and / or with various components of the processing system. The chamber processing module 20 may be configured to provide localized control of the various components forming the processing system 10. In the illustrated embodiment, the chamber processing module 20 is in communication with the processing chambers 16 through conduits, however, one skilled in the art will appreciate that the chamber processing module 20 may communicate with any of the components forming the processing system 10 through conduits, wirelessly, or both.

[0019] As shown in FIG. 1, at least one sampling module 32 can be in fluid communication with the radical gas generator 12 through at least one sampling conduit 30. Those skilled in the art will appreciate that the sampling conduit 30 can be made from any type of material, including, but not limited to, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, plastics, carbon fiber, carbon-based materials, graphite, silicon, silicon dioxide, silicon carbide, and the like. Thus, in some embodiments, the sampling conduit 30 can be configured to chemically react with highly reactive atomic radicals, molecular radicals, and short-lived molecules contained within the radical gas stream flowing therethrough. In yet another embodiment, the sampling conduit 30 can be configured with a catalytic material that facilitates recombination of atomic gas species into molecular gas species such that the recombination energy of the atomic gas is released and measured. In other embodiments, the sampling conduit 30 can be configured to be chemically inert. Optionally, the sampling conduit 30 can include any type of sensor, valve, heating element, cooling element, and the like thereon. In one embodiment, the sampling conduit 30 is directly coupled to and in fluid communication with the radical gas generator 12. In the illustrated embodiment, the sampling conduit 30 is in fluid communication with the radical gas generator 12 through the reactant gas conduit 14. Optionally, the sampling conduit 30 can be in fluid communication with a sampling control valve 22 positioned on the reactant gas conduit 14. For example, the sampling control valve 22 can be configured to selectively direct a specified volume of the reactant gas traversing through the reactant gas conduit 14 through the sampling conduit 30 to the sampling module 32. In another embodiment, the sampling control valve 22 can be configured to selectively direct a specified flow rate of the reactant gas traversing through the reactant gas conduit 14 through the sampling conduit 30 to the sampling module 32. Additionally, any number of additional components, valves, sensors, etc. can be positioned anywhere along the sampling conduit 30.For example, in the illustrated embodiment, at least one sensor and / or control device 50 may be positioned along the sampling conduit 30. Exemplary sensor devices include, but are not limited to, thermocouples, temperature sensors, optical sensors, UV, optical or infrared spectrometers, charged particle detectors, vacuum gauges, mass spectrometers, and the like. For example, in one embodiment, the sensor device 50 includes at least one thermistor. In another embodiment, the sensor device 50 includes at least one calorimetric measurement system or device. An embodiment of a novel calorimetric measurement system is discussed and illustrated in detail in Figures 8-15 of the present application. Optionally, the sensor device 50 may include one or more titration systems or devices. Those skilled in the art will appreciate that the sensor device 50 may include any number of in situ measurement devices or systems, flow valves, flow meters, flow verifiers, and the like.

[0020] Referring again to FIG. 1, in the illustrated embodiment, the sampling module 32 is coupled to at least one molecular compound stream conduit 34. Similar to the sampling conduit 30, the molecular compound stream conduit 34 can be fabricated from any type of material, including, but not limited to, graphite, silica, carbon fiber, silicon dioxide, silica, and silicon carbide, carbon-based materials, silica-based materials, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, and plastics. In one embodiment, at least a portion of at least one of the sampling conduit 30 and / or the molecular compound stream conduit 34 can be configured to react with the radical gas stream flowing therethrough. For example, in one embodiment, at least a portion of the sampling conduit 30 and / or the molecular compound stream conduit 34 can be configured to react with radicals in the radical gas stream to form chemical species that are more stable and more accurately measurable compared to the radicals.

[0021] As shown in FIG. 1 , at least one sensor module 36 is in fluid communication with the sampling module 32 through the molecular compound stream conduit 34. In one embodiment, the sensor module 36 can be configured to detect and measure the concentration of radicals in the at least one gas stream. Any type of device or system can be used for or to form the sensor module 36. For example, in one embodiment, the sensor module 36 includes at least one detector configured to measure radical flux in the radical gas stream. In another embodiment, the sensor module 36 is configured to measure the concentration of at least one chemical species in the gas stream. For example, the sensor module 36 can detect and measure the concentration of at least one chemical species in the gas stream. 2 ), carbon-hydrogen molecule (methylidyne radical), methylene (CH 2 ), methyl group compounds (CH 3 ), methane (CH 4 ), silicon tetrafluoride, and similar compounds. In one particular embodiment, the sensor module 36 includes at least one optical gas imaging camera or device, such as a Fourier transform infrared spectroscopy system (hereinafter FTIR system), a tunable filter spectroscopy system (hereinafter TFS system), mass spectrometry, optical absorption spectroscopy, and the like. Optionally, the sensing module 36 may further include at least one titration system or device. In one embodiment, the sensing module 36 may be configured to reduce or eliminate recombination of radicals in the gas stream into molecular species. In another embodiment, the sensor module 36 may be configured to allow recombination of radicals in the gas stream into molecular species.

[0022] Referring again to FIG. 1, at least one sensor module output conduit 38 is in fluid communication with the sensor module 36 and a flow measurement and / or flow control module 40. In some embodiments, the flow measurement module 40 is configured to accurately measure a portion of the gas stream flowing therethrough. For example, the flow of the gas stream can be measured using a mass flow verifier (MFV). In another embodiment, the flow of the gas stream can be measured using a mass flow meter (MFM). Optionally, the flow can be determined by measuring a pressure difference between an orifice of known size and a fluid conductance in the multi-sensor gas sampling detection system 10. Those skilled in the art will recognize that any type of flow measurement device or system can be used with the gas sampling detection system 10 disclosed herein. As shown in FIG. 1, at least one exhaust conduit 42 can be coupled to or in communication with the flow measurement module 40 and can be configured to exhaust the radical gas stream from the gas sampling detection system 10. Optionally, the exhaust conduit 42 can be in fluid communication with at least one vacuum source (not shown).

[0023] 1, the processing system 10 may include at least one optional processor module 52 that may communicate with at least one of its components. For example, in the illustrated embodiment, the optional processor module 52 is in communication with the radical gas generator 12 through at least one processor conduit 54. Additionally, the optional processor system 52 may be in communication with at least one of the optional sensor 50 through the processor conduit 54 and at least one optional sensor conduit 56, the sampling module 32 through the processor conduit 54 and at least one sampling conduit 58, the sensor module 36 through at least one sensor module conduit 60, and the flow measurement module 40 through at least one flow measurement conduit 62. In one embodiment, the optional processor module 52 may be configured to provide and receive data from at least one of the radical gas generator 12, the optional sensor 50, the sampling module 32, the sensor module 36, and the flow measurement module 40. Thus, the optional processor module 52 can be configured to measure flow conditions within the processing system 10 and selectively vary the operating conditions of the processing system 10 to optimize system performance. More specifically, the optional processor module 52 can be configured to measure the concentration of radicals in the gas stream and vary the operating characteristics of the radical gas generator 12 to increase or decrease it. Additionally, the optional processor module 52 is in communication with at least one of the optional valve device 22, the sensor 24, and the chamber processor module 20 through at least one optional processing conduit 64 and can provide data thereto / receive data therefrom. Optionally, the optional processor module 52 can wirelessly communicate with various components of the processing system 10. Additionally, the optional processor module 52 can be configured to store performance data, processing methods and times, lot numbers, and the like. Additionally, the optional processor module 52 can be configured to communicate with one or more external processors through at least one computer network.

[0024] 1, optionally, at least one analytical system or circuitry 66 may be formed within the processing system 10. As shown, the analytical system 66 may include at least one of the sampling module 32, the sensor module 36, the flow measurement module 49, the optional sensor 50, and the optional processor module 52. Additionally, the analytical system 66 may further include the valve device 22 or other devices and components within the processing system 10.

[0025] FIG. 2 illustrates another embodiment of a gas sampling detection system useful for detecting the concentration of radicals in a gas stream. Various components of a processing system 110 illustrated in FIG. 2 function equivalently to similarly named components illustrated in FIG. 1. As with the immediately preceding embodiment, the gas sampling detection system 110 can include at least one radical gas generator and / or reactive gas generator 112 configured to provide a reactive gas stream having radicals. The radical gas generator 112 can be in fluid communication with at least one processing chamber 116 through at least one gas passage 114. As with the immediately preceding embodiment, the radical gas generator 112 is in communication with at least one sample gas source and at least one plasma source configured to excite and dissociate a sample gas and correspondingly generate at least one reactive gas stream.

[0026] 2, optionally, the reactive gas conduit 114 may include one or more valve devices or systems, sensors or similar devices 122 coupled thereto or in communication therewith. For example, one or more valve devices 122 may be coupled to or otherwise in communication with the reactive gas conduit 114, thereby allowing a user to selectively allow and / or restrict the flow of at least one reactive gas stream through the reactive gas conduit 114. In one embodiment, the valve device 122 may communicate with at least one optional processing module 152 through at least one processor conduit 154. Optionally, the processing module 152 may be configured to wirelessly communicate with various components of the processing system 110. During use, the processor module 152 may be configured to selectively open and / or close the valve device 122, thereby allowing or restricting the flow of the radical gas stream generated by the radical gas generator 112 into the sampling module 132.

[0027] 2, at least one process chamber 116 can be coupled to or in communication with the radical gas generator 112 through a reactive gas conduit 114. At least one exhaust conduit 118 can be coupled to the process chamber 116 and configured to exhaust one or more gases or materials therefrom. Optionally, one or more control sensors, valves, gas scrubbers, or similar devices 124 can be coupled to or positioned proximate the exhaust conduit 118, thereby allowing a user to selectively exhaust one or more gases or other materials from the process chamber 116.

[0028] 2, as in the immediately preceding embodiment, at least one chamber processor module 120 may be coupled to or otherwise in communication with the processing chambers 118 and / or various components of the processing system. The chamber processing module 120 may be configured to provide localized control of the various components forming the processing system 110. In the illustrated embodiment, the chamber processing module 120 is in communication with the processing chambers 116 through conduits, although one skilled in the art will recognize that the chamber processing module 120 may be in communication with any of the components forming the processing system 110 through conduits, wirelessly, or both.

[0029] As shown in FIG. 2, at least one sampling module 132 can be in fluid communication with the radical gas generator 112 through at least one sampling conduit 130. Those skilled in the art will appreciate that the sampling conduit 130 can be made from any type of material, including, but not limited to, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, plastics, carbon fiber, carbon-based materials, graphite, silicon, silicon dioxide, silicon carbide, and the like. Thus, the sampling conduit 130 can be configured to chemically react with highly reactive radicals contained within the radical gas stream flowing therethrough. In another embodiment, the sampling conduit 130 can be configured to be chemically inert. In one embodiment, the sampling conduit 130 is directly coupled to and in fluid communication with the radical gas generator 112. In the illustrated embodiment, the sampling conduit 130 is in fluid communication with the radical gas generator 112 through the reactive gas conduit 114. Optionally, the sampling conduit 130 may be in fluid communication with a sampling control valve 122 positioned on the reactant gas conduit 114. For example, the sampling control valve 122 may be configured to selectively direct a specified volume of the reactant gas traversing through the reactant gas conduit 114 through the sampling conduit 130 to the sampling module 132. Optionally, the sampling control valve 122 may be configured to selectively direct a specified flow rate of the reactant gas traversing through the reactant gas conduit 114 through the sampling conduit 130 to the sampling module 132. Additionally, any number of additional components, valves, sensors, and the like may be positioned anywhere along the sampling conduit 130. For example, in the illustrated embodiment, at least one sensor and / or control device 150 may be positioned along the sampling conduit 130. Exemplary sensor devices include, but are not limited to, thermocouples, temperature sensors, vacuum gauges, and the like. For example, in one embodiment, the sensor device 150 includes at least one thermistor. In another embodiment, the sensor device 150 includes at least one calorimetric system or device.Optionally, the sensor device 150 can include one or more titration systems or devices. Those skilled in the art will appreciate that the sensor device 150 can include any number of in situ measurement devices or systems, flow valves, flow meters, flow verifiers, and the like.

[0030] 2, the sampling module 132 can be in fluid communication with the processing chamber 116 through at least one chamber sample gas conduit 144. Thus, the sampling module 132 can be configured to analyze the radical gas stream upstream of and within the processing chamber 116. Such analysis can be performed sequentially or simultaneously. Like the sampling conduit 130, the chamber sample gas conduit 144 can include one or more valves, sensors, and the like thereon. Thus, the flow of sample gas from the processing chamber 116 to the sampling module 132 can be selectively varied.

[0031] 2, the sampling module 132 can be coupled to at least one molecular compound stream conduit 134. Similar to the sampling conduit 130, the molecular compound stream conduit 134 can be fabricated from any type of material, including, but not limited to, graphite, silica, carbon fiber, silicon dioxide, silica, and silicon carbide, carbon-based materials, silica-based materials, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, and plastics. In an embodiment, at least a portion of at least one of the sampling conduit 130 and / or the molecular compound stream conduit 134 can be configured to react with the radical gas stream flowing therethrough. For example, in an embodiment, at least a portion of the sampling conduit 130 and / or the molecular compound stream conduit 134 can be configured to react with radicals contained within the radical gas stream to form chemical species that are more stable and more accurately measurable compared to these radicals.

[0032] As shown in FIG. 2, similar to the immediately preceding embodiment, at least one sensor module 136 can be in fluid communication with the sampling module 132 through the molecular compound stream conduit 134. Optionally, the sensor module 136 can be configured to detect and measure the concentration of radicals in the at least one gas stream. Any type of device or system can be used for or to form the sensor module 136. For example, in one embodiment, the sensor module 136 includes at least one detector configured to measure radical flux in the radical gas stream. In another embodiment, the sensor module 136 is configured to measure the concentration of at least one chemical species in the gas stream. For example, the sensor module 136 can detect and measure the concentration of at least one chemical species in the gas stream. For example, the sensor module 136 can detect and measure the concentration of at least one chemical species in the gas stream. 2 ), carbon-hydrogen molecule (methylidyne radical), methylene (CH 2 ), methyl group compounds (CH 3 ), methane (CH 4 ), silicon tetrafluoride, and similar compounds. In one particular embodiment, the sensor module 136 includes at least one optical gas imaging camera or device, such as a Fourier transform infrared spectroscopy system (hereinafter FTIR system), a tunable filter spectroscopy system (hereinafter TFS system), mass spectrometry, optical absorption spectroscopy, and the like. Optionally, the sensing module 136 may further include at least one titration system or device. In one embodiment, the sensing module 136 may be configured to reduce or eliminate recombination of radicals in the gas stream into molecular species. In another embodiment, the sensor module 136 may be configured to allow recombination of radicals in the gas stream into molecular species.

