SYSTEMS AND METHODS FOR RECOVERING ORGANIC CONTAMINANTS FROM SEMICONDUCTING WAFERS

Abstract

Systems and methods are described for systems and methods for integrated decomposition and scanning of a semiconducting wafer for organic and inorganic impurities. In an aspect, a method includes, but is not limited to, positioning a nozzle above a surface of a semiconducting wafer, the semiconducting wafer supported adjacent to or within an interior of a chamber body; introducing a first scan fluid including one or more organic fluids to an inlet port of the nozzle; directing a portion of the first scan fluid onto the surface of the semiconducting wafer to permit interaction between the scan fluid and one or more organic contaminants present on the surface of the semiconducting wafer; and removing the first scan fluid containing at least a portion of the one or more organic contaminants from the surface of the semiconducting wafer via the nozzle.

Description

BACKGROUND

Mass spectrometry is an analysis technique used for the determination of trace impurities (e.g., elemental, organic, or other impurities) in liquid or gaseous samples. Sample introduction systems may be employed to introduce fluid samples into various analysis instrumentations. A sample introduction system can transport an aliquot of liquid sample to a nebulizer that converts the sample into a polydisperse aerosol suitable for ionization in the mass spectrometry instrumentation. For elemental impurities Inductively Coupled Plasma (ICP) ionization sources are used whereas for organic impurities Electrospray, Atmospheric Pressure Chemical Ionization (APCI), or other ionization sources are used. These ionization sources are coupled to a mass spectrometer, such as a Quadrupole mass spectrometer, a Time of Flight mass spectrometer, an Iontrap mass spectrometer, or the like.

SUMMARY

Systems and methods are described for systems and methods for integrated decomposition and scanning of a semiconducting wafer for organic and inorganic impurities. In an aspect, a method for scanning a surface of a semiconducting wafer for organic contaminants utilizing a nozzle includes, but is not limited to, positioning a nozzle above a surface of a semiconducting wafer, the semiconducting wafer supported adjacent to or within an interior of a chamber body; introducing a first scan fluid including one or more organic solvents to an inlet port of the nozzle; directing a portion of the first scan fluid onto the surface of the semiconducting wafer to permit interaction between the first scan fluid and one or more organic contaminants present on the surface of the semiconducting wafer; removing the first scan fluid containing at least a portion of the one or more organic contaminants from the surface of the semiconducting wafer via the nozzle; introducing a second scan fluid including one or more organic solvents to the inlet port of the nozzle; directing a portion of the second scan fluid onto the surface of the semiconducting wafer to permit interaction between the second scan fluid and one or more residual organic contaminants present on the surface of the semiconducting wafer following the first scan fluid removal; and removing the second scan fluid containing at least a portion of the one or more residual organic contaminants from the surface of the semiconducting wafer via the nozzle.

In an aspect, a method for scanning a surface of a semiconducting wafer for organic contaminants utilizing a nozzle includes, but is not limited to, positioning a nozzle above a surface of a semiconducting wafer, the semiconducting wafer supported adjacent to or within an interior of a chamber body; introducing a first scan fluid including one or more organic solvents to an inlet port of the nozzle; directing a portion of the first scan fluid onto the surface of the semiconducting wafer to permit interaction between the first scan fluid and one or more organic contaminants present on the surface of the semiconducting wafer; while directing the portion of the first scan fluid onto the surface of the semiconducting wafer, introducing a second portion of the first scan fluid to the nozzle to replenish a volume of the first scan fluid on the surface of the semiconducting wafer; and removing the first scan fluid containing at least a portion of the one or more organic contaminants from the surface of the semiconducting wafer via the nozzle.

In an aspect, a method for scanning a surface of a semiconducting wafer for organic contaminants utilizing a nozzle includes, but is not limited to, positioning a nozzle above a surface of a semiconducting wafer, the semiconducting wafer supported adjacent to or within an interior of a chamber body; introducing a first scan fluid including one or more organic fluids to an inlet port of the nozzle; directing a portion of the first scan fluid onto the surface of the semiconducting wafer to permit interaction between the scan fluid and one or more organic contaminants present on the surface of the semiconducting wafer; and removing the first scan fluid containing at least a portion of the one or more organic contaminants from the surface of the semiconducting wafer via the nozzle.

This Summary is provided to introduce a selection of concepts in a simplified form that are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in determining the scope of the claimed subject matter.

DRAWINGS

The Detailed Description is described with reference to the accompanying figures. The use of the same reference numbers in different instances in the description and the figures may indicate similar or identical items.

FIG. 1A is an isometric view of a system for recovering organic contaminants from a semiconducting wafer, in accordance with an embodiment of this disclosure.

FIG. 1B is an isometric view of the system of FIG. 1A with a semiconducting wafer positioned within a chamber.

FIG. 2A is cross-sectional view of the system of FIG. 1A, with the semiconducting wafer positioned at a scanning position.

FIG. 2B is a cross-sectional view of the system of FIG. 1A, with the semiconducting wafer positioned at a decomposition position.

FIG. 2C is a cross-sectional view of the system of FIG. 1A, with the semiconducting wafer positioned at a rinse position.

FIG. 3 is an isometric view of a portion of a chamber body of the system of FIG. 1A, in accordance with an embodiment of this disclosure.

FIG. 4 is an isometric view of the system of FIG. 1A, with a scan arm positioning a nozzle over a surface of the semiconducting wafer positioned at a scanning position.

FIG. 5 is a partial isometric view of the system of FIG. 1A, with the scan arm positioned at a rinse station for the nozzle.

FIG. 6 is a top view of the scan arm positioned at a first position over the semiconducting wafer and a subsequent second position of the semiconducting wafer during a scanning process of the semiconducting wafer, in accordance with an embodiment of this disclosure.

FIG. 7A is an isometric view of a nozzle for a semiconductor wafer decomposition and scanning system, in accordance with an embodiment of this disclosure.

FIG. 7B is a top view of the nozzle of FIG. 7A.

FIG. 7C is a bottom view of the nozzle of FIG. 7A.

FIG. 7D is a cross-sectional view of the nozzle of FIG. 7B, taken along 7D-7D.

FIG. 8A is a partial cross-sectional view of a nozzle mount assembly for a system for integrated decomposition and scanning of a semiconducting wafer, in accordance with an embodiment of this disclosure.

FIG. 8B is a partial cross-sectional view of the nozzle mount assembly of FIG. 8A in contact with a surface.

FIG. 8C is a partial cross-sectional view of the nozzle mount assembly of FIG. 8A lifted from the surface and leveled.

FIG. 9A is a schematic of a fluid handling system for a semiconductor wafer decomposition and scanning system, in accordance with an embodiment of this disclosure.

FIG. 9B is a schematic of the fluid handling system of FIG. 9A in a chemical blank load configuration, in accordance with an embodiment of this disclosure.

FIG. 9C is a schematic of the fluid handling system of FIG. 9A in a chemical inject configuration, in accordance with an embodiment of this disclosure.

FIG. 9D is a schematic of the fluid handling system of FIG. 9A in a nozzle loop load configuration, in accordance with an embodiment of this disclosure.

FIG. 9E is a schematic of the fluid handling system of FIG. 9A in a nozzle load configuration, in accordance with an embodiment of this disclosure.

FIG. 9F is a schematic of the fluid handling system of FIG. 9A in a recovery configuration, in accordance with an embodiment of this disclosure.

FIG. 10 is a schematic of a nebulizer fluid handling system for a semiconductor wafer decomposition and scanning system, in accordance with an embodiment of this disclosure.

FIG. 11A is a diagrammatic side view of a semiconducting wafer having organic contaminants present on a surface of the semiconducting wafer.

FIG. 11B is a diagrammatic side view of a system including a scan nozzle shown introducing a scan solution to the semiconducting wafer of FIG. 11A, in accordance with an embodiment of this disclosure.

FIG. 11C is a diagrammatic side view of the system of FIG. 11B, shown with a scan solution replenishment system to replenish scan solution as it evaporates from the surface of the semiconducting wafer, in accordance with an embodiment of this disclosure.

FIG. 11D is a diagrammatic side view of the system of FIG. 11B with the organic contaminants introduced into the scan solution, where the scan nozzle is shown drawing the scan solution from the surface of the semiconducting wafer, in accordance with an embodiment of this disclosure.

FIG. 11E is a diagrammatic view of the system of FIG. 11D with the scan nozzle transferring the scan solution with organic contaminants to an analysis system, in accordance with an embodiment of this disclosure.

FIG. 12 is a chart showing example experimental results of recovery of organic contaminants from a semiconducting wafer surface, in accordance with an embodiment of this disclosure.

FIG. 13 is a schematic illustration of a system for collecting and combining multiple scan samples for analysis of a semiconductor wafer, in accordance with embodiments of this disclosure.

FIG. 14 is a schematic illustration of a system for collecting and combining multiple scan samples for analysis of a semiconductor wafer shown with a sample collection vessel having a conical bottom in communication with an outlet valve, in accordance with embodiments of this disclosure.

FIG. 15 is a schematic illustration of a system for inline generation of organic solvent scan solutions and calibration standards, in accordance with embodiments of this disclosure.

FIG. 16 is a schematic illustration of a system for inline generation of organic solvent scan solutions and calibration standards shown with a plurality of pumps to dispense organic solvents or calibration standard solutions to a mixing valve, in accordance with embodiments of this disclosure.

DETAILED DESCRIPTION

Overview

Determination of trace elemental concentrations or amounts in a sample can provide an indication of purity of the sample, or an acceptability of the sample for use as a reagent, reactive component, or the like. For instance, in certain production or manufacturing processes (e.g., mining, metallurgy, semiconductor fabrication, pharmaceutical processing, etc.), the tolerances for impurities can be very strict, for example, on the order of fractions of parts per billion. For semiconductor wafer processing, the wafer is tested for impurities, such as metallic impurities, organic impurities or residues, or the like, that can degrade the capabilities of the wafer or render the wafer inoperable. For instance, metallic impurities on the wafer can diminish carrier lifetimes, cause dielectric breakdown of wafer components, and the like, whereas organic impurities can slow silicon dioxide growth, cause unintentional doping, neutralize photo-generated acids, degrade gate-oxide constructs, alter hydrophobicity or hydrophilicity, and the like.

Vapor phase decomposition (VPD) and subsequent scanning of the wafer is a technique to analyze the composition of the wafer to determine whether metallic impurities are present. Traditional VPD and scanning techniques have limited throughput for facilitating the treatment and scanning of silicon wafers for impurity analysis. For instance, systems often utilize separate chambers for the VPD procedure and for the scanning procedure. In the VPD chamber, silicon dioxide and other metallic impurities present at the surface are contacted with a vapor (e.g., hydrofluoric acid (HF), hydrogen peroxide (H₂O₂), combinations thereof) and removed from the surface as vapor (e.g., as silicon tetrafluoride (SiF₄)). The treated wafer is transported to a separate chamber for scanning, where a liquid droplet is introduced to the treated wafer surface to collect residue following reaction of the decomposition vapor with the wafer.

