|Publication number||US7166524 B2|
|Application number||US 11/003,000|
|Publication date||Jan 23, 2007|
|Filing date||Dec 1, 2004|
|Priority date||Aug 11, 2000|
|Also published as||US20050191828|
|Publication number||003000, 11003000, US 7166524 B2, US 7166524B2, US-B2-7166524, US7166524 B2, US7166524B2|
|Inventors||Amir Al-Bayati, Rick J. Roberts, Kenneth S. Collins, Ken MacWilliams, Hiroji Hanawa, Kartik Ramaswamy, Biagio Gallo, Andrew Nguyen|
|Original Assignee||Applied Materials, Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (100), Non-Patent Citations (6), Referenced by (42), Classifications (12), Legal Events (3)|
|External Links: USPTO, USPTO Assignment, Espacenet|
This application is a continuation-in-part of U.S. application Ser. No. 10/838,052 filed May 3, 2004 entitled LOW TEMPERATURE CVD PROCESS WITH CONFORMALITY, STRESS AND COMPOSITION by Hiroji Hanawa, et al., the disclosure of which is incorporated herein by reference and of which is a continuation-in-part of U.S. patent application Ser. No. 10/786,410 filed Feb. 24, 2004 now U.S. Pat. 6,893,907 entitled FABRICATION OF SILICON-ON-INSULATOR STRUCTURE USING PLASMA IMMERSION ION IMPLANTATION by Dan Maydan et al., which is a continuation-in-part of U.S. patent application Ser. No. 10/646,533 filed Aug. 22, 2003 entitled PLASMA IMMERSION ION IMPLANTATION PROCESS USING A PLASMA SOURCE HAVING LOW DISSOCIATION AND LOW MINIMUM PLASMA VOLTAGE by Kenneth Collins et al., which is a continuation-in-part of U.S. patent application Ser. No. 10/164,327 filed Jun. 5, 2003 now U.S. Pat. No. 6,939,434 entitled EXTERNALLY EXCITED TORROIDAL PLASMA SOURCE WITH MAGNETIC CONTROL OF ION DISTRIBUTION by Kenneth Collins et al., which is a continuation-inpart of U.S. patent application Ser. No. 09/636,435 filed Aug. 11, 2000 entitled EXTERNALLY EXCITED MULTIPLE TORROIDAL PLASMA SOURCE by Hiroji Hanawa et al., now issued as U.S. Pat. No. 6,494,986 B1, all of which are assigned to the present assignee.
With recent advances in integrated circuit design, there are now as many as six to ten insulated interconnect layers overlying the semiconductor transistors for devices using the current 90 nm design rules. The next generation may employ 35 nm design rules and may have as many as 12 to 14 insulated interconnect layers. These interconnect layers can have completely different conductor patterns and are connected to one another and to the transistor layer at different locations through contact vias extending vertically between the horizontal layers. It is the formation of the contact vias with which the present invention is concerned.
Due to the large number of interconnect layers and the total electrical path length they represent, the interconnect layers account for a significant proportion if not a majority of the total power losses in the integrated circuit.
To reduce resistive power losses in the integrated circuit, the interconnect layers and the contact vias typically employ copper as the principal conductor and silicon dioxide as the insulator. Because copper tends to diffuse through the silicon dioxide insulator material, a barrier layer is placed between the copper material and the silicon dioxide material wherever the two materials interface in the integrated circuit. The barrier layer is typically formed of an underlying tantalum nitride layer contacting the silicon dioxide insulator, and overlying pure (or nearly pure) tantalum layer and, finally, a copper seed layer over the pure tantalum layer. The copper conductor is deposited on the copper seed layer. Such a barrier layer prevents migration or diffusion of copper atoms into the silicon dioxide insulator material.