[0033] Referring again to FIG. 2, at least one sensor module output conduit 138 is in fluid communication with the sensor module 136 and is further in fluid communication with a flow measurement and / or flow control module 140 that can be configured to accurately measure a portion of the gas stream flowing therethrough. As with the immediately preceding embodiment, the flow of the gas stream can be measured using a mass flow verifier (MFV). In another embodiment, the flow of the gas stream can be measured using a mass flow meter (MFM). Optionally, the flow volume or flow rate can be determined by measuring a pressure difference between an orifice of known size and a fluid conductance in the multi-sensor gas sampling detection system 110. Those skilled in the art will recognize that any type of flow measurement device or system can be used with the gas sampling detection system 110 disclosed herein. As shown in FIG. 2, at least one exhaust conduit 142 can be coupled to or in communication with the flow measurement module 140 and can be configured to exhaust the radical gas stream from the gas sampling detection system 110. Optionally, the exhaust conduit 142 can be in fluid communication with at least one vacuum source (not shown).

[0034] As described above, the processing system 110 may include at least one optional processor module 152 in communication with at least one component thereof. For example, the optional processor module 152 may be in communication with the radical gas generator 112 through at least one processor conduit 154. Additionally, the optional processor system 152 may be in communication with the optional sensor 150 through the processor conduit 154 and at least one optional sensor conduit 156, with the sampling module 132 through the processor conduit 154 and at least one sampling conduit 158, with the sensor module 136 through at least one sensor module conduit 160, and with the flow measurement module 140 through at least one flow measurement conduit 162. In one embodiment, the optional processor module 152 may be configured to provide and receive data to and from at least one of the radical gas generator 112, the optional sensor 150, the sampling module 132, the sensor module 136, and the flow measurement module 140. Thus, the optional processor module 152 can be configured to measure flow conditions within the processing system 110 and selectively vary operating conditions of the processing system 110 to optimize system performance. More specifically, the optional processor module 152 can be configured to measure a concentration of radicals within the gas stream and vary operating characteristics of the radical gas generator 112 to increase or decrease it. Additionally, the optional processor module 152 is in communication with at least one of the optional valve device 122, the sensor 124, and the chamber processor module 120 through at least one optional process conduit 164 and can provide data thereto / receive data therefrom. Optionally, the processor module 152 can be in communication with an external network.

[0035] Optionally, as in the immediately preceding embodiment, at least one analytical system or circuit 166 may be formed within the processing system 110, as shown in Figure 2. As shown, analytical system 166 may include at least one of sampling module 132, sensor module 136, flow measurement module 149, optional sensor 150, and optional processor module 152. Additionally, analytical system 166 may further include valve device 122 or other devices and components within processing system 110.

[0036] FIG. 3 illustrates yet another embodiment of a gas sampling detection system useful for detecting the concentration of radicals in a gas stream. As with FIG. 2, various components of a processing system 210 illustrated in FIG. 3 function equivalently to similarly named components illustrated in FIG. 1 and FIG. 2. As with the previous embodiment, the gas sampling detection system 210 can include at least one radical gas generator and / or reactive gas generator 212 configured to provide a reactive gas stream having radicals. The radical gas generator 212 can be in fluid communication with at least one processing chamber 216 through at least one gas passage 214. As with the immediately preceding embodiment, the radical gas generator 212 is in communication with at least one sample gas source and at least one plasma source configured to excite and dissociate a sample gas and correspondingly generate at least one reactive gas stream.

[0037] 3, optionally, the reactant gas conduit 214 can include one or more valve devices or systems, sensors or similar devices 222 coupled thereto or in communication therewith. For example, one or more valve devices 222 can be positioned within or coupled to the reactant gas conduit 214, thereby allowing a user to selectively allow and / or restrict the flow of at least one reactant gas stream through the reactant gas conduit 214.

[0038] 3, at least one processing chamber 216 can be coupled to or in communication with the radical gas generator 212 through a reactive gas conduit 214. At least one exhaust conduit 218 can be coupled to the processing chamber 216 and configured to exhaust one or more gases or materials therefrom. Optionally, one or more control sensors, valves, gas scrubbers, or similar devices 224 can be coupled to or positioned proximate the exhaust conduit 218, thereby allowing a user to selectively exhaust one or more gases or other materials from the processing chamber 216.

[0039] 3, as in the immediately preceding embodiment, at least one chamber processor module 220 can be coupled to or otherwise in communication with the processing chambers 218 and / or various components of the processing system. The chamber processing module 220 can be configured to provide localized control of the various components forming the processing system 210. In the illustrated embodiment, the chamber processing module 220 is in communication with the processing chambers 216 through conduits, although one skilled in the art will recognize that the chamber processing module 220 can be in communication with any of the components forming the processing system 210 through conduits, wirelessly, or both.

[0040] As shown in FIG. 3, at least one sampling module 232 can be in fluid communication with the radical gas generator 212 through at least one sampling conduit 230. Those skilled in the art will appreciate that the sampling conduit 230 can be made from any type of material, including, but not limited to, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, plastics, carbon fiber, carbon-based materials, graphite, silicon, silicon dioxide, silicon carbide, and the like. Thus, the sampling conduit 230 can be configured to chemically react with highly reactive radicals contained within the radical gas stream flowing therethrough. In another embodiment, the sampling conduit 230 can be configured to be chemically inert. In one embodiment, the sampling conduit 230 is directly coupled to and in fluid communication with the radical gas generator 212. In the illustrated embodiment, the sampling conduit 230 is in fluid communication with the radical gas generator 212 through the reactive gas conduit 214. Optionally, the sampling conduit 230 may be in fluid communication with a sampling control valve 222 positioned on the reactant gas conduit 214. For example, the sampling control valve 222 may be configured to selectively direct a specified volume of reactant gas traversing through the reactant gas conduit 214 to the sampling module 232 through the sampling conduit 230. Optionally, the sampling control valve 222 may be configured to selectively direct a specified flow rate of reactant gas traversing through the reactant gas conduit 214 to the sampling module 232 through the sampling conduit 230. Additionally, any number of additional components, valves, sensors, and the like may be positioned anywhere along the sampling conduit 230. For example, in the illustrated embodiment, at least one sensor and / or control device 250 may be positioned along the sampling conduit 230. Exemplary sensor devices include, but are not limited to, thermocouples, temperature sensors, vacuum gauges, and the like. For example, in one embodiment, the sensor device 250 includes at least one thermistor. In another embodiment, the sensor device 250 includes at least one calorimetric system or device.Optionally, the sensor device 250 can include one or more titration systems or devices. Those skilled in the art will appreciate that the sensor device 250 can include any number of in situ measurement devices or systems, flow valves, flow meters, flow verifiers, and the like.

[0041] 3, the sampling module 232 can be in fluid communication with the process chamber 116 and the exhaust conduit 218 through at least one of the at least one chamber sample gas conduit 244 and / or the sample exhaust conduit 246. Thus, the sampling module 232 can be configured to analyze the radical gas stream upstream of the process chamber 216, the radical gas stream within the process chamber 216, and the radical gas stream being emitted from the process chamber through the exhaust conduit 218. Such analysis can be performed sequentially or simultaneously. Similar to the sampling conduit 230, the chamber sample gas conduit 244 and / or the exhaust conduit 218 can include one or more valves, sensors, and the like thereon. Thus, the flow of sample gas from the process chamber 216 to the sampling module 232 and / or the flow of sample gas from the exhaust conduit 218 to the sampling module 232, or both, can be selectively varied.

[0042] 3, the sampling module 232 can be coupled to at least one molecular compound stream conduit 234. Similar to the sampling conduit 230, the molecular compound stream conduit 234 can be fabricated from any type of material, including, but not limited to, graphite, silica, carbon fiber, silicon dioxide, silica, and silicon carbide, carbon-based materials, silica-based materials, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, and plastics. In one embodiment, at least a portion of at least one of the sampling conduit 230 and / or the molecular compound stream conduit 234 can be configured to react with the radical gas stream flowing therethrough. For example, in one embodiment, at least a portion of the sampling conduit 230 and / or the molecular compound stream conduit 234 can be configured to react with radicals contained within the radical gas stream to form chemical species that are more stable and more accurately measurable compared to these radicals.

[0043] As shown in FIG. 3, as in the previous embodiment, at least one sensor module 236 is in fluid communication with the sampling module 232 through the molecular compound stream conduit 234. Optionally, the sensor module 236 can be configured to detect and measure the concentration of radicals in the at least one gas stream. Any type of device or system can be used to use in or form the sensor module 236. For example, in one embodiment, the sensor module 236 includes at least one detector configured to measure the radical flux in the radical gas stream. In another embodiment, the sensor module 236 is configured to measure the concentration of at least one chemical species in the gas stream. For example, the sensor module 236 can detect and measure the concentration of at least one chemical species in the gas stream. For example, the sensor module 236 can detect and measure the concentration of at least one chemical species in the gas stream. 2 ), carbon-hydrogen molecule (methylidyne radical), methylene (CH 2 ), methyl group compounds (CH 3 ), methane (CH 4), silicon tetrafluoride, and similar compounds. In one particular embodiment, the sensor module 236 includes at least one optical gas imaging camera or device, such as a Fourier transform infrared spectroscopy system (hereinafter FTIR system), a tunable filter spectroscopy system (hereinafter TFS system), mass spectrometry, optical absorption spectroscopy, and the like. Optionally, the sensing module 236 may further include at least one titration system or device. In one embodiment, the sensing module 236 may be configured to reduce or eliminate recombination of radicals in the gas stream into molecular species. In another embodiment, the sensor module 236 may be configured to allow recombination of radicals in the gas stream into molecular species.

[0044] Referring again to FIG. 3, at least one sensor module output conduit 238 is in fluid communication with the sensor module 236 and is further in fluid communication with a flow measurement and / or flow control module 240 that can be configured to accurately measure a portion of the gas stream flowing therethrough. As with the immediately preceding embodiment, the flow of the gas stream can be measured using a mass flow verifier (MFV). In another embodiment, the flow of the gas stream can be measured using a mass flow meter (MFM). Optionally, the flow can be determined by measuring a pressure difference between an orifice of known size and a fluid conductance in the multi-sensor gas sampling detection system 210. Those skilled in the art will recognize that any type of flow measurement device or system can be used with the gas sampling detection system 210 disclosed herein. As shown in FIG. 3, at least one exhaust conduit 242 can be coupled to or in communication with the flow measurement module 240 and can be configured to exhaust the radical gas stream from the gas sampling detection system 210. Optionally, the exhaust conduit 242 can be in fluid communication with at least one vacuum source (not shown).

[0045] As described above, the processing system 210 may include at least one optional processor module 252 in communication with at least one of its components. For example, the optional processor module 252 may be in communication with the radical gas generator 212 through at least one processor conduit 254. Additionally, the optional processor system 252 may be in communication with at least one of the following: the optional sensor 250 through the processor conduit 254 and at least one optional sensor conduit 256; the sampling module 232 through the processor conduit 254 and at least one sampling conduit 258; the sensor module 236 through at least one sensor module conduit 260; and the flow measurement module 240 through at least one flow measurement conduit 262. In one embodiment, the optional processor module 252 may be configured to provide and receive data from at least one of the radical gas generator 212, the optional sensor 250, the sampling module 232, the sensor module 236, and the flow measurement module 240. Thus, the optional processor module 252 can be configured to measure flow conditions within the processing system 210 and selectively vary operating conditions of the processing system 210 to optimize system performance. More specifically, the optional processor module 252 can be configured to measure a concentration of radicals within the gas stream and vary operating characteristics of the radical gas generator 212 to increase or decrease it. Additionally, the optional processor module 252 is in communication with at least one of the optional valve device 222, the sensor 224, and the chamber processor module 220 through at least one optional processing conduit 264 and can provide data thereto / receive data therefrom. Optionally, the processor module 252 can be in communication with an external network.

[0046] Optionally, as in the previous embodiments, at least one analytical system or circuit 266 may be formed within the processing system 210, as shown in Figure 3. As shown, the analytical system 266 may include at least one of a sampling module 232, a sensor module 236, a flow measurement module 249, an optional sensor 250, and an optional processor module 252. Additionally, the analytical system 266 may further include a valve device 222 or other devices and components within the processing system 210.

[0047] FIG. 4 illustrates another embodiment of a gas sampling detection system useful for detecting the concentration of radicals in a gas stream. Unlike the previous embodiment, this embodiment includes multiple sampling modules that provide data to one or more sensor modules. As with the previous embodiment, the various components of the processing system 310 illustrated in FIG. 4 function equivalently to similarly named components illustrated in FIGS. 1-3. As with the previous embodiment, the gas sampling detection system 310 can include at least one radical gas generator and / or reactive gas generator 312 configured to provide a reactive gas stream having radicals. The radical gas generator 312 can be in fluid communication with at least one processing chamber 316 through at least one gas passage 314. Optionally, the reactive gas conduit 314 can include one or more valve devices or systems, sensors or similar devices 322 coupled thereto or in communication therewith. For example, one or more valve devices 322 can be positioned relative to or coupled to the reactant gas conduit 314, thereby enabling a user to selectively allow and / or restrict the flow of at least one reactant gas stream through the reactant gas conduit 314.

[0048] 4, at least one processing chamber 316 can be coupled to or in communication with the radical gas generator 312 through a reactive gas conduit 314. At least one exhaust conduit 318 can be coupled to the processing chamber 316 and configured to exhaust one or more gases or materials therefrom. Optionally, one or more control sensors, valves, gas scrubbers, or similar devices 324 can be coupled to or positioned proximate the exhaust conduit 318, thereby allowing a user to selectively exhaust one or more gases or other materials from the processing chamber 316.

[0049] 4, as with the previous embodiment, at least one chamber processor module 320 can be coupled to or otherwise in communication with the processing chamber 318 and / or various components of the processing system. The chamber processor module 320 can be configured to provide localized control over the various components forming the processing system 310. In the illustrated embodiment, the chamber processing module 320 is in communication with the processing chamber 316 through conduits, however, one skilled in the art will appreciate that the chamber processing module 320 can be in communication with any of the components forming the processing system 310 through conduits, wirelessly, or both.

