"US 200902! (2) Patent Application Publication cu») United States Raviet al. 0A (10) Pub, No, US 2009/0280050 AI (4s) Pub, Dat Nov. 12, 2009 (54) APPARATUS AND METHODS FOR CASTING. MULTI-CRYSTALLINE SILICON INGOTS, KramadhatiV; Ravi, Atherton, CA (US); Hans J. Walitzk, Portland, OR WS) (75) Inventors Comrespondence Address: DIEHL SERVILLA LLC 77 BRANT AVENUE, SUITE 210 CLARK, NJ 07066 (US) (73) Assignee: Applied Materials, Ine. Santa Clara, CA (US) (21) Appl. No: 12428,835 (22) File Ape. 23,2009 20 Related US. Application Data (60) Provisional application No, 61/047,939, filed on Ape. 25, 2008, Publication Classification G1) Inch, CIR 3302 (200601) BOLD 9700 (200601), CxO 28700 (2006.01), (2) US.CL 423/849; 422/245.1; 422/109 on ABSTRACT Apparatoses and methods for making a multi-crystallne sil ‘eon ingot by’ directional solidification comprising (Wo oF ‘ore moveable heat shields located beneath the crucible, the eat shields being opened in contrlled manner to remove beat and produce « high quality silicon ingot. 10Patent Application Publication Nov. 12,2009 Sheet 1 of 6 ‘US 2009/0280050 AI 20Patent Application Publication Nov. 12, 2009 Sheet 2 of 6 US 2009/0280050 AI 18a 180 « 18b LJ 18 oe 12 Les 18 Rig 2A oe Fig. 2B 184 ct C 18a 18b 18 2 C 18 18c 186 18d Fig. 2C Fig. 2DPatent Application Publication Nov. 12, 2009 Sheet 3 of 6 US 2009/0280050 AI 19 30a 30b Fig. 3A sa 2a 21bPatent Application Publication Nov. 12, 2009 Sheet 4 of 6 US 2009/0280050 AI 23a [ omPatent Application Publication Nov. 12, 2009 Sheet 5 of 6 US 2009/0280050 A1 (- 24 Fig. 4 (prior art)Patent Application Publication Nov. 12, 2009 Sheet 6 of 6 US 2009/0280050 AI 26 26 12 12 \ 24 24 Fig. 5A Fig. 5BUS 2009/0280050 AI APPARATUS AND METHODS FOR CASTING “MULTI-CRYSTALLINE SILICON INGOTS, ‘CROSS REFERENCE TO RELATED "APPLICATION {0001} This application claims the benef of priority under SS USC. § 119(¢) o US. Patent Application No. 61/047, 939, fled Apr. 25, 2008, which is hereby incorporated by reference in its entirety ‘TECHNICAL FIELD [0002] Embodiments of the present invention generally relate to methods and associated apparatuses forthe prepani- tion of multi-erystalline silicon ingots. More spocfialy, ‘emboviments of the present invention relate to apparatuses and methods forthe directional solidification of multe talline silicon ingots having fewer erystal defets than ventional methods BACKGROUND 10003] _Aliemative power sources have heen studied with rear interest a a result of the sharp rise in oil and gasoline Prices, Solar power is one ofthe promising technologies for enerating clean, renewable electricity. Solar cells, aso called photovoltaic cells, are devices which convert solar ‘energy into electricity These cells have evolved significantly ‘over the past two decades, with experimental ellicencies ‘increasing from les than about 5% in 1980 to almost 0% in 2008. 10004) Inthe early development of solar cell, single-erys- tal or semi-conductor grade silicon was employed. However, ‘ensalline silicon ingots of this type are expensive due to the ‘cos associated With eeatig the crystalline stracture. One of the traditional methods of creating a singe crystal of silicon Js by the Caochyalski process. In this process, polysilicon is rnelted in a eylindrical crucible. The melt can be doped to ‘create n-ypeor p-ypesilicon. seed erytal is introduced to themelt causing crystal growth. Theenystal is pulled fom the rl, creating aeylindrical single crystal ingot. Single-crystal silicon wafers, less han about 300 um thick, are then ea rom this evlindrieal ingot 10005] "However, iis ow known that single-crystal silicon is not required for producing efficient sola alls, Muli-cnys- talline also referred w as muli-rystalline, silicon ingots ean be ereted using the directional solidification process, some- times called the oriented solidification process, Diretional solidification employs a rectangularshaped crucible, often hated from the sides and bottom, Generally the erie is filled with polysilicon and melted in an inert atmosphere ‘Once melted, the crucible is allowed w eoo! ia a eontolled ‘manner from the bottom up. Heat loss during eooling occurs ‘atthe sides of the erucible by vertically moving graphite heat ‘his, o allow radiative heat loss from the crucible and the silicon! 