Meniscus Confined Three Dimensional Electrodeposition for Direct-Writing of Wire Bonds

DOI: 10.1126/science.1190496

, 313 (2010);

329 Science Jie Hu and Min-Feng Yu Writing of Wire Bonds Meniscus-Confined Three-Dimensional Electrodeposition for Direct

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w w w .s c i e n c e m a g .o r g D o w n l o a d e d f r o m

in considerably more active designs.On the ex-perimental side,by analogy with our previous results with computationally designed Kemp elim-inases (5),it should be possible to increase the activity of these enzymes by directed evolution.The agreement between the designed and the experimentally observed substrate specificity and stereoselectivity of DA_20_10is notable given the importance of selectivity in organic chemistry reactions.The capability to rationally control both substrate specificity and stereoselectivity via de-signed enzymes opens up new avenues of research in both basic and applied chemistry.

References and Notes

1.T.Ose et al .,Nature 422,185(2003).

2.J.M.Serafimov,D.Gillingham,S.Kuster,D.Hilvert,J.Am.Chem.Soc.130,7798(2008).

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4.Materials and methods are available as supporting material on Science Online.

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1678(1971).

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10383(2000).

13.Single-letter abbreviations for the amino acid residues

are as follows:A,Ala;C,Cys;D,Asp;E,Glu;F,Phe;G,Gly;H,His;I,Ile;K,Lys;L,Leu;M,Met;N,Asn;P,Pro;Q,Gln;R,Arg;S,Ser;T,Thr;V,Val;W,Trp;and Y,Tyr.

14.J.T.Yli-Kauhaluoma et al .,J.Am.Chem.Soc.117,7041

(1995).

15.R.Breslow,S.D.Dong,Chem.Rev.98,1997

(1998).

16.C.E.Cannizzaro,J.A.Ashley,K.D.Janda,K.N.Houk,

J.Am.Chem.Soc.125,2489(2003).

17.The PyMOL Molecular Graphics System,Schr?dinger,LLC,

Version 1.2r3pre.

18.This work was supported by the Defense Advanced

Research Projects Agency (DARPA),the Howard Hughes Medical Institute (HHMI),a Molecular Biophysics traineeship from the NIH for J.B.S.,and the Lawrence Livermore National Laboratory Lawrence Scholars program for G.K.We thank M.Toscano (ETH)and C.Rosewall (University of Washington)for chemical synthesis and B.Siegel

and https://www.sodocs.net/doc/0c4447180.html,m for helpful comments on the manuscript.The x-ray crystallographic coordinates have been deposited in the Protein Data Bank with

accession ID 3I1C.The University of Washington has submitted a patent application on the protein sequence coding for the engineered enzymes reported here as well as some of the design methodology.

Supporting Online Material

https://www.sodocs.net/doc/0c4447180.html,/cgi/content/full/329/5989/309/DC1Materials and Methods SOM Text

Figs.S1to S13Tables S1to S5References

30March 2010;accepted 1June 201010.1126/science.1190239

Meniscus-Confined Three-Dimensional Electrodeposition for Direct Writing of Wire Bonds

Jie Hu and Min-Feng Yu *

Continued progress in the electronics industry depends on downsizing,to a few micrometers,the wire bonds required for wiring integrated chips into circuit boards.We developed an electrodeposition method that exploits the thermodynamic stability of a microscale or nanoscale liquid meniscus to “write ”pure copper and platinum three-dimensional structures of designed shapes and sizes in an ambient air

environment.We demonstrated an automated wire-bonding process that enabled wire diameters of less than 1micrometer and bond sizes of less than 3micrometers,with a breakdown current density of more than 1011amperes per square meter for the wire bonds.The technology was used to fabricate high-density and high-quality interconnects,as well as complex three-dimensional microscale and even nanoscale metallic structures.