[0050] As shown in FIG. 4, at least one upstream sampling module 332 can be in fluid communication with the radical gas generator 312 through at least one sampling conduit 330. One skilled in the art will appreciate that the sampling conduit 330 can be made from any type of material, including, but not limited to, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, plastics, carbon fiber, carbon-based materials, graphite, silicon, silicon dioxide, silicon carbide, and the like. Thus, the sampling conduit 330 can be configured to chemically react with highly reactive radicals contained within the radical gas stream flowing therethrough. In another embodiment, the sampling conduit 330 can be configured to be chemically inert. In one embodiment, the sampling conduit 330 is directly coupled to and in fluid communication with the radical gas generator 312. In the illustrated embodiment, the sampling conduit 330 is in fluid communication with the radical gas generator 312 through the reactive gas conduit 314. Optionally, the sampling conduit 330 may be in fluid communication with a sampling control valve 322 positioned on the reactant gas conduit 314. For example, the sampling control valve 322 may be configured to selectively direct a specified volume of the reactant gas traversing through the reactant gas conduit 314 through the sampling conduit 330 to an upstream sampling module 332. Optionally, the sampling control valve 322 may be configured to selectively direct a specified flow rate of the reactant gas traversing through the reactant gas conduit 314 through the sampling conduit 230 to the upstream sampling module 332. Additionally, any number of additional components, valves, sensors, and the like may be positioned anywhere along the sampling conduit 330. For example, in the illustrated embodiment, at least one sensor and / or control device 380 may be positioned along the sampling conduit 330. Exemplary sensor devices include, but are not limited to, thermocouples, temperature sensors, vacuum gauges, and the like. For example, in one embodiment, the sensor device 380 includes at least one thermistor.In another embodiment, the sensor device 380 includes at least one calorimetric system or device. Optionally, the sensor device 380 can include one or more titration systems or devices. Those skilled in the art will appreciate that the sensor device 380 can include any number of in situ measurement devices or systems, flow valves, flow meters, flow verifiers, and the like.

[0051] 4, at least one chamber sampling module 342 can be in fluid communication with the processing chamber 316 through at least one chamber sample gas conduit 340. Thus, the chamber sampling module 342 can be configured to analyze the radical gas stream within the processing chamber 316. Similar to the sampling conduit 330, the chamber sample gas conduit 340 can include one or more valves, sensors, and the like thereon. Thus, the flow of sample gas from the processing chamber 316 to the sampling module 342 can be selectively varied.

[0052] 4, optionally, at least one exhaust sampling module 352 can be in fluid communication with the process chamber 316 through at least one exhaust sample gas conduit 350. Thus, the chamber sampling module 352 can be configured to analyze the radical gas stream emitted from the process chamber 316 through the exhaust conduit 318. Optionally, the exhaust sample gas conduit 350 can include one or more valves, sensors, and the like thereon. Thus, the flow of sample gas emitted from the process chamber 316 through the exhaust conduit 318 can be selectively varied.

[0053] 4, at least one of the upstream sampling module 332, the chamber sampling module 342, and the exhaust sampling module 352 can be coupled to at least one molecular compound stream conduit 334. Similar to the sampling conduit 330, the molecular compound stream conduit 334 can be fabricated from any type of material, including, but not limited to, graphite, silica, carbon fiber, silicon dioxide, silica, and silicon carbide, carbon-based materials, silica-based materials, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, and plastics. In an embodiment, at least a portion of at least one of the upstream sampling conduit 330, the chamber sampling module 340, the exhaust sampling module 350, and / or the molecular compound stream conduit 334 can be configured to react with the radical gas stream flowing therethrough. For example, in an embodiment, at least a portion of the sampling conduit 330 and / or the molecular compound stream conduit 334 can be configured to react with radicals contained within the radical gas stream to form chemical species that are more stable and more accurately measurable compared to these radicals.

[0054] As shown in FIG. 4, similar to the immediately preceding embodiment, at least one sensor module 336 is in fluid communication with at least one of the upstream sampling module 332, the chamber sampling module 342, and the exhaust sampling module 352 through the molecular compound stream conduit 334. The sensor module 336 can be configured to detect and measure the concentration of radicals in the at least one gas stream. Any type of device or system can be used to use or form the sensor module 336. For example, in one embodiment, the sensor module 336 includes at least one detector configured to measure radical flux in the radical gas stream. In another embodiment, the sensor module 336 is configured to measure the concentration of at least one chemical species in the gas stream. For example, the sensor module 336 can detect and measure the concentration of at least one chemical species in the gas stream. For example, the sensor module 336 can detect and measure the concentration of at least one chemical species in the gas stream. 2 ), carbon-hydrogen molecule (methylidyne radical), methylene (CH 2 ), methyl group compounds (CH 3 ), methane (CH 4 ), silicon tetrafluoride, and similar compounds. In one particular embodiment, the sensor module 336 includes at least one optical gas imaging camera or device, such as a Fourier transform infrared spectroscopy system (hereinafter FTIR system), a tunable filter spectroscopy system (hereinafter TFS system), mass spectrometry, optical absorption spectroscopy, and the like. Optionally, the sensing module 336 may further include at least one titration system or device. In one embodiment, the sensing module 336 may be configured to reduce or eliminate recombination of radicals in the gas stream into molecular species. In another embodiment, the sensor module 336 may be configured to allow recombination of radicals in the gas stream into molecular species.

[0055] Referring again to FIG. 4, at least one sensor module output conduit 362 is in fluid communication with the sensor module 336 and is further in fluid communication with a flow measurement and / or flow control module 370 that can be configured to accurately measure a portion of the gas stream flowing therethrough. As with the immediately preceding embodiment, the flow of the gas stream can be measured using a mass flow verifier (hereafter MFV). In another embodiment, the flow of the gas stream can be measured using a mass flow meter (hereafter MFM). Optionally, the flow can be determined by measuring a pressure difference between an orifice of known size and a fluid conductance in the multi-sensor gas sampling detection system 310. Those skilled in the art will recognize that any type of flow measurement device or system can be used with the gas sampling detection system 310 disclosed herein. As shown in FIG. 4, at least one exhaust conduit 372 can be coupled to or in communication with the flow measurement module 370 and can be configured to exhaust the radical gas stream from the gas sampling detection system 310. Optionally, the exhaust conduit 372 can be in fluid communication with at least one vacuum source (not shown).

[0056] The processing system 310 may include at least one optional processor module 382 in communication with at least one of its components. For example, the optional processor module 382 may be in communication with the radical gas generator 312 through at least one processor conduit 384. Additionally, the optional processor system 382 may be in communication with at least one or both of the optional sensor 380 and the upstream sampling module 332 through the processor conduit 384 and at least one optional sensor conduit 356, and the sensor module 336 through at least one sensor module conduit 386. Thus, the optional processor module 382 may be configured to measure flow conditions within the processing system 310 and selectively vary operating conditions of the processing system 310 to optimize system performance. More specifically, the optional processor module 382 may be configured to measure and / or calculate the concentration of radicals in the gas stream and vary the operating characteristics of the radical gas generator 312 to increase or decrease it. Additionally, the optional processor module 382 is in communication with at least one of the optional valve device 322, the sensor 324, and the chamber processor module 320 through at least one optional process conduit 364 and can provide data thereto / receive data therefrom.

[0057] FIG. 5 illustrates an embodiment of a gas sampling detection system useful for detecting the concentration of radicals in a gas stream. As shown, the gas sampling detection system 410 includes at least one plasma generator and / or radical gas generator 412 in fluid communication with at least one process chamber 416 through at least one gas passage 414. In one embodiment, the radical gas generator 412 is in communication with at least one sample gas source and at least one plasma source configured to excite and dissociate a sample gas to generate at least one reactive gas stream. In one particular embodiment, the radical gas generator 412 includes an RF toroidal plasma source, although one skilled in the art will recognize that any type of plasma source or radical gas source can be used with the system of the present invention. In one embodiment, the radical gas generator 412 generates hydrogen (H 2 ) to generate atomic hydrogen. 2 In another embodiment, the radical gas generator 412 uses an oxygen (O ) plasma to generate atomic oxygen. 2 Optionally, the radical gas generator 412 utilizes nitrogen trifluoride (NF ) plasma to generate a reactive plasma containing one or more radicals in the gas stream. 3 ), fluorine (F 2 ), Chlorine (Cl 2 ), or any type of other material may be utilized. Alternatively, the radical gas may be generated by other gas excitation methods, including electron beam excitation, laser excitation, or hot filament excitation. Additionally, while the above description discloses various embodiments of RF-based plasma generation systems, one skilled in the art will recognize that any type of alternative radical gas generation system may be used with the systems of the present invention. Exemplary alternative radical gas generation systems include, but are not limited to, glow discharge plasma systems, capacitively coupled plasma systems, cascaded arc plasma systems, inductively coupled plasma systems, wave heated plasma systems, arc discharge plasma systems, corona discharge plasma systems, dielectric barrier discharge systems, capacitive discharge systems, and piezoelectric direct discharge plasma systems.

[0058] 5, at least one processing chamber 416 can be in fluid communication with the radical gas generator 412 through at least one reactive gas conduit 414. In some applications, the reactive gas conduit 414 is fabricated from a chemically inert material or a material having only low chemical reactivity. Exemplary materials include, but are not limited to, quartz, sapphire, stainless steel, reinforced steel, aluminum, ceramic materials, glass, brass, nickel, YBCO, and the like. 2 O 3 , YAlO x , various alloys, and coated metals such as anodized aluminum. In one embodiment, a single reactive gas conduit 414 is in fluid communication with a single radical gas generator 412. In another embodiment, multiple reactive gas conduits 414 are in fluid communication with a single reactive gas generator 412. In yet another embodiment, a single reactive gas conduit 414 is in fluid communication with multiple radical gas generators 412. Thus, any number of reactive gas conduits 414 can be in communication with any number of radical gas generators 412. Optionally, the reactive gas conduit 414 can include one or more valve devices or systems, sensors or similar devices 422 coupled thereto or in communication therewith. For example, one or more valve devices 422 can be coupled to the reactive gas conduit 414, thereby allowing a user to selectively allow and / or restrict the flow of at least one reactive gas stream through the reactive gas conduit 414.

[0059] The processing chamber 416 may be coupled to or in communication with the radical gas generator 412 through a reactive gas conduit 414. In one embodiment, the processing chamber 416 includes one or more vacuum chambers or vessels configured to have one or more substrates, semiconductor wafers, or similar materials positioned therein. Optionally, the processing chamber 416 may be used for atomic layer processing of semiconductor substrates or semiconductor wafers. Optionally, the processing chamber 416 may be used to process any type of substrate or material using any type of processing method or system. Exemplary processing methods include, but are not limited to, physical vapor deposition (PVD), chemical vapor deposition (CVD), rapid thermal chemical vapor deposition (RTCVD), atomic layer deposition (ALD), and atomic layer etching (ALE), etc. One skilled in the art will appreciate that the processing chamber 416 may be fabricated from any type of material, including, but not limited to, stainless steel, aluminum, mild steel, brass, high density ceramic, glass, acrylic, etc. In one embodiment, at least one inner surface of the processing chamber 416 can include at least one coating, anodized material, sacrificial material, physical features or elements, etc., intended to selectively alter its reactivity, durability, and / or fill microporosity. At least one exhaust conduit 418 can be coupled to the processing chamber 416 and configured to exhaust one or more gases or materials therefrom. Optionally, one or more control sensors, valves, gas scrubbers, or similar devices 424 can be coupled to or positioned proximate to the exhaust conduit 418, thereby allowing a user to selectively exhaust one or more gases or other materials from the processing chamber 416.

[0060] 5, at least one chamber processor module 420 may be coupled to or otherwise in communication with the processing chambers 418 and / or various components of the processing system. The chamber processing module 420 may be configured to provide localized control of the various components forming the processing system 10. In the illustrated embodiment, the chamber processing module 420 is in communication with the processing chambers 416 through conduits, however, one skilled in the art will appreciate that the chamber processing module 420 may be in communication with any of the components forming the processing system 410 through conduits, wirelessly, or both.

[0061] As shown in FIG. 5, at least one sampling module 432 can be in fluid communication with the radical gas generator 412 through at least one sampling conduit 430. One skilled in the art will appreciate that the sampling conduit 430 can be made from any type of material, including, but not limited to, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, plastics, carbon fiber, carbon-based materials, graphite, silicon, silicon dioxide, silicon carbide, and the like. Thus, the sampling conduit 430 can be configured to chemically react with highly reactive radicals contained within the radical gas stream flowing therethrough. In yet another embodiment, the sampling conduit 430 can be configured with a catalytic material that facilitates recombination of atomic gas species into molecular gas species such that the recombination energy of the atomic gas is released and measured. In other embodiments, the sampling conduit 430 can be configured to be chemically inert.

[0062] 5, at least one reactant gas feed or source 472 can be configured to provide at least one reactant or stream 474 to the sampling module 432. Alternatively, the reactant source 472 can be in communication with the radical gas generator 412 through at least one stream conduit 475. Any type of reactant source 472 configured to provide any type of reactant or stream 474 can be used with the system. For example, in one embodiment, the reactant source 472 includes at least one source of reactant gas configured to react with atomic radicals, molecular radicals, and short-lived molecules within the sampling module 432. Exemplary reactant gases include, but are not limited to, nitrogen, oxygen, hydrogen, NH 3 , H.O. 2 The reaction source 472 may include any type of atomic radicals generated using a gas such as a compound such as , or a separate plasma source. In another embodiment, the reaction source 472 includes at least one excitation source configured to provide excitation energy to the atomic radicals, molecular radicals, and short-lived molecules in the sampling module 432. For example, in one embodiment, the reaction source 472 includes at least one source of optical radiation configured to provide excitation energy to the sampling module 432.