While the VPD techniques can be appropriate for detection and identification of metallic impurities, there are significant restrictions in use of traditional VPD techniques for recovery and identification of organic contaminants or residues present in or on semiconducting wafers that can adversely affect semiconductor processing. For example, decomposition fluids used in traditional VPD techniques can break down organic molecules or otherwise react with the organic molecules to prevent identification of the original contaminants and prevent determination of concentrations of the original contaminants present on the semiconducting wafer. Similarly, certain analysis systems used in VPD systems do not facilitate the recovery and identification of organic contaminants or residues. For instance, inductively-coupled plasma systems used in the identification of metallic impurities can prevent the identification of the arrangement of the elements present in the organic sample, where such arrangement would be used to determine the appropriate identity of the original organic molecule.

Additionally, attempting to use a single scan solution for recovery of organic contaminants can fail to draw all organic impurities present on a semiconducting wafer. For instance, a scan may only collect residues from 80% of all residues present on the semiconducting wafer in one scan, leaving the remainder of the residues on the semiconducting wafer. Inability to collect all resides can be due to the particular makeup of the contaminants (e.g., metallic, organic, etc.), the chemical composition of the scan solution (e.g., polar, non-polar, etc.), whether a decomposition process occurred prior to the scan, or the like. For example, organic molecules can have varying recovery efficiencies relative to other organic molecules where the type of solvent used by the scan nozzle can impact which organic residues are removed from the semiconducting wafer, how much of the organic residue is removed, and which organic residues are retained on the surface. Analysis of the scan would therefore only give partial insight into the total contaminants present, where the remainder of the unknown contaminants could drastically and negatively impact semiconductor fabrication and integration. Attempting to premix scan solutions can provide inaccurate ratios of chemicals due to interaction between the chemicals during storage, due to imprecise transfer methods to mix the chemicals, due to contamination risks during storage and transport, or the like, which in turn can lead to an inability to collect organic contaminants or portions thereof.

Accordingly, the present disclosure is directed, at least in part, to systems and methods for integrated decomposition and scanning of a semiconducting wafer for organic and inorganic impurities. In an aspect, a system can facilitate both semiconductor wafer decomposition and scanning, where a chamber facilitates decomposition and scanning of the semiconducting wafer with a single chamber footprint. Alternatively or additionally, the system can operate without an initial decomposition step, such as to avoid breaking down organic contaminants prior to scanning (e.g., to preserve subsequent identification of the organic contaminants). During scanning, a nozzle directs a stream of fluid along a surface of the semiconducting wafer between a first port of the nozzle and a second port of the nozzle guided by a nozzle hood defining an elongated channel to direct the stream along the wafer surface. Alternative or additional nozzles can be utilized, such as to support scan solutions including organic solvents to collect organic contaminants.

In aspects, the chamber defines at least two apertures through which the semiconducting wafer can pass through operation of a wafer support and associated motor system, with a ledge to provide zones within the chamber for decomposition and rinsing while controlling fluid movement within the chamber, such as for draining and preventing cross contamination. The motor system controls a vertical position of the wafer support with respect to the chamber body to move the semiconductor within the chamber body, with positioning above the chamber body supported by the motor system to load and unload wafers, provide access to the nozzle, and the like. The chamber further incorporates a nebulizer or other spray device to direct decomposition fluid that is aerosolized by the nebulizer directly onto the surface of the semiconducting wafer while the wafer support positions the semiconducting wafer within an interior region of the chamber. A chamber can incorporate a lid that can open and close with respect to the chamber to isolate the interior region of the chamber from the region exterior to the chamber, such as during the decomposition process. The nozzle can be positioned with respect to the chamber by a rotatable scan arm, where the nozzle can be positioned away from the chamber to facilitate lid closure (e.g., during the decomposition procedure) or to facilitate rinsing of the nozzle at a rinse station. Further, the rotatable scan arm can position the nozzle over the semiconducting wafer during the scanning procedure. The system can utilize a fluid handling system including switchable selector valves and pumps to control introduction of fluid to the nozzle, from the surface of the wafer, for preparation of blanks, for rinsing system components, and the like. Following or during the scanning procedure, the scanning fluid can be collected and sent to an analysis device (e.g., ICPMS device) for analytical determination of the composition of the scanning fluid.

In aspects, a scan nozzle can introduce an organic scan solution to one or more surfaces of a semiconducting wafer. The scan nozzle is moved relative to the surface of the semiconducting wafer to draw organic contaminants into the scan solution. The scan solution is recovered from the surface of the semiconducting wafer (e.g., through a pump in fluid communication with the scan nozzle) and transferred to an analysis system for identification and concentration determination. The analysis system can include a Time of Flight (TOF) mass spectrometer, a Triple Quadrupole (Triple Quad or QQQ) mass spectrometer, a gas chromatography-mass spectrometry (GC-MS) system, a gas chromatography-flame ionization detector (GC-FID), or other analysis system utilized for organic molecule analysis, or combinations thereof.

In aspects, the present disclosure is directed, at least in part, to systems and methods for collecting and combining multiple scan samples for analysis of contaminants that may be present on a semiconductor wafer. A sample collection vessel can be used to collect multiple scans from a scan nozzle or scan nozzles prior to transfer of a combined sample to an analysis device (e.g., ICP-MS, time of flight spectrometer, etc.). Multiple wafer scans are collected in the sample collection vessel and permitted to mix into a single sample for transfer to the analysis device. In implementations, the scan nozzle or scan nozzles can utilize the same or different scan solutions to target different compositions of contaminants (e.g., metallic, organic, etc.) to provide a single sample that includes a full recovery profile of wafer contaminants. For example, one or more scans can be performed utilizing polar solvents, non-polar solvents, aqueous solutions, or combinations thereof, where the scans are introduced to the sample collection vessel, mixed as a single sample, and transferred to the analysis device for identification and quantification of the contaminants.

In aspects, the present disclosure is directed, at least in part, to systems and methods for inline generation of organic scan solutions and internal standards for analysis of organic contaminants that may be present on a semiconductor wafer. A pump system is fluidically coupled with a plurality of organic solvents, internal standards, or combinations thereof to transfer two or more of the organic solvents and internal standards to an inline mixing device (e.g., a mixing port of a multiport valve, a multiport mixing manifold, etc.). A controller can control operation of the system to draw, on demand, the precise amounts of organic solvents and internal standards for mixing and the timing of delivery to the scan nozzle for dispensing onto one or more surfaces of the semiconducting wafer. The system provides for auto-calibration of organic analysis systems by allowing for varying concentrations of internal standards to be introduced to organic solvents to create calibration curves with high precision. Further, the system can generate a variety of organic scan solutions utilizing any combination of solvents and analytes that are fluidically coupled to the pump system. Inline generation of the organic scan solutions reduces the likelihood of environmental contamination to the semiconducting wafer or the chemicals used in the analysis thereof, while also permitting precise control of fluids introduced to the scan nozzle which can allow for small volumes of organic solvents to be utilized (e.g., thereby increasing analytical capability for lower contaminant detection limits).

Example Implementations

FIGS. 1A through 16 illustrate aspects of a system for integrated decomposition and scanning of a semiconducting wafer to recover organic and inorganic contaminants from the wafer (“system 100”) in accordance with various embodiments of this disclosure. The system 100 generally includes a chamber 102, a scan arm assembly 104, and a fluid handling system 106 (e.g., shown at least in part in FIGS. 9A-10) to facilitate at least decomposition and scanning procedures of a semiconducting wafer 108 (sometimes referred to herein as the “wafer”) through introduction of decomposition fluids to the wafer and through introduction to and removal of scanning fluids from a surface of the wafer 108. In implementations, the system 100 can facilitate scanning procedures prior to or without introduction of decomposition fluids to the wafer, which can avoid breaking down organic contaminants prior to scanning (e.g., to preserve subsequent identification of the organic contaminants). The chamber 102 provides an environment for each of wafer decomposition and wafer scanning with a single chamber footprint, and includes a wafer support 110 to hold the wafer 108 and a motor system 112 to control a vertical position of the wafer support 110 with respect to the chamber 102 (e.g., within the chamber 102, above the chamber 102, etc.) to position the wafer 108 for the decomposition and scanning procedures or during other procedures of the system 100. The motor system 112 additionally provides rotational control of the wafer support 110 to rotate the wafer 108 during various procedures of the system 100, and provides rotational and vertical control of the scan arm assembly 104 to bring a nozzle of the scan arm assembly 104 into positions over the wafer 108 during scanning procedures and into positions of a rinse station 114 for nozzle cleaning. In implementations, the wafer support 110 includes a vacuum table to hold the wafer 108 fixed relative to the wafer support 110, such as during movement of the wafer support 110.

The chamber 102 includes a chamber body 116 defining an interior region 118 to receive the wafer 108 for processing. A ledge 120 projects into the interior region 118 between a top portion 122 of the chamber body 116 and a bottom portion 124 of the chamber body 116. In implementations, the chamber body 116 defines a first aperture 126 at the top portion 122 through which the wafer 108 can be received into the interior region 118. In implementations, the ledge 120 defines a second aperture 128 at an intermediate portion of the interior region 118 between the top portion 122 and the bottom portion 124 (e.g., between the first aperture 126 and the bottom portion 124). During an example operation shown in FIG. 1A, the system 100 can receive a semiconducting wafer 108 onto the wafer support 110, such as through operation of an automated arm 50 selecting a wafer 108 from a front end unified pod (FOUP) or other location and introducing the selected wafer 108 onto the wafer support 110 (e.g., centered on the wafer support 110). The motor system 112 can position the wafer support 110 at, above, or adjacent to the top portion 122 of the chamber body 116 to permit access to the wafer support 110 by the automated arm 50 to set the wafer 108 onto the wafer support 110. For instance, the wafer support 110 can be positioned at a first position (e.g., shown in FIG. 2A) adjacent to the first aperture 126 during loading of the wafer 108. In implementations, the first position of the wafer support 110 is positioned outside the interior region 118 (e.g., extended through the first aperture 126) to receive the wafer 108.

