This invention relates to methods and systems for mixing of chemicals for use in semiconductor processing.
The removal of resist coatings is a critical process in semiconductor manufacturing and has historically been performed in a batch type processing mode with 25 to 100 wafers being immersed in a mixture of sulfuric acid and peroxide (SPM) for up to 20 minutes. As semiconductor devices shrink in size, defectivity is a significant challenge. To address the high defectivity associated with batch processing, industry focus has switched to developing and using single wafer type processes.
For many reasons, both economic and technical, single wafer SPM processes operate at higher temperatures (170°-220° C.) than batch processes (120°-150° C.). To make single wafer SPM processing economically feasible, the resist strip time must be reduced from 10 minutes to ideally less than 2 minutes. This can be achieved with the higher process temperatures.
High dose ion implant resist strip (HDIRS) is also a driving factor for high temperature single wafer SPM processing, as the crust created when the photoresist is bombarded by high-energy ions is notoriously difficult to remove. A key advantage for single wafer processing is that higher temperatures can be utilized to strip resist coatings. Higher process temperatures have been shown to significantly improve resist strip performance for higher dosed resists (e.g. 1×1014 atoms/cm2).
One disadvantage of using higher temperature SPM is that material selection for processing chamber materials is restricted to those that would be stable in contact with 220° C. SPM. Another disadvantage is that significant silicon nitride and silicon dioxide film loss is measured at temperatures above 170° C. Typically, the process should strip photoresist without any loss of silicon nitride (Si3N4) or silicon dioxide (SiO2).
Yet another disadvantage is the high level of mist generation in the process chamber. This is a challenge to make multi-chemical processing possible. SPM processing is typically followed by a Standard Clean 1 (SC1) step to remove residual particles from the wafer. The presence of SPM mist during a SC1 process creates a defectivity challenge due to the two chemicals forming an undesirable precipitate that could be deposited on the wafer, e.g., H2SO4+NH4OH=NH4SO4+H2O.
A significant difference between batch and single wafer SPM processing is the time scale. In a wet bench injection, mixing of hydrogen peroxide into sulfuric acid can occur over periods of minutes and the wafer cleaning process can take from 5 to 20 minutes. In contrast, in a single wafer tool, the hydrogen peroxide is injected into and mixed with the sulfuric acid in less than a couple of seconds and in some designs, time periods of less than 5 ms. In a single wafer tool, cleaning times on the wafer are less than 2 minutes, for example, about 30 seconds. The shorter time scale makes the single wafer tool performance more sensitive to the method of how the hydrogen peroxide is injected into the sulfuric acid.
There is thus a need for improved injection of hydrogen peroxide liquid into the sulfuric acid in a single wafer SPM process.
A method for rapidly mixing process chemicals to generate a treatment liquid for processing a single substrate is provided. The method comprises flowing a first process chemical in a process chemical delivery system with a first direction of flow having a center axis, and injecting a second process chemical from a nozzle into the flow of the first process chemical in the process chemical delivery system to effect a mixing of the first process chemical with the second process chemical to form a treatment liquid. The nozzle is oriented at or near the center axis to produce uniformity in the mixing of the first and second process chemicals within a target mixing distance between the nozzle and an outlet of the process chemical delivery system and within a target mixing time.
Additionally, a system for mixing of process chemicals to optimize resist strip performance is provided. The system includes a process chamber containing a single substrate, where the substrate has a high dose ion implant resist strip and the process chamber is configured to strip the resist, and a process chemical delivery system configured to deliver a treatment liquid comprising a first process chemical, a second process chemical, and reaction products of the first and second process chemicals from an outlet onto a portion of the surface of the substrate. The process chemical delivery system comprises a first process chemical supply line configured to deliver the first process chemical at a first temperature, a first flow rate, and a first direction of flow, and a second process chemical supply line configured to deliver the second process chemical at a second temperature and a second flow rate, the second process chemical supply line having an injection tube with a nozzle arrangement that includes at least one nozzle positioned to inject the second process chemical in the center of flow of the first process chemical in the first process chemical supply line. The first process chemical supply line, the second process chemical supply line, and the nozzle arrangement are operably configured to complete uniform mixing of the first and second process chemicals within the first process chemical supply line along a target mixing distance between the nozzle arrangement and the outlet and within a target mixing time.
