# Patent

## Title
Methods for cleaning utilizing multi-stage filtered carbon dioxide

## Abstract

A cryogenic cleaner for and a method of performing cleaning of a surface that must be substantially free of contaminants utilizing a multi-stage, multi-mode filtered carbon dioxide-containing cleaning medium. Multiple stages and multiple types of filtration/purification are provided to remove contaminants such as hydrocarbons from the medium. In accordance with preferred embodiments, a filtering/purification process is provided that desirably utilizes one or more of: condensation of the hydrocarbon; particulate filtration; chemical filtration using activated filters; and catalytic oxidation. In certain embodiments, a resiliently mounted nozzle is provided for spraying a cryogenic cleaning medium on the surface. The nozzle may be driven in an oscillatory manner at a predetermined amplitude and frequency so the nozzle spray is delivered in a manner to provide pulsing of the spray and to provide as “snow plow” effect on contaminants as the spray delivers the cleaning medium against the surface. The surface is transported past the nozzle, and the cleaning occurs in an enclosed controlled environment.

## Background
This application is a con of Ser. No. 10/359,806, Feb. 7, 2003, U.S. Pat. No. 6,719,613 which is a CIP of Ser. No. 09/636,265 Aug. 10, 2000 U.S. Pat. No. 6,530,823.


FIELD OF THE INVENTION
This invention relates to systems and methods for cleaning surfaces on hard disks, semiconductor wafers, delicate optics, etc., preferably with an oscillating nozzle cleaning system, preferably dispensing cryogenic, solvent or solvent combination cleaning mediums such as carbon dioxide, and preferably utilizing filtered carbon dioxide.
BACKGROUND OF THE INVENTION
Articles such as hard disks, semiconductor wafers, delicate optics, etc., often must precisely cleaned in order to remove contaminants, either during or after the process for manufacturing the articles. A variety of cleaning methods have been employed with varying degrees of success. Certain of such methods that have been attempted involve imparting carbon dioxide snow onto the article to be cleaning.
An example of such a conventional system is described in U.S. Pat. No. 5,766,061. As a general/summary description of this system, a conveyor transports a wafer carrying cassette to be cleaned through an enclosure. Jet spray nozzles generate carbon dioxide spray that cleans the cassettes. While methods such as described in this patent provide a certain level of cleaning efficacy, improved methods for cleaning a variety of articles are still very much in demand.
In particular, the inventors of the present invention have determined that contaminants in the source carbon dioxide, particularly hydrocarbons, have limited the utility and/or performance of carbon dioxide-based processes such as carbon dioxide-based cleaning processes, and a need exists for improved filtering of carbon dioxide in such processes.
SUMMARY OF THE INVENTION
The present invention relates to systems and methods preferably using filtered carbon dioxide, preferably as a cryogenic cleaning medium for cleaning a surface on an article. A summary of a exemplary preferred embodiment of such a cleaning process is as follows, although it should be noted that the present invention is not limited to such a cleaning process (the cleaning process being exemplary, although it is noted that the present invention is particularly advantageous in such cleaning processes).
An enclosure is provided for maintaining a controlled environment during the cleaning process. The enclosure provides ingress and egress from and to a surrounding environment. A holding chuck is provided that is configured to secure the article to be cleaned. A stage or stage means is mounted on the support structure and the holding chuck is mounted on the stage means in a manner so that movement of the article relative to the support structure is provided within the enclosure on a predetermined path between the ingress and the egress points. A preheater is mounted in a first position adjacent the predetermined path in thermal communication with the surface of the article at the first position. A cryogenic spray nozzle assembly is provided wherein a spray nozzle is mounted in the spray nozzle assembly. The spray nozzle is in communication with the cryogenic cleansing medium for providing a cleaning spray at a second position adjacent the predetermined path so that the cleaning spray impinges on the surface to be cleaned at the second position. A post heater is mounted in a third position adjacent to the predetermined path in thermal communication with the surface of the article at the third position. The cryogenic spray nozzle assembly further includes means for imparting cyclic motion in the spray nozzle so that the cleaning spray is moved bidirectionally relative to the predetermined path.
In another aspect of the present invention, systems and methods are provided for cleaning a surface of an article, wherein a preferred system includes a frame work, a holding means that holds the article with the surface exposed, and means for moving the holding means along a predetermined path. A nozzle having a nozzle axis and a nozzle tip is spaced from and adjacent to the predetermined path for delivering a cleaning spray onto the article surface. Means is mounted between the framework and the nozzle for supporting and driving the nozzle tip through a cyclic motion.
In yet another aspect of the present invention, an oscillating nozzle assembly for use in cryogenic cleaning of a surface of an article that must be cleaned substantially free of contaminants is provided. The oscillating nozzle assembly includes an assembly mounting block, a nozzle mounting block, and means for resiliently connecting the nozzle mounting block to the assembly mounting block. Further, the oscillating nozzle assembly includes an eccentric and a driver connected to the eccentric. In addition, means is provided for mounting the eccentric and the driver between the nozzle mounting block and the assembly mounting block. At least one nozzle is included having a nozzle tip, wherein the nozzle is mounted on the nozzle mounting block so that the driver operates to move the nozzle tip cyclically when the driver is energized.
In yet another aspect of the present invention, the oscillating nozzle assembly for dispensing a cleaning medium toward a surface on an article includes a nozzle, a tip on the nozzle for dispensing the cleaning medium, and means for mounting the nozzle. A nozzle assembly base is included together with means for controllably moving the means for mounting the nozzle relative to the nozzle assembly base in a cyclic pattern having a predetermined frequency and amplitude.
In accordance with preferred embodiments, the cryogenic cleaning medium consists of carbon dioxide that is filtered, preferably with a multi-stage filtering process. As commercial sources of carbon dioxide tend to include undesirable amounts of hydrocarbons (due, at least in part, to the solubility of many hydrocarbons in carbon dioxide), a preferably multi-stage filtering process that removes contaminants such as hydrocarbons is implemented.
In preferred embodiments, the filtering process utilizes one or more of the following: A coalescent-type filter that preferably removes the bulk of the contaminant (typically hydrocarbon); this filter preferably consists of multiple stages, such two to four stages, with three stages used in certain preferred embodiments (three separate filters). A heated/catalytic stage preferably removes contaminants such as hydrocarbons; a high temperature pre-heater preferably is utilized to heat the CO2 to accelerate the catalytic reaction; the temperature range preferably is about 250° C.-1000° C., with the preferred set point temperature about 500° C.; a heated catalytic stage (preferably multi-stage), with a heater used to maintain a constant temperature for the catalytic process (preferred temperature ranges may be as stated previously); a multistage catalytic process preferably is utilized that removes contaminants such as hydrocarbons based on multi-heater/catalyst stages; a multi-stage catalytic process preferably is utilized in order to, for example, ensure a near complete reduction/oxidation of hydrocarbons, with the multistage process helping ensure that the majority of CO2 molecules will be in contact with one or more catalytic surface; Activated and non-activated carbon filters (preferably replaceable) preferably are utilized to extract residual contaminants such as hydrocarbons in the CO2 after the catalytic oxidation; in preferred embodiments, this filter is implemented downstream of the catalytic process, where the amount of hydrocarbon in the CO2 is greatly reduced; as a result, filter replacement will be less frequent; A particle filter, preferably a multistage filtration system, consists of one or more ceramic core particulate filters to remove larger particles (e.g., 0.1 micron and larger), which preferably is followed by an all metal electronic grade filter to remove finer particles (e.g., 0.005-0.1 microns); A chiller preferably is provided to control the quality and the conditions of the CO2 entering the nozzle (for a nozzle-based cleaning process, etc.); the chiller core preferably is electro-polished stainless steel to prevent contamination of the CO2.
Methods in accordance with the present invention relate to processing an article having a surface to be cleaned substantially free of contaminates. The process includes the steps of performing a plurality of pre-cleaning fabrication steps, conducting a cleaning process at a cleaning position using a cleaning spray, and performing a plurality of post-cleaning fabrication steps. The step of conducting a cleaning process includes the steps of transporting the surface to be cleaned to the cleaning position together with positioning the surface to be cleaned proximate to the cleaning spray at the cleaning position. Further, the step of oscillating the cleaning spray at the cleaning position in a predetermined pattern is performed to provide improved cleaning in accordance with the present invention.