10006] | Upon cooling, nucleation occurs, resulting in exys- tal geowth upward from the bottom of the eroible. The ingot produced is rectangular in shape, a8 opposed to the eylini- ‘ally shape ingot from the Czochralski process. The direc tional soliification process causes any impurities in the ‘con to be pushed to the top of the cnicible where they ‘concentrate in the top layer of the ingot. This layer is subse “quently cut from the ingot, leaving substantially pure ml ensialli Nov. 12, 2009 [0007] Today, the majority of solar cells are manufactured ‘Using erstlline silicon wafers, Over 50% of erystalline con solar cells are manufactured using mulierystalline con wafers which are manufactured by directional solidifca- tion. However, there are several undesirsble aspects to the ‘current process: excessive power consumption and the inter face isalways concave resulting in higher defect density inthe resulting ingot. To remove these defects, the sides of the rectangblae ingot must be ground off, resulting in loss of bout I em ofthe outer silicon surfice. Therefore, there is a continuing need in the art for methods andapparatusto create :nult-crystalline silicon ingots with lower defect deasiy SUMMARY, [0008] Aspects ofthis invention involve the we of horizon- tally moving heat shields at the botiom of the erucible in iretional solidification process and apparatus. This allows for controlled hoat loss from the bottom of the crucible, sulting in controled growth of erystals anda convex inter face between the solid and liquid silicon during solidification ascomparedto concave interfacein the prior This design also results ina ater erysalization interface, lower defect ‘density, lest stress and fewer defects inthe ingot center as compared to current state of the an. This invention. also ‘enables faster erystallization rates while maintaining a desi fable interface shape (no bending st edges and an overall ‘convex shape). Furthermore the total heat fos through the ‘movable bottom heat shields will be lower than the heat loss ‘uring exystalization a compared wo prior ar. [0009] One or more embodiments of the invention are rccted to an apparatus for producing multi-crytalline sil «con ingots by directional solidification, The apparatus com- prises a crucible having four sides and a bottom, The top of the erucible ean be open or closed depending upon the spe- cille application. The erucible is placed within a erucible holder. plurality ofheaterssurroundsat lest portion of the cnicible holder, The heuiers are capable of casing silicon ‘within tecrucibleto mel. At Teast wo moveable het shields below the enicble holder are adapts to move in the same plane as the encible bottom. The moveable heat shields ean bbe made of any suitable material, such as graphite, graphite {alt or other graphite insulation, but isnt himited to graphitic materials and may also be made of suitable metals, such as ‘molybdenum, seting as heat reflector. [0010] ‘The heaters of some embodiments are located adja- ‘eat the four sides of the ervcible holder. In other embodi- ‘ments a heater is located above the erucible. In still further ‘embodiments heaters located below the erucible. cooler located below the ervcible may also be present. A water cooked jacket surrounding the apparatus may also be employed [0011] Themoveable eat shields according to one oF more ‘embodiments comprises four members adapted to move so thatan opening having a similar shape to the eruible bottom is formed, The members of some embodiments can move independently ofeach other. A specific embodiment has wo ‘movable, partially overlapping shields. Another embodiment jnvolves to rotating overlapping shields. [0012] In other embodiments, one of more temperature probes are disposed within the apparatus. A control mecha- bism for monitoring the tempertire probes may be preset. Thecontrol mechanism may also beable oadjstthe locationUS 2009/0280050 AI ‘of, and the extent of movement of, individual moveable heat Shields o controllably extract heat from the molten silicoa in the crucible 10013] Additional embodiments of the invention are directed to methods of producing muttierysalline silicon ingots by directional