The system 100 can include a lid 130 to isolate the interior region 118 from an exterior region 132 to facilitate wafer decomposition while limiting exposure of the decomposition fluid to the exterior region 132. For example, the lid 130 can have a size and a shape to cover the first aperture 126 when positioned over the first aperture 126. The lid 130 can be positionable between an open position (e.g., shown in FIG. 1A) and a closed position (e.g., shown in FIG. 1B). The open position can be utilized during wafer loading to provide access to the automated arm, during scanning procedures, during wafer unloading procedures, and the like. In implementations, the lid 130 is in the open position when the wafer support 110 is in the first position adjacent to the first aperture 126 to provide access to the wafer 108 by the nozzle of the scan arm assembly 104. The closed position can be utilized during wafer decomposition procedures to prevent the decomposition fluid from leaving the chamber 102 through the first aperture 126. In implementations, at least a portion of the lid 130 contacts the chamber body 116 to isolate the interior region 118 from the exterior region 132. The wafer 108 is moved within the interior region 118 through control of the vertical position of the wafer support 110 by the motor system 112 to a second position. For instance, the motor system 112 moves the wafer support 110 to the second position within the interior region 118 prior to or during movement of the lid 130 from the open position to the closed position. In implementations, the lid 130 is positioned adjacent the chamber body 116 and rotatably coupled to a mount 134 via a lid arm 136 to transition the lid 130 between the open position and the closed position.

Following introduction of the wafer 108 to the wafer support 110, the system 100 can transition to a decomposition configuration to facilitate decomposition of one or more surfaces or edges of the wafer 108. For instance, the system 100 can support decomposition of the wafer 108 prior to scanning for inorganic contaminants, although decomposition could be utilized for detecting certain organic contaminants. Alternatively or additionally, the system 100 can transition to a scanning configuration (e.g., described further herein) without a prior decomposition procedure. For the decomposition configuration, the motor system 112 can move the wafer support 110 from the first position to the second position to position the wafer 108 adjacent the second aperture 128 of the ledge 120 (e.g., as shown in FIGS. 1B and 2B). In implementations, the chamber 102 includes a nebulizer 138 positioned between the first aperture 126 and the second aperture 128 to spray a decomposition fluid onto the surface of the wafer 108 when the wafer support 110 is positioned at the second position by the motor system 112. The decomposition fluid is therefore sprayed directly into the chamber 102 by the nebulizer 138. The decomposition fluid can be supplied to the nebulizer 138 via one or more fluids lines from the fluid handling system 106, such as through a conduit 140 into an antechamber 142 housing at least a portion of the nebulizer 138. In implementations, at least a portion of the nebulizer 138 is disposed at least partially within a wall of the chamber 102. For example, the chamber body 116 can define an aperture 144 between the interior region 118 and the antechamber 142 where an outlet of the nebulizer 138 can dispense aerosolized decomposition fluid into the interior region between the first aperture 126 and the second aperture 128 to cover and decompose at least an upper surface 146 of the wafer 108.

In implementations, the chamber 102 induces a pressure beneath the wafer 108 during decomposition to prevent decomposition fluid from passing between the edge of the wafer 108 and the ledge 120. For example, the chamber 102 can include a gas outlet port 148 within the interior region 118 positioned between the second aperture 128 and the bottom portion 124 of the chamber body 116 to introduce a gas or other fluid into the interior region 118 during introduction of the decomposition fluid from the nebulizer 138 into the interior region 118. The gas from the gas outlet port 148 can be introduced at a pressure greater than the pressure of aerosolized decomposition fluid supplied from the nebulizer 138 to provide an upward flow of the gas through the second aperture 128 (e.g., between the edge of the wafer 108 and the ledge 120) to prevent the passage of the decomposition fluid beneath the wafer 108. In implementations, the system 100 includes a controller coupled to a gas source to introduce gas from the gas source to the gas outlet port 148 during introduction of the decomposition fluid onto the surface 146 of the wafer 108 by the nebulizer 138 when the wafer support 110 is positioned at the second position. For example, the gas can be fed to the gas outlet port 148 via a fluid line through the conduit 140 and the antechamber 142. In implementations, the motor system 112 induces rotation of the wafer support 110 during the decomposition procedure to spin the wafer 108 when the aerosolized decomposition fluid is present in the interior region 118.

The chamber 102 can facilitate removal of the fluids from the interior region 118 through one or more channels in the chamber body 116 in fluid communication with one or more drains, where such fluids can include, for example, excess decomposition fluid, silicon tetrafluoride (SiF₄), gas supplied by the gas outlet port 148, water, water vapor, rinse fluids, or other fluids. For example, the chamber body 116 can include a base portion 200, an intermediate portion 202, and a top portion 204 (e.g., shown in FIG. 2B) stacked on each other (e.g., via interlocking grooves). The base portion 200 can define one or more drains 206 (e.g., drains 206A and 206B) providing an outlet from the interior region 118 of the chamber 102 to one or more drain receptacles (not shown) via drain conduits. In implementations, drain 206A is fluidically coupled with channels in the chamber body 116 to provide access of fluids located between the first aperture 126 and the second aperture 128 to the drain 206A. For example, the intermediate portion 202 can define one or more channels 208 at least a portion of which extend through the intermediate portion to vertically align with at least a portion of one or more channels 210 formed by the base portion 200. The channels 208 can be positioned between an interior surface 212 of the chamber body 116 (e.g., of the top portion 204, the intermediate portion 202, or combinations thereof) and the ledge 120 to permit flow of fluids held in the interior region 118 between the lid 130 and the second aperture 128 or the surface 146 of the wafer 108 into the channels 208, through to the channels 210, and out the drains 206A. In implementations, the drains 206B permit rinse fluids or other fluids to leave the interior region 118 of the chamber 102 during rinse procedures (described herein with reference to FIG. 2C).

Following decomposition of the wafer 108, or in implementations where no prior decomposition is desired, the system 100 can transition to a scanning configuration to permit access to the surface 146 of the wafer 108 by the scan arm assembly 104 without transferring the wafer 108 to a separate scanning system. To transition to the scanning configuration, the motor system 112 can position the wafer support 110 from the second position adjacent the second aperture 128 to the first position adjacent the first aperture 126, or otherwise closer to the top portion 122 of the chamber body 116 to permit access to the surface 146 of the wafer 108 by the scan arm assembly 104. Alternatively, the motor system 112 can maintain the wafer 108 near the top portion 122 following loading if no decomposition procedure is utilized for a particular scan.

The scan arm assembly 104 generally includes a rotatable arm support 300 coupled to a nozzle housing 302 that supports a nozzle 304 configured to introduce the scan fluid to the surface 146 of the wafer 108 and recover the scan fluid from the surface 146 of the wafer 108. The motor system 112 can control rotation of the rotatable arm support 300, vertical positioning of the rotatable arm support 300, or combinations thereof, to position nozzle housing 302 and nozzle 304 from one or more positions at the rinse station 114 (e.g., shown in FIG. 2A) to one or more positions adjacent or above the wafer 108 (e.g., shown in FIG. 4). An example implementation of the nozzle 304 is described further herein with reference to FIGS. 7A through 7D. In implementations, the rotatable arm support 300 rotates or otherwise moves the nozzle 304 to position the nozzle 304 adjacent the wafer 108 when the wafer support 110 is positioned at the first position by the motor system 112 and to position the nozzle 304 outside a path of the lid 130 from the open position to the closed position when the wafer support 110 is positioned at the second position by the motor system 112.

With the nozzle 304 in position adjacent or above the wafer 108 (e.g., shown in FIG. 4), the fluid handling system 106 can control introduction of scanning fluids to and from the nozzle 304 to facilitate scanning procedures of the surface 146 of the wafer 108. The scan fluids can include, for example, one or more organic solvents to recover organic contaminants from the wafer 108, one or more aqueous solutions to recover inorganic contaminants from the wafer 108, or combinations thereof. Referring to FIGS. 7A through 7D, an example implementation of the nozzle 304 is shown. The nozzle 304 is configured to deliver a stream of fluid across the surface 146 of the wafer 108, which can cover a greater surface area of the wafer 108 in a shorter period of time than moving a spot-size droplet over the wafer 108. The stream of fluid is guided over the surface 146 of the wafer 108 by the nozzle 304 to controllably scan the desired surface area of the wafer 108. In implementations, the nozzle 304 guides the stream of fluid over substantially the entire surface 146 in a single revolution of the wafer 108. In implementations, a wedge of the surface 146 (e.g., a sector of the wafer 108 or portion thereof) can be scanned in a fraction of a single revolution of the wafer 108. The nozzle 304 includes a nozzle body 500 defining an inlet port 502, an outlet port 504, a first nozzle port 506, a second nozzle port 508, and a nozzle hood 510. The nozzle 304 can also include one or more mounting apertures to mount the nozzle 304 within the nozzle housing 302. The inlet port 502 and the outlet port 504 receive fluid lines to direct the flow of fluid into and out from the nozzle 304 during operation of the system 100. For example, the nozzle 304 receives fluid through action of a first pump (e.g., syringe pump) pushing the fluid from a holding line or loop (e.g., a sample holding loop) into the nozzle 304, where it is directed into the inlet port 502 and through a channel 503 in the nozzle body 500 fluidically connecting the inlet port 502 and the first nozzle port 506. The fluid is then deposited onto the surface 146 of the wafer 108 through the first nozzle port 506. The fluid is directed along the surface 146 of the wafer 108 as a continuous fluid stream via a channel 512 defined between the nozzle hood 510 and the nozzle body 500, where the fluid is subsequently removed from the surface 146 of the wafer 108. For example, the fluid can be removed from the surface 146 via action of a second pump (e.g., syringe pump) pulling the fluid through the second nozzle port 508 at the end of the channel 512 distal from the first nozzle port 506 through fluid communication between the outlet port 504 and the second nozzle port 508 through the nozzle body 500. As such, the fluid is permitted to contact the wafer 108 during transit from the first nozzle port 506 to the second nozzle port 508. The channel 512 permits a volume of fluid to travel over the wafer, assisted by the nozzle hood 510. In implementations, the channel 512 has a volume of approximately 300 μL. However, the volume of the channel 512 is not limited to 300 μL and can include volumes less than 300 μL and volumes greater than 300 μL. For example, the volume of the channel 512 can depend on the size of the wafer 108 being processed by the system 100 to provide a desired amount of fluid (e.g., scanning fluid) to the surface 146. The length of the channel 512 can be selected based on the size of the wafer 108 to be processed by the system 100, where in implementations, the channel 512 has a length of approximately the radius of the wafer 108. In implementations, the length of the channel 512 can be from approximately 20 mm to approximately 500 mm. For example, the length of the channel 512 can be approximately 150 mm (e.g., to accommodate a 300 mm diameter wafer), approximately 100 mm (e.g., to accommodate a 200 mm diameter wafer), approximately 225 mm (e.g., to accommodate a 450 mm diameter wafer). Other nozzle designs and configurations can be utilized, depending on the type of scan solution utilized.