BRIEF DESCRIPTION OF THE DRAWINGS
The present invention may be more fully understood by a description of certain preferred embodiments in conjunction with the attached drawings in which:
FIG. 1 is a perspective showing one embodiment of the system of the present invention;
FIG. 2 is a schematic showing gas and vacuum paths for one embodiment of the system of the present invention;
FIG. 3 is a perspective of one embodiment of the spray nozzle assembly of the present invention with the outer cover removed;
FIG. 4 is a perspective of another embodiment of the nozzle assembly of the present invention with the outer cover removed;
FIG. 5 is a perspective of an additional embodiment of the system of the present invention;
FIG. 6 is a block diagram relating to the process of the present invention;
FIG. 7 is another block diagram illustrating the details of the process of the present invention; and
FIG. 8 is a schematic illustrating preferred multi-stage cleaning of contaminants such as hydrocarbons from a medium such as carbon dioxide.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described in greater detail with reference to certain preferred embodiments and certain other embodiments, which may serve to further the understanding of preferred embodiments of the present invention. As described elsewhere herein, various refinements and substitutions of the various embodiments are possible based on the principles and teachings herein. Preferred embodiments of the present invention utilize a preferably multi-stage filtering process to remove contaminants such as hydrocarbons from the medium, preferably carbon dioxide. Before discussing the particle features of such preferred embodiments, exemplary apparatus and methods relating to a cryogenic cleaning process wherein the multi-stage filtering process of the preferred embodiments may be desirably utilized. It should be understood, however, that the multi-stage filtering process of the preferred embodiments is not limited to be used in such a cryogenic cleaning process/apparatus.
Very small quantities of contamination are detrimental to the fabrication processes involved in producing integrated circuit wafers, hard discs, optical elements, etc. Contamination in the form of particulates, films, or microscopic clusters of molecules can produce fatal defects in any of the aforementioned products before, during or after fabrication processes. Cleaning of the surfaces on these produces is therefore essential at various phases during fabrication. Cryogenic cleaning of surfaces utilizing impingement of solid particles of relatively inert gases such as argon and CO2 are known and the manner in which solid particles of such gases are generated for cleaning purposes need not be described herein. Without being bound by theory, in such cases it is thought that the combination of sublimation of the solid particles as they impinge the surface to be cleaned as well as the impact momentum transfer by the particles provides the vehicle for removing contamination from a surface. It is further recognized that sublimation occurs, and therefore a major portion of the cleaning, only while the surface to be cleaned is at a higher temperature than that of the cryogenic spray. The thermophoresis due to the heated surface also helps to remove the particles from the surface and reduce the chance of re-deposition of the detached particles. As a consequence, pre-heating and post-heating of the surface being cleaned is required within the vicinity of the impinging cleaning spray. Cleaning by various other solvents and solvent combinations where the levels of residual contaminants following the cleaning process need not be held quite as low, is also envisioned for use in the systems and methods of the present invention.
Reference is now made to FIG. 1 of the drawings, wherein one exemplary embodiment of the present invention is illustrated. A system 10 is shown in FIG. 1 having an enclosure 11 depicted in phantom line. The environment within the enclosure is maintained at a level of cleanliness depending on the level of cleanliness to be imposed on articles to be cleaned within the enclosure. A scavenging line 12 is shown exiting the enclosure 11 at the bottom thereof and proceeding to a filter 13 for removing particulates from the enclosure environment that may be generated by the cleaning process or by mechanical components within the enclosure. Rudimentary support structure is shown including a base plate 14 and two uprights 16 and 17 attached at their bases to the base plate. The description herein makes reference to an XYZ coordinate system, wherein the Z direction is substantially vertical and the mutually orthogonal Z and Y axes are substantially horizontal. An XY stage is shown having an X stage 18 for movement on a Y stage 19, that is mounted on the base plate 14 (other X/Y stage configurations are within the scope of the present invention). A holding chuck 21, in this instance a vacuum chuck connected through a line 22 to a vacuum source 23, is mounted for movement on the X stage 18. An article to be cleaned, in this exemplary illustration an integrated circuit wafer 24, is shown in FIG. 1 mounted to the vacuum chuck 21 and held in place by known means (e.g., held in place by the vacuum). FIG. 1 shows the integrated circuit wafer 24 in an initial position, and subsequently in a cleaning position at 24a and a post-heating position at 24b. The integrated circuit wafer 24 preferably is transportable along a predetermined path governed by the movement of the X stage 18 on the Y stage 19 and the movement of the vacuum chuck 21 on the X stage 18. Chuck 21 is driven over the upper surface of the X stage by known means, which may include a carriage portion within the X stage driven by a lead screw and a servo motor (not shown), for example. A cable connection 26 is shown at one end of the X stage for introducing power to energize the aforementioned servo motor. A similar cable connection (not shown) is provided to power the Y stage 19 so that the X stage, mounted on a moveable carriage of the Y stage, may be moved in the Y direction by a lead screw and servo motor similar to that mentioned hereinbefore in conjunction with the X stage.