A

s an essential part of any integrated chip,interconnects provide the electrical paths needed in a circuit to pass signals and

data among electrical devices or device units.The increasing device density in electronic chips has led to exponential growth in the density of inter-connects and the complexity of their design.With the introduction of three-dimensional (3D)chip ar-chitecture,interchip vias (1)constitute one method to integrate devices in 3D stacks,but alternative interconnect technologies that can provide flexible means to electrically wire microscale device components in three dimensions are still required.Traditional wire-bonding technology has served the electronics industry for many decades,satisfying the interconnection needs for device packaging (2).Recently,flip-chip interconnect technology was introduced as a means of increas-ing the interconnect density and improving de-vice performance for high-frequency operation (3).However,downscaling this technology to interconnect pad pitches on the order of a few micrometers has proven to be difficult.Thermo-sonic gold wire bonding has a limiting pitch of ~40m m,whereas flip-chip technology can achieve a pitch of ~100m m in industrial practices.This increases the on-chip space needed for the inter-connect pads,reduces the number of chips that can be produced per wafer,and consequently increases the cost per chip.It is expected that downscaling the traditional solder-based inter-connect cannot meet either the thermomechanical reliability requirement or the current density requirement at very fine pitches (4).

Among the 3D microfabrication technologies that are compatible with electronic devices,e-beam –or focused ion beam –based deposition (5)and direct writing with metal colloidal ink (6)have been explored as methods for fabricating 3D interconnects with nanoscale or microscale di-mensions.E-beam –or focused ion beam –based

Department of Mechanical Science and Engineering,University of Illinois,1206West Green Street,Urbana,IL 61801,USA.*To whom correspondence should be addressed.E-mail:

mfyu@https://www.sodocs.net/doc/0c4447180.html,

Fig.1.(A )Schematic showing the general setup for meniscus-confined 3D electrodeposition.The long-travel piezostages (nominal resolution <10nm)provide the fine positioning needed to con-trol the travel path of the micropipette in the 3D space.The high-sensitivity electrometer circuit (resolution <1pA)monitors and controls the ionic current.A magnified view at the nozzle –metal wire interface shows the formation of a meniscus (liquid bridge)serving as the stable confinement needed for the continuous electrodeposition of a uniform-diameter microscale or nanoscale metal wire as the micropipette is continuously withdrawn from the substrate surface.(B )SEM image showing the nozzle at the end of a glass micropipette with a side cut made by focused ion beam machining.(C )Electro-deposited Cu wires with different inclination angles fabricated with the use of a side-cut micropipette.