The nozzle hood 510 extends from the nozzle body 500 adjacent each of the first nozzle port 506 and the second nozzle port 508 and defines the channel 512 between the nozzle hood 510 and the nozzle body 500 between the first nozzle port 506 and the second nozzle port 508. The nozzle hood 510 can further extend to include each of the first nozzle port 506 and the second nozzle port 508 within the channel 512 such that the nozzle hood 510 encloses the first nozzle port 506 and the second nozzle port 508 within the nozzle hood 510 (e.g., as shown in FIG. 7C). In implementations, the nozzle body 500 includes substantially opposing side walls 514 longitudinally across the nozzle 304. The opposing side walls 514 each include a tapered wall portion 516 that are coupled to or otherwise extend to provide opposing portions 518. In implementations, the opposing portions 518 are substantially vertical to form at least a portion of the nozzle hood 510. The nozzle 304 can be formed from a single unitary piece, or portions of the nozzle 304 can be formed separately and fused or otherwise coupled together. In implementations, the nozzle 304 is formed from chlorotrifluoroethylene (CTFE), polytetrafluoroethylene (PTFE), or combinations thereof.

The channel 512 of the nozzle 304 have an elongated shape with rounded ends 513A and 513B. Rounded ends can promote superior fluid handling characteristics as compared to angled ends, such as by providing more consistent delivery and uptake of fluid through the nozzle 304. In implementations, the first nozzle port 506 (where the fluid is dispensed from the nozzle 304 onto the wafer 108) is positioned tangent to the edge of the rounded end 513A of the channel 512. Such positioning can assist with a clean break of the fluid stream from the first nozzle port 506 once all fluid has been introduced to the wafer 108, while avoiding segmentation of the fluid on the surface of the wafer 108. In implementations, the rotatable arm support 300 rotates the nozzle housing 302 to cause the rounded end 513A of the nozzle 304 to extend over the edge of the wafer 108 (e.g., following the scan procedure) to promote uptake of the stream of fluid through the second nozzle port 508 via operation of the fluid handling system 106. For example, as shown in FIG. 6, the nozzle is positioned at a first position (e.g., a scan position) at a first time (t₁) whereby the channel 512 is positioned over the surface 146. The rotatable arm support 300 then rotates the nozzle housing 302 at a second time (t₂) to cause the rounded end 513A to extend past the edge of the wafer 108 (e.g., to overhang the edge) in a second position approximately 7 degrees rotated from the first position. In implementations, the second nozzle port 508 is positioned approximately at the center of the rounded end 513B distal from the first nozzle port 506. Positioning the second nozzle port 508 at the center of the rounded end 513B, as opposed to tangent to the edge of the rounded end 513B, can facilitate uptake of the fluid while facilitating the maintenance of the fluid stream on the surface 146 without segmentation of the fluid stream to precisely control movement of the fluid over the surface 146 of the wafer 108.

The position of the nozzle 304 above the surface 416 of the wafer 108 can influence the amount of fluid supported within the channel 512 during the scan procedure. The system 100 can include a zeroing procedure to ensure a desired height above the surface 416 is achieved prior to introduction of scanning fluid to the nozzle to facilitate the desired amount of fluid to be guided by the nozzle hood 510 along the surface 146 of the wafer 108. An example zeroing procedure is shown with respect to FIGS. 8A through 8C, where aspects of the scan arm assembly 104 are shown in accordance with various embodiments of this disclosure. The scan arm assembly 104 facilitates alignment of the nozzle 304 with respect to the wafer 108, such that the first nozzle port 506 and the second nozzle port 508 are level with respect to the surface 146 of the wafer 108 to which the fluid will be applied and removed. The system 100 can undergo an alignment or leveling procedure for each wafer 108 processed by the system 100 (e.g., in between scanning of a first wafer that is removed from the chamber 102 and scanning of a second wafer that is introduced to the chamber 102) or as needed to ensure the nozzle 304 is level with respect to the wafer 108 held by the chamber 102, such as prior to the next scanning procedure. In general, the nozzle 304 is movably coupled with a nozzle housing 302 to permit the nozzle 304 to have a range of motion with respect to the nozzle housing 302while being supported by the nozzle housing 302. The nozzle housing 302 defines an aperture 520 through which at least a portion of the nozzle 304 can pass when transitioning between an extended position (e.g., shown in FIG. 8A) and a retracted position (e.g., shown in FIGS. 8B and 8C). For example, a top portion of the nozzle 304 can be positioned within the nozzle housing 302, where additional portions of the nozzle 304 can be introduced into the interior of the nozzle housing 302 via the aperture 520 when the nozzle 304 is transitioned from the extended portion to the retracted portion. For instance, when the nozzle 304 is positioned to contact a zeroing surface 522, the nozzle hood 128 can contact the surface 522 to push the nozzle 304 into a level position with respect to the surface 522. The nozzle housing 302 can then actuate to lock the position of the nozzle 304 in place, to keep the nozzle 304 level with the surface 522 when the nozzle 304 is lifted from the surface 522 (e.g., to a scan position). The nozzle housing 302 can include a mechanical, electrical, or electromechanical locking device to releasably secure the nozzle 304 with respect to the nozzle housing 302. In implementations, the surface 522 includes the surface 146 of the wafer 108, a surface of the wafer support 110 (e.g., prior to loading the wafer 108 onto the wafer support 110), a surface of rinse station 114, or another surface having a structure consistent with level characteristics of a semiconducting wafer, such that when the nozzle 304 contacts the surface 522, the nozzle hood 128, the first nozzle port 506, the second nozzle port 508, etc. will be properly positioned with respect to the wafer 108.

In implementations, the nozzle mount assembly 500 includes the nozzle housing 302 to couple the nozzle 304 to the rotatable arm support 300. Alternatively or additionally, one or more different scan nozzles can be coupled directly to the rotatable arm support 300, or can utilize a different nozzle housing to facilitate coupling to the rotatable arm support 300. As shown, the nozzle 304 can be coupled to the nozzle housing 302 via a coupler 524 defining an aperture 526 to interact with a protrusion 528 of the nozzle housing 302. The protrusion 528 can include a fastener, pin, or other structure having a width or diameter that is less than a width or diameter of the aperture 526, such that when the scan arm assembly 104 is in a first state (e.g., a leveling state), the top of the aperture 526 rests on the protrusion 528, which provides a lower or extended position of the nozzle 304 with respect to the nozzle housing 302 via the coupler 524 (e.g., as shown in FIG. 8A). The system 100 can implement an alignment or leveling procedure by causing the rotatable arm support 300 to lower the nozzle housing 302 to cause the nozzle 304 to contact the surface 522 (e.g., as shown in FIG. 8B). For example, as the nozzle 304 contacts the surface 522, the coupler 524 is pushed upwards with respect to the protrusion 528, such that the protrusion 528 does not support the coupler 524 via contact with the top of the aperture 526. Following contact of the nozzle 304 with the surface 522, the nozzle 304 is in the retracted position and the system 100 can actuate a lock structure 530 (e.g., integrated within the nozzle housing 302) to secure the position of the nozzle 304 with respect to the nozzle housing 302. For example, the coupler 524 can include a ferrous material to be secured by a magnetic field generated by an electromagnet incorporated in the lock structure 530. While an electromagnet is shown as part of the lock structure 530 in the example embodiments, other lock structures can be utilized, including but not limited to, pneumatic solenoid actuators, mechanical locks, electromechanical locks, or the like.

The nozzle housing 302 can include sensors to monitor a position of the nozzle 304 with respect to the nozzle housing 302, such as to determine whether the nozzle 304 is in the extended state, in the retracted state, or in a different position. For example, in implementations, the nozzle housing 302 includes a sensor 532 to detect the presence or absence of the coupler 524 and generate or cease generating a signal received by a controller of the system 100. The sensor 532 can include an optical switch with a light source on a first side of the coupler 524 and a detector on a second opposing side of the coupler 524. The coupler 524 can include an indexing cutout, a portion of which passes between the light source and the detector of the sensor 532. When the nozzle 304 is in the extended position (e.g., the lock structure 530 is not engaged), light from the light source passes through the indexing cutout of the coupler 524 and is detected by the detector on the other side of the coupler 524. The sensor 532 then outputs a signal or ceases outputting a signal indicating detection of the light, which indicates to the system 100 that the nozzle 304 is in the extended position. When the nozzle 304 is in the retracted position, such as after being leveled on the surface 522, the body of the coupler 524 is positioned between the light source and detector of the sensor 532, blocking the light from reaching the detector. The sensor 532 would output a signal or cease outputting a signal indicating no detection of the light source. Such a signal or lack thereof indicates to the system 100 that the nozzle 304 is in the retracted position (e.g., supported in the nozzle housing 302 by the lock structure 530). Operation of the sensor 532 can provide a system check to ensure that the nozzle 304 is still in a retracted and leveled position after a period of operation. Changes in the output from the sensor 532 can indicate that a releveling procedure may be appropriate, the lock structure 530 should be evaluated, etc. Alternatively, the indexing cutout could be repositioned such that when the nozzle 304 is in the retracted position, the detector is aligned with the indexing cutout, and when the nozzle 304 is in the extended position, the body of the coupler 524 blocks the light.

When the nozzle 304 is leveled with respect to the surface 522 and locked into position via the lock structure 530, the rotatable arm support 300 can lift the nozzle 304 from the surface 522 (e.g., as shown in FIG. 8C), while maintaining the nozzle 304 in the leveled position. The rotatable arm support 300 can then position the nozzle 304 in a scan position or otherwise move the nozzle 304 (e.g., to permit a wafer 108 to be positioned on the wafer support 110 if the surface 522 used to level the nozzle 304 is the support 106).

The nozzle housing 302 can include one or more sensors to facilitate introducing fluid to the nozzle 304 and removing fluid from the nozzle 304. For example, in implementations, the nozzle housing 302 includes one or more sensors (sensors 534A and 534B are shown) adjacent to or more of the inlet port 502 and the outlet port 504 of the nozzle 304 to control operation of the fluid handling system 106 to control the flow of fluid into and out of the nozzle 304. The sensors 534A and 534B can include an optical sensor, a capacitive sensor, an ultrasonic sensor, or other sensor, or combinations thereof to sense the flow of liquid or the absence thereof within the fluid lines of the system 100. For example, the system 100 can include fluid lines from the fluid handling system coupled to fluid line couplers 536A and 536B through which the sensors 534A and 534B, respectively, can detect the present or absence of fluid therein. Output signals, or the lack thereof, can control operation of one or more components of the fluid handling system 106 including, but not limited to, pumps utilized to introduce fluid to or remove fluid from the nozzle 304.