From the foregoing it is seen that the integrated circuit wafer 24 shown in an initial position in FIG. 1 may be moved to the left in FIG. 1 to pass beneath a pre-heater 27 at a pre-heat position along the aforementioned predetermined path, which preferably pre-heats the integrated circuit wafer prior to cleaning. Further movement of the chuck 21 brings the integrated circuit wafer to a cleaning position indicated in FIG. 1 at 24a. Continuing movement of the chuck along the predetermined path defined by the X and Y stages 18 and 19 delivers the integrated circuit wafer to a post-heat position shown at 24b, wherein post-heating of the integrated circuit wafer preferably is performed by a post-heater 28. The pre and post heaters may be infra red lamps or other heating sources. These heaters preferably impart surface temperatures to the article that enhance cleaning, prevent re-contamination and remove static electricity. In alternative embodiments, the pre and post heaters are supplemented with, or replaced by, a heated vacuum chuck, with the heated vacuum chuck providing heat to the article to be cleaned, etc. The use of such a heated vacuum chuck also may be used in accordance with other embodiments of the present invention as described herein.
A nozzle assembly support plate 29 is shown extending between the two uprights 16 and 17. The support plate preferably is attached at the upright 16 in a Z position by a friction clamp 31. The support plate 29 preferably is mounted on the opposing end to upright 17 in the Z position by an additional friction clamp 32. It should be noted that the position of the mounting plate 29 in the Z direction may be governed by a servo motor 33 and associated mechanism (not shown) similar to that of the X and Y stages, so that the Z position of the support plate 29 is dictated by a control 34, which may controllably raise or lower the support plate 29 either before, during or after cleaning or other processing.
A spray nozzle assembly 36 is shown mounted to the support plate 29 at a pivot 37. A nozzle 38 is shown extending from the spray nozzle assembly 36 at a lower portion thereof at the cleaning position shown by the position of integrated circuit wafer 24a in FIG. 1. A preferred exemplary angle of the nozzle 38 to the surface to be cleaned on the integrated circuit wafer 24 is seen in FIG. 1 to be obtuse to the direction of approach of the integrated circuit wafer. Expressed alternatively, the angle of the nozzle 38, and the subsequent spray emitted therefrom, is acute to the downstream portion of the predetermined path along which the wafer travels on the XY stage. The point to be made here is that the spray emanating from the spray nozzle 38 preferably is set to impinge the surface to be cleaned at an angle to facilitate contaminant removal and to add any velocity of the surface to be cleaned to the spray velocity for purposes of enhancing contaminant removal. That angle of impingement as seen in FIG. 1 preferably is adjustable by moving the spray nozzle assembly 36 rotationally about the pivot 37 and fixing the angle in the adjusted position.
It should also be noted that, in preferred embodiments, one or more jets for cleaning an article, with the oscillatory-type movement of the present invention, such jets, although having a non-uniform spray pattern, may result in a more substantially uniform and improved spray distribution due to the oscillatory-type movement, which preferably enables an article to be more uniformly cleaned in a single pass, etc.
Turning to the diagram of FIG. 2, the spray nozzle assembly 36 is shown poised in position above the integrated circuit wafer in the position represented by 24a wherein the wafer is moving to the left in FIG. 2 relative to the spray nozzle assembly. Nozzle 38 is shown directing a cleaning spray 39 onto the surface of the article to be cleaned (integrated circuit wafer 24a in FIG. 2) at the spray impingement angle referred to hereinbefore in conjunction with FIG. 1. A second spray nozzle 41 is shown just visible in the diagram of FIG. 2 for preferably delivering a heated inert gas spray 42 for heating, drying and removing static electricity from the surface just cleaned by the spray 39. The heated inert gas spray nozzle 41 may fill the requirements of the post-heater 28 shown in FIG. 1. Details of construction of the nozzles 38 and 41 will be described in more detail hereinafter.
FIG. 2 shows an inert gas source 43 connected through a flow line to a temperature control module 44 and subsequently to a gas filter 46. Inert gas flow is subsequently directed through an ionizer 47 and a flexible line 48 to the nozzle 41 contained in the, spray nozzle assembly 36. A cleaning medium container 49 (such as an argon or CO2 gas container) preferably is connected through a gas flow line to a temperature control 51. The temperature controlled cleaning medium preferably is connected to a pressure booster 52 and subsequently to a filter 53 for removing contaminants. The filtered, temperature controlled and pressurized cleaning medium preferably is connected through a flexible line 54 to the nozzle 38 in the spray nozzle assembly 36. The manner in which a gas cleaning medium is conditioned for cryogenic cleaning is known, and teachings from the art submitted contemporaneously herewith are incorporated herein by reference. In certain applications the cleaning medium contained in the container 49 may be a solvent different from the cryogenic gas, known to those in this art, descriptions of which will not be undertaken here. A flexible vacuum line 56 is shown in FIG. 2 to remove contaminants generated by functions taking place within the case of the spray nozzle assembly 36 so that they are not deposited upon the surface to be cleaned. The flexible vacuum line 56 is led to the outside of the enclosure 11 when the system containing the spray nozzle assembly 36 is enclosed therein. The location of the pivot 37 of FIG. 1 is shown by the hole 37a depicted in FIG. 2.