solidification. The methods comprise the transfering of silicon into a erucible located within 9 fumace, The ervciblemay havea hottomand four sides. top for the erucible may also be present. The crucible is held within «crucible holder. The ericble is heated with heating ‘elements located adjacent the crucible holder sides. The er ‘ible is surrounded at least on the bottom with a moveable heat shield. Th silicon within the crucible meted and then ‘cooled in a coatsolled manner to achieve controlled sol cation of the silicon by moving the heat shields, A multieys= talline silicon ingot is produced where the grain size in the ‘center ofthe ingo is substantially uniform with respect tothe rain size a the ede ofthe ingot 10014} In oxher embodiments, the heat shield comprises Tour members adapted to move so that aa opening having @ similar shape to the erseble bottom can be formed. [0015] Further embodiments ofthe invention are directed to mult-erystaine silicon ingots. The ingots comprise Four sides and solid-liguidsilionn interface during solciication. ‘The solid-ligud interface is controlled by moving the heat shields. The multicrystalline silicon ingot of some embod ments hasan interface which curls downward atthe intersec- tionof the soid-iguid interface with the walls of the crucible ‘Themult-erystalline silicon ingot of other embodiments has ‘an interface which is perpendicular to the ingot side. The ‘ult-erytaline silicon ingot of further embodiments shows "niform gain size fom the center ofthe ingot to the eds oF the ingot, BRIEE DESCRIPTION OF THE DRAWINGS. 10016) _FIG.1 shows a schematic ofa directional sliifi- «ation chamber aecoring to one oe more embodiments of the [0017] FIGS. 2A-2D show positioning of moveable heat Shields acconding to one or more embodiments; [0018] FIGS. 3A-3C show additional embodiments of ‘movable heat shields [0019] FIG. 4 shows the shape of a solidtiqud silicon ‘interface achieved using methods and apparatus aecording 10 the prior ant and 10020] FIGS, SA-SB show the shape of stid-tiquid silicon ‘interfaces achieved using methods and apparatus according to ‘embosiiments othe invention, DETAILED DESCRIPTION 10021] Before describing several exemplary embodiments ‘ofthe invention, itso be understood thatthe invention is not limited tothe details of consirotion or process steps set fort nthe following description. The invention is eapable of other ‘embodiments and of being practiced or being carried out in Saris ways. 10022] As used in this specification and the appended ‘claims, the singular forms “a “an and “the” inelude plural roferents unless the context clearly indicates otherwise. Thus, {or example, reference to “an ingot” includes a combination ‘of wo or more ingots, ante like 0023] -Refering to FIG. 1, a schematic representation of 2 izectional solidiication chamber 10 according 10 one oF Nov. 12, 2009 nore embodiments ofthe invention is shovsn, Crucible 12 is spportd win crib holder 14 which is locate within seaite enclosure 20, Silicon with the eucile 12 smelted Withheat generated by heaters 16, nce milled, thomoveable heat shields 18 are opened ina direction parallel to the er ibe 12 bottea. The bat shields 18 are opened ina con- telled manner to remove heat from the chamber 10. The lig silicon 22 cools toa solid mass 24 in the bottom of the cmible. An interface 6beteen the iguidsilicon 22 andthe Solid silicon 24 is formed. The shape ofthis interlace 26 is Indicative ofthe quality of the resultant ingot, a discussed below with reereace 1 FIG. 4 (0024) Inoneormore embodiments, thehet shields 18 are ‘pened by’ contol mechsnism (aot showin). The contol ‘mechanism ean be a simple contol mechanism such as a handle andor wack that allows the heat shields 18 10 be copened and closed manually in certain embodiments, the contol mechanism may ince an automated mechani ‘ich asa moor or other suitable device to conte the extet ‘opening of the heat sick 18 In specie embodiment, ‘he control mcchanismisin communication witha sensor ht can measure the temperature within the chaaber 10 wsing Strategically placed temperature probes 28 thovahout the tuber 10, Suitable temperature probes may inlude thee ‘mocouples orpyromsters. By evaluating to tempertre pro- feat various locations