In order to reduce power losses and interference by capacitive coupling between adjacent interconnect layers, it is desirable to employ an insulating material with the lowest possible dielectric constant. Silicon dioxide can be employed because it has superior mechanical properties. However, silicon dioxide has a relatively high dielectric constant (about 4.0) and is therefore not ideal. It has been found that combining silicon dioxide with a species such as boron or phosphorus produces a glassy material having a lower dielectric constant. For example, combining silicon dioxide with boron produces boron silicate glass (BSG). BSG has a dielectric constant of 3.2. Other insulator materials have been developed having even lower dielectric constants, such as insulation material sold by Applied Materials, Inc., the present assignee, under the trademarks Black Diamond I (dielectric constant of <3.0) and Black Diamond II (dielectric constant of <2.6). These materials with such low dielectric constants provide very good electrical performance with minimum capacitive coupling between interconnect layers. Unfortunately, their mechanical properties are inferior to those of silicon dioxide because these materials tend to be porous and therefore are not as hard as silicon dioxide. This is a particularly difficult problem because the insulator layer deposited over an interconnect layer tends to form a very uneven top surface and must therefore be smoothed to a plane surface by chemical mechanical polishing. While silicon dioxide is a sufficiently hard material to be relatively impervious to flaking or cracking during chemical mechanical polishing, porous materials with low dielectric constant can be susceptible to damage during chemical mechanical polishing.
Therefore, what is needed is a hard insulator material having a low dielectric constant that can reliably withstand chemical mechanical polishing. Currently available insulator materials suitable for use in multiple interconnect layers of integrated circuits are either porous and weak or else have a relatively high dielectric constant.
An integrated microelectronic circuit has a multi-layer interconnect structure overlying the transistors consisting of stacked metal pattern layers and insulating layers separating adjacent ones of said metal pattern layers. Each of the insulating layers is a dielectric material with plural gas bubbles distributed within the volume of the dielectric material to reduce its dielectric constant, the gas bubbles being formed by ion implantation of a gaseous species into the dielectric material.
The method can include regulating the average diameter of the gas bubbles by regulating the energy of the ions of the gaseous species during the step of ion implanting, or by regulating the temperature of the workpiece during the ion implanting step or by regulating the ion implantation dose of the ion implantation step, or by ion implanting a bubble-enhancing species. The gaseous species can be a light, heavy or combination of light and heavy gaseous species (e.g, H, He, Ar, Xe, H and He, He and Xe, F and Xe, H and Ar, etc).
The step of ion implanting can be carried out by plasma immersion ion implantation in a torroidal source plasma reactor having at least one external reentrant conduit, by introducing a process gas comprising a precursor of the gaseous species to be ion implanted, and then coupling RF power to process gases in the reentrant conduit to generate an oscillating plasma current in a torroidal path that includes the reentrant conduit and a process zone adjacent the surface of the workpiece. The ion energy and implant depth profile is controlled by applying RF plasma bias power to the workpiece.
In the present invention, an insulating material having excellent mechanical properties but poor electrical properties (a relatively high dielectric constant) is subject to ion implantation of a light gaseous species such as hydrogen or helium. The ion energy and dosage of the implantation process and the temperature of the insulating material are selected so that implanted atoms of the gaseous species inside the insulating material migrate or coalesce toward one another to form small gas bubbles throughout the insulating material. The gas bubbles within the insulating material have a very low dielectric constant (e.g., about 1.04). The result is that the total dielectric constant of the insulating layer is significantly reduced due to the presence of the bubbles. In the case of silicon dioxide containing bubbles formed by ion implantation of a gaseous species, the dielectric constant may be as low as 3.5. The reduction in dielectric constant depends upon the proportion of the volume within the insulating material occupied by the gas bubbles.
Other “bubble-enhancing” species, both gaseous and non-gaseous, may be implanted in addition to the gaseous species. The “enhancing” species may promote small bubble size. Also or alternatively, the “enhancing” species may promote bubble stability within the insulator (to avoid bubble growth or conjoining of adjacent bubbles). Small bubble size is desirable in order to ensure a smooth insulator material surface after etching or chemical mechanical polishing. Good bubble stability is desirable to permit close spacing between bubbles and a concomitantly higher bubble density within the insulating material for greater reduction in dielectric constant.