FIG. 3 depicts the spray nozzle assembly 36 with the cover removed. The article to be cleaned represented by the integrated circuit wafer 24a is seen to be moving to the left in FIG. 3 relative to the spray nozzle assembly. The spray nozzle assembly is pivoted about the pivot 37 (FIG. 1) to assume the position shown in FIG. 3 so that the cleaning nozzle 38 dispenses the cleaning spray 39 at an obtuse angle relative to the approaching portion of the surface to be cleaned. The cleaning nozzle 38 preferably has a nozzle axis and a nozzle tip with an elongated nozzle opening therein to provide the exemplary preferred fan-shaped spray 39 seen in FIG. 3. A friction lock 57 is shown on the nozzle 38 which allows the tip of the nozzle to be rotated around the nozzle axis and to be locked in the rotated position. Rotation of the tip of nozzle 38 preferably allows the fan-shaped spray 39 to impinge the surface to be cleaned at an angle of rotation about the nozzle axis. This angle of rotation allows the fan-shaped spray 39 to push contaminates to one side of the surface to be cleaned as to the spray nozzle is oscillated to thereby affect a “snow plow” function. This will be further explained in conjunction with the description of the oscillation of the nozzle 38. In like fashion, nozzle 41 for dispensing inert drying gas, preferably has a friction lock 58 functioning in the same manner as the friction lock 57 on nozzle 38. Nozzle 41 also has a tip with an elongated opening therein for preferably producing a fan shaped emission of inert drying gas 42. Nozzle 38 preferably is attached to a nozzle mounting block 59 through a tube 61 and a connector 62 coupling the nozzle 38 to the flexible line 54 (FIG. 2). Nozzle 41 also preferably has a tube 63 connected thereto which is mounted in the nozzle mounting block 59. A connector 64 connects the tube 63 to the flexible line 48 (FIG. 2) to deliver heated inert gas to the surface to be cleaned immediately after cleaning when that method is used for post-heating of and removal of static charge from the surface being cleaned.
Nozzle mounting block 59 in FIG. 3 is cut away to show installation of the outer diameter of an outer bearing race 66 mounted within a bore 67 in the nozzle mounting block. An inner race 68 on the bearing within the bore 67 has an eccentric cam-member 69 mounted therein. A shaft 71 on a pulley 72 is passed through an offset hole 73 in the eccentric cam and fixed therein. The pulley 72 is driven by a belt 74 which in turn is driven by a pulley 76 mounted on the end of a shaft 77 driven by a motor 78. The motor 78 is mounted in a motor mount block 79 (partly cut away for clarity) secured to the outer case of the spray nozzle assembly 36. The motor mount block 79 also serves to mount the pulley 72 for rotation thereon. A plurality of arms 81, two of which are shown in FIG. 3, are fastened to the motor mounting block 79 extending outwardly therefrom to a position beyond the nozzle mounting block 59. Yieldable structure such as coil springs 82, extend from the ends of the arms 81 to the nozzle mounting block 59 and from the motor mounting block 79 to the opposing side of the nozzle mounting block 59. The ends of the coil springs 82 are encompassed by buttons or caps 83 that are seated in counter bores in the structural members 59, 79 and 81 that receive respective ends of the coil springs 82. The material for the end caps 83 is preferably Delrin AF. Very little particulate is sloughed off of the Delrin AF surfaces when the material is subjected to friction. As a result, the springs 82 are anchored on one end within the bores 84 at the ends of the arms 81 and in the motor mounting block 79 and anchored at an opposing end within bores 84 in the nozzle mounting block 59. Nozzle mounting block 59 is therefore suspended by the springs 82 in position spaced from the remainder of the spray nozzle assembly. Consequently, when the spray nozzles 38 and 41 are mounted on the nozzle mounting block 59, and when the nozzle mounting block is moved, the sprays 39 and 42 are moved relative to the surface to be cleaned on the integrated circuit wafer 24a in FIG. 3. An optimum offset from the geometric center of the offset cam 69 has been found to be about 0.075 inches. As a result an optimum peak to peak amplitude for cam excursion is about 0.150 inches. An optimum cam rotation frequency through the pulleys 76 and 72 has been found to be approximately 27.5 revolutions per second or about 271⁄2 Hertz. Thus, in a preferred embodiment, the optimum amplitude provided by the cam 69 falls within the range of about 0.120 to 0.180 inches peak to peak. The optimum frequency falls within the range of about 25 to 30 Hertz. Other amplitudes and frequencies for optimum cleaning of specific contaminants from surfaces are envisioned as within the scope of the present invention.
Springs 82, in this preferred embodiment, preferably have coils of 0.043 inch diameter stainless steel wire, with one half (1⁄2) inch diameter coils and lengths of one and one-half (11⁄2) inches. Such springs generally should provide adequately support the mass of the nozzle mounting block 59 and members attached thereto. It should further be noted that motor 78 could be mounted on motor mounting block 79 to directly drive shaft 71 connected to the eccentric cam 69 in those instances where the rotational output speed of the motor shaft 77 imparts an acceptable frequency to the oscillatory motion induced by the rotation of the eccentric cam 69. In any event, the nozzle mounting block 59 and the nozzles 38 and 41 attached thereto are driven at a predetermined frequency and amplitude, so that the nozzles are driven in a circular pattern having a diameter of the peak to peak oscillation amplitude and a frequency determined by the rotational frequency of the eccentric cam 69. The physical dimensions of springs 82 will depend on the mass of the spray nozzle assembly 36. Therefore, heavier or lighter springs 82 may be used as the spray nozzle assembly assumes greater or lesser mass. It is noted that the preferred structure for imparting the cyclic motion to the nozzles 38 and 41 relative to the surface to be cleaned are exemplary.
FIG. 4 depicts the spray nozzle assembly 36 with the motor mounting block 79 removed from the drawing for clarity. As seen in FIG. 4, a single nozzle 38 is shown having the aforementioned preferred elongated aperture therein for providing emission of the fan-shaped spray 39 for impingement on the surface to be cleaned. The surface shown in FIG. 4 is the surface of the integrated circuit wafer 24a. Friction lock 57 in the illustration of FIG. 4 is loosened and the nozzle 38 is rotated counter-clockwise (looking at the elongated aperture therein). The orientation of the aperture of nozzle 38 is locked in the adjusted position by the friction lock 57. When the motor 78 is energized and an oscillation in the nozzle 38 is imparted by the oscillation of the nozzle mounting block 59 on the support provided by the springs 82, the nozzle tip, and therefore the spray 39 describes a circular pattern at the predetermined amplitude and frequency. The rotation of the oscillation is indicated by the arrow 84 in FIG. 4.
