Agglomeration of solid colloidal particles is a well-known problem. Conventionally, agglomeration of colloids is prevented using either electrostatic stabilization or steric stabilization. In electrostatic stabilization, the surface charge of the colloids is adjusted to increase the electrostatic repulsion between particles. However, the addition of salts or change in working pH required to affect this change may not be practical. In addition, this method may not be effective for the colloid of interest. Steric stabilization typically involves either chemically or physically attaching larger molecules, often surfactants or polymers, to the colloid surfaces. The large molecules act as bumpers, preventing the surfaces of two particles from approaching near enough to be influenced by van der Waals or Coulombic forces. Unfortunately, these large molecules also block active sites on the colloid surface, which renders them inaccessible for binding or chemical reaction. Colloids stabilized in this way often exhibit reduced activity.
Thus, there is a need in the art for more effective ways of preventing agglomeration of colloidal particles in a suspension without compromising their activity.
Embodiments of the present invention generally relate to aqueous suspensions that include solid colloidal particles. More specifically, certain embodiments of the present invention provide a method for stabilizing a suspension to prevent agglomeration of such colloidal particles while maintaining the chemical or mechanical activity level of these particles.
Some embodiments of the present invention provide a suspension that includes a solvent and a plurality of solid particles supported in the solvent. Each of the plurality of solid particles has a first charge layer that has a first polarity and is disposed over an outer surface of the solid particle and a second charge layer (referred to herein as the electric double layer (EDL) that overlies the first charge layer that has a second polarity that is different from the first polarity. The suspension also includes a charged species that has a plurality of charged ions/particles/molecules, which have a charge polarity that is same as the first polarity. At least some of the plurality of the charged species is attached to the second charge layer. In some embodiments, the first polarity may be negative and the second polarity may be positive. In other embodiments, the first polarity may be positive and the second polarity may be negative. In a particular embodiment, the surfactant may include anions or cations based on the first polarity of the first charge layer. Some examples of surfactants include Ammonium Lauryl Sulphate (ALS), Sodium Dodecyl Benzene Sulfonate, Phosphate esters, or Cetyl trimethylammonium bromide (CTAB). In some embodiments, the surfactant may include an anionic surfactant if the first polarity is negative or the surfactant may include a cationic surfactant if the first polarity is positive.
In an embodiment, a system for polishing a substrate is provided. The system comprises a polishing unit including a polishing pad and a slurry delivery system operable to provide slurry to the polishing pad. The slurry may further include a solvent and a plurality of solid particles supported in the solvent. Each of the plurality of solid particles may further include (i) a first charge layer disposed proximate to an outer surface of the solid particle where the first charge layer has a first polarity and (ii) a second charge layer overlying the first charge layer and which has a second polarity opposite from the first polarity. The slurry may also include charged species that have a plurality of ions, particles or molecules, which have a third polarity. At least some of the plurality of charged species is directly attached to the second charge layer. In a particular embodiment, the third polarity is same as the first polarity and the charged species may include a surfactant. In some embodiments, the first polarity may be negative. In an embodiment, the surfactant can include one of Ammonium Lauryl Sulphate (ALS), Sodium Dodecyl Benzene Sulfonate, Phosphate esters, or Cetyl trimethylammonium bromide (CTAB). In a particular embodiment, the surfactant includes a cationic surfactant. In certain embodiments, the slurry can include ceria, zirconia, alumina, or silica based compound. In a specific embodiment, the substrate is a silica-based optical component.
Another embodiment of the present invention provides a slurry that includes a solvent and a plurality of solid ceria particles provided in the solvent. Each solid ceria particle may be surrounded by an electric double layer. The electric double layer may include (i) a first charge layer disposed along an outer surface of the ceria particle and having a first polarity and (ii) a second charge layer disposed over the first charge layer and having a second polarity. The slurry may also include a surfactant that includes a plurality of cations and at least some of the plurality of cations may be attached to the second charge layer of the ceria particle. In some embodiments, the first polarity is opposite from the second polarity. In an embodiment, the second polarity is positive. In certain embodiments, the stabilizing ionic species having the third polarity are separable from the second charge layer by application of a shear force and may reattach to the second charge layer after removal of the shear force. The shear force, manifested as e.g., fluid flow or abrasion, can be generated either mechanically or electrically.