[0063] 5, the sampling conduit 430 may include any type of sensors, valves, heating elements, cooling elements, and the like thereon. In one embodiment, the sampling conduit 430 is directly coupled to and in fluid communication with the radical gas generator 412. In the illustrated embodiment, the sampling conduit 430 is in fluid communication with the radical gas generator 412 through the reactant gas conduit 414. Optionally, the sampling conduit 430 may be in fluid communication with a sampling control valve 422 positioned on the reactant gas conduit 414. For example, the sampling control valve 422 may be configured to selectively direct a specified volume of the reactant gas traversing through the reactant gas conduit 414 through the sampling conduit 430 to the sampling module 432. In another embodiment, the sampling control valve 422 may be configured to selectively direct a specified flow rate of the reactant gas traversing through the reactant gas conduit 414 through the sampling conduit 430 to the sampling module 432. Additionally, any number of additional components, valves, sensors, and the like may be positioned anywhere along the sampling conduit 430. For example, in the illustrated embodiment, at least one sensor and / or control device 450 may be positioned along the sampling conduit 430. Exemplary sensor devices include, but are not limited to, thermocouples, temperature sensors, optical sensors, UV, optical, or infrared spectrometers, charged particle detectors, vacuum gauges, mass spectrometers, and the like. For example, in one embodiment, the sensor device 450 includes at least one thermistor. In another embodiment, the sensor device 450 includes at least one calorimetric measurement system or device. In another embodiment, a novel calorimetric measurement system embodiment is discussed in detail and illustrated in Figures 8-15 of this application. Optionally, the sensor device 450 may include one or more titration systems or devices. Those skilled in the art will recognize that the sensor device 450 may include any number of in situ measurement devices or systems, flow valves, flow meters, flow verifiers, and the like.

[0064] 5, in the illustrated embodiment, the sampling module 432 is coupled to at least one molecular compound stream conduit 434. Similar to the sampling conduit 430, the molecular compound stream conduit 434 can be fabricated from any type of material, including, but not limited to, graphite, silica, carbon fiber, silicon dioxide, silica, and silicon carbide, carbon-based materials, silica-based materials, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, and plastics. In one embodiment, at least a portion of at least one of the sampling conduit 430 and / or the molecular compound stream conduit 434 can be configured to react with the radical gas stream flowing therethrough. For example, in one embodiment, at least a portion of the sampling conduit 430 and / or the molecular compound stream conduit 434 can be configured to react with radicals in the gas stream to form chemical species that are more stable and more accurately measurable compared to these radicals.

[0065] As shown in FIG. 5, at least one sensor module 436 is in fluid communication with the sampling module 432 through at least one molecular compound stream conduit 434. In one embodiment, the sensor module 436 can be configured to detect and measure the concentration of radicals in at least one gas stream. Any type of device or system can be used for or to form the sensor module 436. For example, in one embodiment, the sensor module 436 includes at least one detector configured to measure radical flux in the radical gas stream. In another embodiment, the sensor module 436 is configured to measure the concentration of at least one chemical species in the gas stream. For example, the sensor module 436 can detect and measure the concentration of at least one chemical species in the gas stream. 2 ), carbon-hydrogen molecule (methylidyne radical), methylene (CH 2 ), methyl group compounds (CH 3 ), methane (CH 4), silicon tetrafluoride, and similar compounds. In one particular embodiment, the sensor module includes at least one optical gas imaging camera or device, such as a Fourier transform infrared spectroscopy system (hereinafter FTIR system), a tunable filter spectroscopy system (hereinafter TFS system), mass spectrometry, and optical absorption spectroscopy. Optionally, the sensing module 436 may further include at least one titration system or device. In one embodiment, the sensing module 436 may be configured to reduce or eliminate recombination of radicals in the gas stream into molecular species. In another embodiment, the sensor module 436 may be configured to allow recombination of radicals in the gas stream into molecular species.

[0066] Referring again to FIG. 5, at least one sensor module output conduit 438 is in fluid communication with the sensor module 436 and a flow measurement and / or flow control module 440. In some embodiments, the flow measurement module 440 is configured to accurately measure a portion of the gas stream flowing therethrough. For example, the flow of the gas stream can be measured using a mass flow verifier (MFV). In another embodiment, the flow of the gas stream can be measured using a mass flow meter (MFM). Optionally, the flow can be determined by measuring a pressure difference between an orifice of known size and a fluid conductance in the multi-sensor gas sampling detection system 410. Those skilled in the art will recognize that any type of flow measurement device or system can be used with the gas sampling detection system 410 disclosed herein. As shown in FIG. 5, at least one exhaust conduit 442 can be coupled to or in communication with the flow measurement module 440 and can be configured to exhaust the radical gas stream from the gas sampling detection system 410. Optionally, the exhaust conduit 442 can be in fluid communication with at least one vacuum source (not shown).

[0067] 5, the processing system 410 may include at least one optional processor module 452 in communication with at least one component thereof. For example, in the illustrated embodiment, the optional processor module 452 is in communication with the radical gas generator 412 through at least one processor conduit 454. Additionally, the optional processor system 452 may be in communication with at least one of the following: an optional sensor 450 through the processor conduit 454 and at least one optional sensor conduit 456; a sampling module 432 through the processor conduit 454 and at least one sampling conduit 458; a sensor module 436 through at least one sensor module conduit 460; and a flow measurement module 440 through at least one flow measurement conduit 462. Additionally, a reactive source 472 may be in communication with the optional processor system 452 through the processor conduit 454. In one embodiment, the optional processor module 452 can be configured to provide and receive data to and from at least one of the radical gas generator 412, the optional sensor 450, the sampling module 432, the sensor module 436, and the flow measurement module 440. Thus, the optional processor module 452 can be configured to measure flow conditions within the processing system 410 and selectively vary the operating conditions of the processing system 410 to optimize system performance. More specifically, the optional processor module 452 can be configured to measure the concentration of radicals in the gas stream and vary the operating characteristics of the radical gas generator 412 to increase or decrease it. Furthermore, the optional processor module 452 is in communication with at least one of the optional valve device 422, the sensor 424, and the chamber processor module 420 through at least one optional processing conduit 464 and can provide / receive data thereto. Optionally, the optional processor module 452 can wirelessly communicate with various components of the processing system 410. Additionally, the processor 452 may be configured to store performance data, processing methods and times, lot numbers, and the like.Additionally, the processor 452 can be configured to communicate with one or more external processors over at least one computer network.

[0068] Optionally, at least one analytical system or circuit 466 can be formed within the processing system 410, as shown in Figure 5. As shown, analytical system 466 can include at least one of a sampling module 432, a sensor module 436, a flow measurement module 449, an optional sensor 450, and an optional processor module 452. Additionally, analytical system 466 can further include a valve device 422 or other devices and components within processing system 410.

[0069] FIG. 6 illustrates an embodiment of a gas sampling detection system useful for detecting the concentration of radicals in a gas stream. As illustrated, the gas sampling detection system 510 includes at least one plasma generator and / or radical gas generator 512 in fluid communication with at least one process chamber 516 through at least one gas passage 514. In one embodiment, the radical gas generator 512 is in communication with at least one sample gas source and at least one plasma source configured to excite and dissociate a sample gas to generate at least one reactive gas stream. In one particular embodiment, the radical gas generator 512 includes an RF toroidal plasma source, although one skilled in the art will recognize that any type of plasma source or radical gas source can be used with the system of the present invention. In one embodiment, the radical gas generator 512 generates hydrogen (H 2 ) to generate atomic hydrogen. 2 In another embodiment, the radical gas generator 512 uses an oxygen (O ) plasma to generate atomic oxygen. 2 Optionally, the radical gas generator 512 utilizes nitrogen trifluoride (NF ) plasma to generate a reactive plasma containing one or more radicals in the gas stream. 3 ), fluorine (F 2 ), Chlorine (Cl 2), or any other type of material may be utilized. Alternatively, the radical gas may be generated by other gas excitation methods, including electron beam excitation, laser excitation, or hot filament excitation. Additionally, while the above description discloses various embodiments of RF-based plasma generation systems, one skilled in the art will recognize that any type of alternative radical gas generation system may be used with the systems of the present invention. Exemplary alternative radical gas generation systems include, but are not limited to, glow discharge plasma systems, capacitively coupled plasma systems, cascaded arc plasma systems, inductively coupled plasma systems, wave heated plasma systems, arc discharge plasma systems, corona discharge plasma systems, dielectric barrier discharge systems, capacitive discharge systems, and piezoelectric direct discharge plasma systems.

[0070] 6, at least one processing chamber 516 can be in fluid communication with the radical gas generator 512 through at least one reactive gas conduit 514. In some applications, the reactive gas conduit 514 is fabricated from a chemically inert material or a material having only low chemical reactivity. Exemplary materials include, but are not limited to, quartz, sapphire, stainless steel, reinforced steel, aluminum, ceramic materials, glass, brass, nickel, YBCO, and the like. 2 O 3 , YAlO x, various alloys, and coated metals such as anodized aluminum. In one embodiment, a single reactive gas conduit 514 is in fluid communication with a single radical gas generator 512. In another embodiment, multiple reactive gas conduits 514 are in fluid communication with a single reactive gas generator 512. In yet another embodiment, a single reactive gas conduit 514 is in fluid communication with multiple radical gas generators 512. Thus, any number of reactive gas conduits 514 can be in communication with any number of radical gas generators 512. Optionally, the reactive gas conduit 514 can include one or more valve devices or systems, sensors or similar devices 522 coupled thereto or in communication therewith. For example, one or more valve devices 522 can be coupled to the reactive gas conduit 514, thereby allowing a user to selectively allow and / or restrict the flow of at least one reactive gas stream through the reactive gas conduit 514.

[0071] As shown in FIG. 6, the processing chamber 516 can be coupled to or in communication with the radical gas generator 512 through a reactive gas conduit 514. In one embodiment, the processing chamber 516 includes one or more vacuum chambers or vessels configured to have one or more substrates, semiconductor wafers, or similar materials positioned therein. For example, the processing chamber 516 can be used for atomic layer processing of semiconductor substrates or semiconductor wafers. Optionally, the processing chamber 516 can be used to process any type of substrate or material using any type of processing method or system. Exemplary processing methods include, but are not limited to, physical vapor deposition (PVD), chemical vapor deposition (CVD), rapid thermal chemical vapor deposition (RTCVD), atomic layer deposition (ALD), and atomic layer etching (ALE), etc. One skilled in the art will appreciate that the processing chamber 516 can be fabricated from any type of material, including, but not limited to, stainless steel, aluminum, mild steel, brass, high density ceramic, glass, acrylic, etc. For example, at least one inner surface of the processing chamber 16 may include at least one coating, anodized material, sacrificial material, physical features or elements, etc., intended to selectively alter its reactivity, durability, and / or fill microporosity. At least one exhaust conduit 518 may be coupled to the processing chamber 516 and configured to exhaust one or more gases or materials therefrom. Optionally, one or more control sensors, valves, gas scrubbers, or similar devices 524 may be coupled to or positioned proximate the exhaust conduit 518, thereby allowing a user to selectively exhaust one or more gases or other materials from the processing chamber 516.

[0072] 6, at least one chamber processor module 520 can be coupled to or otherwise in communication with the processing chambers 518 and / or various components of the processing system. The chamber processing module 520 can be configured to provide localized control of the various components forming the processing system 510. In the illustrated embodiment, the chamber processing module 520 is in communication with the processing chambers 516 through conduits, although one skilled in the art will appreciate that the chamber processing module 520 can be in communication with any of the components forming the processing system 510 through conduits, wirelessly, or both.

[0073] As shown in FIG. 6, at least one sampling module 532 can be in fluid communication with the radical gas generator 512 through at least one sampling conduit 530. One skilled in the art will appreciate that the sampling conduit 530 can be made from any type of material, including, but not limited to, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, plastics, carbon fiber, carbon-based materials, graphite, silicon, silicon dioxide, silicon carbide, and the like. Thus, in some embodiments, the sampling conduit 530 can be configured to chemically react with highly reactive atomic radicals, molecular radicals, and short-lived molecules contained within the radical gas stream flowing therethrough. In yet another embodiment, the sampling conduit 530 can be configured with a catalytic material that facilitates recombination of atomic gas species into molecular gas species such that the recombination energy of the atomic gas is released and measured. In other embodiments, the sampling conduit 530 can be configured to be chemically inert. In yet another embodiment, the sampling conduit 530 can be configured with a catalytic material that facilitates recombination of radical species into molecular gas species. Optionally, the sampling conduit 530 may include any type of sensors, valves, heating elements, cooling elements, and the like thereon. In one embodiment, the sampling conduit 530 is directly coupled to and in fluid communication with the radical gas generator 512. In the illustrated embodiment, the sampling conduit 530 is in fluid communication with the radical gas generator 512 through the reactive gas conduit 514. Optionally, the sampling conduit 530 may be in fluid communication with a sampling control valve 522 positioned on the reactive gas conduit 514. For example, the sampling control valve 522 may be configured to selectively direct a designated volume of the reactive gas traversing through the reactive gas conduit 514 through the sampling conduit 530 to the sampling module 532. In another embodiment, the sampling control valve 522 may be configured to selectively direct a designated flow rate of the reactive gas traversing through the reactive gas conduit 514 to the sampling module 532 through the sampling conduit 530.Additionally, any number of additional components, valves, sensors, and the like, may be positioned anywhere along the sampling conduit 530. For example, in the illustrated embodiment, at least one sensor and / or control device 550 may be positioned along the sampling conduit 530. Exemplary sensor devices include, but are not limited to, thermocouples, temperature sensors, optical sensors, UV, optical, or infrared spectrometers, charged particle detectors, vacuum gauges, mass spectrometers, and the like. For example, in one embodiment, the sensor device 550 includes at least one thermistor. In another embodiment, the sensor device 550 includes at least one calorimetric measurement system or device. An embodiment of a novel calorimetric measurement system is discussed and illustrated in detail in Figures 8-15 of the present application. Optionally, the sensor device 550 may include one or more titration systems or devices. Those skilled in the art will recognize that the sensor device 550 may include any number of in situ measurement devices or systems, flow valves, flow meters, flow verifiers, and the like.

[0074] 6, in the illustrated embodiment, the sampling module 532 is coupled to at least one molecular compound stream conduit 534. Similar to the sampling conduit 530, the molecular compound stream conduit 534 can be fabricated from any type of material, including, but not limited to, graphite, silica, carbon fiber, silicon dioxide, silica, and silicon carbide, carbon-based materials, silica-based materials, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, and plastics. In one embodiment, at least a portion of at least one of the sampling conduit 530 and / or the molecular compound stream conduit 534 can be configured to react with the radical gas stream flowing therethrough. For example, in one embodiment, at least a portion of the sampling conduit 530 and / or the molecular compound stream conduit 534 can be configured to react with radicals in the gas stream to form chemical species that are more stable and more accurately measurable compared to these radicals.