The system 100 facilitates rinsing procedures for the wafer 108 and for the nozzle 304, such as following scan procedures. Referring to FIG. 2C, the chamber 102 is shown in a rinse configuration to facilitate rinsing of the wafer 108. To transition to the rinse configuration, the motor system 112 can position the wafer support 110 from the first position adjacent the first aperture 126 (e.g., the scanning position) or other position to a rinse position between the ledge 120 and the bottom portion 124 of the chamber body 116. A rinse fluid can be introduced to the wafer 108, such as through a rinse port on the nozzle housing 302 or otherwise provided in the system 100, whereby the motor system 112 can spin the wafer 108 to induce removal of the rinse fluid. The rinse fluid can then impact the interior of the chamber body 116 and flow to the drains 206B to leave the interior region 118 of the chamber 102. To clean the nozzle 304, the rotatable arm support 300 can position the nozzle 304 with respect to one or more troughs of the rinse station 114. For instance, the rinse station 114 can include a first trough 115A (e.g., shown in FIG. 5) having an elongated channel into which rinse fluid is introduced from a rinse fluid source to interact with the nozzle hood 510, the channel 512, or other portions of the nozzle 304. The nozzle 304 is shown positioned in the first trough 115A in FIGS. 1A and 1B. The rinse station 114 can also include a second trough 115B having an elongated channel coupled with a drying gas source (e.g., nitrogen or other inert gas) to introduce a drying gas into the elongated channel to impact against the nozzle 304. The nozzle 304 is shown positioned in the second trough 115B in FIG. 5.

Referring now to FIGS. 9A through 10, an example fluid handling system 106 of system 100 is described in accordance with various embodiments of this disclosure. For example, the fluid handling system 106 can facilitate preparation of chemical blanks of chemicals utilized by the system 100 for analysis by an analytic system, can facilitate preparation of decomposition fluids on demand and according to desired ratios for use in the chamber 102, can facilitate preparation of scanning fluids on demand and according to desired ratios for use in the chamber 102, and combinations thereof. As shown, the fluid handling system 106 includes a pump system including pumps 600, 602, 604, 606, 608, 610, and 612 to draw and push fluids through the fluid handling system to interact with other components of the system 100 (e.g., the nozzle 304), analysis systems, and the like. The pump system is shown incorporating syringe pumps, however the system 100 can utilize different pumps types or systems, combinations of pump types or systems, and the like. An example configuration of the fluid handling system 106 is shown in FIG. 10 to introduce a decomposition fluid to the nebulizer 138 of the chamber 102 during the decomposition procedure of the wafer 108. The pump 612 can draw hydrofluoric acid (HF) or other decomposition fluid(s) from a decomposition fluid source 613 into a holding line (e.g., decomposition fluid holding loop 614) with a valve 616 in a first configuration and a valve 618 in a first configuration. In a second configuration of the valve 616 gas from a gas source 619 can be introduced into the fluid line holding the decomposition fluid to provide a barrier between a working fluid used to push the decomposition fluid to the nebulizer 138. In a second configuration of the valve 618, the pump 612 can draw a working solution (e.g., deionized water or other fluid), whereby the valve 618 can switch to the first position and the valve 616 can switch to a third configuration to provide fluid communication between the pump 612 and the nebulizer 138, whereby the pump 612 pushes the working solution against the decomposition fluid held in the decomposition fluid holding loop 614 (e.g., via any intermediate air gap) to introduce the decomposition fluid to the nebulizer 138. Following decomposition of the wafer 108, the system 100 can scan the wafer 108 for determination of impurities.

Referring to FIG. 9A, the fluid handling system 106 is shown in an example chemical load configuration. The pumps 604, 606, and 608 draw chemicals from chemical sources 620, 622, and 624, respectively, via valve 626 in a first valve configuration. The chemicals can include, for example, hydrofluoric acid (HF), hydrogen peroxide (H₂O₂), deionized water (DIW), one or more organic solvents, or other fluids. In a second valve configuration (shown in FIG. 9A) of valve 626, each of pumps 604, 606, and 608 are fluidically coupled with a fluid line connector (e.g., manifold 628 or other connector) whereby the chemicals drawn by each pump are combined and permitted to mix. The combined fluids are directed to valve 630, which in a first valve configuration directs the combined fluids to a holding line (e.g., holding loop 632). In implementations, a system controller controls operation of each of pumps 604, 606, and 608 independently to control the flow rate of each fluid handled by the respective pumps, thereby providing a controlled composition of the mixed fluids directed into the holding loop 632 following mixing. In implementations, a first fluid mixture can be used to interact with the wafer 108 during a first scan procedure, and a second fluid mixture can be prepared on demand with different operational control of the pump systems 604, 606, and 608 to introduce the second fluid mixture to interact with the wafer 108 during a second scan procedure. Additional fluid mixtures can be prepared on demand and introduced to the wafer 108 as desired. In implementations, the holding loop 632 has a volume that supports scanning procedures for multiple wafers without need to refill. For example, the scanning solution can be prepared, where a portion of the scanning solution (e.g., a “blank” sample) can be sent to an analytic system for verification that the solution is within operational constraints for use on wafers. The remainder of the scanning solution in the holding loop 632 can then be used in multiple scanning procedures, with the scanning solution pre-verified as suitable for use. An example loading of a chemical blank for analysis is shown with reference to FIG. 9B.

Referring to FIG. 9B, the fluid handling system 106 is shown in an example nozzle bypass configuration to send a chemical blank for analysis without passing the blank through the nozzle 304. In the nozzle bypass configuration, the pump 610 is in fluid communication with the holding loop 632 (e.g., with valve 630 in a second valve configuration) to push the fluid held in the holding loop 632 to a sample holding line (e.g., sample holding loop 634) via valve 636 in a first valve configuration and valve 638 in a first valve configuration. When the fluid is isolated in the sample holding loop 634, the fluid handling system 106 can switch configurations to a sample inject configuration to transfer the sample to an analytic system for analysis. The analytic system can include, but is not limited to, inductively coupled plasma spectrometry instrumentation for trace element composition determinations, ionization sources that facilitate organic chemical analysis (e.g., Electrospray, Atmospheric Pressure Chemical Ionization (APCI), or other ionization sources), or the like, or combinations thereof.

Referring to FIG. 9C, the fluid handling system 106 is shown in an example chemical inject configuration, whereby the holding loop 632 is in fluid communication with one or more transfer mechanisms. For example, in an implementation, the valve 638 is in a second configuration (shown dashed in FIG. 9C) to fluidically couple the holding loop 632 with a gas transfer source (e.g., nitrogen pressure source 640) to push the sample held in the holding loop 632 to a transfer line 642 to a sample analytic system via valve 644 in a first valve configuration and valve 646 in a first valve configuration. In an implementation, the valve 638 is in a third valve configuration (shown in FIG. 9C solid line) to fluidically couple the holding loop 632 with pump 602 via valve 648 in a first valve configuration (shown in FIG. 9C solid line) which pushes the sample held in the holding loop 632 to the transfer line 642 to the sample analytic system via valve 644 in the first valve configuration and valve 646 in the first valve configuration. The pump 602 can use a working solution (e.g., deionized water from DIW source 650) to push against the sample to the transfer line 642. In implementations, the fluid handling system 106 introduces a fluid gap between the working fluid and the sample, such as by introducing a bubble (e.g., from nitrogen pressure source 640) into the holding loop 632 prior to pushing of the working solution. In implementations, the fluid handling system 106 includes a sensor 652 adjacent the transfer line 642 to detect the presence or absence of a fluid in the transfer line 642. For example, the sensor 652 can detect the back end of the sample pushed from the holding loop 632 (e.g., by detecting a bubble in the line), where the sensor signal or lack thereof can inform a controller of the fluid handling system 106 to switch configurations of valve 646 and 648 to second valve configurations (shown dashed in FIG. 9C) to fluidically connect pump 602 with the transfer line 642 via fluid line 654. In such a configuration, the other portions of the fluid handling system 106 are isolated from the transfer of the sample to the sample analyzer to permit rinsing of those other portions during sample transfer.

Referring to FIG. 9D, the fluid handling system 106 is shown in an example nozzle loop load configuration, whereby the holding loop 632 is in fluid communication with a nozzle holding line (e.g., nozzle holding loop 656) to prepare to introduce the fluid to the nozzle 304. As described herein, the composition of the fluid can depend on the type of contaminants sought to recover from the wafer 108, where organic solvents or solutions can be utilized to recover organic contaminants, aqueous or acidic solutions can be utilized to recover inorganic contaminants, or combinations thereof. In the nozzle loop load configuration, the pump 610 is in fluid communication with the holding loop 632 (e.g., with valve 630 in the second valve configuration) to push the fluid held in the holding loop 632 to the nozzle holding loop 632 via valve 636 in a second valve configuration and valve 658 in a first valve configuration. In implementations, the nozzle holding loop 632 has a volume of approximately 500 μL, whereas the hold loop 632 has a volume of approximately 5-20 mL to permit fills of the nozzle holding loop 632 for each preparation of the scan solution through operation of the pumps 604, 606, 608. When the fluid is isolated in the nozzle holding loop 656, the fluid handling system 106 can switch configurations to a nozzle load configuration to transfer the fluid to the nozzle 304 for a scanning procedure of the wafer 108 or to take a nozzle blank sample (e.g., introduce the fluid to an inert surface, such as a surface of the rinse station 114, and remove the sample from the inert surface for analysis).