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deposition is capable of fabricating 3D structures with feature sizes as small as ~10nm.However,the process must be performed in a high-vacuum environment and the throughput is low.The choice of materials that can be deposited is lim-ited by the scarcity of the special chemical com-pounds,and the deposited metals tend to have low electrical quality (5).Direct writing with metal colloidal ink has been used to fabricate intercon-nect bridges,~10m m in diameter,made of Ag with the use of an Ag colloidal dispersion (6).The limi-tation,however,lies in the further downsizing of the fabricated wires:The finite size of the colloidal particles,and hence the fluidics involved with a dispersion of these particles,ultimately limit the min-imum nozzle size that can be used to dispense the colloidal dispersion.Further,a specific metallic col-loidal material system must be developed for each type of metallic wire while taking into consideration how to convert the resulting colloidal wires into metal-lic ones,for instance,through thermal annealing (6).We demonstrate an automated direct-writing wire-bonding technology that exploits meniscus-confined 3D electrodeposition and operates in an ambient air environment.We show the direct-writing fabrication of conductive interconnect bridges with submicrometer diameters and bond sizes of less than 10m m 2.The interconnects are made of pure Cu,or even noble metals such as Pt,and potentially can be made from other metals that can be electrochemically deposited with the use of readily available electrolyte solutions.These interconnects achieve a breakdown current den-sity of >1011A/m 2,six orders of magnitude higher than that for solder-based interconnects.The meniscus-confined 3D electrodeposition relies on an electrolyte-containing micropipette with a microscopic dispensing nozzle (several micro-meters down to 100nm in diameter)as the working toolbit (Fig.1A).As the micropipette approaches a conductive substrate surface,a meniscus (liquid bridge)is established between the dispensing nozzle and the substrate surface.With an appropriate elec-trical potential applied between the electrolyte contained in the micropipette and the substrate sur-face,electrodeposition is initiated within the sub-strate surface confined by the meniscus.The key to fabricating the interconnect is to synchronize the withdrawal speed of the micropipette away from the substrate surface with the growth rate of the local deposit,which maintains the stable formation of the meniscus now established between the nozzle and the growth front of the deposited wire,thereby sustaining the continuous growth of the off-surface micro-or nanowires.The method thus represents an advance over technologies such as electro-chemical dip-pen lithography,in which the dep-osition is limited to surface patterning (7),or electric field –enhanced electrodeposition with a sharpened metal tip,in which the local electro-deposition is realized through the localization of the electric field near the end of the tip and fabrication must be performed with both the work piece and the tip immersed in an electrolyte environment (8).The size and shape of the meniscus formed between the nozzle and the growing metal wire is defined by the size of the nozzle,by the thermo-dynamic properties of the liquid solution and the involved interfaces,and by the separation be-tween the nozzle and the growth front of the wire (thus,by the withdrawal speed of the micro-pipette and the growth rate of the wire).Theoret-ically,a meniscus as narrow as ~2nm can be established (9),and the thermodynamic stability of such a small meniscus was recently studied both experimentally and theoretically (10,11).Because the size of the meniscus defines the di-ameter of the deposited wire when a stable growth is established,this method is intrinsically capable of fabricating wires down to nanometer sizes.Prac-tically,the mechanical stability of the physical system,the availability of nozzles of small size,the ion transport behavior through small nozzles,the interaction between the electrodeposit and substrate surface related to nucleation and growth,and the electrochemical process in a confined meniscus environment all affect the minimum feature size and the quality of nanostructures that can be fab-ricated with this method.We have used this method to grow straight metal wires (vertical to the substrate surface)of various diameters down to ~100nm with the use of a micropipette with a nozzle diameter of ~100nm;we achieved wire lengths of >80m m,limited only by the travel range of the piezoelectric linear stage (fig.S1)(12,13).To facilitate interconnect bridge fabrication,which involves the lateral growth of a metallic wire over a sufficient span,we shaped the micro-pipette nozzle to allow the stable meniscus to form sideways to the nozzle.Figure 1B shows a shaped glass micropipette with a nozzle diameter of ~3m m.The nozzle end and the side opening allow the formation of a stable meniscus with the wire oriented along any direction between 0°(parallel to the substrate surface)and 90°(normal to the substrate surface).The shaping of the nozzle is done with focused ion beam machining,which provides the requisite precision.Figure 1C shows a series of angled Cu wires grown with a side-cut nozzle.The vertical and lateral lengths,as well as the orientation of the Cu wires,were controlled by the travel path of the micropipette,and the diameter was determined by the nozzle size and the size of the side opening in the nozzle.The wires were fabricated from a simple 0.05M CuSO 4aqueous solution and biased at 0.2V with respect to the Au-coated sample surface.The micropipette had a nominal nozzle diameter of ~3m m.The growth rate for the Cu wire at those conditions was ~0.25m m/s,and the corresponding ionic current was main-tained at ~3.5nA.The deposition was carried out with the substrate exposed to a humidity-controlled ambient air environment at room temperature.To form a connected wire (Fig.2A)(14),we formed the second bond by mechanically push-ing the suspended end of the laterally grown metal wire down to the substrate,with the nozzle end in close proximity so that the electrolyte me-niscus under the nozzle extended to immerse both the wire end and the region of contact on the

Fig.2.(A )Schematic showing the steps involved in the wire-bonding process with the meniscus-confined 3D electrodeposition.(B )SEM image showing 20electrodeposited inter-connects with submicrometer diam-eters fanning out from a central pad with an area of 50m m by 50m m.(C )SEM image showing the uniform quality of the first and the second bonds.(D )SEM image showing multi-layered interconnection over three steps of 5m m each in height.(E )SEM image showing overlap inter-connects over steps of 5m m in height.Scale bar,10m

m.

Fig.3.Constant-current mode I -V characteristics of a Cu interconnect (diameter ~740nm,length ~40m m)showing the linear ohmic contact behavior of the bonds measured in an ambient air environment.The inset shows the failed wire at high current.

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substrate surface.Several voltage pulses with amplitude at the electrodeposition potential were then applied to initiate the electrodeposition.The distance needed to push the wire end toward the surface was determined by an automated sensing procedure in which the micropipette was shifted sideways to detach from the wire end and driven with the piezoelectric stage to approach the sub-strate surface with the electrolyte biased at a dep-osition potential.At the moment of meniscus formation between the nozzle and the substrate surface,an ionic current could be detected and the distance between the wire end and the under-lying substrate surface was determined.The micro-pipette was then withdrawn to reengage with the wire end to form the second bond as described.Figure 2,B to D,shows the result of this electrodeposition-based wire bonding of submi-crometer-diameter Cu wires.The wire-bonding process was performed to form 20interconnects fanning out from a central bonding pad with an area of 50m m by 50m m,resembling a typical device layout (Fig.2B).Multilayered intercon-nection without (Fig.2D)or with (Fig.2E)over-lap wiring was also realized.The diameter of the Cu wires (Fig.2,B,D,and E)was ~800nm,and the size of the formed bonds was ~3m m.