[0075] As shown in FIG. 6, at least one sensor module 536 is in fluid communication with the sampling module 532 through at least one molecular compound stream conduit 534. In one embodiment, the sensor module 536 can be configured to detect and measure the concentration of radicals in at least one gas stream. Any type of device or system can be used for or to form the sensor module 536. For example, in one embodiment, the sensor module 536 includes at least one detector configured to measure radical flux in the radical gas stream. In another embodiment, the sensor module 536 is configured to measure the concentration of at least one chemical species in the gas stream. For example, the sensor module 536 can detect and measure the concentration of at least one chemical species in the gas stream. 2 ), carbon-hydrogen molecule (methylidyne radical), methylene (CH 2 ), methyl group compounds (CH 3 ), methane (CH 4 ), silicon tetrafluoride, and similar compounds. In one particular embodiment, the sensor module includes at least one optical gas imaging camera or device, such as a Fourier transform infrared spectroscopy system (hereinafter FTIR system), a tunable filter spectroscopy system (hereinafter TFS system), mass spectrometry, and optical absorption spectroscopy. Optionally, the sensing module 536 may further include at least one titration system or device. In one embodiment, the sensing module 536 may be configured to reduce or eliminate recombination of radicals in the gas stream into molecular species. In another embodiment, the sensor module 536 may be configured to allow recombination of radicals in the gas stream into molecular species. At least one sensor module return conduit 535 may be in fluid communication with the sensor module 536 and the processing chamber 520. During use, radical gas or similar material output from the sensing module 535 may be selectively directed to the processing chamber 520.

[0076] 6, the processing system 510 may include at least one optional processor module 552 in communication with at least one component thereof. For example, in the illustrated embodiment, the optional processor module 552 is in communication with the radical gas generator 512 through at least one processor conduit 554. Additionally, the optional processor system 552 may be in communication with at least one of the optional sensor 550 through the processor conduit 554 and at least one optional sensor conduit 556, the sampling module 532 through the processor conduit 554 and at least one sampling conduit 558, and the sensor module 536 through at least one sensor module conduit 560. In one embodiment, the optional processor module 552 may be configured to provide and receive data to and from at least one of the radical gas generator 512, the optional sensor 550, the sampling module 532, and the sensor module 536. Thus, the optional processor module 552 can be configured to measure flow conditions within the processing system 510 and selectively vary the operating conditions of the processing system 510 to optimize system performance. More specifically, the optional processor module 552 can be configured to measure the concentration of radicals and / or short-lived molecules in the radical stream and vary the operating characteristics of the radical gas generator 52 to increase or decrease it. Additionally, the optional processor module 552 is in communication with at least one of the optional valve device 522, the sensor 524, and the chamber processor module 520 through at least one optional processing conduit 564 and can provide / receive data thereto. Optionally, the optional processor module 552 can wirelessly communicate with various components of the processing system 510. Additionally, the processor 552 can be configured to store performance data, processing methods and times, lot numbers, and the like. Additionally, the processor 552 can be configured to communicate with one or more external processors through at least one computer network.

[0077] Optionally, as shown in Figure 6, at least one analytical system or circuitry 566 can be formed within the processing system 510. As shown, analytical system 566 can include at least one of a sampling module 532, a sensor module 536, an optional sensor 550, and an optional processor module 552. Additionally, analytical system 566 can further include a valve device 522 or other devices and components within processing system 510.

[0078] As with the previous embodiment, FIG. 7 illustrates an embodiment of a gas sampling detection system useful for detecting the concentration of radicals in a gas stream. As shown, the gas sampling detection system 610 includes at least one plasma generator and / or radical gas generator 612 in fluid communication with at least one gas passage 614. In one embodiment, the radical gas generator 612 is in communication with at least one sample gas source and at least one plasma source configured to excite and dissociate a sample gas to generate at least one reactive gas stream. In one particular embodiment, the radical gas generator 612 includes an RF toroidal plasma source, although one skilled in the art will recognize that any type of plasma source or radical gas source can be used with the system of the present invention. In one embodiment, the radical gas generator 612 generates hydrogen (H 2 ) to generate atomic hydrogen. 2 In another embodiment, the radical gas generator 612 uses an oxygen (O ) plasma to generate atomic oxygen. 2 Optionally, the radical gas generator 612 utilizes nitrogen trifluoride (NF ) plasma to generate a reactive plasma containing one or more radicals in the gas stream. 3 ), fluorine (F 2 ), Chlorine (Cl 2), or any other type of material may be utilized. Alternatively, the radical gas may be generated by other gas excitation methods, including electron beam excitation, laser excitation, or hot filament excitation. Additionally, while the above description discloses various embodiments of RF-based plasma generation systems, one skilled in the art will recognize that any type of alternative radical gas generation system may be used with the systems of the present invention. Exemplary alternative radical gas generation systems include, but are not limited to, glow discharge plasma systems, capacitively coupled plasma systems, cascaded arc plasma systems, inductively coupled plasma systems, wave heated plasma systems, arc discharge plasma systems, corona discharge plasma systems, dielectric barrier discharge systems, capacitive discharge systems, and piezoelectric direct discharge plasma systems.

[0079] 7, at least one reactive gas conduit 614 can be in fluid communication with the radical gas generator 612. In some applications, the reactive gas conduit 614 is fabricated from a chemically inert material or a material having only low chemical reactivity. Exemplary materials include, but are not limited to, quartz, sapphire, stainless steel, reinforced steel, aluminum, ceramic materials, glass, brass, nickel, YBCO, and the like. 2 O 3 , YAlO x, various alloys, and coated metals such as anodized aluminum. In one embodiment, a single reactive gas conduit 614 is in fluid communication with a single radical gas generator 12. As with the immediately preceding embodiment, any number of reactive gas conduits 614 can be in communication with any number of radical gas generators 612. Additionally, optionally, the reactive gas conduit 614 can include one or more valve devices or systems, sensors or similar devices 622 coupled thereto or in communication therewith. For example, one or more valve devices 622 can be coupled to the reactive gas conduit 614, thereby allowing a user to selectively allow and / or restrict the flow of at least one reactive gas stream through the reactive gas conduit 614. The reactive gas conduit 614 can be coupled to or otherwise in communication with any type of inspection system, vessel, container, processing accessory and / or processing system, and the like.

[0080] As shown in FIG. 7, at least one sampling module 632 can be in fluid communication with the radical gas generator 612 through at least one sampling conduit 630. One skilled in the art will appreciate that the sampling conduit 630 can be made from any type of material, including, but not limited to, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, plastics, carbon fiber, carbon-based materials, graphite, silicon, silicon dioxide, silicon carbide, and the like. Thus, in some embodiments, the sampling conduit 630 can be configured to chemically react with highly reactive atomic radicals, molecular radicals, and short-lived molecules contained within the radical gas stream flowing therethrough. In yet another embodiment, the sampling conduit 630 can be configured with a catalytic material that facilitates recombination of atomic gas species into molecular gas species such that the recombination energy of the atomic gas is released and measured. In other embodiments, the sampling conduit 630 can be configured to be chemically inert. In yet another embodiment, the sampling conduit 630 can be configured with a catalytic material that facilitates recombination of radical species into molecular gas species. Optionally, the sampling conduit 30 may include any type of sensors, valves, heating elements, cooling elements, and the like thereon. In one embodiment, the sampling conduit 630 is directly coupled to and in fluid communication with the radical gas generator 612. In the illustrated embodiment, the sampling conduit 630 is in fluid communication with the radical gas generator 612 through the reactive gas conduit 614. Optionally, the sampling conduit 630 may be in fluid communication with a sampling control valve 622 positioned on the reactive gas conduit 614. For example, the sampling control valve 622 may be configured to selectively direct a designated volume of the reactive gas traversing through the reactive gas conduit 614 through the sampling conduit 630 to the sampling module 632. In another embodiment, the sampling control valve 622 may be configured to selectively direct a designated flow rate of the reactive gas traversing through the reactive gas conduit 614 to the sampling module 632 through the sampling conduit 630.Additionally, any number of additional components, valves, sensors, and the like, may be positioned anywhere along the sampling conduit 630. For example, in the illustrated embodiment, at least one sensor and / or control device 650 may be positioned along the sampling conduit 630. Exemplary sensor devices include, but are not limited to, thermocouples, temperature sensors, optical sensors, UV, optical, or infrared spectrometers, charged particle detectors, vacuum gauges, mass spectrometers, and the like. For example, in one embodiment, the sensor device 650 includes at least one thermistor. In another embodiment, the sensor device 650 includes at least one calorimetric measurement system or device. An embodiment of a novel calorimetric measurement system is discussed and illustrated in detail in Figures 8-15 of the present application. Optionally, the sensor device 650 may include one or more titration systems or devices. Those skilled in the art will recognize that the sensor device 650 may include any number of in situ measurement devices or systems, flow valves, flow meters, flow verifiers, and the like.

[0081] 7, in the illustrated embodiment, the sampling module 632 is coupled to at least one molecular compound stream conduit 634. Similar to the sampling conduit 630, the molecular compound stream conduit 634 can be fabricated from any type of material, including, but not limited to, graphite, silica, carbon fiber, silicon dioxide, silica, and silicon carbide, carbon-based materials, silica-based materials, stainless steel, alloys, aluminum, brass, ceramic materials, glass, polymers, and plastics. In one embodiment, at least a portion of at least one of the sampling conduit 630 and / or the molecular compound stream conduit 634 can be configured to react with the radical gas stream flowing therethrough. For example, in one embodiment, at least a portion of the sampling conduit 630 and / or the molecular compound stream conduit 634 can be configured to react with radicals in the gas stream to form species that are more stable and more accurately measurable compared to these radicals.

[0082] As shown in FIG. 7, at least one sensor module 636 is in fluid communication with the sampling module 632 through the molecular compound stream conduit 634. In one embodiment, the sensor module 636 can be configured to detect and measure the concentration of radicals in the at least one gas stream. Any type of device or system can be used for or to form the sensor module 636. For example, in one embodiment, the sensor module 636 includes at least one detector configured to measure radical flux in the radical gas stream. In another embodiment, the sensor module 636 is configured to measure the concentration of at least one chemical species in the gas stream. For example, the sensor module 636 can detect and measure the concentration of at least one chemical species in the gas stream. 2 ), carbon-hydrogen molecule (methylidyne radical), methylene (CH 2 ), methyl group compounds (CH 3 ), methane (CH 4 ), silicon tetrafluoride, and similar compounds. In one particular embodiment, the sensor module includes at least one optical gas imaging camera or device, such as a Fourier transform infrared spectroscopy system (hereinafter FTIR system), a tunable filter spectroscopy system (hereinafter TFS system), mass spectrometry, and optical absorption spectroscopy. Optionally, the sensing module 636 can further include at least one titration system or device. In one embodiment, the sensing module 636 can be configured to reduce or eliminate recombination of radicals in the gas stream into molecular species. In another embodiment, the sensor module 636 can be configured to allow recombination of radicals in the gas stream into molecular species.

[0083] Referring again to FIG. 7, at least one sensor module output conduit 638 is in fluid communication with the sensor module 636 and a flow measurement and / or flow control module 640. In some embodiments, the flow measurement module 640 is configured to accurately measure a portion of the gas stream flowing therethrough. For example, the flow of the gas stream can be measured using a mass flow verifier (MFV). In another embodiment, the flow of the gas stream can be measured using a mass flow meter (MFM). Optionally, the flow can be determined by measuring a pressure difference between an orifice of known size and a fluid conductance in the multi-sensor gas sampling detection system 610. Those skilled in the art will recognize that any type of flow measurement device or system can be used with the gas sampling detection system 610 disclosed herein. As shown in FIG. 7, at least one exhaust conduit 642 can be coupled to or in communication with the flow measurement module 640 and can be configured to exhaust the radical gas stream from the gas sampling detection system 610. Optionally, the exhaust conduit 642 can be in fluid communication with at least one vacuum source (not shown).

[0084] 7, the processing system 610 can include at least one optional processor module 652 that can communicate with at least one component thereof. For example, in the illustrated embodiment, the optional processor module 652 is in communication with the radical gas generator 612 through at least one processor conduit 654. Additionally, the optional processor module 652 can be in communication with at least one of: an optional sensor 650 through the processor conduit 654 and at least one optional sensor conduit 656; a sampling module 632 through the processor conduit 654 and at least one sampling conduit 658; a sensor module 636 through at least one sensor module conduit 660; and a flow measurement module 640 through at least one flow measurement conduit 662. In one embodiment, the optional processor module 652 can be configured to provide and receive data from at least one of the radical gas generator 612, the optional sensor 650, the sampling module 632, the sensor module 636, and the flow measurement module 640. Thus, the optional processor module 652 can be configured to measure flow conditions within the processing system 610 and selectively vary operating conditions of the processing system 610 to optimize system performance. More specifically, the optional processor module 652 can be configured to measure a concentration of radicals within the gas stream and vary operating characteristics of the radical gas generator 612 to increase or decrease it. Additionally, the optional processor module 652 is in communication with at least one of the optional valve device 622 and the sensor 624 and can provide / receive data thereto. Optionally, the optional processor module 652 can wirelessly communicate with various components of the processing system 610. Additionally, the processor 652 can be configured to store performance data, processing methods and times, lot numbers, and the like. Additionally, the processor 652 can be configured to communicate with one or more external processors over at least one computer network.

[0085] 7, at least one analytical system or circuit 666 can be formed within the processing system 610. As shown, analytical system 666 can include at least one of a sampling module 632, a sensor module 636, a flow measurement module 649, an optional sensor 650, and an optional processor module 652. Additionally, analytical system 666 can further include a valve device 622 or other devices and components within processing system 610.

[0086] As mentioned above, various embodiments of the processing system disclosed in Figures 1-7 include at least one sampling module and at least one sensor module. Optionally, as shown in Figures 1-7, a portion of the sampling module and the sensor module can be combined into a single unit or device. For example, as shown in Figure 1, the sampling module 32 and the sensor module 36 can be combined into at least one sampling reaction module 700. Figures 1-7 show various embodiments of the processing system having at least one sampling reaction module 700 therein. In the illustrated embodiment, the sampling module and the sensor module are included in the sampling reaction module 700. Optionally, a portion of the sampling module and a portion of the sensor module can be included in the sampling reaction module 700. Figures 8 and 9 show various views of an embodiment of a sampling reaction module 700 configured for use with a processing device disclosed herein, and Figures 10-15 show various views of the components forming the sampling reaction module 700. Furthermore, one skilled in the art will recognize that the sampling reaction module 700 can be used in any type of system. Optionally, the processing system disclosed herein can be operated without including the sampling reaction module 700 .