In accordance with another aspect of the invention, materials having superior electrical properties but inferior mechanical properties relative to silicon dioxide can have their mechanical properties improved without compromising their superior electrical properties. Examples of such materials include carbon-doped silicon dioxide, formed in a plasma containing silicon dioxide precursors (silane and oxygen) and a carbon precursor. Such materials tend to be porous and therefore mechanically weaker. Their superior electrical property is a dielectric constant (electrical permittivity) that is lower than that of silicon dioxide. Such materials may have their mechanical properties improved by ion implantation of a light gaseous species. In this process, ion implant dosage and energy and material temperature are selected so that the implanted gaseous species atoms gather within the empty pores of the insulator material to form a pressurized gas inside each pore. With each pore thus internally pressurized, the compressive strength or hardness of the insulator material is enhanced. Such a process may in some cases be referred to as a “hardening ion implantation” step. Ion implantation can also reduce tensile stress in the film (making it more compressive) through bond breaking and formation of damage.
In accordance with a yet further aspect of the invention, the porous material that has been mechanically improved by the foregoing “hardening ion implantation” step may also be electrically improved by the bubble-forming ion implantation step previously described. In this ion implantation step, a light gaseous species is implanted in the insulator material with the implant energy and dosage and material temperature adjusted so that the implanted gaseous atoms migrate toward one another within local regions to form gas bubbles within the material. These gas bubbles may be about 1–5 nm in diameter, which may be about the same size or smaller than the pores of the porous material. This addition of gas bubbles into the porous insulator material reduces its dielectric constant from its nominal value (e.g., <3.0 or <2.6 for carbon-doped silicon dioxide) to a lower level.
In a related aspect, the “hardening ion implantation” step and the bubble-formation ion implantation step may be one and the same ion implantation step or may be performed as part of the same ion implantation process, with the process parameters being changed during implantation to perform bubble formation, and then (or beforehand) hardening.
An important aspect is the ability to control both ion implantation dosage and ion energy in order to control bubble size. A lower ion energy enables the process to form smaller and more numerous bubbles. On the other hand, an entire wafer must be implanted, and therefore a large ion flux is necessary to complete the implantation process within a reasonable amount of time. In view of these requirements, the preferred way of performing the bubble-forming ion implantation step is to employ a torroidal source plasma ion immersion implantation reactor described in the above-referenced parent application. This is because such a reactor is capable of very high maximum ion flux and a very low minimum ion energy. In addition, in order to minimize the material temperature during ion implantation (to minimize bubble size), the minimum plasma source power level in such a reactor is extremely low, relative to other plasma immersion ion implantation reactors. By minimizing plasma source power, the temperature of the insulator material during ion implantation can be significantly reduced to achieve a minimum bubble size. Such a reactor, adapted particularly for bubble-forming ion implantation, is illustrated in
Referring now to
A pair of external reentrant conduits 34, 36 establish reentrant torroidal paths for plasma currents passing through the process region, the torroidal paths intersecting in the process region 32. Each of the conduits 34, 36 has a pair of ends 38 coupled to opposite sides of the chamber. Each conduit 34, 36 is a hollow conductive tube. Each conduit 34, 36 has a D.C. insulation ring 40 preventing the formation of a closed loop conductive path between the two ends of the conduit.
An annular portion of each conduit 34, 36, is surrounded by an annular magnetic core 42. An excitation coil 44 surrounding the core 42 is coupled to an RF power source 46 through an impedance match device 48. The two RF power sources 46 coupled to respective ones of the cores 44 may be of two slightly different frequencies. The RF power coupled from the RF power generators 46 produces plasma ion currents in closed torroidal paths extending through the respective conduit 34, 36 and through the process region 32. These ion currents oscillate at the frequency of the respective RF power source 34, 36. Bias power is applied to the wafer support pedestal 16 by a bias power generator 49 through an impedance match circuit 50.
Plasma immersion ion implantation of the wafer 18 is performed by introducing a gas or multiple of gases containing the species to be ion implanted into the chamber 32 through the gas distribution plate 20 and applying sufficient source power from the generators 46 to the reentrant conduits 34, 36 to create torroidal plasma currents in the conduits and in the process region 32. The ion implantation depth is determined by the wafer bias voltage applied by the RF bias power generator 49. The ion implantation rate or flux (number of ions implanted per square cm per second) is determined by the plasma density, which is controlled by the level of RF power applied by the RF source power generators 46. The cumulative implant dose (ions/square cm) in the wafer 18 is determined by both the flux and the total time over which the flux is maintained.