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with a general description of the invention given above, and the detailed description given below, serve to explain the invention.
During certain steps of semiconductor wafer processing, Caro's Acid, a solution of sulfuric acid and hydrogen peroxide, is utilized to remove photoresist or organic contaminants. Because of its inherent instability, Caro's Acid is often prepared immediately prior to use. In certain applications, it is prepared by mixing sulfuric acid and hydrogen peroxide, in-situ, as the solution is dispensed from an outlet of a small diameter tube (typically ¼ inch). More specifically, hydrogen peroxide is often injected perpendicularly into the flowing sulfuric acid using a simple t-junction. However, a t-junction is not an efficient method to uniformly mix hydrogen peroxide into the sulfuric acid, since the t-junction introduces the hydrogen peroxide into a relatively low velocity and low turbulence region of the sulfuric acid flow. This inefficient mixing is particularly problematic during single wafer processing operations, wherein the goal is to ensure that the hydrogen peroxide is properly mixed into the sulfuric acid in the shortest time possible.
For wet bench applications, mixing times of 2-5 minutes can be tolerated. For single wafer tools, mixing times of 1-2 ms are advantageous. As depicted in
To address the non-uniformity in mixing, and in accordance with the invention, one embodiment of a chemical mixing system 10 is configured as shown in
Injecting at the center 28 of the process chemical delivery system 26 (i.e., along a center axis of the flow stream) is advantageous because it introduces hydrogen peroxide 16 into a mixing zone 24, that utilizes the region of highest fluid velocity (i.e., as a result of frictional forces against a container wall, the center of a column of moving fluid has a higher velocity relative to the perimeter of the column of fluid). Also, the injection tube 20, itself, creates localized disturbances in the flow that enhances mixing efficiency. In addition, injecting the hydrogen peroxide 16 in the opposite flow direction to the flow of sulfuric acid 14 (i.e., counter-flow) creates a disturbance in the flow that aids in uniform mixing.
The design of the nozzle 22 in this embodiment is also compatible for efficient dispensing of the SPM onto a rotating silicon wafer. For the sake of clarity, the disclosed embodiments show the intermixing of two substances. However, a plurality of substances, supplied at various pressures and flow volumes, may also be used.
The descriptions of embodiments below are related to the drawings in
Under certain operating conditions, fluid forces and reaction temperatures may result in distortion or damage to the injection tube 20. Therefore, support mechanisms 32 may be utilized to provide additional structural reinforcement to the injection tube 20. The support mechanism 32 may include fins or ribs that extend radially from the injection tube 20. These fins may be configured to support the injection tube 20 by contacting the interior wall 25 of the process chemical delivery system 26, either at discrete locations, or continuously along the length of the injection tube 20. In the alternative, the support mechanism 32, by utilizing fins, longitudinal flutes, or other stiffening members, may provide enhanced rigidity to the injection tube 20 without contacting the interior wall 25 of the process chemical delivery system 26. The support mechanism 32 may be designed to advantageously increase turbulence, thus improving mixing efficiency.
Alternatively, as seen in
Static mixing elements 34 may be included downstream of the nozzles 22a-22g along the mixing distance 30 at one or more locations to augment the mixing action, as will be discussed in further detail below in the discussion of
While earlier discussed embodiments have contemplated injecting hydrogen peroxide 16 at some distance away from the center 28 of the flow,
While sulfuric acid 14 and hydrogen peroxide 16 have been used to describe the embodiments above, many types of process chemicals may benefit from the disclosed embodiments. Thus, the invention is applicable to injecting a second process chemical into the flow of a first process chemical to achieve uniform mixing of the first and second process chemicals quickly and efficiently before exiting a delivery system into a processing chamber. The invention is particularly useful where the first and second process chemicals react to form reaction products, but may also be applicable to carrier gases and diluents.