The impingement of the spray pattern 39 on the surface to be cleaned is illustrated in FIG. 4. The nozzle 38 and the spray pattern 39 moves during half of each rotational cycle toward the integrated circuit wafer. Further, during the subsequent half of each rotational cycle the nozzle and spray move away from the wafer surface. This is seen when it is recognized that the nozzle tip describes a circle during oscillation, wherein the plane of the circle substantially includes an extension of the nozzle axis. This is illustrated in FIG. 4 by the rotational arrow 84 and the arrows 85 representing oscillation circle diameters. The nozzle 38 sweeps the spray 39 side to side on the wafer surface because the edge of the circle represented by diameters 85 appears as a straight line when viewed from the wafer surface.
Now considering the rotation of the flat fan shaped spray 39 about the nozzle axis by the adjustment of the friction lock 57, the fan 39 impinges the surface at a compound angle (displaced from the side to side sweep) preferably resulting in the “snow plow” effect of the fan-shaped spray 39 during half of each cycle as it rotates in the direction of the arrow 84. Further, the disclosed oscillation of the fan-shaped spray 39 provides the benefits of pulsing which enhances cleaning. Pulsing in the past has been provided in a spray by interrupting the spray periodically. However, such interruption causes the spray jet to lose optimum characteristics as the, spray is cut off and restarted when the spray is a cryogenic cleaning medium comprised of solid gas particles. The pulsing occurs in the embodiments disclosed herein due to increasing velocity (or acceleration) as the spray 39 converges on the surface to be cleaned during one half (1⁄2) of the oscillatory cycle and the decrease in velocity (negative acceleration) as the spray 39 diverges from the surface to be cleaned during the other half of the oscillatory cycle. Spray nozzle 38 describing a circular pattern during oscillation as described hereinbefore, preferably lays down a laterally oscillating spray pattern on the surface to be cleaned. The angle of the spray pattern impingement on the surface is therefore formed by adjustment of the spray nozzle assembly 36 rotationally about the pivot 37 (FIG. 1) and adjustment to the spray fan orientation about the nozzle axis through adjustment of the friction lock 57. Pulsing and compound angle “snow plow” effects in cleaning are believed to provide advantages in obtaining thorough contaminant removal. It should be mentioned that the shaft 71 for driving the eccentric cam 69 (FIG. 3) could be driven directly by the motor 78, allowing elimination of the pulleys 72 and 76 and the belt 74 as discussed in conjunction with FIG. 3. On the other hand, selection of relative diameters of pulleys 72 and 76 may be used to adjust the frequency of oscillation if desired.
The embodiment of FIG. 5 depicts a robot 86 having an extendable and retractable arm 87, providing movement in a vertical direction, and a laterally extending arm segment 88 disposed for rotation about an axis 89 at the upper end of the arm 87. An additional robot arm 91 is provided that moves translationally in a horizontal direction. Translationally moving arm 91 extends through an egress/ingress port 92 in the enclosure 11 of FIG. 5 to insert an article having a surface to be cleaned, such as the integrated circuit wafer 24, into a controlled environment within the enclosure 11 as discussed in conjunction with the enclosure 11 of FIG. 1. The wafer 24 is shown at the limit of its insertion within the enclosure 11, having passed the pre-heater and post-heater combination 93 immediately inside the ingress/egress port. Wafer 24 is therefore pre-heated at the position shown in FIG. 5 and then withdrawn toward the ingress/egress port 92 to pass beneath a bank (plurality) of cleaning nozzles 94. The bank of nozzles extend across the entire dimension of the wafer, providing impingement by a plurality of fan shaped sprays on the surface to be cleaned, thereby cleaning the surface in a single pass beneath the bank of cleaning nozzles 94. Immediately following passage of the surface to be cleaned beneath the cleaning nozzles 94, an inert drying gas and anti-static electricity array 96 is positioned that also extends across the entire dimension of the wafer 24. As the wafer is withdrawn toward the ingress/egress port 92, the surface is dried by the inert drying gas nozzle array and further heated by the pre/post heater 93 to a temperature that will prohibit condensation on the clean surface as it is withdrawn from the enclosure 11 by the robot arm 91. Positioned adjacent the cleaning nozzle array 94 is a scavenging intake 97 that operates to remove particulates cleaned from the surface of the wafer 94 as well as particulates generated within the enclosure 11. Scavenging intake is connected to an exhaust 98, which carries the contaminants from within the enclosure to the ambient environment. Pressure within the enclosure 11 preferably is maintained slightly higher than ambient pressure to prevent contaminants from entering the enclosure through the ingress/egress port 92. Further, as in the description of the embodiment of FIG. 1, the scavenging line 12 is provided to withdraw the enclosed atmosphere and deliver it to the cleaning filter 13 to further reduce contaminants within the enclosure.
With regard to an exemplary preferred method in accordance with the present invention, there preferably exist certain pre-cleaning fabrication steps for the article having a surface to be cleaned followed by the step of cleaning the surface, and culminating in post-cleaning fabrication steps for the article having a surface to be cleaned. The block diagram of FIG. 6 depicts these steps. Details of a preferred surface cleaning process of FIG. 6 are found in the block diagram of FIG. 7. FIG. 7 illustrates the pre-cleaning fabrication steps of FIG. 6 followed by mounting the article having a surface to be cleaned on an article transport. In one embodiment of the cleaning process the article is transported to a cleaning position and the shape of the spray is configured to assume a fan shape. The spray nozzle in then oriented to cause the spray to impinge the surface to be cleaned at an angle to the lateral dimension of the surface as it passes the spray. This angle is called a compound angle. The nozzle is then aimed at the surface to be cleaned to form an obtuse angle with the surface relative to the approaching portion of the surface to be cleaned. Subsequently, the nozzle is oscillated so that the spray functions as a pulsing spray as the forward motion of the nozzle is added to the velocity of the cleaning spray during one portion of the oscillation cycle and is subtracted from the velocity of the cleaning spray during the subsequent portion of the oscillation cycle. Moreover, the orientation of the nozzle aperture and the fan-shaped spray about the nozzle axis preferably provides a “snow plow” effect facilitating cleaning as previously described. Subsequent to the cleaning by the oscillating fan-shaped spray the article preferably is moved onto the post-cleaning fabrication steps as illustrated in FIG. 7.