These and other embodiments of the invention along with many of its advantages and features are described in more detail in conjunction with the text below and attached figures.
Embodiments of the present invention provide a method for stabilizing a suspension that includes charged colloidal particles. Other embodiments of the present invention provide a stabilized slurry for use in polishing of substrates, e.g., silica-based optical components and other types of substrates.
Solid surfaces in an aqueous suspension carry a charge. Ions in the suspension that have an opposite charge than the solid will assemble around the surface in two layers, termed the electric double layer (EDL). The layer nearest to the surface of the solid particle is tightly bound to the particle. The outer layer is diffuse and weakly bound to the solid particle because it includes free ions which move in the fluid under the influence of electrical attraction and thermal motion rather than being firmly bound. This weak outer layer is referred to as a “diffuse layer”. Embodiments of the present invention provide a chemical stabilizer or stabilizing agent—e.g., a charged species—that binds to the diffuse layer surrounding the colloidal particles, rather than binding to the particle surface. The charged species sterically hinders the particles from close approach, preventing them from aggregating. However, because the charged species are weakly incorporated within the diffuse layer rather than tightly bound to the particle surface, shear forces—such as those created by flow, or mechanical action such as grinding or polishing—are enough to tear the stabilizing charged species away from the double layer. Once the charged species is removed, the functional sites on the surface of the colloidal particle are exposed and become available for binding or chemical reaction. When the shear forces on the colloids cease, the stabilizing agent (or charged species) re-associate with the diffuse layer of the EDL and again sterically stabilize the particles, thus preventing agglomeration or aggregation. This EDL binding method prevents the colloids from agglomerating, while preserving their surface functionality.
In a particular embodiment, the pH of the suspension is maintained at a level that is greater than the isoelectric point of the colloidal particles in the suspension. In addition a charged species 106 having an opposite charge from that of outer diffuse layer 104 (and having the same charge as that at the surface of the particle) is added to the suspension, as illustrated in
Since charged species 106 has a charge that is opposite to the charge of outer diffuse layer 104, charged species 106 attaches itself to outer diffuse layer 104 rather than to the surface of particle 102, as illustrated in
Particles 102 described above may be part of a suspension that is used in some type of physical or chemical process and hence it is important that the particles remain in an active state when the physical or chemical process is being performed. Conventional techniques where a surfactant is bound to the surface of a charged particle often reduce the activity of the charged particle since it is very hard to dislodge the surfactant from the tight bond that it has with the surface of the charged particle. One of the advantages of the embodiments of the present invention is that since the charged species is loosely bound to the outer diffuse layer of the charged particle, it can be easily dislodged from the particle by applying a force. When that force is removed, the charged species then re-attaches itself to the outer diffuse layer and acts to prevent agglomeration of the particles. Thus, embodiments of the present invention provide the benefit of preventing agglomeration of particles when the suspension is idle (i.e. when the suspension is not being used in any process) and easy dislodgment of the charged species to return the particles to their active state when needed. None of the conventional techniques provide such a benefit.
In addition, conventional wisdom suggests that using a charged species having a like charge as that at the surface of the colloidal particle will not work since it is widely understood that like charges repel each other. Thus, such a charged species that has the same polarity of charge as that at the surface of the particle, would not attach itself to the particle. However, embodiments of the present invention provide techniques for adding a charged species having the same charge as that at the surface of a colloidal particle and coupling the charged species to the particle using an outer oppositely charged layer, referred to herein as the diffuse layer. The resulting coupling of the charged species to the particle is strong enough to prevent agglomeration but is also weak enough so that the charged species can be decoupled from the particle by application of a shear force as described above. This has not been attempted before and is contrary to the conventional wisdom prevalent in the industry as of the present day.
As described above, it is not enough just to prevent agglomeration of particles in a suspension when that suspension is also to be used to perform a mechanical or chemical process. In this instance, it is equally important that the particles be returned to their active state where they can affect the process in which the suspension may be used. For example, ceria slurry is often used for polishing substrates, such as glass or silicon. When a charged species is attached to the ceria particles in the slurry, the particles may become ineffective for the polishing process. In order for the particles to be used in the polishing process, the charged species attached to the particles need to be dislodged so that the charged ceria particles are returned to their active state. In slurries stabilized using conventional means, it may be difficult to dislodge the surfactant from the surface of the ceria particles due to their strong bond. This results in a ceria slurry that may resist agglomeration but which also has diminished polishing properties. In contrast, ceria slurry stabilized using embodiments of the present invention shows enhanced polishing properties in addition to reducing the agglomeration.