within the chamber 10, the contol sechnismcanopen any oncorall ofthe heat shields 18. This ould be achieve by utilizing a meroprocessor or compoter ‘sing a feedback contol system that woul adn the extent ‘of opening of the heat shields based upon the temperate ‘edings Irom the temperate probes 28. This em allen for 2 usiform temperature o be maintained aerss the Dotom oF the erie 12 resting in @ uniform ingot {0028} FIGS. 24-2D show exemplary configurations for ‘the moveable hat shields 182-18/ of one oe more embod ‘ments ofthe invention. During the meting stage, the heat Shields 18o-18d are closed, as shown in FIG. 2A, to rain as ‘veh hsat within th chamber 10 a possible: Upon cooling, tne heat shields 180-187 are opened to varying extents, 36 shown ia FIGS. 21-20, to allow Beat to escape fom the haber 10, The eneibe bottom 12s shawn athe enter of te heat shells 18u-18d in FIGS. 28-2D. As relerenced ave, the deree of extent of opening of the heat shiek! 18a-dcouldbecontollesbyacompiterormietoprocsssor in commonieaton with temperature probes, Experimental dts could be lized to determine the optimam temperstare an extentor degre of opening othe heat shields 18-1840 Sptimiz: the mie and extent of opening ofthe heat sbilds able heat shields below the crucible bolder are adapted ‘move inthe same planeas the eruciblebottom. The moveable heat shields ean be made of any suitable material, sul as ‘raphite, graphite felt or other graphite insulation, but isnot Timited to graphite materials, 10033] The heaters of some embodiments are located ada- ‘cent the four sides of the crucible bolder. In other embod ‘ments, heater is located above the ervible, In sill furhee ‘embodiments a heater is located below the crucible. A cooler Tocated below the erucible may be present. A water cooled jacket surounding the apparats may alsa be employed 10034] The moveable heat shields of one or more embod ‘ments comprise upto four members adapted to move so that ‘an opening having a similar shape tothe crucible bottom is, Tormed, The members of some embodiments can move inde- pendently of each other. Other embodiments include wo Fincar movable shields which overlap when closed (FIG. 14) ‘0 rotating heat shields (FIGS. 38 and 3C) Nov. 12, 2009 [0035] In other embodiments, one oF 2 probes are disposed within the apparatus. A control mech nism for monitoring the temperature probes may be present. The control mechanism may also beable to adjust the location of individual moveable heat shields to controllably extract heat from the molten silicon inthe erible [0036] Additonal embodiments of the invention are rected to methods of producing mult-crytalline silicon ingots by directional solidification. The methods comprise the tmasfering of silicon into a crucible located within a {urmoee. The crucible may have bottom and four sides. top for the crucible may algo be present. The ericible is het ‘within a crucible holder. The ervcible is heated with heating elements located adjacent the crucible holder sides. The en cible is surrounded atleast on the bottom with @ moveable heat shield. The silicon within the erveible melted and then cooled in controlled manner to achieve controled soli cation ofthe silicon by moving the heat shields. A multicry talline silicon ingot is produced whore the grain size in the eater ofthe ingot is substantially uniform with respect tothe igtain size at the edge ofthe ingot. [0037] In other embodiments, the heat shield comprises our members adapted to move So that an opening having a similar shape tothe crucible bottom can be ferme. Iwill be ‘understood thatthe configuration of four shields shown FIGS. 24-28 is exemplary only. Accordingly, fewer or sareater than four movable shies may be uilized in acoor- {dance with altemative embodiments. For example, ‘wo ‘opposing shields could be utilized, Other variats, such as those shown in FIG. 3) are within the seope ofthe invention. [0038] Further embodiments of the invention are directed ‘to multi-crystaline stioon ingots. The ingots comprise four sides anda solidliguid silicon interface during solicifcation The solid-liquid interface is controlled by moving the heat shields. The multi-crystalline silicon ingot of some embod- ‘meals isan interface which curls