The bonded wires were found to be of high electrical quality.Figure 3shows the acquired current-voltage (I -V )curve from a bonded wire with a diameter of ~740nm and a length of ~40m m,tested in an ambient air environment.The linear behavior in the broad current range reflected the ohmic contact of the bonds.The nonlinear be-havior at high current implied the potential effect of heating (thus,oxidation of the Cu wire)(15).The overall resistance of the bonds and the wire

was ~2.9ohms when deducting the resistance contributed from the peripheral connections in the measurement,very close to the expected value for a Cu wire of this size (~1.6ohms,as-suming an electrical resistivity of 1.68×10?8ohm·m of bulk Cu)with the bonds contributing a small contact resistance.At high current,the bonded Cu wire failed in the middle of the bridge and not at the bonds (inset,Fig.3).The break-down current density was ~1.25×1011A/m 2,in agreement with reported values for similar-sized Cu wires (16–18).Mechanically,we measured the bonding strength with an atomic force micro-scope (AFM)cantilever-based pull test.By moni-toring the deflection of the AFM cantilever while pulling a Cu wire vertically grown on an Au-coated substrate and with the free end glued onto the AFM tip with epoxy,we calculated that the strength of this electrodeposition-formed bond was more than ~39MPa,well above the nominal bonding strength required in traditional wire bonding (8.5MPa,according to the MIL-STD-883G test standard).

We also carried out such fabrication and char-acterization for Pt interconnects deposited with the use of an aqueous solution of chloroplatinic acid (H 2PtCl 6)as the electrolyte.Similar results were obtained (fig.S2).

The remarkable dexterity of this method for fabricating interconnect bridges relies on the ther-modynamic stability of the meniscus maintained during the deposition process.In general,the sta-bility of the meniscus is largely governed by wet-ting conditions involved with the nozzle and the wire growth front.To maintain the growth of a uniform-diameter wire,the thermodynamic con-sideration of the interfacial forces at the three-phase contact line between the meniscus and the growing wire requires the classical Neumann quad-rilateral relation to be met (19),which would then require the establishment of an equilibrium angle ?0between the growth direction and the slope of the meniscus at the contact line (inset,Fig.4)

?0?arccos g 2L tg 2S ?g 2SL

2g L g S

e1T

where g L and g S are the surface energies of the electrolyte and the metal wire with absorbing fluid,respectively,and g SL is the interfacial energy of the metal-liquid interface.This angle is determined to be ~12°for the copper-water-air system (taking g L =0.07119J/m 2,g S =0.07112J/m 2,and g SL =0.01456J/m 2)(20).Solving the meniscus shape equations then defines a region of stability for the stable growth of a uniform-diameter wire governed by

H M D W ?1

2

cos ?0cosh ?1D N D W cos ?0?cosh

?1

1cos ?0

e2T

(21),where H M is the height of the meniscus,D N

is the diameter of the micropipette nozzle,and

D W is the wire diameter.For a micropipette with a nozzle diameter of D N ,the diameter of a wire that can be stably grown lies within the range D N to ~0.5D N .Within the stable growth region,the deviation d ?of the contact angle ?from the equilibrium angle ?0leads to the fluctuation of the wire size according to

dD W

dt

?2ev N ?v W Ttan d ?e3T

where v N is the withdrawal speed of the micro-pipette and v W is the growth rate of the wire.The growth rate of the wire is simply defined by Faraday ’s law

v W ?4iM

nF rp D 2

W e4T

where i is the electrodeposition current;M and r are the molar mass and the mass density of the deposited material,respectively;n is the number of electrons per ion;and F is the Faraday con-stant.Figure 4shows the experimentally acquired parameter window for the stable wire growth in terms of the resulting wire diameter,the with-drawal speed,and the applied ionic current,in comparison to the prediction from the model.In the modeling,the diameter of the nozzle was measured from the scanning electron microscopy (SEM)image,and the surface energy and inter-facial energy values for the Cu –water vapor system were obtained from the literature.The agreement between the experimental and model-ing data covered a broad range of wire diameters up to near the predicted minimum diameter.