[0087] As shown in Figures 8 and 9, the sampling reaction module 700 includes at least one module body 702 having at least one coupling body 704 extending therefrom. At least one coupling body flange 706 can be positioned on the coupling body 704. The module body 702 further includes at least one coupling surface 708 having at least one coupling flange 710 formed thereon. At least one vacuum passage 712 can be formed in the coupling surface 708 proximate to the coupling flange 710. One or more coupling devices 714 can be positioned anywhere on the module body 702. In one embodiment, the module body 702 is made from stainless steel. In another embodiment, the module body 702 is made from brass. In yet another embodiment, the module body 702 is made from copper. Optionally, the module body 702 can be made from any type of material, including, but not limited to, aluminum alloys, copper alloys, tungsten alloys, tungsten, metal alloys, ceramics, and similar materials.

[0088] 8 and 9, at least one analytical accessory 720 may be positioned on or otherwise coupled to the module body 702. At least one coupling body 740 defining at least one coupling passage 742 may extend from the module body 702. In the illustrated embodiment, at least one fluid inlet port 760 and at least one fluid outlet port 762 may be positioned on or otherwise in communication with the analytical accessory 720. One or more thermal control modules 750, 752 may be positioned within the analytical accessory 720 proximate at least one of the module bodies 702. Various features and components of the module body 702 and analytical accessory 720 are described in more detail in the following paragraphs.

[0089] 10-13 show various views of the elements forming the analytical accessory 720. As shown, the analytical accessory 720 includes at least one analytical accessory body 722 having at least one analytical accessory cover plate 724 positioned thereon. In the illustrated embodiment, the analytical accessory cover plate 724 is selectively separable from the analytical accessory body 722, although one skilled in the art will appreciate that the analytical accessory cover plate 724 need not be separable from the analytical accessory body 722. The coupling body 740 having at least one coupling passage 742 included therein can further include at least one coupling passage support 744 extending from at least one passage mount mounting plate 746. One or more fasteners 748 can be configured to traverse through the passage mounting plate 746 and couple at least a portion of the analytical accessory 720 to the module body 702 (see FIGS. 5-6).

[0090] As shown in Figures 10-13, one or more thermal control modules 750, 752 can be positioned proximate to the analysis accessory 720. In one embodiment, the thermal control modules 750, 752 include a thermoelectric module configured to regulate the temperature of the sampling tube 780 in the analysis accessory 720. In another embodiment, the thermal control modules 750, 752 can include at least one thermistor or similar device. Thus, the thermal control modules 750, 752 can include various heating and cooling devices. Optionally, any type of temperature regulation device, temperature regulation accessory, temperature regulation component, or temperature regulation device can be used with the analysis accessory 720. In the illustrated embodiment, two thermal control modules 750, 752 are used to regulate the temperature of various components of the analysis accessory 720, which in turn can regulate the temperature of the radical gas stream under analysis. In one embodiment, the thermal control modules 750, 752 can be in communication with at least one optional processor module used in the processing system (see reference numbers 52, 152, 252, 382, ​​452, 552, and 652, respectively, in Figures 1-7).

[0091] 10-13, at least one connector relief 754 may be formed in at least one of the analytical accessory body 722 and the analytical accessory cover plate 724. As shown, at least one sampling tube 780 may be positioned within the coupling body 740. Additionally, the sampling tube 780 may be positioned proximate to the thermal control modules 750, 752. In one embodiment, the sampling tube 780 is fabricated from at least one chemically reactive material. For example, in one embodiment, at least a portion of the sampling tube 780 is fabricated from carbon, graphite, silica, carbon fiber, silicon dioxide, silica, and silicon carbide, carbon-based materials, silica-based materials, and the like. Thus, at least a portion of the sampling tube 780 reacts with radicals contained within the radical gas stream flowing through the sampling tube passage 782 formed within the sampling tube 780, thereby producing carbon monoxide (CO), carbon dioxide (CO 2 ), carbon-hydrogen molecule (methylidyne radical), methylene (CH 2 ), methyl group compounds (CH 3 ), methane (CH 4 ), silicon tetrafluoride, and similar compounds. Optionally, the sampling tube 780 can be made from any type of chemically inert material, such as stainless steel, ceramic, aluminum, various alloys, and the like. Similarly, the coupling body 740 can be made from any type of material. In the illustrated embodiment, the coupling body 740 is made from a substantially chemically inert material, such as stainless steel, whereas the sampling tube 780 is made from a chemically reactive material, such as silicon carbide. Thus, the coupling body 740 can be made from a chemically inert material or a chemically reactive material.

[0092] In one embodiment, the sampling tube 780 is insulated from the surrounding environment. For example, the sampling tube 780 can be positioned within the coupling body 740. A vacuum can be maintained in the gap between the connecting tube 740 and the sampling tube 780, thereby insulating the sampling tube 780 from the environment. Optionally, the sampling tube 780 can be manufactured in any number of diameters, lengths, and / or cross-sectional dimensions.

[0093] As shown in FIGS. 10-13, one or more sealing devices or members may be positioned on or proximate to the sampling passage 780. In the illustrated embodiment, at least one sealing device 784 is positioned on the sampling tube 780 and configured to isolate the sampling tube 780 from the coupling body 740. In one embodiment, the sealing device 784 is configured to minimize thermal conduction between the coupling body 740 and the sampling tube 780. Additionally, at least one sealing member 786 is positioned on or near the sampling tube 780 proximate to at least one plate member 790. In one embodiment, the sealing member 786 includes at least one crush seal, although one skilled in the art will recognize that any type of sealing member may be used.

[0094] 10-13, the fluid inlet port 760 and the fluid outlet port 762 can be in communication with one or more fluid port receivers 764 formed in the analytical accessory body 722. Through the fluid port receivers 764, one or more fluid channels 772 can be in fluid communication with the fluid inlet port 760 and the fluid outlet port 762. During use, one or more fluids can be directed through the fluid inlet port 760, the fluid channels 772, and the fluid outlet port 762. Thus, various fluids can be directed through the analytical accessory body 722 to selectively control the temperature of the analytical accessory 720 and the radical gas stream flowing proximate thereto. Additionally, optionally, at least one sealing member 770 can be positioned proximate to the fluid channels 772.

[0095] 10-13, a plate member 790 can be positioned proximate to the thermal control modules 750, 752. In one embodiment, the plate member 790 is configured to position the thermal control modules 750, 752 proximate to the sampling tube 780 and the analytical accessory body 722. In one embodiment, at least one seal body 800 and / or at least one interface seal body 802 can be positioned on or proximate to the plate member 790. As shown, the plate member 790 can include at least one sampling tube orifice 804 configured to allow at least a portion of the sampling tube 780 to traverse therethrough.

[0096] 14 and 15 show various views of a module body 702 for use with the sampling reaction module 700. As shown, the module body 702 includes at least one module body surface 718. Optionally, at least one fastener receiver can be formed on the at least one module body surface 718. In one embodiment, the module body surface 718 can be configured to receive at least one cooling element, body, and / or feature (not shown) thereon or formed thereon. For example, in one embodiment, a cooling element or fin configured to increase the area of ​​the module body 702 can be formed on the surface of the at least one module body surface 718. Additionally, the module body surface 718 can include at least one sampling tube receiver 716 configured to receive at least a portion of a sampling tube 780 therein (see FIGS. 10-13). As shown in FIG. 12, at least a portion of the sampling tube receiver 716 is in fluid communication with at least a portion of a vacuum passage 712 formed in the module body 712. During use, the vacuum passage 712 is coupled to or otherwise in fluid communication with a vacuum source (not shown). Thus, the sampling tube receiver 716 is in fluid communication with the vacuum created within the vacuum passage 712.

[0097] The present application further discloses various methods for measuring the concentration of radicals in a radical gas stream. FIG. 16 shows a general flow chart of a measurement process when used in conjunction with the processing system 10 shown in FIG. 1, however, one skilled in the art will recognize that the processes disclosed herein can be readily adapted for use with the various embodiments of the processing system shown in FIGS. 2-7. As shown, a radical gas stream is generated, shown in FIG. 16 at reference numeral 2000. Generally, the radical gas stream is generated by the radical gas generator 12 shown in FIG. 1. Thereafter, a known volume and / or flow rate of the radical gas stream is directed to at least one analysis circuit 66, shown in FIG. 16 at reference numeral 2006, while a remaining portion of the radical gas stream is directed to the processing chamber 16, shown at reference numeral 2002, for processing at least one substrate or otherwise used within the processing chamber, shown at reference numeral 2004. As shown in Figure 16 at reference numeral 2008, the radical gas of known volume and / or flow rate reacts with a reagent in the analytical circuit 66 to produce new chemical species or molecules that are easier to detect / measure, or in alternative embodiments recombine back to its molecular species. Exemplary reagents include, but are not limited to, Ni, Al, W, Cu, Co, Zn, C, quartz, alumina, organic carbohydrate-containing materials, and various related oxides and nitrides, etc.

[0098] Optionally, one or more reagents, reactive materials, and / or excitation energy can be provided to the sample module 432 using one or more reactive sources 472 to react with the radical gas stream to produce new chemical species or molecules that are easier to detect / measure (see FIG. 5). Typically, the reagents are reacted with the radical gas stream in the vicinity of the sampling module 32 to provide a compound stream. The compound stream can then be directed into the sensor module 36, as shown in FIG. 16 at reference numeral 2010, which measures the concentration of the new chemical species or molecules in the compound stream. The concentration of radicals in the process chamber can then be calculated, as shown in FIG. 16 at reference numeral 2012, by comparing the ratio of the concentration of the chemical species in the compound stream for each defined volume of the radical gas stream forming the sampling gas stream with the remaining volume of at least one radical gas stream. Optionally, the optional processor module 52 can be configured to accept the data of the sensor module 36 and selectively adjust the radical gas generator to optimize the concentration of radicals in the radical gas stream, as shown in FIG. 16 at reference numeral 2014. Optionally, as shown in FIG. 6, the radical gas stream 535 from the sensor module 536 can be directed to the process chamber 520. In another embodiment, one skilled in the art will recognize that the measurement systems and methods disclosed herein can be used to measure the concentration of atomic radicals, molecular radicals, and other short-lived molecules in any type of application. Thus, the measurement systems described herein need not include or be coupled to a process chamber 16 (see FIG. 1). For example, FIG. 7 shows an embodiment of a measurement system 610 in which the process chamber is eliminated. Thus, the measurement systems described herein can be used in any type of application in which in situ measurements of atomic radicals, molecular radicals, and / or other short-lived molecules are desired.

[0099] As described above, the sampling reaction module 700 shown in Figures 1-15 can be used to determine the concentration of atomic radicals, molecular radicals, short-lived molecules, and other difficult-to-measure molecules or compounds in situ. In one embodiment, the multi-sensor gas sampling detection system disclosed herein can be configured to use calorimetry to measure recombination reactions using the sampling reaction module 700 to determine the concentration of molecules or other compounds in a gas stream. Figure 17 shows a flow chart of one calorimetry-based method utilizing the sampling reaction module 700 shown in Figures 1 and 8-15. In this embodiment, the flow of the radical gas stream is established in the multi-sensor gas sampling detection system 10 at a defined flow rate (X sccm), as shown at 2016. A defined flow rate (Y sccm) or volume of the radical gas stream is then directed to the sampling reaction module 700 (see reference number 2018 in Figure 17). The flow of the radical gas stream through the sampling reaction module 700 increases (or in some circumstances decreases) the temperature of the sampling tube 780 relative to the temperature of the plate member 790 (hereinafter dT), and this increase is recorded (see reference numeral 2020). Furthermore, the rate of temperature change between the sampling tube 780 and the plate member 790 (dT m 17 as reference numeral 2024, the calculated harvested power can then be calculated as follows: Harvesting power = C p * m * dT m / dt+P loss (dT) Where: p = specific heat capacity, m = mass of the sampling tube, P loss = Power loss.

[0100] As shown in FIG. 17 at reference numeral 2026, the total power can be calculated as follows: Total power = Harvesting power * Ysccm / Xsccm

[0101] In another embodiment, the multi-sensor gas sampling and detection system disclosed herein can be configured to use alternative calorimetric methods to determine the concentration of molecules or other compounds in a gas stream. Figure 18 illustrates the function P of the components of the sampling and reaction module 700 shown in Figures 1 and 8-15. loss 2 shows a flow chart of an alternative calorimetric-based method utilizing a pre-calibrated curve to determine the . As in the previous embodiment, a radical gas stream flow is established, as shown in reference number 2028. A defined volume, flow rate, or portion of the radical gas stream is directed to at least one sensing unit or device (see reference number 2030). The thermal control module 750 is activated and the time it takes for the sampling tube 780 to reach a stable temperature is observed (see reference number 2032). Thus, the recombination reaction is measured at a fixed sampling tube temperature (U degrees). In addition to this, to calculate the harvesting power, the mass of the sampling tube 780 is calculated based on the effective mass m, not the total mass of the sampling tube. eff The mass of the sampling tube 780 is determined by only a portion of the mass of the sampling tube 780, denoted as . As a result, in this case, the response time of the sampling reaction module 700 is faster due to the smaller thermal mass. The total power can be calculated based on the collected power.

[0102] During use, the sampling tube 780 is heated (reference numeral 2032) to a higher temperature (U) and then allowed to cool to its steady state temperature (see reference numeral 2034). A pre-calibration curve can then be established based on the observed thermal characteristics of the sampling reaction module 700. With the pre-calibration curve established, a defined flow rate (Xsccm) of radical gas is established. A defined flow rate (Ysccm) or volume of radical gas is directed into the sampling reaction module 700. The thermal control module 750 of the sampling reaction module 700 is set to a specified temperature. The thermal control module 750 is then shut down and the temperature change (dT) and rate of temperature change (dt m ) is recorded (reference number 2034).

[0103] The calculated harvested power can then be calculated (reference number 2036) as follows: Harvesting power = C p * m eff * dT m / dt+P loss (dT) Where: p = specific heat capacity. m eff = effective mass of the sampling tube, P loss = Power loss.