In one embodiment of a method of the invention for rapidly mixing process chemicals to generate a treatment liquid for processing a single substrate, the method comprises flowing a first process chemical in a process chemical delivery system with a first direction of flow having a center axis, and injecting a second process chemical from a nozzle into the flow of the first process chemical in the process chemical delivery system to effect a mixing of the first process chemical with the second process chemical to form a treatment liquid. The nozzle is oriented at or near the center axis to produce uniformity in the mixing of the first and second process chemicals within a target mixing distance between the nozzle and an outlet of the process chemical delivery system and within a target mixing time. By “at or near the center axis” is meant that the injection occurs primarily within a central portion of the stream of the first process chemical, and is not injected solely at the perimeter of the stream where uniformity is least likely to be achieved. By way of example and not limitation, an offset from the center axis may be 0.4 mm or less.
By way of example, the target mixing distance may be 50 mm or less, or may be 10 mm or less. By way of example, the target mixing time may be 2 ms or less. The first process chemical may be an acid and the second process chemical may be an oxidizer, for example sulfuric acid and hydrogen peroxide, respectively. The sulfuric acid may be a 98 weight percent solution and the hydrogen peroxide may be a 30 weight percent solution. In one embodiment, a mixing ratio or efficiency of sulfuric acid solution to the hydrogen peroxide solution is optimized to the lowest value of a hydrogen peroxide metric at the nozzle exit. For example, the hydrogen peroxide metric is hydrogen mass fraction at the nozzle exit.
In a further embodiment, the nozzle includes a plurality of nozzles for injecting the second process chemical into more than one location in the flow of the first process chemical and/or in more than one direction. For example, one nozzle may inject the first process chemical coaxially with the center axis in an opposite direction to the flow of the first process chemical (e.g., nozzle 22a); one nozzle may inject the first process chemical coaxially with the center axis in the same direction to the flow of the first process chemical (e.g., nozzle 22c); one nozzle may inject the first process chemical at an offset distance to the center axis in an opposite direction to the flow of the first process chemical (e.g., nozzles 22b and 22f); one nozzle may inject the first process chemical at an offset distance to the center axis in the same direction to the flow of the first process chemical; one nozzle may inject the first process chemical at an angle from the center axis, such as a perpendicular angle, to traverse the direction of the flow of the first process chemical (e.g., nozzle 22d); and one nozzle may inject the first process chemical at an offset distance and angle from the center axis to traverse the direction of the flow of the first process chemical (e.g., nozzle 22g). Any one or combination of these nozzles may be used to inject the second process chemical at or near the center axis. One or more additional nozzles may be used to inject the second process chemical in perimeter locations within the process chemical delivery system (e.g., nozzle 22e) to supplement the central injection. Injection at an angle to the center axis may be any non-parallel angle, for example perpendicular, less than 90 degrees, or greater than 90 degrees, so as to at least partially traverse the direction of flow, and thereby create a turbulent action that facilitates mixing.
The method may further include dispensing the treatment liquid onto a portion of a surface of the substrate. The first process chemical may be sulfuric acid and the second process chemical may be hydrogen peroxide, and the substrate may comprise a layer of a high dose implant resist strip, wherein the method uniformly mixes the sulfuric acid and hydrogen peroxide to create reaction products that efficiently strip the high dose implant resist strip.