Referring to FIG. 9E, the fluid handling system 106 is shown in an example nozzle load configuration, whereby the pump 600 is in fluid communication with the nozzle holding loop 656 and the nozzle 304 via valve 658 is a second valve configuration to push the fluid from the nozzle holding loop 656 to the nozzle 304. In implementations, during scanning procedures, the wafer 108 is held stationary while the nozzle 304 is loaded by the pump 600. In implementations, the system 100 performs a zeroing operation of the nozzle 304 (e.g., described with reference to FIGS. 8A through 8C) prior to filling of the nozzle 304 with the fluid. The nozzle is then placed in scan position over the wafer 108, where pump 600 can operate to push the fluid from the nozzle holding loop 656 to the inlet port 506 of the nozzle 304 through the nozzle body 500 to the first nozzle port 506 and onto the surface 146 of the wafer 108 (or onto the inert surface for nozzle blank analyses). In implementations, a controller of the fluid handling system 106 controls operation of the pump 600 based on sense signals or lack thereof from sensors 534A and 534B detecting the presence or lack thereof of fluid introduced to or fluid leaving the nozzle 304 indicating a filled nozzle 304. In implementations, the detection of the front end of the fluid by the sensor 534A causes the pump 600 to decrease the flow rate of the fluid introduced to the nozzle 304 (e.g., from an approximately 50 μL/min flow rate to a 10-20 μL/min flow rate). In implementations, the pump 600 operates to fill the nozzle 304 until the back end of the fluid is registered by the sensor 534B. The pump 600 can then operate for a time period to push the back end of the fluid into the nozzle 304, and then stops operation, whereby all the fluid previously held by the nozzle holding loop 656 is positioned on the surface 146 of the wafer 108 (or on the inert surface if a nozzle blank is being performed). The fluid is then supported on the surface 146 by the nozzle 304. In implementations, a portion of the fluid may protrude out from the nozzle hood 510, but can be maintained in contact with the remainder of the fluid within the channel 512, such as through adhesion forces. The system 100 then transitions to scanning the nozzle 304 over the surface 146 of the wafer 108. During the scanning procedure, the motor system 112 rotates the wafer 108 (e.g., at approximately 2 rpm), whereby the fluid supported by the nozzle 304 is transferred over the surface 146 of the wafer 108. In implementations, the fluid interacts with substantially the whole surface 146 of the wafer 108 in a single rotation of the wafer 108, however additional rotations can be performed. For example, the scanning procedure can involve two rotations of the wafer 108 by the motor system 112 to permit the fluid to contact the entire surface of the wafer 108 twice. Following scanning, the nozzle can be rotated to cause an end of the nozzle to extend over the edge of the wafer (e.g., as described with reference to FIG. 6), such as to assist in uptake of the fluid from the surface into the nozzle 304 via the second nozzle port 508.

Referring to FIG. 9F, the fluid handling system 106 is shown in an example recovery configuration, whereby the pump 602 is in fluid communication with the nozzle 304 via valve 648 in the first configuration, valve 638 in the third configuration, and valve 644 in a second configuration. In the recovery configuration, the pump 602 operates to draw the fluid from the surface 146 of the wafer 108 through the second nozzle port 508 and out the nozzle 304 via the outlet port 504, where the fluid is pulled into the sample holding loop 634. Alternatively or additionally, a single port on the nozzle can be utilized to introduce fluid to the wafer 108 and draw fluid from the wafer following or during scanning. A sensor (e.g., sensor 660) can be utilized to control operation of the pump 602 similar to control of the pump 600 by output of the sensors 534A/534B. For example, sensor 660 can detect the back end of the fluid flowing into the sample holding loop 634 which can signal the pump 602 to stop operation (e.g., via a controller of the fluid handling system 106). Once the fluid is held in the sample holding loop 634, the fluid handling system 106 can transition to the chemical inject configuration, described with reference to FIG. 9C, to introduce the fluid to the sample analyzer via the transfer line 642. In implementations, the sample holding loop 634 has a larger volume (e.g., 1.5 mL) than the volume of the fluid provided to the nozzle 304 (e.g., 500 μL) to permit total recovery of the fluid following scanning.

Organic Contaminant Detection without VPD

While VPD techniques can be appropriate for detection and identification of metallic impurities, there may be significant restrictions in use of traditional VPD techniques for recovery and identification of organic contaminants or residues present in or on semiconducting wafers that can adversely affect semiconductor processing. For example, plasticizers, such as di-butyl phthalate and di-octyl phthalate, can slow silicon dioxide growth. Organophosphates may cause unintentional doping. Amines can neutralize photo-generated acids. Antioxidants, such as butylated hydroxytoluene and butylated hydroxyanisole, can degrade gate-oxide constructs on a wafer. Surfactants, such as cetrimonium bromide and sodium dodecylsulfate, can add hydrophilicity to wafers. Decomposition fluids used in traditional VPD techniques can break down organic molecules or otherwise react with the organic molecules to prevent identification of the original contaminants and prevent determination of concentrations of the original contaminants present on the semiconducting wafer. Similarly, certain analysis systems used in VPD systems do not facilitate the recovery and identification of organic contaminants or residues. For instance, inductively-coupled plasma systems used in the identification of metallic impurities can prevent the identification of the arrangement of the elements present in the organic sample, where such arrangement would be used to determine the appropriate identity of the original organic molecule.

FIGS. 11A through 12 illustrate aspects of an automated system for recovering and identifying organic contaminants, such as organic residues, on semiconductor wafers (“system 1100”) in accordance with various embodiments of this disclosure. In implementations, the system 1100 operates to recover organic contaminants without a VPD step acted upon the semiconductor wafers. The system 1100 generally includes a scan nozzle 1102 configured to introduce a scan solution 1104 onto a surface of a semiconducting wafer 1106 to recover organic contaminants (e.g., organic contaminants 1108, 1110 are shown) from the semiconducting wafer 1106 for transfer to an analysis system 1112 to identify and/or quantify the organic contaminants. The system 1110 can share one or more structures, functions, or features with the system 100 described herein. For instance, the nozzle 1102 can include the nozzle 304 or features thereof, can include a different structure, function, or feature, or combinations thereof, fluid pathways between components can be the same, similar, or different, the scanning techniques described herein can be facilitate by the chamber 102, by a different structure, by a structure sharing one or more features, or the like.

The semiconducting wafer 1106 is shown in FIG. 11A having two different organic contaminants (shown as 1108 and 1110) on a surface of the semiconducting wafer 1106. As described herein, various organic materials can have adverse effects on the semiconducting manufacturing process and on the suitability of the semiconducting wafer 1106 to be further manufactured into electronic devices. The system 1100 can be utilized to recover each of the organic contaminants and differentiate between the identity and amount of each of the organic contaminants. Such identification can provide insight into a source of organic contamination for a semiconducting process, such as determination that a solvent can be leeching contaminants from a container in which the solvent is stored.

Referring to FIG. 11B, the system 1100 is shown with the scan nozzle 1102 introducing the scan solution 1104 to the semiconducting wafer 1106 in order to draw the organic contaminants 1108 and 1110 into the scan solution 1104 (e.g., through dissolution or other mechanisms). The positioning of the scan nozzle 1102 can be manipulated by the scan arm assembly 104 described herein to move the scan nozzle 1102 relative to the semiconducting wafer 1106 to introduce the scan solution 1104 to one or more surfaces of the semiconducting wafer 1106 or portions thereof, where one or more pumps can be fluidically coupled with the nozzle 1102 to introduce fluids to the scan nozzle 1102 and onto the surface(s) of the semiconducting wafer 1106 or remove fluids from the semiconducting wafer 1106 through the nozzle 1102. For instance, one or more portions of the pump system (e.g., pumps 600, 602, 604, 606, 608, 610, and 612) can be utilized to draw and push fluids through the nozzle 1102, the analysis system 1112, and the like.

Organic solvents can have a relatively high vapor pressure in ambient environments, which causes the organic solvent to vaporize over time, resulting in less liquid solvent available to interact with organic contaminants present on the semiconducting wafer 1106. Alternatively or additionally, organic solvents have a tendency to spread onto the surface of the semiconducting wafer 1106 due to the relatively low surface tension of the fluids, causing portions of the scan solution to spread out from the area underneath the scan nozzle and onto the surface away from normal control by the nozzle 1102. In implementations, the system 1110 includes an organic scan solution replenishment system to facilitate introduction of organic scan solutions to the semiconducting wafer 1106 while maintaining suitable amounts of the organic scan solutions for manipulation by the scan nozzle 1102. For example, referring to FIG. 11C, the system 1110 is shown including an organic scan solution replenishment system 1118 to introduce organic scan solutions to the nozzle 1102 to replenish amounts of organic solvents in the scan solution as the organic solvent vaporize (e.g., shown diagrammatically as 1120) or spreads onto the semiconducting wafer 1106.

The organic scan solution replenishment system 1118 is shown generally including a scan solution reservoir 1122, a pump 1124, and corresponding fluid lines 1126 to fluidically couple the scan solution reservoir 1122 with the nozzle 1102. The scan solution reservoir 1122 can be any suitable container to house a portion of organic scan solution for subsequent transfer to the nozzle 1102 to replenish the amount of scan solution positioned underneath the scan nozzle 1102 for movement across the semiconducting wafer 1106. In implementations, the scan solution reservoir 1122 is a closed container to prevent evaporation of organic scan solution from the scan solution reservoir 1122. The scan solution reservoir 1122 is fluidically coupled with the nozzle 1102 via the fluid lines 1126 through which the pump 1124 can transfer the scan solution held within the scan solution reservoir 1122 to the nozzle 1102. The pump 1124 can include a peristaltic pump, a syringe pump, another pump, or combinations thereof, suitable to transfer the scan solution held within the scan solution reservoir 1122 to the nozzle 1102 to replenish organic scan solution that has evaporated or otherwise spread from surface of the semiconducting wafer 1106 that is maintained under control underneath the nozzle 1102. In implementations, the pump 1124 is controlled to transfer the scan solution held within the scan solution reservoir 1122 to the nozzle 1102 via the fluid lines 1126 at a substantially constant flow rate. For example, the pump 1124 can continuously transfer scan solution to the nozzle 1102. The rate of the transfer from the pump 1124 generally depends on the makeup of the organic scan solution, where higher flow rates can be facilitated by the pump 1124 for more volatile organic solvents. Alternatively or additionally, the system 1110 can include one or more sensors to determine a volume of scan solution manipulated by the nozzle 1102, where when the volume is determined to be at or less than a threshold volume, the system 1110 can activate the pump 1124 to transfer replenishment scan solution (e.g., for a predetermined time, until the volume is determined to be above the threshold volume, or the like).

After the organic scan solution is permitted to interact with the surface of the semiconducting wafer to draw organic contaminants or residue into the scan solution, the scan nozzle 1102 can then draw the scan solution from the semiconducting wafer 1106 with the organic contaminants 1108 and 1110 included in the scan solution (e.g., shown as 1114), as shown in FIG. 11D. For example, the system 1100 can include a pump fluidically coupled with the scan nozzle 1102 to draw the scan solution including the organic contaminants 1114 into the scan nozzle 1102 or associated fluid line for subsequent transfer to the analysis system 1112. For instance, FIG. 11E shows transfer of the scan solution including the organic contaminants 1114 from the scan nozzle 1102 to the analysis system 1112 via a transfer line 1116. The analysis system 1112 can include a Time of Flight (TOF) mass spectrometer (e.g., a quadrupole TOF-MS (Q-TOF-MS)), a Triple Quadrupole (Triple Quad or QQQ) mass spectrometer, a gas chromatography-mass spectrometry (GC-MS) system, a gas chromatography-flame ionization detector (GC-FID), or other analysis system utilized for organic molecule analysis, or combinations thereof.