[0104] The total power (reference number 2038) can be calculated as follows: Total power = Harvesting power * Ysccm / Xsccm

[0105] FIG. 19 shows a flow chart of an alternative method utilizing the sampling reaction module 700 shown in FIGS. 1 and 8-15 in which the recombination reaction is measured at a fixed sampling tube temperature. In this embodiment, the flow of the radical gas stream is established in the multi-sensor gas sampling detection system 10 at a defined flow rate (X sccm) (reference numeral 2040). A defined flow rate (Y sccm) or volume of the radical gas stream is then directed to the sampling reaction module 700 (reference numeral 2042). The temperature of the sampling tube 480 is then selectively increased using the thermal control module 750 of the sampling reaction module 700 (reference numeral 2044). When the sampling tube 780 is heated to a specified elevated temperature (dT H ), the thermal control module 750 is shut off, thereby allowing the sampling tube 780 to return to equilibrium temperature (reference number 2046). The temperature of the sampling tube 480 is then selectively reduced (reference number 2048) using the thermal control module 750 of the sampling reaction module 700. When the sampling tube 780 reaches the designated low temperature (dT L ), the thermal control module 750 is shut off, thereby allowing the sampling tube 780 to return to equilibrium temperature (reference numeral 2050).

[0106] Thereafter, the calculated sample upper and lower power limits may be calculated (reference numeral 2052) as follows: Harvesting power limit = P loss (dT H ) Harvesting power lower limit = P loss (dT L ) Here: loss = Power loss. The upper and lower bounds of the response can be calculated as follows (reference number 2054): Total power upper bound = Harvesting power limit * Ysccm / Xsccm Total power lower bound = Harvesting power lower bound * Ysccm / Xsccm The upper and lower bounds determine the error limits of the actual response.

[0107] Figure 20 graphically illustrates an example process flow as described above in Figure 19. As shown, a thermal control module 750, labeled TEC in Figure 20, is activated to provide an upper bound on the process and is deactivated to provide a lower bound on the process.

[0108] In some cases, due to the difficulty in distinguishing between heat generated from radical recombination and heat generated from the hot gas of the plasma source, the determination of the sampling power may require further calibration. Accordingly, FIG. 21 illustrates a calibration process configured to distinguish between heat generated from radical recombination and heat generated from the hot gas of the plasma source. As shown, a defined flow rate (X sccm) of radical gas is established (reference numeral 2056). A defined flow rate (Y sccm) or volume of the radical gas stream is then directed to the sampling reaction module 700 (reference numeral 2058). The flow of the radical gas stream through the sampling reaction module 700 increases (or in some circumstances decreases) the temperature of the sampling tube 780 relative to the temperature of the plate member 790 (hereinafter dT). The temperature change of the sampling tube 780 and the plate member 790 is recorded (reference numeral 2060). Additionally, the rate of temperature change between the sampling tube 780 and the plate member 790 (dT m / dt) is recorded (reference number 2062). The calculated harvested power can then be calculated (reference number 2064) as follows: Harvesting power = C p * m * dT m / dt+P loss (dT) Where: p = specific heat capacity, m = mass of the sampling tube, P loss = Power loss.

[0109] The total power can be calculated (reference number 2066) as follows: Total power = Harvesting power * Ysccm / Xsccm

[0110] The flow rate (Y'sccm) or volume of the radical gas stream directed to the sampling reaction module 700 can then be selectively adjusted (reference number 2068). For example, at least one valve device 22 (see FIG. 1) can be adjusted to vary the flow of radical gas into the sampling reaction module 700. As shown in FIG. 22, after collecting the harvest power at several different harvest sampling flows, the results can be plotted and used to extrapolate the reading at zero flow (valve closed). The slope of the extrapolation line is then the measurement sensitivity to the harvest flow, which will have a greater dependence on radical recombination and less dependence on heat from the hot gas.

[0111] Optionally, the multi-sensor gas detection sampling system 700 can include at least one photo-reactive material and at least one detector, such as FTIR or TFS, thereby using optical-based determination of the sampling power. Thus, instead of performing in-situ diagnostics exposed to radical elemental materials, a user may wish to first recombine the radical species into molecular gas species and then transport these molecular gas species to an optical sensing device, which may now be located at a remote location. For example, in one particular example, a carbon material can be used in the multi-sensor gas detection sampling system 700. During use, atomic species such as oxygen react with the carbon to produce CO or CO. 2 Then, CO gas or CO 2 The gas is transmitted to a remote optical sensor to detect any CO or CO present. 2 The amount of CO, CO 2 The concentration of O radicals can be optically determined, thereby providing the concentration of O radicals in the gas stream. The reagent material can be selected such that it reacts only with atomic species and not with molecular species.

[0112] (table) TIFF0007650942000001.tif55155

[0113] 24 shows a flow chart of an exemplary optical-based measurement process. As shown, the thermal control module 750 of the sampling reaction module 700 is set to a stable desired temperature (U) (reference numeral 2070). A defined flow rate (Xsccm) of radical gas is then established (reference numeral 2072). Furthermore, a defined flow rate (Ysccm) or volume of radical gas stream is directed to the sampling reaction module 700 (reference numeral 2074). A spectrum from the optical sensor or photodetector (FTIP / TFS) in the thermal control module 750 can be recorded (reference numeral 2076). The radical output can then be calculated (reference numeral 2078) as follows: Radical power = f(spectral peak) * Xsccm / Ysccm

[0114] The flow rate (Y'sccm) or volume of the radical gas stream directed to the sampling reaction module 700 can be selectively adjusted (reference number 2080). For example, at least one valve device 22 (see FIG. 1) can be adjusted to vary the flow of radical gas into the sampling reaction module 700. The resulting measurements indicate the relative amplitude of a given radical stream that can be used for process monitoring. Also, to improve the selectivity of the reaction, the sampling tube 780 can be set to a fixed temperature. For example, the temperature can be selected such that the reacting material will selectively react with atomic radical species rather than molecular gas species.

[0115] In another embodiment, the sampling reaction module 700 can include a semiconductor-based sampling architecture with at least one semiconductor material positioned within the sampling reaction module 700. More specifically, as shown in FIG. 25, the thermal control module 750 of the sampling reaction module 700 is set to a stable desired temperature (U) (reference numeral 2082). A defined flow rate (Xsccm) of radical gas is then established (reference numeral 2084). Furthermore, a defined flow rate (Ysccm) or volume of radical gas stream is directed to the sampling reaction module 700 (reference numeral 2086). The resistance from at least one semiconductor sensor positioned within the sampling reaction module 700 can be recorded (reference numeral 2088). The radical output can then be calculated (reference numeral 2090) as follows: Radical output = % of change in resistance

[0116] FIG. 26 graphically illustrates the resulting resistance changes as the radical output stream is activated and deactivated when using the resistive-based sampling architecture described above and shown in FIG.

[0117] FIG. 6 above illustrates an embodiment of a gas sampling detection system useful for detecting the concentration of radicals in a gas stream. In contrast to the system described in FIG. 6, FIG. 27 illustrates an embodiment of a gas sampling detection system 910 including a novel calorimetric architecture positioned downstream of a radical gas generator or remote plasma source. As shown in FIG. 27, the gas sampling detection system 910 includes at least one plasma generator and / or radical gas generator 912 in fluid communication with at least one process chamber 916 through at least one reactive gas passage 914. In one embodiment, the radical gas generator 912 is in communication with at least one sample gas source and at least one plasma source configured to excite and dissociate a sample gas, generating at least one reactive gas stream. In one particular embodiment, the radical gas generator 912 includes an RF toroidal plasma source, although one skilled in the art will recognize that any type of plasma source or radical gas source can be used with the system of the present invention. In one embodiment, the radical gas generator 912 is in communication with hydrogen (H ) to generate atomic hydrogen. 2 In another embodiment, the radical gas generator 912 uses an oxygen (O ) plasma to generate atomic oxygen. 2 Optionally, the radical gas generator 912 utilizes nitrogen trifluoride (NF ) plasma to generate a reactive plasma containing one or more radicals in the gas stream. 3 ), fluorine (F 2 ), Chlorine (Cl 2 ), ammonia (NH 3), or any other type of material may be utilized. Alternatively, the radical gas may be generated by other gas excitation methods, including electron beam excitation, laser excitation, or hot filament excitation. Additionally, while the above description discloses various embodiments of RF-based plasma generation systems, one skilled in the art will recognize that any type of alternative radical gas generation system may be used with the systems of the present invention. Exemplary alternative radical gas generation systems include, but are not limited to, glow discharge plasma systems, capacitively coupled plasma systems, cascaded arc plasma systems, inductively coupled plasma systems, wave heated plasma systems, arc discharge plasma systems, corona discharge plasma systems, dielectric barrier discharge systems, capacitive discharge systems, and piezoelectric direct discharge plasma systems.

[0118] 27, at least one processing chamber 916 can be in fluid communication with the radical gas generator 912 through at least one reactive gas conduit 914. In some applications, the reactive gas conduit 914 is fabricated from a chemically inert material or a material having only low chemical reactivity. Exemplary materials include, but are not limited to, quartz, sapphire, stainless steel, reinforced steel, aluminum, ceramic materials, glass, brass, nickel, YBCO, and the like. 2 O 3 , YAlO x, various alloys, and coated metals such as anodized aluminum. In one embodiment, a single reactive gas conduit 914 is in fluid communication with a single radical gas generator 912. In another embodiment, multiple reactive gas conduits 914 are in fluid communication with a single radical gas generator 912. In yet another embodiment, a single reactive gas conduit 914 is in fluid communication with multiple radical gas generators 912. Optionally, the reactive gas conduit 914 may include a sampling conduit or sampling tubes performing a similar function as the sampling tube 780 described above and shown in FIGS. 11-13. Thus, any number of reactive gas conduits 914 may be in communication with any number of radical gas generators 912. Additionally, at least one valve device or sensor device 922 may be included on the reactive gas conduit 914 between the radical gas generator 912 and the process chamber 916. For example, in one embodiment, the valve device 922 can be configured to selectively allow or restrict flow of at least one fluid through the reactant gas conduit 914 to generate a desired pressure differential between the radical gas generator 912 and the processing chamber 916. In one embodiment, the valve device 922 can include a variable valve or alternatively a fixed size orifice. In one embodiment, the valve device 922 can be positioned downstream of the sensor device 950, as shown in FIG. 27. Alternatively, the valve device 922 can be positioned upstream of the sensor device 950.

[0119] As shown in FIG. 27, the processing chamber 916 can be coupled to or in communication with the radical gas generator 912 through a reactive gas conduit 914. In one embodiment, the processing chamber 916 includes one or more vacuum chambers or vessels configured to have one or more substrates, semiconductor wafers, or similar materials positioned therein. For example, the processing chamber 916 can be used for atomic layer processing of semiconductor substrates or semiconductor wafers. Optionally, the processing chamber 916 can be used to process any type of substrate or material using any type of processing method or system. Exemplary processing methods include, but are not limited to, physical vapor deposition (PVD), chemical vapor deposition (CVD), rapid thermal chemical vapor deposition (RTCVD), atomic layer deposition (ALD), and atomic layer etching (ALE), etc. One skilled in the art will appreciate that the processing chamber 916 can be fabricated from any type of material, including, but not limited to, stainless steel, aluminum, mild steel, brass, high density ceramics, glass, acrylic, etc. For example, at least one inner surface of the processing chamber 916 can include at least one coating, anodized material, sacrificial material, physical features or elements, etc., intended to selectively alter its reactivity, durability, and / or fill microporosity. At least one exhaust conduit 918 can be coupled to the processing chamber 916 and configured to exhaust one or more gases or materials therefrom. Optionally, one or more control sensors, valves, gas scrubbers, or similar devices 924 can be coupled to or positioned proximate to the exhaust conduit 918, thereby allowing a user to selectively exhaust one or more gases or other materials from the processing chamber 916.

[0120] 27, at least one chamber processor module 920 can be coupled to or otherwise in communication with the processing chambers 916 and / or various components of the processing system. The chamber processing module 920 can be configured to provide localized control of the various components forming the processing system 910. In the illustrated embodiment, the chamber processing module 920 communicates with the processing chambers 916 through at least one conduit, although one skilled in the art will appreciate that the chamber processing module 920 can communicate with any of the components forming the processing system 910 through conduits, wirelessly, or both.

[0121] As shown in Figure 27, the reaction gas conduit 914 may include one or more sensor systems and / or similar devices 950 coupled thereto or in communication therewith. For example, in the illustrated embodiment, at least one calorimetric sensor device 950 may be positioned within and / or coupled to the reaction gas conduit 914, although one skilled in the art will recognize that any type of sensor device or sensor system may be used in the system. Unlike the embodiment shown in Figure 6 and described above, the embodiment of the gas sampling detection system 910 shown in Figure 27 need not include the embodiment of the sample reaction module 700 included within the gas sampling detection system 510 shown in Figure 6.

[0122] 27, the processing system 910 may include at least one optional processor module 952 in communication with at least one component thereof. For example, in the illustrated embodiment, the optional processor module 952 may communicate with the radical gas generator 912 and the power source 926 through at least one processor conduit 954. Additionally, the optional processor system 952 may communicate with the sensor 950 through the processor conduit 954 and the sensor conduit 958. In one embodiment, the optional processor module 952 may be configured to provide and receive data to and from at least one of the radical gas generator 912, the power source 926, and the sensor device 950. Thus, the optional processor module 952 may be configured to measure flow conditions within the processing system 910 by the sensor device 950 and selectively vary operating conditions of the processing system 910 or the power source 926 to optimize system performance. More specifically, the optional processor module 952 can be configured to measure the concentration of radicals and / or short-lived molecules in the radical gas stream and change the operating characteristics of the radical gas generator 912 to increase or decrease it. As described above, the sensor device 950 can include a calorimetric sensor device 950. Additionally, the optional processor module 952 can be in communication with the optional valve device 922 (through conduit 958) and / or the chamber processor module 920 (through conduit 964) and can provide / receive data thereto. The optional processor module 952 can be configured to provide and receive plasma power or input power to the power source 926. Optionally, the processor 952 can wirelessly communicate with various components of the processing system 910. Additionally, the processor 952 can be configured to store performance data, processing methods and times, lot numbers, and the like. Additionally, the processor 952 can be configured to communicate with one or more external processors through at least one computer network.