As described above, embodiments of the present invention provide a method for adding a surfactant that has a charge polarity that is opposite to the polarity of the outer diffuse layer of the charged colloidal particle and has the same charge polarity as the charge at the surface of the colloidal particle. Some of the compounds that can be used as surfactants can include cationic as well as anionic surfactants. Charged species that are used as stabilizing agents may include but are not limited to surfactant molecules combining a branched or linear alkyl or alkyl-ether tail and a charge-carrying head group (e.g. sulfate, sulfonate, phosphate, amine, quaternary ammonium, or carboxyl). Some specific examples of surfactants that can be used in embodiments of the present invention include but are not limited to Ammonium Lauryl Sulphate (ALS), Sodium Dodecyl Benzene Sulfonate, Phosphate esters, Cetyl trimethylammonium bromide (CTAB), and the like. The choice of the stabilizing agent/charged species depends on the charge associated with the colloidal particle of interest. For example, if the colloidal particle has a negative surface charge and positively charged diffuse layer, then an anionic surfactant may be used. On the other hand, if the colloidal particle has a positive surface charge and negatively charged diffuse layer, then a cationic surfactant may be used.
The amount of charged species needed for stabilizing a particular suspension depends of various factors such as pH of the suspension relative to the isoelectric point, the size and number density of the particles to be stabilized, the charge of the stabilizing agent, ionic strength of the suspension, etc. In a particular embodiment where a surfactant is used as the stabilizing agent, the concentration of the surfactant can range between 0.01% to about 2% of the volume of the suspension to be stabilized.
Although ceria is used herein as an example to describe the various embodiments of the invention, it is to be understood that the embodiments described herein can be used in many other types of suspensions such as those containing zirconia, alumina, silica-based compounds, suspensions containing inorganic particles such as those used in catalysts, paints/coatings, inks, sunscreens, makeup, etc., or even suspensions that have organic colloidal particles such as polystyrene latex spheres, etc.
Another aspect that affects the effectiveness of a suspension having solid colloidal particles is the settling time. Settling is a phenomenon where the solid particles within a suspension settle down at the bottom of the container in which the suspension is stored thus separating the liquid phase from the solid. An un-stabilized or poorly stabilized suspension will experience rapid settling without some form of agitation. The separation of the solid particles from the liquid portion of the suspension results in decreased efficacy of the suspension.
Where ts=settling time; ηL=water viscosity (0.01 poise); α=particle size (μm); g=9.8 m/s2; ρp=ceria density (7.1 gm/cm3); ρL=water density (1 gm/cm3); and ds settling distance.
Another advantage of stabilizing a suspension, e.g., a slurry, using embodiments of the present invention is that upon drying the slurry does not form irreversibly agglomerated particles making it easier to re-disperse the settled slurry for use.
It is to be noted that stabilizing agents other than a surfactant may also be used to stabilize a suspension to prevent agglomeration of particles.
In a particular embodiment of the present invention, a ceria slurry stabilized using the embodiments of the present invention can be used in a polishing system for polishing silica-based optical components. Details of the polishing system are provided in PCT Application No. PCT/US2012/029837.
It is to be noted that the particular polishing systems described above in connection with
Several advantages are realized using embodiments of the present invention described above. A suspension treated as described above experiences reduced settling. In addition such a stabilized suspension is easier to re-suspend after drying and/or settling. Another advantage of a suspension stabilized using embodiments of the present invention is that any filtration system that may be used in conjunction with the suspension can be more effective and have a higher lifetime since there is less agglomeration of particles and hence reduced load on the filtration equipment. Also, since the average particle size is reduced in the embodiments described above, there is less build-up of particles at the filter further increasing the filter lifetime and reducing the costs associated with filter changes and slurry replenishment. Preventing agglomeration of suspended particles using embodiments of the present invention leads to easier clean-up of the suspension following drying since the particles now have reduced internal adhesion and reduced adhesion to other surfaces that they may come in contact with. By preventing agglomeration of particles, large particles may be prevented from forming which leads to reduced scratching of substrate surfaces when the suspension is used in a polishing-type application. In addition, by preventing agglomeration, the average particle size can be kept smaller which helps in the overall performance of the suspension and may lead to less usage of the suspension.