In another aspect of the cleaning process of the present invention a cryogenic cleaning medium is used. As mentioned hereinbefore an inert gas such as argon or CO2 is in substantially solid or “snow” form as it is emitted from the nozzle so that sublimation of the gas occurs at the surface to be cleaned. In this process the surface to be cleaned preferably is preheated to a temperature such that the surface to be cleaned will remain at a temperature above ambient during the impingement of the cryogenic spray on the surface. The spray preferably is shaped into a fan shape and the spray nozzle aperture preferably is oriented about the nozzle access to provide impingement of the fan spray on the surface to be cleaned at an angle to the lateral dimension of the surface (the compound angle). The spray nozzle preferably is then aimed at the surface at an obtuse angle relative to the surface portion approaching the cleaning spray and the nozzle preferably is oscillated in a cyclic pattern having a pre-determined amplitude and frequency. The nozzle preferably oscillates in a substantially circular pattern in a plane including the nozzle axis so that the spray pattern is lateral and linear on the surface. Moreover, due to the orientation of the nozzle rotationally about the nozzle axis, the spray impinges the surface at the compound angle and performs a “snow plow” function. This function is believed to tend to push contaminants to one side of the surface to be cleaned. Following exposure to the oscillation cleaning spray, the surface preferably is post-heated to a temperature above ambient temperature to prevent condensation and recontamination of the surface and also to remove static charge. It should be noted that the step of shaping the spray preferably reside in both embodiments of the process described in conjunction with FIG. 7 and includes expanding the width of the cleaning spray to cover the lateral dimension of the surface to be cleaned. As a result, the cleaning of the surface may be obtained in a single pass of the surface to be cleaned past the spray. Subsequently the post-heated article surface is passed to the post-cleaning fabrication steps as seen in FIG. 7.
With reference to FIG. 8, a preferably multi-stage filtering process, which desirably may be utilized with the foregoing cleaning apparatus/method, will now be described. Preferred embodiments of the present invention implement a CO2 purification technique, which preferably utilizes a multi-stage, multi-filtering type/mode (multiple, distinct types of filtering processes).
Carbon dioxide typically is a byproduct of a process, and has been determined typically to be contaminated with contaminants such as hydrocarbons and other chemicals. Hydrocarbons typically are soluble in CO2, especially at more elevated temperatures. When using CO2 for example as a cleaning medium in a supersonic nozzle system, the temperature at the exit of the nozzle tends to be very low (e.g., about −110° F.). It has been discovered that, in such processes, hydrocarbons in the CO2 can be released and deposited on the surface being cleaned (e.g., silicon wafer), which can severely limit the utility of the (preferably) cleaning process.
In accordance with preferred embodiments of the present invention, it is important to purify the CO2 gas before it can be used for cleaning the wafer or other article. According to investigations by the inventors herewith, the best grade CO2 available in the market tends to contain as much as about 5 PPB of hydrocarbons. In accordance with preferred embodiments of the present invention, however, the level of contaminant such as hydrocarbons is reduced by orders of magnitude to about 0.01 PPT before it is utilized in a subsequent process, which may be, for example, a wafer cleaning process. Removing the hydrocarbon contaminant from CO2 has been determined to be a very challenging problem. In fact, it has been very difficult to accomplish this task because of the minute amounts of hydrocarbon needed to be removed, given that hydrocarbons tend to have excellent solubility in CO2.
Preferred embodiments of the present invention preferably utilize a series of filtering/purification processes to remove hydrocarbon contaminants from the CO2. In accordance with such preferred embodiments, a filtering/purification process is provided that desirably utilizes one or more of: condensation of the hydrocarbon; particulate filtration; chemical filtration using activated filters; and catalytic oxidation. The schematic provided in FIG. 8 illustrates outlines a desirable combination of distinct filtering/purification steps or implements in an exemplary preferred embodiment.
CO2 gas is provided by source 100, which preferably provides the CO2 gas at about 300 to 900 psia pressure range, which preferably flows through condensing device 101. Condensing device 101 preferably removes a majority of the contaminant, preferably hydrocarbon. Condensing device 101 preferably removes hydrocarbons by condensation and through surface tension phenomenon and gravity force.
The gas preferably will then be heated in heater 102 to prepare it for a subsequent, preferably catalytic, oxidation process. The preferably catalytic reduction/oxidation process is implemented in catalytic reactor 103, which preferably is heated via heater 103A to a temperature to provide more optimum conditions for catalytic reduction/oxidization of the hydrocarbons, assisted by catalyst 103B. Catalyst 103B may be of a type known in the art, that serves to facilitate and accelerate the reduction/oxidization of hydrocarbons. For example, catalyst 103B may be Titanium Dioxide (TiO2) or other suitable catalytic material, which could be enhanced by the use of UV light (the use of UV light on such a catalyst is known in the art). Catalyst 103B preferably is imbedded into, or integrated with, heater 103A in order to maintain the preferably high temperature required for effective burning of residual hydrocarbon.