[0123] 28 and 29 illustrate various embodiments of sensor architectures or sensor devices that can be used to form the sensor device 950. As shown in FIG. 28, in one embodiment, the sensor device 950 can be coupled or otherwise in communication with the reactive gas conduit 914 through at least one conduit 974. Additionally, at least one sensor body 970 can be positioned in at least one gas passage 915 formed in the reactive gas conduit 914 and in communication with the sensor device 950 through the conduit 974. In the illustrated embodiment, a single sensor body 970 is positioned in the reactive gas conduit 914, but one skilled in the art will appreciate that any number of sensor bodies can be positioned in the reactive gas conduit 914 and coupled to the sensor device 950. Additionally, in one embodiment, the sensor body 970 is insulated from the reactive gas conduit 914 using at least one thermal insulation device 972. Alternatively, one skilled in the art will appreciate that the sensor body 970 does not need to be thermally insulated from the reactive gas conduit 914. The sensor body 970 can be fabricated from any type of material including, but not limited to, carbon, graphite, silica, carbon fiber, silicon dioxide, silica, and silicon carbide, carbon-based materials, and silica-based materials. Thus, at least a portion of the sensor body 970 reacts with radicals contained within the radical gas stream flowing through the reactive gas conduit 914, thereby producing carbon monoxide (CO), carbon dioxide (CO 2 ), carbon-hydrogen molecule (methylidyne radical), methylene (CH 2 ), methyl group compounds (CH 3 ), methane (CH 4), silicon tetrafluoride, and similar compounds. Optionally, the sensor body 970 can be fabricated from any type of chemically inert material, such as stainless steel, ceramic, nickel, tungsten, aluminum, various alloys, and the like. Optionally, the sensor body 970 can be fabricated from a catalytic material, such as platinum, palladium, nickel, that can react with one or more elements or chemical compounds in the radical gas stream to provide a chemical composition and / or concentration of a particular gas in the radical gas.

[0124] During use, reactive gas 913 generated by the plasma generator is guided through the reactive gas conduit 914. A sensor body 970 positioned in a gas passage 915 formed in the reactive gas conduit 914 is placed in the radical gas stream 913. The temperature of the insulated sensor body 970 is measured by the sensor device 950. The sensor device 950 then provides calorimetric data measured by the sensor body 970 to at least one of the optional processor module 952 and / or the plasma generator 912. Thus, operating parameters of the radical gas generator 912 can be adjusted based on the calorimetric measurements performed by the sensor device 950.

[0125] FIG. 29 illustrates another embodiment of a reactive gas conduit 914 with which a sensor device 950 is in communication. More specifically, the sensor device 950 includes a first sensor body 976 and a second sensor body 978 positioned on or otherwise coupled to at least one thermal body 980. As shown in the illustrated embodiment, the first sensor body 976 can be positioned within at least one gas passage 915 formed in the reactive gas conduit 914 (and within the radical gas stream 913), whereas the second sensor body 978 is positioned away from the reactive gas conduit 914. In an alternative embodiment, both the first sensor body 976 and the second sensor body 978 are positioned within proximity to the reactive gas conduit 914. Additionally, the thermal body 980 can include at least one fluid inlet 982 and at least one fluid outlet 984. In one embodiment, the thermal body 980 can be configured to maintain at least a portion of the reactive gas conduit 914 at a desired temperature. As in the immediately preceding embodiment, at least one of the first sensor body 976 and / or the second sensor body 978 is in communication with the sensor device 950 through at least one conduit 978. In use, the temperature of the first sensor body 976 positioned in the gas passage 915 formed in the radical gas stream is measured by the sensor device 950 as the reactant gas 913 flows through the reactant gas conduit 914. In addition to this, the temperature of the second sensor body 978 is also measured by the sensor device 950. The temperature gradient between the first sensor body 976 and the second sensor body 978 can then be calculated in the sensor device 950 and / or the optional processor module 952. The performance characteristics of the radical gas generator 912 can then be adjusted to optimize performance. Optionally, the temperature of the fluid flowing into the thermal body 980 through the fluid inlet 982 can be compared to the temperature of the fluid flowing out of the thermal body 980 through the fluid outlet 984, thereby allowing a user to calculate the heat transfer within the thermal body 980. In one embodiment, the reactive gas conduit 914 can be configured to allow radicals within the gas stream flowing therethrough to recombine.From the foregoing, one skilled in the art will appreciate that the recombined power (output calorimetry) of the gas stream by at least one of the sensor bodies 950 can be calculated within the optional processor module 952 .

[0126] 30 illustrates an alternative embodiment of a reactive gas conduit 1014 in which at least one surface of the reactive gas conduit 1014 forms a thermal sensor device. More specifically, the reactive gas conduit 1014 includes a conduit body 1016 having at least one inner surface 1018 and at least one outer surface 1019. The inner surface 1016 of the reactive gas conduit 1014 thus defines at least one gas passage 1015. Additionally, at least one thermal body 1020 may be coupled to or otherwise in communication with at least a portion of the reactive gas conduit 1014. As illustrated, the thermal body 1020 may include at least one inlet 1022 and at least one outlet 1024. The inlet 1022 and the outlet 1024 may be in communication with at least one conduit 1026 traversing through or positioned proximate to the thermal body 1020. In one embodiment, at least one fluid may be flowed through the thermal body 1020 via the inlet 1022, the outlet 1024, and the conduit 1026. In the illustrated embodiment, the thermal body 1020 is positioned proximate to a section of the reactant gas conduit 1014. Optionally, the thermal body 1020 may be positioned along the entire length of the reactant gas conduit 1014.

[0127] 30, at least one sensor device 1028 can be positioned within the conduit body 1016 of the reactive gas conduit 1014. For example, in the illustrated embodiment, the sensor device 1028 is positioned on or adjacent to the inner surface 1015 of the conduit body 1016. In one embodiment, the sensor device 1028 includes at least one sensor therein. In the illustrated embodiment, the sensor device 1028 includes a first sensor region 1030 and at least a second sensor region or device 1032. In the illustrated embodiment, the first sensor 1030 can be positioned within or adjacent to the inner surface 1018 of the conduit body 1016. Optionally, the entire inner surface 1018 can be configured to form the first sensor region 1030. Thus, the first sensor region 1030 can be configured to measure the recombination temperature / energy of the radical stream within the reactive gas conduit 1014. The second sensor region 1032 may be positioned outside the conduit body 1016. For example, in one embodiment, the second sensor region 1032 may be positioned proximate the outer surface 1019 of the conduit body 1016. In one embodiment, the second sensor region 1032 is configured to measure a temperature outside the conduit body 1016. In use, a user may calculate a temperature gradient between the first sensor region 1030 positioned within the conduit body 1016 on or proximate the inner surface 1018 and the second sensor region 1032 positioned outside the conduit body 1016 proximate the outer surface 1019. Optionally, additional sensor regions 1029 may be positioned on the gas conduit 1014. For example, in the illustrated embodiment, the additional sensor 1029 is positioned proximate the thermal body 1020. The first sensor region 1030 and the second sensor region 1032 can be separated by at least one thermal region 1034 in communication with the thermal body 1020. Optionally, the thermal region 1034 can include one or more conduits (not shown) configured to flow one or more fluids therethrough. Thus, the thermal region 1034 can be in communication with an inlet 1022 and an outlet 1024 formed on the thermal body 1020. In another embodiment, the inner surface 1018 of the conduit body 1016 can be configured to act as a sensor.As with the immediately preceding embodiment, the sensor device 1028 can communicate with at least one sensor controller 1040 through at least one sensor conduit 1042 .

[0128] During use, the temperature of the recombination heat of the reaction gas stream flowing through the reaction gas conduit 1014 is measured by the sensor device 1028 for the sensor area 1030 and by an additional sensor area 1029 for the sensor area 1032, both of which are in communication with the sensor device 1040. The performance characteristics of the radical gas generator 912 can then be adjusted to optimize performance (see FIG. 27). Optionally, the temperature of the fluid flowing into the thermal body 1020 through the fluid inlet 1022 is compared to the temperature of the fluid flowing out of the thermal body 1020 through the fluid outlet 1024, allowing a user to calculate the heat transfer within the thermal body 1020. In one embodiment, the reaction gas conduit 1014 can be configured to allow radicals in the gas stream flowing therethrough to recombine. From the above, one skilled in the art will recognize that the recombination power (total power calorimetry) of the gas stream by at least one of the sensor bodies 1040 can be calculated in the optional processor module 952 (see FIG. 27).

[0129] Figure 31 shows a flow chart of an alternative method utilizing the sampling reaction module 910 shown in Figures 27, 29, and 30. In this embodiment, the flow of the radical gas stream is established in the multi-sensor gas sampling detection system 910 at a defined flow rate (X sccm) (reference numeral 2092). Thereafter, the temperature changes of the first sensor body 982 and the second sensor body 984 are recorded (reference numeral 2094). Additionally, the rate of temperature change of the reaction gas conduit 914 (dT m / dt) is also recorded (reference number 2096). The harvested power can then be calculated (reference number 2098) as follows: Harvesting power = C p * m rgc * dTm / dt+P loss (dT) Where: p = specific heat capacity, m eff = effective mass of the sampling tube, P loss = Power loss.

[0130] Figure 32 shows another flow chart of an alternative method utilizing the sampling reaction module 910 shown in Figures 27, 29, and 30. In this embodiment, the flow of the radical gas stream is established in the multi-sensor gas sampling and detection system 910 at a defined flow rate (X sccm) (reference numeral 2100). Thereafter, the power delivered to the reactant gas stream may be recorded 2102. In addition, the temperature rise (dT) and the rate of temperature rise (dT m 27, 29, and 30, 31, reference numeral 2104). Optionally, the temperature rise (dT) and the rate of temperature rise (dT m / dT) can be measured (reference number 2106). The harvested power can then be calculated (reference number 2108) as follows: Harvesting power = C p * m * dT m / dt+P loss (dT) Where: p = specific heat capacity, m = mass of the sampling tube, P loss = Power loss.

[0131] The harvested power can then be compared (reference number 2110) with the gas flow rate and the power of the reactive gas, thereby allowing the efficiency of the radical gas generator to be accurately calculated. Furthermore, the output of the radical gas generator 912 can be evaluated (reference number 2112) and selectively adjusted (reference number 2114) by the optional processor module 952, the power supply 926, or both.

[0132] Figure 33 graphically illustrates the temperature change (dT) of the fluid into the reactive gas conduit 914 downstream of the radical gas generator 912 as the radical gas generator 912 is repeatedly cycled on and off. As shown, when the radical gas generator 912 is first activated, the temperature of the fluid rises and then drops to a lower value during the off cycle. As shown in Figure 33, the temperature change (dT) during each cycle is far from reaching a steady state, and the slope of the temperature rise is proportional to the power absorbed by the reactive gas conduit 914 from the radical gas stream generated by the radical gas generator 912.

[0133] Figures 34A and 34B show that two different radical gas generators can have different radical outputs. More specifically, the data for radical gas generator unit #1 shown in Figure 34A has a lower slope of temperature rise (dT / dt) compared to the data for radical generator unit #2 shown in Figure 34B. Meanwhile, the power input to radical generator unit #1 is higher than the power to radical gas generator unit #2.

[0134] As shown in FIG. 34A, the input power to the radical gas generator unit #1 increases from about 7.5 kW to 10 kW during 300 operating cycles. During the same time, the power at the radical gas output decreases. There is a sharp drop during the first few cycles as the surface of the radical gas generator changes due to plasma-surface interactions with the process chemistry. Then, there is a slow drop in the power in the radical gas output stream while the input plasma power increases. This behavior is quite different from the radical gas generator unit #2 shown in FIG. 34B. Not only is the power in the output radical gas stream higher by about 30-40%, but the input power to the radical gas generator unit #2 is also lower during the entire test. This indicates that the radical gas generator unit #2 is more efficient than unit #1. The higher input power and lower power in the output radical gas stream indicates a higher loss of radical gas in the radical gas generator unit #1, which is related to the difference in the surface composition of the two radical gas generators. Thus, the method of Figure 32 can be used not only to control or regulate the operation of a radical gas generator, but also to determine and characterize the performance status of a radical gas generator. The ability to separate faulty or degraded radical gas generators from good ones is particularly useful in industrial manufacturing environments to ensure product consistency.

[0135] The embodiments disclosed herein are illustrative of the principles of the present invention. Other modifications may be used that are within the scope of the invention. Thus, the devices disclosed in this application are not limited to those precisely as shown and described herein.

Claims

1. 1. A system for measuring a concentration of radicals in a gas stream, comprising: at least one radical gas generator in communication with the at least one gas source and configured to generate at least one radical gas stream; at least one processing chamber in fluid communication with the at least one radical gas generator and configured to receive at least a portion of the at least one radical gas stream; at least one sampling reaction module in fluid communication with the at least one radical gas generator, the at least one sampling reaction module having a thermal control module in thermal communication with at least one sampling tube, the at least one sampling tube receiving a portion of the radical gas stream from the at least one radical gas generator therein and reacting at least one reagent with the at least one radical gas within a defined volume of the at least one radical gas stream to produce at least one chemical species within the at least one compound stream; at least one sensor module positioned within the at least one sampling reaction module, the at least one sensor module configured to measure a temperature change of the at least one sampling tube due to a reaction of the at least one compound stream with the chemical species in the sampling tube, and to determine a concentration of the at least one chemical species in the at least one compound stream in the sampling tube based on the measured temperature change in the at least one sampling tube; at least one flow measurement module in fluid communication with the at least one sampling reaction module and configured to measure a volume of at least one of the at least one radical gas stream and the at least one compound stream; and at least one exhaust conduit for exhausting the at least one radical gas stream from the flow measurement module. A system characterized by:

2. the at least one reagent comprises a carbon-based material; The system of claim 1 .

3. the at least one reagent comprises a silicon-based material; The system of claim 1 .

4. the at least one reagent comprises at least one material selected from the group consisting of graphite, silica, carbon fiber, silicon dioxide, and silicon carbide; The system of claim 1 .

5. the at least one sampling module comprises at least one calorimetric measurement system; The system of claim 1 .

6. The at least one sampling module comprises at least one titration system. The system of claim 1 .

7. the at least one sampling module comprises at least one chemisorption system; The system of claim 1 .

8. the at least one sensor module includes at least one Fourier transform infrared spectroscopy system; The system of claim 1 .

9. the at least one sensor module includes at least one tunable filter spectroscopic system; The system of claim 1 .

10. The at least one flow measurement module comprises at least one mass flow meter. The system of claim 1 .

11. at least one flow measurement module includes at least one mass flow verifier; The system of claim 1 .

12. and at least one processor in communication with at least one of the at least one radical gas generator, at least one analysis circuit, at least one sampling module, at least one sensor module, and at least one flow measurement module, and configured to controllably adjust to generation of at least one radical gas stream emitted from the at least one radical gas generator based on data received from at least one of the at least one analysis circuit, at least one sampling module, at least one sensor module, and at least one flow measurement module. The system of claim 1 .

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