In one embodiment of a system of the invention for mixing process chemicals to optimize resist strip performance, the system comprises a process chamber containing a single substrate, where the substrate has a high dose ion implant resist strip and the process chamber is configured to strip the resist, and a process chemical delivery system configured to deliver a treatment liquid comprising a first process chemical, a second process chemical, and reaction products of the first and second process chemicals from an outlet onto a portion of the surface of the substrate. The process chemical delivery system comprises a first process chemical supply line configured to deliver the first process chemical at a first temperature, a first flow rate, and a first direction of flow, and a second process chemical supply line configured to deliver the second process chemical at a second temperature and a second flow rate, the second process chemical supply line having an injection tube with a nozzle arrangement that includes at least one nozzle positioned to inject the second process chemical in the center of flow of the first process chemical in the first process chemical supply line. The first process chemical supply line, the second process chemical supply line, and the nozzle arrangement are operably configured to complete uniform mixing of the first and second process chemicals within the first process chemical supply line along a target mixing distance between the nozzle arrangement and the outlet and within a target mixing time.
In one embodiment, the nozzle arrangement includes a plurality of nozzles coupled to the injection tube, wherein the plurality of nozzles includes at least two nozzles positioned at different locations to inject the second process chemical in two different positions or directions relative to the direction of flow. In another embodiment, the second process chemical supply line includes a plurality of injection tubes each with a nozzle arrangement, at least one of which includes the at least one nozzle positioned to inject the second process chemical in the center of flow of the first process chemical, and wherein the plurality of injection tubes enter the process chemical delivery system at different locations along the direction of flow to inject the second process chemical in two different positions or directions relative to the direction of flow. The system may further include a support mechanism on the injection tube or tubes sufficient to prevent bending thereof within the first process chemical supply line.
In accordance with another method of the invention for rapidly mixing process chemicals to generate a treatment liquid for stripping a resist layer on a single substrate, the method includes flowing a first process chemical in a first process chemical delivery system, where the first process chemical delivery system has a first direction of flow, a center of the flow, and a first mixing zone, and the first process chemical has a first chemical temperature and a first chemical concentration. The method further includes injecting a second process chemical into the first mixing zone of the first process chemical delivery system using a nozzle, where the second process chemical has a second process chemical temperature and a second process chemical concentration, and the injection of the second process chemical is at a second direction of flow. The method further includes mixing the first process chemical with the second process chemical, and causing a reaction of the first process chemical and the second process chemical to create reaction products, where the first process chemical, the second process chemical, and the reaction products form a treatment liquid. The injection of the second process chemical is operably designed to produce uniform mixing of the first and second process chemicals within a target mixing distance in the first mixing zone of the first process chemical delivery system and within a target mixing time.
In accordance with another system of the invention for mixing of process chemicals to optimize resist strip performance, the system includes a process chamber containing a single substrate, the substrate having a resist layer, the resist layer being a high dose ion implant resist strip, and the process chamber configured to strip the resist layer. The system further includes a process chemical delivery system configured to deliver a treatment liquid comprising a first process chemical, a second process chemical, and reaction products of the first and second process chemicals onto a portion of the surface of the substrate. The process chemical delivery system includes a first process chemical supply line configured to deliver the first process chemical at a first temperature, a first flow rate, and a first direction of flow; and a second process chemical supply line configured to deliver the second process chemical at a second temperature and a second flow rate. The delivery of the second process chemical is performed using a nozzle to inject the second process chemical in the center of flow of the first process chemical in the first process chemical supply line in the opposite direction of flow as the first process chemical supply line, the nozzle having a mixing zone of the first and second process chemicals. The delivery of the second process chemical is operably designed to complete uniform mixing of the first and second process chemicals within a target mixing distance in the mixing zone of the nozzle and within a target mixing time.
While the present invention has been illustrated by the description of one or more embodiments thereof, and while the embodiments have been described in considerable detail, they are not intended to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative apparatus and method and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the scope of the general inventive concept.
Pursuant to 37 C.F.R. §1.78(a)(4), this application claims the benefit of and priority to prior filed co-pending Provisional Application Serial No. 61/654,938 filed Jun. 3, 2012, which is expressly incorporated herein by reference.
Number | Date | Country | |
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61654938 | Jun 2012 | US |