In an implementation, the analysis system 1112 of the system 1100 includes a Q-TOF-MS calibrated using a method of standard addition (MSA) calibration. The quantification methodology of the analysis system 112 can depend on whether the detected contaminant is part of the calibration standard used for the MSA calibration. For instance, if the detected contaminant is part of the calibration standard used for the MSA calibration, then the Q-TOF-MS can be operated in Full Quant analysis mode. If the detected contaminant is not part of the calibration standard used for the MSA calibration, then the Q-TOF-MS can be operated in Near Quant analysis mode. For example, operating the Q-TOF-MS in Near Quant analysis mode can include utilizing a response factor (RF) for an organic compound having similar characteristics (e.g., polarity, functional groups, molecular weight, etc.) as the detected contaminant.

In an example experiment, an analysis was performed utilizing the system 1100 to determine collection and analysis of multiple organic contaminants from a semiconducting wafer. During the analysis, a sample of isopropyl alcohol (IPA) was spiked with twenty-four contaminants, each at a concentration of 10 parts per billion (ppb). The contaminants included bromide, phosphate, ethylisopropylamine, diethanolamine, heptylamine, diethylaminoethanol, tripropylamine, tributylamine, sodiumdodeculsulfate, aminopropanol, L-proline, trimethyl glycine, L-leucine, bisethylhexylphosphate, tributylphosphate, trischloropethylphosphate, triphenylphosphate, trisethylhexylphosphate, dibutylphthalate, butylbenzylphthalate, dioctylphthalate, diisononylphthalate, diisodecylphthalate, and tris (2,4-ditert-butylphenyl) phosphate (e.g., a potential contaminant for IPA stored in a high density polyethylene (HDPE) container). A 1 mL amount of the spiked IPA was introduced to the semiconductor wafer as small drops in differing locations on the surface of the wafer. The IPA was permitted to evaporate, leaving the contaminants behind on the surface of the wafer as residue. The wafer surface was then scanned with an organic scan solution to dissolve the residue in the organic scan solution. The scan solution containing the contaminants was collected and transferred to an analysis system for identification and quantification of the recovery of the contaminants. Referring to FIG. 12, results of the recovery of the organic contaminants from the wafer are shown following analysis by the analysis system (e.g., a Q-TOF-MS system).

Multiple Scan Sample Collection and Combination

FIGS. 13 and 14 illustrate aspects of a system for collecting and combining multiple scans of a semiconducting wafer (“system 1300”) in accordance with various embodiments of this disclosure. The system 1300 is shown generally including a nozzle 1302 and a collection vessel 1304 fluidically coupled with an analysis system 1306 The system 1300 can share one or more structures, functions, or features with the system 100 and/or the system 1100 described herein. For instance, the nozzle 1302 can include the nozzle 304 and/or the nozzle 1102 or features thereof, can include a different structure, function, or feature, or combinations thereof, fluid pathways between components can be the same, similar, or different, the scanning techniques described herein can be facilitate by the chamber 102, by a different structure, by a structure sharing one or more features, or the like.

The nozzle 1302 is configured to introduce a scan solution to the semiconducting wafer (e.g., wafer 108, wafer 1106, etc.), perform a scan procedure through movement of the scan solution relative to one or more surfaces of the wafer, and remove the scan solution from the wafer. For instance, fluid handling by the nozzle 1302 can be facilitated through operation of one or more fluid pumps (e.g., syringe pumps, peristaltic pumps, or the like). The scan solution is transferred from the nozzle 1302 to the collection vessel 1304 to hold the scan solution within an interior volume of the collection vessel 1304 until one or more additional scan solutions are transferred from the nozzle 1302 (or a different nozzle) to the collection vessel 1304 for collection and combination with the first scan solution. For example, the nozzle 1302 can introduce a first scan solution to the wafer, perform a first scan procedure, remove the first scan solution from the wafer as a first scan sample 1308, and transfer the first scan sample 1308 to the collection vessel 1304. The system 1300 can then facilitate a second scan, where the nozzle 1302 (or a different nozzle) introduces a second scan solution to the same wafer, perform a second scan procedure, remove the second scan solution from the wafer as a second scan sample 1310, and transfer the second scan sample 1310 to the collection vessel 1304 for combination with the first scan sample 1308. The system 1300 can further facilitate additional scans for combination with the other scans (e.g., one or more additional scan samples 1312 can optionally be added to the collection vessel 1304 for mixing with the other samples present, such as the first scan sample 1308 and/or the second scan sample 1310). The collection vessel 1304 then provides a combined scanned sample 1314 within the vessel interior for transfer to the analysis system 1306.

The collection vessel 1304 can be provided according to a variety of configurations suitable to hold a plurality of scan samples. For instance, the collection vessel 1304 can include, but is not limited to, a tubular structure, a tubular structure having a conical or angled bottom, a laboratory tube or vial, a length of fluid tubing configured to mix received samples back and forth, a sample bottle, or the like, or combinations thereof. For example, the collection vessel 1304 shown in FIG. 14 is provided as a tubular structure 1400 having a conical or angled bottom 1402 with an outlet line 1404 fluidically coupled with a valve 1406. The valve 1406 can change configurations to restrict flow of fluid from the collection vessel 1304 (e.g., during a sample collection procedure to receive a plurality of scan samples from the nozzle(s) 1302) or to permit the transfer of the combined scan sample 1314 to the analysis system 1306. In implementations, the collection vessel 1304 includes a vent port 1408 to permit the release of gases into the ambient environment from the collection vessel 1304 or to permit the introduction of gases from the atmosphere into the collection vessel 1304.

The system 1300 can facilitate combining multiple scans into a single scan sample to increase recovery efficiency for the sample. For instance, rather than relying on a single scan to collect all contaminants of interest from the wafer (e.g., wafer 108), the system 1300 can utilize a first scan solution to recover a first portion of the contaminants or residues present on the wafer (e.g., 80% of contaminants on a single scan). The system 1300 can then utilize the same scan solution or a different scan solution for a second scan to recover a portion of the remaining contaminants on the same wafer (e.g., 80% of the remaining 20% of contaminants on a second scan). Additional scan(s) can be performed to target more of any residual contaminants. The system 1300 can utilize multiple scans to target different types of contaminants including, but not limited to, polar molecules, non-polar molecules, metal contaminants, ionic contaminants, or the like, or combinations thereof using one or more scan solutions or combinations of scan solutions including, but not limited to, polar organic solvents, non-polar organic solvents, aqueous solutions (e.g., acidic solutions, basic solutions, neutral solutions, etc.), or the like. The collection vessel 1304 facilitates combining and mixing scans with the same or different scan solutions to provide a full recovery profile of contaminants of the wafer.

Following collection of two or more scans in the collection vessel 1304, the system 1300 facilitates transfer of the combined scan sample 1314 to the analysis system 1306 for identification and/or quantification of the contaminants. For example, the system 1300 can utilize one or more pumps or vacuum sources to pull or push the combined scan sample 1314 out from the collection vessel 1304 and through the valve 1406 to the analysis system via one or more fluid lines (e.g., fluid line 1410 is shown). The analysis system 1306 can include one or more detectors used to process the combined scan sample 1314 or portions thereof. For example, the analysis system 1306 can include one or more of a Time of Flight (TOF) mass spectrometer, a Triple Quadrupole (Triple Quad or QQQ) mass spectrometer, a gas chromatography-mass spectrometry (GC-MS) system, a gas chromatography-flame ionization detector (GC-FID), or other analysis system utilized for organic molecule analysis, an ICP spectrometry instrumentation (e.g., an Inductively Coupled Plasma Mass Spectrometer (ICP/ICP-MS), an Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES), or the like), or other analysis system utilized for metal analysis, or combinations thereof.

Inline Generation of Organic Scan Solutions

Referring to FIGS. 15 and 16, a system for inline generation of organic scan solutions and internal standards for analysis of organic contaminants that may be present on a semiconductor wafer (“system 1500”) is shown in accordance with various embodiments of this disclosure. As described further herein, the scan fluid can include an organic scan solution formed on demand through inline mixing of a plurality of organic solvents through pump action under control by a system controller to precisely control the ratio of organic solvents. Alternatively or additionally, a plurality of calibration standards can be prepared using the organic solvents for calibrating an organic analysis instrument.

The system 1500 is shown in FIG. 15 as generally including a nozzle 1502, a pump system 1504 fluidically coupled with the nozzle 1502 via a valve system 1506 and with a plurality of organic chemical sources 1508 (e.g., via one or more fluid lines 1510). The nozzle 1502 can include one or more of nozzle 304, nozzle 1102, nozzle 1302, a point nozzle to generate a droplet on the semiconducting wafer, a nozzle with one or more elongated channels to generate a stream of scan solution across the semiconducting wafer, or the like. The organic chemical sources 1508 include, but are not limited to, organic solvents, chemical standards, or other chemicals used to form organic scan solutions or calibration standards, such as diluents, aqueous solutions, or the like to combine with one or more organic chemicals.

In implementations, the system 1500 includes a controller 1512 that controls and coordinates operation of the pump system 1504 and the valve system 1506 to draw a plurality of organic solvents or chemical standards from the organic chemical sources 1508 and introduce the plurality of organic solvents together to form an organic scan solution or introduce one or more chemical standards with one or more organic solvents or diluents to form a calibration standard. The fluids can be introduced to mix within one or more valves of the valve system 1510 (e.g., via one or more mixing ports of a multi-port valve or multiple multiport valves), can be introduced to mix within a multiport mixing manifold, can be introduced to another mixing device, or combinations thereof.

The mixed organic fluids can then be transferred to the nozzle 1502 for introduction to the semiconductor wafer 108 for the scanning procedure. For example, the controller 1512 can coordinate operation of the pump system 1504 and the valve system 1506 to transfer the mixed organic scan solution or the mixed calibration standard to the nozzle 1502 whereby one or more of the scan arm assembly 104 and the motor system 112 induce relative motion between the nozzle 1502 and the semiconductor wafer 108 to move the mixed organic scan solution across the surface of the semiconductor wafer 108. Following or during the scanning procedure, the nozzle 1502 recovers the mixed organic scan solution from the wafer 108 and directs the sample to an analysis system 1514. The analysis system 1514 can include one or more of a Time of Flight (TOF) mass spectrometer, a Triple Quadrupole (Triple Quad or QQQ) mass spectrometer, a gas chromatography-mass spectrometry (GC-MS) system, a gas chromatography-flame ionization detector (GC-FID), or other analysis system utilized for organic molecule analysis, an ICP spectrometry instrumentation (e.g., an Inductively Coupled Plasma Mass Spectrometer (ICP/ICP-MS), an Inductively Coupled Plasma Atomic Emission Spectrometer (ICP-AES), or the like), or other analysis system utilized for metal analysis, or combinations thereof. In implementations, a series of mixed calibration standards can be transferred directly to the analysis system 1514 to generate calibration curves for analysis of samples provided through inline generated organic scan solutions.