If the wafer support pedestal 16 is an electrostatic chuck, then a buried electrode 52 is provided within an insulating plate 54 of the wafer support pedestal, and the buried electrode 52 is coupled to the bias power generator 49 through the impedance match circuit 50. The wafer support pedestal 16 may be of the type disclosed in
The dielectric constant (electrical permittivity) of an insulating layer on a semiconductor wafer is reduced by placing the wafer 18 on the wafer support pedestal 16, introducing a gaseous species into the chamber 10 and striking a plasma so that the gaseous species is ion implanted into the insulating layer. The wafer bias voltage delivered by the RF bias power generator 49 is adjusted so that the implant depth of the gaseous species is within the insulating layer. The gaseous species may be any one of or combination of hydrogen, helium, nitrogen, neon, argon, krypton, xenon, fluorine, chlorine, iodine, bromine, oxygen.
The PMOS transistor 102 includes heavily p-doped source and drain regions 108 a, 108 b in the active layer and heavily p-doped source and drain extensions 110 a, 110 b separated by an n-doped channel 112. A polycrystalline silicon gate electrode 114 overlies the channel 112 and is separated from it by a thin gate silicon dioxide layer 116. A titanium silicide (or cobalt silicide) gate contact 118 overlies the gate electrode 114. A titanium silicide (or cobalt silicide) source contact region 120 is formed in the source region 108 a. A silicon nitride insulation layer 122 overlies the source and drain region 108 a, 108 b and surrounds the gate electrode structure 114, 116, 118. Silicon dioxide islands 124 lie within the insulation layer 122. A thin silicon nitride etch stop layer 126 overlies the PMOS transistor 102. The bottom insulation layer 130 of what will become an overlying multiple interconnect layer 132 overlies the etch stop layer 126. After the insulation layer 130 is formed, it is subjected to a chemical mechanical polishing process to render its top surface 130 a perfectly flat as illustrated in
The NMOS transistor 202 includes heavily n-doped source and drain regions 208 a, 208 b in the active layer and heavily n-doped source and drain extensions 210 a, 210 b separated by a p-doped channel 212. A polycrystalline silicon gate electrode 214 overlies the channel 212 and is separated from it by a thin gate silicon dioxide layer 216. A titanium silicide gate contact 218 overlies the gate electrode 214. A titanium silicide source contact region 220 is formed in the source region 208 a. A silicon nitride insulation layer 222 overlies the source and drain region 208 a, 208 b and surrounds the gate electrode structure 214, 216, 218. Silicon dioxide islands 224 lie within the insulation layer 222. A thin silicon nitride etch stop layer 226 overlies the NMOS transistor 202. The bottom insulation layer 130 of the overlying multiple interconnect layer 132 overlies the etch stop layer 226. A metallic (e.g., TiN) drain contact 234 extends vertically through the insulation layer 130 and through the etch stop layer 226 to the titanium silicide source contact region 220.
The insulating layer 130 (which may be, for example, PSG, BSG, CSG or SiO2) is unique in that it holds a three-dimensional matrix of gas bubbles formed by ion implantation of a gaseous species.
The spacing or density of the gas bubbles 330 within the insulating layer 320 determines the reduction of the dielectric constant of the insulating layer 320. This is because the reduction in the dielectric constant of the insulating layer 320 is determined at least in large part by the proportion of volume within the insulating layer 320 occupied by all the gas bubbles. This is depicted in the graph of
With regard to chemical mechanical polishing, the insulator layer 410 initially has a rough or non-planar surface 410 a immediately following its formation, as indicated in dashed line. In order to form a high quality conductor pattern over the insulator, it must first be chemically mechanically polished. This removes a top layer 410 b of the material 410 to form a smooth planar surface 410 c. However, prior to the chemical mechanical polishing step that removed the top layer 410 b, some of the gas bubbles 420 lay across the boundary that eventually became the planar surface 410 c, and may be referred to as boundary gas bubbles 420′. The boundary gas bubbles 420′ are cut open and become small holes upon removal of the top layer 410 b. As a result, the otherwise smooth surface 410 c has holes in it. These holes have no effect upon subsequent process steps (e.g., deposition of a metal conductor pattern on the top surface 410 c) provided the hole size (bubble diameter D) is small. For this purpose, the bubble diameter is preferably within a range of 1–5 nm.