While a number of specific embodiments were disclosed with specific features, a person of skill in the art will recognize instances where the features of one embodiment can be combined with the features of another embodiment. Also, those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the inventions described herein. Such equivalents are intended to be encompassed by the following claims.
This application claims priority to U.S. Provisional Patent Application No. 61/721,588, filed on Nov. 2, 2012, the disclosure of which is hereby incorporated by reference in its entirety for all purposes. This application is related to PCT Application No. PCT/US2012/029837, filed on Mar. 20, 2012, the content of which is incorporated by reference herein in its entirety for all purposes.
The United States Government has rights in this invention pursuant to Contract No. DE-AC52-07NA27344 between the United States Department of Energy and Lawrence Livermore National Security, LLC for the operation of Lawrence Livermore National Laboratory.
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/US2013/065290 | 10/16/2013 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2014/070461 | 5/8/2014 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
5527423 | Neville | Jun 1996 | A |
5858813 | Scherber | Jan 1999 | A |
6447373 | Lack | Sep 2002 | B1 |
6561876 | Tateyama | May 2003 | B1 |
6827752 | Nojo | Dec 2004 | B2 |
6866793 | Singh et al. | Mar 2005 | B2 |
7144301 | Kim | Dec 2006 | B2 |
7368388 | Small | May 2008 | B2 |
7427361 | Small | Sep 2008 | B2 |
8486169 | Carter | Jul 2013 | B2 |
8932479 | Kamimura | Jan 2015 | B2 |
9558959 | Mishra | Jan 2017 | B2 |
20020086618 | Ota | Jul 2002 | A1 |
20030168627 | Singh | Sep 2003 | A1 |
20040055993 | Moudgil et al. | Mar 2004 | A1 |
20040060502 | Singh | Apr 2004 | A1 |
20040152316 | Ono | Aug 2004 | A1 |
20040265177 | Nicoli | Dec 2004 | A1 |
20050075052 | Kim | Apr 2005 | A1 |
20050076581 | Small | Apr 2005 | A1 |
20050106874 | Matsui | May 2005 | A1 |
20050126080 | Kon | Jun 2005 | A1 |
20050287931 | Saegusa | Dec 2005 | A1 |
20060234509 | Small | Oct 2006 | A1 |
20070093187 | Takenouchi | Apr 2007 | A1 |
20080045018 | Yoon | Feb 2008 | A1 |
20080045020 | Kim | Feb 2008 | A1 |
20080086950 | Kon | Apr 2008 | A1 |
20080227297 | Matsui | Sep 2008 | A1 |
20090258493 | Matsui | Oct 2009 | A1 |
20090321390 | Li | Dec 2009 | A1 |
20090325323 | Ueno et al. | Dec 2009 | A1 |
20100178768 | Li et al. | Jul 2010 | A1 |
20100252774 | Shida | Oct 2010 | A1 |
20110114872 | Kroell | May 2011 | A1 |
20120270343 | Jiang | Oct 2012 | A1 |
Number | Date | Country |
---|---|---|
1616927 | Jan 2006 | EP |
19960257898 | Sep 1996 | JP |
08257898 | Oct 1996 | JP |
2000269169 | Sep 2000 | JP |
2014070461 | May 2014 | WO |
Entry |
---|
EP13850914.6, “Extended European Search Report”, dated Sep. 5, 2016, 8 pages. |
EP13850914.6, “Office Action”, dated May 19, 2016, 3 pages. |
PCT/US2013/065290, “International Search Report and Written Opinion”, PCT/US2013/065290, dated Feb. 21, 2014, 17 pages. |
JP2015540689, “Office Action”, dated Nov. 17, 2017, 14 pages. |
JP2015-540689, “Notice of Allowance”, dated Mar. 6, 2018, 3 pages. |
Number | Date | Country | |
---|---|---|---|
20150275048 A1 | Oct 2015 | US |
Number | Date | Country | |
---|---|---|---|
61721588 | Nov 2012 | US |