An example implementation of the system 1500 is shown in FIG. 16 with the pump system 1504 including a plurality of syringe pumps (syringe pumps 1504A, 1504B, 1504C, 1504D, 1504E, 1504F are shown) in fluid communication with a multiport valve 1506A of the valve system 1506. The syringe pumps are fluidically coupled with the organic chemical sources 1508 to draw organic solvents or standard solutions into respective syringe pumps (e.g., during a syringe loading procedure under control by the controller 1512) and then dispense (e.g., under control by the controller 1512) the organic fluids to the valve 1506A for mixing. The mixed organic fluid is then transferred to the nozzle 1502, multiple nozzles 1502, or one or more detectors of the analysis system 1514. In implementations, the valve 1506A includes a mixing port 1600 configured to mix two or more fluids from two or more of the syringe pumps to provide the mixed organic fluid. For example, the valve 1506A can include internal fluid channels 1602 on one or more of the rotor or the stator to direct fluid received in two or more ports (e.g., coupled with fluid lines) to a single mixing port 1600 or an internal channel fluidically coupled thereto to join and mix the multiple received fluids into a fluid channel 1604 and/or a fluid line 1606 coupled with the mixing port. Alternatively or additionally, the valve system 1506 includes one or more mixing manifolds for receiving two or more streams of fluids from the syringe pumps to permit the streams to mix to provide the mixed organic scan solution or mixed calibration standards. For example, the mixed organic scan solution or standard solution can be transferred to the nozzle 1502 and/or to the analysis system 1514 via operation of a valve 1506B of the valve system 1506.

Electromechanical devices (e.g., electrical motors, servos, actuators, or the like) may be coupled with or embedded within the components of the systems described herein (e.g., systems 100, 1100, 1300, 1500 or combinations thereof) to facilitate automated operation via control logic embedded within or externally driving the systems. The electromechanical devices can be configured to cause movement of devices and fluids according to various procedures, such as the procedures described herein. The systems may include or be controlled by a computing system having a processor or other controller configured to execute computer readable program instructions (i.e., the control logic) from a non-transitory carrier medium (e.g., storage medium such as a flash drive, hard disk drive, solid-state disk drive, SD card, optical disk, or the like). The computing system can be connected to various components of the system 100, either by direct connection, or through one or more network connections (e.g., local area networking (LAN), wireless area networking (WAN or WLAN), one or more hub connections (e.g., USB hubs), and so forth). For example, the computing system can be communicatively coupled to the chamber 102, the motor system 112, valves described herein, pumps described herein, other components described herein, components directing control thereof, or combinations thereof. The program instructions, when executed by the processor or other controller, can cause the computing system to control the systems (e.g., control pumps, selection valves, actuators, spray nozzles, positioning devices, etc.) according to one or more modes of operation, as described herein.

It should be recognized that the various functions, control operations, processing blocks, or steps described throughout the present disclosure may be carried out by any combination of hardware, software, or firmware. In some embodiments, various steps or functions are carried out by one or more of the following: electronic circuitry, logic gates, multiplexers, a programmable logic device, an application-specific integrated circuit (ASIC), a controller/microcontroller, or a computing system. A computing system may include, but is not limited to, a personal computing system, a mobile computing device, mainframe computing system, workstation, image computer, parallel processor, or any other device known in the art. In general, the term “computing system” is broadly defined to encompass any device having one or more processors or other controllers, which execute instructions from a carrier medium.

Program instructions implementing functions, control operations, processing blocks, or steps, such as those manifested by embodiments described herein, may be transmitted over or stored on carrier medium. The carrier medium may be a transmission medium, such as, but not limited to, a wire, cable, or wireless transmission link. The carrier medium may also include a non-transitory signal bearing medium or storage medium such as, but not limited to, a read-only memory, a random access memory, a magnetic or optical disk, a solid-state or flash memory device, or a magnetic tape.

The systems described herein (e.g., systems 100, 1100, 1300, 1500) can include one or more features of another system of the systems described herein, unless context dictates that such features would be otherwise incompatible. For example, and without limitation, the system 100 can include one or more of the organic scan solution replenishment system 1118, the collection vessel 1304, and the inline organic scan solutions and internal standards generation system 1500 in combination with, or to the exclusion of, one or more other features of another system described herein.

Furthermore, it is to be understood that the invention is defined by the appended claims. Although embodiments of this invention have been illustrated, it is apparent that various modifications may be made by those skilled in the art without departing from the scope and spirit of the disclosure.

Claims

1. A method for scanning a surface of a semiconducting wafer for organic contaminants utilizing a nozzle, comprising: positioning a nozzle above a surface of a semiconducting wafer, the semiconducting wafer supported adjacent to or within an interior of a chamber body;introducing a first scan fluid including one or more organic solvents to an inlet port of the nozzle;directing a portion of the first scan fluid onto the surface of the semiconducting wafer to permit interaction between the first scan fluid and one or more organic contaminants present on the surface of the semiconducting wafer;removing the first scan fluid containing at least a portion of the one or more organic contaminants from the surface of the semiconducting wafer via the nozzle;introducing a second scan fluid including one or more organic solvents to the inlet port of the nozzle;directing a portion of the second scan fluid onto the surface of the semiconducting wafer to permit interaction between the second scan fluid and one or more residual organic contaminants present on the surface of the semiconducting wafer following the first scan fluid removal; andremoving the second scan fluid containing at least a portion of the one or more residual organic contaminants from the surface of the semiconducting wafer via the nozzle.

2. The method of claim 1, wherein the first scan fluid and the second scan fluid have a same composition of organic solvents.

3. The method of claim 1, wherein the first scan fluid and the second scan fluid have different compositions of organic solvents.

4. The method of claim 3, further comprising: introducing a third scan fluid including one or more organic solvents to the inlet port of the nozzle;directing a portion of the third scan fluid onto the surface of the semiconducting wafer to permit interaction between the third scan fluid and one or more further residual organic contaminants present on the surface of the semiconducting wafer following the second scan fluid removal; andremoving the third scan fluid containing at least a portion of the one or more further residual organic contaminants from the surface of the semiconducting wafer via the nozzle.

5. The method of claim 4, wherein the third scan fluid has a different composition than either of the first scan fluid and the second scan fluid.

6. The method of claim 4, wherein the third scan fluid has a same composition as one or more of the first scan fluid and the second scan fluid.

7. The method of claim 1, wherein directing a portion of the first scan fluid onto the surface of the semiconducting wafer to permit interaction between the first scan fluid and one or more organic contaminants present on the surface of the semiconducting wafer includes: directing the portion of the first scan fluid onto the surface of the semiconducting wafer to permit interaction between the first scan fluid and one or more organic contaminants present on the surface of the semiconducting wafer; andintroducing a second portion of the first scan fluid to the nozzle to replenish a volume of the first scan fluid on the surface of the semiconducting wafer.

8. The method of claim 7, wherein the second portion is commensurate with an evaporated volume of the first scan fluid from the surface of the semiconducting wafer.

9. The method of claim 7, wherein the second portion is commensurate with a volume of the first scan fluid that spread away from control by the nozzle on the surface of the semiconducting wafer.

10. A method for scanning a surface of a semiconducting wafer for organic contaminants utilizing a nozzle, comprising: positioning a nozzle above a surface of a semiconducting wafer, the semiconducting wafer supported adjacent to or within an interior of a chamber body;introducing a first scan fluid including one or more organic solvents to an inlet port of the nozzle;directing a portion of the first scan fluid onto the surface of the semiconducting wafer to permit interaction between the first scan fluid and one or more organic contaminants present on the surface of the semiconducting wafer;while directing the portion of the first scan fluid onto the surface of the semiconducting wafer, introducing a second portion of the first scan fluid to the nozzle to replenish a volume of the first scan fluid on the surface of the semiconducting wafer; andremoving the first scan fluid containing at least a portion of the one or more organic contaminants from the surface of the semiconducting wafer via the nozzle.

11. The method of claim 10, wherein the second portion is commensurate with an evaporated volume of the first scan fluid from the surface of the semiconducting wafer.

12. The method of claim 10, wherein the second portion is commensurate with a volume of the first scan fluid that spread away from control by the nozzle on the surface of the semiconducting wafer.

13. The method of claim 10, wherein introducing a second portion of the first scan fluid to the nozzle to replenish a volume of the first scan fluid on the surface of the semiconducting wafer includes: introducing the second portion of the first scan fluid from a scan solution reservoir via a pump to the nozzle to replenish the volume of the first scan fluid on the surface of the semiconducting wafer.

14. The method of claim 13, wherein introducing the second portion of the first scan fluid from a scan solution reservoir via a pump to the nozzle to replenish the volume of the first scan fluid on the surface of the semiconducting wafer includes: introducing the second portion of the first scan fluid from the scan solution reservoir via the pump at a substantially constant flow rate to the nozzle to replenish the volume of the first scan fluid on the surface of the semiconducting wafer.

15. A method for scanning a surface of a semiconducting wafer for organic contaminants utilizing a nozzle, comprising: positioning a nozzle above a surface of a semiconducting wafer, the semiconducting wafer supported adjacent to or within an interior of a chamber body;introducing a first scan fluid including one or more organic fluids to an inlet port of the nozzle;directing a portion of the first scan fluid onto the surface of the semiconducting wafer to permit interaction between the scan fluid and one or more organic contaminants present on the surface of the semiconducting wafer; andremoving the first scan fluid containing at least a portion of the one or more organic contaminants from the surface of the semiconducting wafer via the nozzle.

16. The method of claim 15, further comprising: introducing a second scan fluid including one or more organic fluids to the inlet port of the nozzle;directing a portion of the second scan fluid onto the surface of the semiconducting wafer to permit interaction between the second scan fluid and one or more residual organic contaminants present on the surface of the semiconducting wafer following the first scan fluid removal; andremoving the second scan fluid containing at least a portion of the one or more residual organic contaminants from the surface of the semiconducting wafer via the nozzle.

17. The method of claim 16, wherein the first scan fluid and the second scan fluid have different compositions of organic fluids.

18. The method of claim 16, further comprising: while directing the portion of the first scan fluid onto the surface of the semiconducting wafer, introducing a second portion of the first scan fluid to the nozzle to replenish a volume of the first scan fluid on the surface of the semiconducting wafer.

19. The method of claim 18, wherein the second portion is commensurate with an evaporated volume of the first scan fluid from the surface of the semiconducting wafer.

20. The method of claim 18, wherein introducing a second portion of the first scan fluid to the nozzle to replenish a volume of the first scan fluid on the surface of the semiconducting wafer includes: introducing the second portion of the first scan fluid from a scan solution reservoir via a pump to the nozzle to replenish the volume of the first scan fluid on the surface of the semiconducting wafer.