As in a regular wire-bonding process,the de-sign of small interconnect bridges requires taking certain mechanical considerations into account.One is the stress sustained by the wire during the fabrication process,which ideally should be well below the failure stress of the wire;another is the spring force sustained by the second bond,which should be lower than the bonding force.Consider a simple interconnect bridge as shown in Fig.2A.The maximum stress occurs at the left edge of the 90°bend and can be estimated according to s c =3EHr /L 2,and the spring force sustained by the second bond according to F s =3p EHr 4/4L 3,where E is the Y oung ’s modulus of the metal wire,H is the standoff height,and L and r are the length and radius of the lateral segment of the wire,respectively.For a typical Cu interconnect bridge of 1m m in wire diameter,5m m in standoff height,and 30m m in span,the maximum stress is calculated to be ~1GPa,which is beyond the yield strength of Cu.Thus,the Cu wire at the bend will experience a plastic deformation in the bonding process.The problem can be readily solved (if needed)by growing a tiled wire from the first bond (Fig.2C)instead of a vertical one to allow the formation of a smooth bend instead of a 90°bend.The maximum spring force on the second bond is ~3m N,and if the size of the second bond is assumed to be 10m m 2,the loading stress is ~0.3MPa,much lower than the debonding strength we measured for such an electrodeposited

bond.

Fig.4.Meniscus stability –defined parameter window for the stable electrodeposition of uniform-diameter metal wires.Plots show the dependence of wire diameter on the withdrawal speed of the micropipette (circles)at a fixed ionic current of ~12nA with the use of a micropipette with a nozzle diameter of ~1.6m m,and the dependence of wire diameter on ionic current (squares)at a fixed withdrawal speed of ~0.3m m/s with the use of the same pipette.The solid lines represent the relevant modeling data.The inset shows a schematic of the meniscus and the angle ?0between the growth direction and the slope of the meniscus at the three-phase contact line relevant to the stable electrodeposition of uniform-diameter metal wires.

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Overall,reducing the wire diameter and increasing the lateral length of the wire can also effectively benefit the lowering of such stresses.

The growth rate of an electrodeposited wire is intrinsically limited by the rate of electrore-duction,or more specifically by the diffusion-limited ionic current (22)described by a recessed microelectrode (the growth front of the deposited metal wire)in a truncated cone (the tapered dispensing end of the micropipette).Nonetheless,the growth rate might be increased through an increase in electrolyte concentration and/or the use of a short tapered micropipette.Alternatively,an array of micropipettes can be deployed to in-crease the wire-bonding throughput.

With the proper mechanical design and sys-tem control,this meniscus-confined 3D electro-deposition method can be used to fabricate more intricate microscale and nanoscale structures than those described here.Such structures could in-clude designed structural and device functionali-ties integrating a variety of metallic materials,such as magnetic and noble metals and even metal alloys.Moreover,because it is intrinsically a low-cost direct-writing technology,this technique can be used to fabricate such micro-or nanostructures

on existing micro-or nanostructures when such fabrication becomes difficult or expensive with the traditional lithography process (fig.S3).

References and Notes

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2.G.Harman,Wire Bonding in Microelectronics (McGraw-Hill,New York,2009).

3.C.Harper,Electronic Packaging and Interconnection Handbook (McGraw-Hill,New York,2005).

4.International Technology Roadmap for Semiconductors (ITRS-2007)(https://www.sodocs.net/doc/0c4447180.html,/Links/2007ITRS/Home2007.htm).

5.T.Morita et al .,J.Vac.Sci.Technol.B 21,2737(2003).

6.B.Y.Ahn et al .,Science 323,1590(2009);published online 12February 2009(10.1126/science.1168375).

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14.See supporting material on Science Online.

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(2003).

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104,023709(2008).

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185403(2009).

19.R.Defay,I.Prigogine,Surface Tension and Adsorption

(Longman,London,1966).

20.H.Ghasemi,C.A.Ward,J.Phys.Chem.C 114,5088

(2010).

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Academic,New York,1993).

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(2007).

23.Supported by the Grainger Foundation.We acknowledge

the use of microscopy facilities in the Center for

Microanalysis of Materials at the University of Illinois at Urbana-Champaign.A U.S.patent application based on this work was filed by the University of Illinois on 7June 2010.