It should be noted that CO2 normally contains oxygen that is required for the catalytic oxidation process. If, however, the amount of oxygen in the CO2 is not sufficient to enable conditions for a stoichiometric reaction, oxygen optionally can be injected into the gas line via inlet 111, such as illustrated in FIG. 8. It should be further noted that, in certain embodiments, heater 102 is optional or integrated into heated catalytic reactor 103.
In accordance with preferred embodiments, and as further illustrated in FIG. 8, the CO2 gas preferably is then passed through chemical filter 104, which preferably consists of a series of chemical filters 104, which preferably contain what is known in the art as activated carbon for hydrocarbon adsorption. In accordance with preferred embodiments, it should be noted that carbon filter(s) 104 is/are utilized towards the final stage of the filtering/purification process because it adsorbs the hydrocarbon and needs to be replaced (e.g., when nearing or at saturation). As a result, in accordance with the present invention, employing it at or near the last stage will increase the lifetime and decrease the replacement frequency of filter(s) 104, and thus desirably reduce the down time of the processing tool.
In accordance with preferred embodiments, and as further illustrated in FIG. 9, the CO2 gas preferably is then passed through particle filter 105 (or a series of particle filters 105) to remove any particles that may be present in the CO2 or that were shed into the CO2 in the preceding carbon filtering process. As further illustrated, in certain preferred embodiments liquid CO2 is required for, for example, nozzle flow. In such embodiments, the gas is condensed through chiller 106. In embodiments where gas is required in the nozzle or subsequent process, chiller 106 is omitted, and the gas preferably passes via outlet 110 through the particle filters to the nozzle system (or other system implement).
As will be appreciated from the exemplary preferred embodiment illustrated in FIG. 8, in accordance with preferred embodiments, the cryogenic cleaning medium consists of carbon dioxide that is filtered, preferably with a multi-stage, multi-mode/type filtering process. As commercial sources of carbon dioxide tend to include undesirable amounts of hydrocarbons (due, at least in part, to the solubility of many hydrocarbons in carbon dioxide), a preferably multi-stage filtering process that removes contaminants such as hydrocarbons is implemented. Additional details/options in accordance with such embodiments will now be described.
In preferred embodiments, the filtering process utilizes one or more of the following. A coalescent-type, preferably condensing-type, filter 101 is provided that preferably removes the bulk of the contaminant (typically hydrocarbon). Filter 101 preferably consists of multiple stages, such two to four stages, with three stages used in certain preferred embodiments (three separate filters). A heated/catalytic reactor 103 preferably removes contaminants such as hydrocarbons. High temperature pre-heater 102 preferably is utilized in certain embodiments to heat the CO2 to accelerate the catalytic reaction. The temperature range preferably is about 250° C.-1000° C., with the preferred set point temperature about 500° C. Heated catalyst 103B (preferably multi-stage) is provided, with heater 103A used to maintain a constant temperature for the catalytic process (preferred temperature ranges may be as stated previously). A multistage catalytic process preferably is utilized that removes contaminants such as hydrocarbons based on multi-heater/catalyst stages. A multi-stage catalytic process preferably is utilized in order to, for example, ensure a near complete reduction/oxidation of hydrocarbons, with the multistage process helping ensure that the majority of CO2 molecules will come in contact with one or more catalytic surface. Activated (which may also include non-activated) carbon filters 104 (preferably replaceable) preferably are utilized to extract residual contaminants such as hydrocarbons in the CO2 after the catalytic oxidation. In preferred embodiments, filter(s) is/are implemented downstream of the catalytic process, where the amount of hydrocarbon in the CO2 is greatly reduced; as a result, filter replacement will be less frequent. Particle filter 105, preferably a multistage filtration system, consists of one or more preferably ceramic core particulate filters to remove larger particles (e.g., 0.1 micron and larger), which preferably is followed by a preferably all metal electronic grade filter to remove finer particles (e.g., 0.005-0.1 microns). Chiller 106 preferably is provided to control the quality and the conditions of the CO2 entering the nozzle (for a nozzle-based cleaning process, etc.). The core of chiller 106 preferably is electro-polished stainless steel to prevent contamination of the CO2.
Although the invention has been described in conjunction with specific preferred and other embodiments, it is evident that many substitutions, alternatives and variations will be apparent to those skilled in the art in light of the foregoing description. Accordingly, the invention is intended to embrace all of the alternatives and variations that fall within the spirit and scope of the appended claims. For example, it should be understood that, in accordance with the various alternative embodiments described herein, various systems, and uses and methods based on such systems, may be obtained. The various refinements and alternative and additional features also described may be combined to provide additional advantageous combinations and the like in accordance with the present invention. Also as will be understood by those skilled in the art based on the foregoing description, various aspects of the preferred embodiments may be used in various subcombinations to achieve at least certain of the benefits and attributes described herein, and such subcombinations also are within the scope of the present invention. All such refinements, enhancements and further uses of the present invention are within the scope of the present invention.
Reference is also made to co-pending application Ser. No. 09/636,265 by the inventors here for “methods for cleaning surfaces substantially free of contaminants” and co-pending application Ser. No. 09/637,333 by the inventors here for “apparatus for cleaning surfaces substantially free of contaminants.”