There are several ways for regulating the average bubble size. These include selecting ion energy (by selecting plasma bias power), controlling ion implant dose (by controlling plasma ion density and process time), controlling the wafer temperature and selecting a gas species of a particular atomic number, and co-implanting non-gaseous or gaseous species that promotes bubble stability and/or small bubble size. Each of these approaches will now be discussed.
The graph of
The graph of
The graph of
The graph of
The foregoing parameters (ion energy, ion dose, wafer temperature and atomic weight) may be selected to favor a smaller average gas bubble diameter D, with some of these parameters playing a larger role than others. For example, it may not be desirable to radically reduce ion dose, since that might diminish the improvement (reduction) in dielectric constant. The other parameters may be optimized to the maximum, by employing a low ion energy, a low source power level (for small heat load) and using the lightest gas species (hydrogen or helium).
In order to help minimize the gas bubble average diameter D, the ion energy should be reduced or minimized. But this limits the ion implantation depth profile. In attempting to form gas bubbles in a very thick insulation layer, the layer thickness may exceed the implant depth range for a very low energy ion implantation process. One way around this problem is to form the thick insulation layer by successive depositions of very thin insulation layers, and conduct a bubble-forming gas species ion implantation step after the formation of each of the successive thin insulation layers. Such a procedure is depicted in
Another procedure for minimizing the required ion energy to form gas bubbles by ion implantation of a very thick insulation layer is to form the thick insulation layer by deposition of the insulator material (e.g., silicon dioxide) at a controlled rate. Simultaneously with the deposition, gaseous species are implanted at a shallow depth below the surface of the continuously thickening insulation layer, so that the surface is continually rising. In this way, the implantation depth profile can be extremely shallow regardless of the ultimate thickness of the deposited insulation layer. Such a procedure is illustrated in
The ion implantation process can be employed to enhance the adhesion of an upper film of one material onto a lower film or substrate of a different material. This is because the ion implantation process carries some of the atoms of each of the two materials across the interface between the two layers.
In accordance with another aspect, ion implantation of a gaseous species may be used to harden a porous dielectric material, such as (for example) Black Diamond I and Black Diamond II dielectric material sold by Applied Materials, Inc, the present assignee. “Black Diamond” is a trademark of Applied Materials, Inc. Such porous materials have a lower dielectric constant than silicon dioxide or other dielectrics. However, the presence of empty pores distributed throughout the material tends to reduce its mechanical hardness or strength. What is needed is a way of strengthening a porous dielectric material (increase hardness and modulus) while retaining its superior electrical characteristics (low dielectric constant).
Treatment of such a porous dielectric material can include the formation of gas bubbles as in the process depicted in
Ion implantation can reduce tensile stress in the film. This is accomplished through bond breaking within the film by the implanted ions. Making the film less tensile and more compressive reduces problems such as film flaking or delamination. Therefore, ion implantation of the gaseous species to enhance the material hardness can simultaneously reduce the tensile stress of the material. Reducing the tensile stress provides better adhesion of the treated film to underlying layers, making it more resistant to delamination. In one experiment, we have found that such ion implantation can increase the hardness by as much as 50% while changing the stress from tensile (e.g., at +80 megaPascals) to compressive (e.g., at −40 megaPascals). All this may be accomplished without increasing the dielectric constant of the treated layer. In fact, a slight improvement (decrease) in dielectric constant may be attained simultaneously with the foregoing improvements in hardness and stress.
Enhancement of Film Properties by Ion Implantation:
Adhesion between films is enhanced by ion implantation. Kinetic energy of the incident ions moves a portion of the atoms in each of the adjacent layers across the boundary between the two layers. This increases the thickness of the boundary region (straddling the interface between the two layer) occupied by atoms of the two different layers, thereby increasing the number of bonds between atoms of the two different layers. The result is a stronger bond between the two layers. Such adhesion-enhancement can be obtained using any of the ion implantation processes described above in this specification. Such results are described in the above-referenced parent application with reference to
The properties of a porous dielectric film such as CSG may be enhanced by ion implantation. As described above with reference to
Another property of a porous dielectric film that may be enhanced by ion implantation is stress. Specifically, porous films tend to have relatively high tensile stress, and as a result are susceptible to flaking and delamination. Ion implantation tends to break a small proportion of the atomic bonds within the porous layer, which changes the stress within the layer from tensile to compressive. The transition reduces the porous film's susceptibility to flaking or delamination.