Supporting Online Material

https://www.sodocs.net/doc/0c4447180.html,/cgi/content/full/329/5989/313/DC1Materials and Methods Figs.S1to S3

5April 2010;accepted 10June 201010.1126/science.1190496

Cenozoic Tectonics of Western North America Controlled by Evolving Width of Farallon Slab

W.P.Schellart,1*D.R.Stegman,2,3R.J.Farrington,4J.Freeman,4,5L.Moresi 1,4

Subduction of oceanic lithosphere occurs through two modes:subducting plate motion and trench https://www.sodocs.net/doc/0c4447180.html,ing a global subduction zone data set and three-dimensional numerical subduction models,we show that slab width (W )controls these modes and the partitioning of subduction between them.Subducting plate velocity scales with W 2/3,whereas trench velocity scales with 1/W .These findings explain the Cenozoic slowdown of the Farallon plate and the decrease in subduction partitioning by its decreasing slab width.The change from Sevier-Laramide orogenesis to Basin and Range extension in North America is also explained by slab width;shortening occurred during wide-slab subduction and overriding-plate –driven trench retreat,whereas

extension occurred during intermediate to narrow-slab subduction and slab-driven trench retreat.U

nderstanding the partitioning of plate consumption at subduction zones is vital for constraining its effect on mantle an-isotropy,dynamic topography,and overriding plate deformation at subduction zones (1–3).Subduction partitioning also exerts an important control on slab geometry (4,5)and the style of mantle stirring [i.e.,poloidal versus toroidal flow (5–8)],providing

constraints on the geochemical heterogeneity of the mantle.It remains unclear,however,how the rate of plate consumption at oceanic trenches [the subduction velocity (v S ⊥)]is partitioned into its two primary components,the trench-normal subduct-ing plate velocity (v SP ⊥)and trench velocity (v T ⊥),and what controls such partitioning.At present,variation in subduction partitioning (v SP ⊥/v S ⊥)ranges from subducting-plate-motion –controlled (v SP ⊥/v S ⊥>0.5,such as for Sunda and Mexico –Central America)to trench-motion –controlled (v SP ⊥/v S ⊥<0.5,such as for Scotia and Cascadia).Previous research suggests that plate age cor-relates with subducting plate velocity (9,10)and trench velocity (11),but early work on global trench velocities contradicts the latter correlation (12).Other research suggests that plate velocity

is controlled by plate boundary fraction that is a subduction margin (13),but this provides no explanation for the global variation in trench velocity.

We present results from a global compilation of present-day subduction zone kinematics for 17subduction zones and three-dimensional numer-ical models of buoyancy-driven progressive free subduction of a dense four-layer plate into a strat-ified linear-viscous mantle (14).In the models,the plate has a strong viscous core 300times more viscous than the upper mantle;however,because it is only 25km thick,the lithosphere is still weak with respect to bending (15–17),in accordance with slab geometries,slab pull forces,and geoid signatures at subduction zones (5,15,17,18).The subduct-ing plate is laterally homogeneous,and slab width (W )—the trench-parallel extent of a subducted slab that is limited by its lateral slab edges —varies between 300and 7000km.The causes for lateral slab edge formation are manifold,including slab tearing,slab window (gap)formation,subduction termination,and slab detachment.

The global data set of current subduction kin-ematics indicates negligible to moderate correla-tions between plate boundary fraction that is a subduction margin and v SP ⊥(Fig.1A)and between plate age and v SP ⊥or v T ⊥(Fig.1,B and C).In contrast,both the global data set and the dynamic models show that average v SP ⊥,v T ⊥,and v SP ⊥/v S ⊥vary nonlinearly with W along with strong cor-relations (Fig.2).In nature and models,v SP ⊥/v S ⊥and v SP ⊥show a nonlinear increase with increasing W ,whereas v T ⊥shows a nonlinear decrease.

The nonlinear increase of v SP ⊥with W (Fig.2,A and D)can be explained with Stokes-like sink-ing of an oblate ellipsoid (analog for slab)parallel

1

School of Geosciences,Monash University,Melbourne,Victoria 3800,Australia.2Scripps Institution of Oceanography,University of California,San Diego,La Jolla,CA 92093,USA.3

School of Earth Sciences,University of Melbourne,Melbourne,Victoria 3010,Australia.4School of Mathematical Sciences,Monash University,Melbourne,Victoria 3800,Australia.5Bureau of Meteorology,Melbourne,Victoria 3001,Australia.*To whom correspondence should be addressed.E-mail:wouter.schellart@https://www.sodocs.net/doc/0c4447180.html,

16JULY 2010VOL 329

SCIENCE

https://www.sodocs.net/doc/0c4447180.html,

316REPORTS

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