## Claims

1. A process for cleaning an article utilizing a multi-stage filtered carbon dioxide-containing cleaning medium, comprising the steps of:
providing a source of the carbon dioxide-containing cleaning medium, wherein the carbon dioxide-containing cleaning medium contains one or more contaminants including at least a hydrocarbon; 
providing a first mode filtration stage, wherein the first mode filtration stage provides condensation-based filtration and removes one or more contaminants from the carbon dioxide-containing cleaning medium; 
providing a second mode filtration stage, wherein the second mode filtration stage provides catalyst-based oxidation/reduction and removes one or more contaminants from the carbon dioxide-containing cleaning medium; 
providing a third mode filtration stage, wherein the third mode filtration stage provides carbon filter-based removal of one or more contaminants from the carbon dioxide-containing cleaning medium; 
providing the carbon dioxide-containing cleaning medium to one or more surfaces of the article, wherein the article is cleaned.

2. The process of claim 1, wherein the third mode filtration stage is provided downstream of the second mode filtration stage.

3. The process of claim 1, wherein one or more substances including at least a hydrocarbon is removed from the carbon dioxide-containing cleaning medium.

4. The process of claim 1, wherein the second mode filtration stage includes at least a catalyst comprising titanium dioxide.

5. The process of claim 1, wherein the second mode filtration stage includes a catalytic reaction and the use of UV light.

6. The process of claim 1, wherein the second mode filtration stage includes a heated catalytic reaction or the use of oxygen provided to enhance reduction of one or more contaminants from the carbon dioxide-containing cleaning medium.

7. The process of claim 1, wherein the first stage includes multiple stages of filtration.

8. The process of claim 1, further comprising the step of providing a particulate filtration stage.

9. The process of claim 8, wherein the particulate filtration stage includes one or more ceramic core particulate filters and/or at least one metal electronic grade filter.

10. The process of claim 1, wherein the article comprises one or more substrates on which are formed electronic elements.

11. A process for cleaning an article utilizing a multi-stage filtered carbon dioxide-containing cleaning medium, comprising the steps of:
providing a source of the carbon dioxide-containing cleaning medium, wherein the carbon dioxide-containing cleaning medium contains one or more contaminants including at least a hydrocarbon; 
processing the carbon dioxide-containing cleaning medium with a condensation-based filtration; 
processing the carbon dioxide-containing cleaning medium via catalyst-based oxidation/reduction; 
processing the carbon dioxide-containing cleaning medium with a carbon filter-based process or a particulate filtration process; 
providing the carbon dioxide-containing cleaning medium to one or more surfaces of the article, wherein the article is cleaned with the carbon dioxide-containing cleaning medium, wherein the carbon dioxide-containing cleaning medium has a reduced level of the one or more contaminants.

12. The process of claim 11, wherein the step of processing the carbon dioxide-containing cleaning medium via catalyst-based oxidation/reduction occurs prior to the step of processing the carbon dioxide-containing cleaning medium with a carbon filter-based process or a particulate filtration process.

13. The process of claim 11, wherein one or more substances including at least a hydrocarbon is removed from the carbon dioxide-containing cleaning medium.

14. The process of claim 11, wherein the step of processing the carbon dioxide-containing cleaning medium via catalyst-based oxidation/reduction includes processing the carbon dioxide-containing cleaning medium via catalyst-based oxidation/reduction with at least a catalyst comprising titanium dioxide.

15. The process of claim 11, wherein the step of processing the carbon dioxide-containing cleaning medium via catalyst-based oxidation/reduction includes a catalytic reaction and the use of UV light.

16. The process of claim 11, wherein the step of processing the carbon dioxide-containing cleaning medium via catalyst-based oxidation/reduction includes a heated catalytic reaction or the use of oxygen provided to enhance reduction of one or more contaminants from the carbon dioxide-containing cleaning medium.

17. The process of claim 11, wherein the step of processing the carbon dioxide-containing cleaning medium with a condensation-based filtration includes multiple stages of filtration.

18. The process of claim 11, wherein the carbon dioxide-containing cleaning medium is processed with a carbon filter-based process and a particulate filtration process.

19. The process of claim 18, wherein the particulate filtration process includes one or more ceramic core particulate filters and/or at least one metal electronic grade filter.

20. The process of claim 11, wherein the article comprises one or more substrates on which are formed electronic elements.