The ion implantation process for improving the mechanical properties of a porous dielectric layer, (e.g., by increasing its hardness or reducing its tensile stress), has been described with reference to ion implantation of a gaseous species such as hydrogen, nitrogen or one of the inert gas species. However, a non-gaseous species may be employed in such a process. The non-gaseous species is preferably a process-compatible semiconductor species, such as (for example) germanium, silicon, carbon, or non-conductor species such as (for example) boron, arsenic, phosphorus, and the like. The entire process consists of, first, obtaining a dielectric layer that has been doped so as to reduce its dielectric constant. This may be accomplished, for example, by forming a silicon dioxide layer doped with carbon, using chemical vapor deposition or other suitable techniques. Such a low-K material tends to be porous and tends to have significant tensile stress. Then, the hardness of the material is improved and the tensile stress of the material is reduced by ion implanting one of the non-gaseous species listed immediately above.
Formation of a porous low-dielectric constant material (such as carbon-doped silicon dioxide) and enhancing the hardness of that material can be accomplished simultaneously in a single ion implantation step. First, a pure (or nearly pure) dielectric layer (such as silicon dioxide) is deposited using a process such as plasma enhanced chemical vapor deposition. Then, using plasma immersion ion implantation of the type described above, the dielectric layer (e.g., SiO2) is implanted with a first species (e.g., carbon) that reduces its dielectric constant and simultaneously implanted with a second species (e.g., hydrogen) that improves its mechanical properties (increasing hardness and reducing tensile stress). Such a simultaneous ion implantation process may be carried out by plasma immersion ion implantation using a process gas whose constituents are the first and second species. Ion implantation of the first species (e.g., carbon) reduces the dielectric constant through changes in the chemical properties of the dielectric material, while ion implantation of the second species (e.g., hydrogen) changes the material through mechanical changes in the dielectric material (e.g., the filling of voids with the second species). Such a process gas may contain carbon and hydrogen as the first and second species, respectively (in which case the process gas could be methane or acetylene). The first species may be another species such as boron, for example, so that the process gas could consist of boron and hydrogen (B2H6), for example. The dielectric material that is treated in this manner may be silicon dioxide or silicon nitride, for example. Moreover, as discussed in the preceding paragraph, the second species that enhances the mechanical properties of the dielectric layer may be a non-gaseous species of the type listed above (germanium, silicon, carbon, boron, arsenic, phosphorus, and the like). This ion implantation process may be followed immediately by a post-implant annealing step in which the wafer temperature is raised to an elevated temperature less than about 400 degrees C. It is believed that such an elevated temperature promotes the formation of the optimum molecular species for reducing the dielectric constant K of the implanted dielectric material.
Each of the ion implantation steps described above may be followed by post-implant annealing at temperatures less than 400 degrees C. to stabilize the effects of ion implantation. Such temperatures do not distort the process because in standard integration thermal processes, such temperatures are used for various processes such as CVD film deposition. Post-implant annealing, however, is not needed if the ion implantation is performed at a high wafer temperature (e.g., above 500 degrees C.). When such post-implant annealing is performed immediately following an implantation process for reducing tensile stress (described above in this specification), a slight penalty is incurred because the tensile stress increases (slightly). In one example, this increase was from −40 megaPascal to −10 megaPascal, which nevertheless left a great improvement from the pre-implant stress level of the material (+80 megaPascal).
While the invention has been described in detail by specific reference to preferred embodiments, it is understood that variations and modifications thereof may be made without departing from the true spirit and scope of the invention.
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|U.S. Classification||438/530, 438/301, 438/367, 257/288|
|International Classification||H01J37/32, H01L21/425|
|Cooperative Classification||H01L21/76254, H01J37/32082, H01J37/321|
|European Classification||H01L21/762D8B, H01J37/32M8D, H01J37/32M8|
|Mar 2, 2005||AS||Assignment|
Owner name: APPLIED MATERIALS, INC., CALIFORNIA
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:AL-BAYATI, AMIR;ROBERTS, RICK J.;MACWILLIAMS, KEN;AND OTHERS;REEL/FRAME:015820/0386;SIGNING DATES FROM 20050112 TO 20050121
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