downward atthe intersee- tion of the solid-iguid interface withthe walls of thecrucibe, ‘The muli-rystalline silicon ingot of other embodiments has fan interface which is perpendicular to the ingot side, The ‘mult-erystaline silicon ingot of further embodiments shows “nifoem grin size from the center ofthe ingot tothe edges oF the ingot. [0039] Reference throughout this, specification t “one ‘mbodimient"“certan embodiments?""one or moreembodi- ‘meats" or“an embodiment” means that a particular feature, structure, material, or characteristic described in connection ‘with the embodiment is included in at least one embodiment ofthe invention, Thus, the appearances ofthe phrases such as “inoneor moreembodiments.” in erin embodiments.""in ‘one embodiment” of “in an embodimeat” in various places ‘throughout this specification are not necessarily referring to the same embodiment ofthe invention, Furthermore, the par- ticular features, structures, material, or characteristics may bbe combined in any suitable manner in one or more embod ments 0040} Although the invention herein has been deseribed ‘with reference to particular embodiments, i isto be under- stood that these embodiments are merely illustrative of the rinepes and applications of the present invention, I willbe Apparent to those skilled in the art that various modifications ‘an variation can be made tothe method and apparatus ofthe resent invention without departing from the sprit and scope ‘ofthe invention. Thus itis intendes that the present ventionUS 2009/0280050 AI include modifications and variations that are within the seape ‘of the append claims and their equivalents ‘What is claimed is 1. Am apparatos for producing multi-crystallin silicon ingots by directional solidification, the apparatus comprising: ‘a crucible including a sce wall ad «bottom: ‘senicible holder including a side wal and bottom portion for holding the erucble; plurality of fixed heaters surounding atleast portion of ‘thecrucibleholder, the heaters eapable of heating silicon to melting temperature; and atleast two moveable heat shields atthe bottom portion of the crucible holder, the heat shields moveable in the same plane asthe erucible bottom to contr 2. The apparatus of claim 1, wherein heaters are located adjacent the side wall of the crucible holder 3. The apparatus of elaim 1, wherein one or more heat spreaders are disposed between the heater and the erucible holder side walls. 4 The apparatus of claim 1, further comprising @ heater located above the enicible '3. The apparatus of claim 1, further comprising @ heater located below the crucible 6. The apparatus of claim 1, wherein the moveable heat shield comprises graphite insulation. 7. The apparatus of claim 1, further comprising a cooler located below the rucible '8, The apparatus of claim 1, wherein the ervible boom ‘comprises four members arranged to form an opening having ‘a similar shape to the erie, 9, The apparatus ofelaim 1, fore comprising a tempera ture probe for monitoring the temperature, the temperatnre probein communication withacontrol mechanism foradiust- Ing the positon of the moveable heat shields to control the rale of hea extracted Irom the molten silion ia the ertcble. 10. The apparatus of claim 1, farther comprising a water ‘cooled jacket around the apparatus 1. Theapparatus of claim 1, wherein each moveable heat shield is adapted to move independently of the other heat shields. 12, The apparatus of claim 1, whecci the crucible and the ‘enicible holder inelide four side walls Nov. 12, 2009 13. Theapparanisof claims 12, wherein the ingoteon four sides anda solid-Tiqud silieon interface during cation which iscontrolledby he moveableheatshieldand the fnterlace curls downward at the intersection of the solide liquid interface with the walls ofthe crucible 14, The apparatus of claims 12, wherein the interface pro- duced by the apparatus is perpendicular to the ingot side. 15, Theapparats of claim 12, wherein the ingot peodtced by theapparatus exhibits uniform grainsize fom thecenterof the ingot to the edges of the ingot. 16. A method of producing a muli-crystalline silicon ingot by directional solidification, the method comprising: ‘transferring silicon ino crucible located within a nace, the crucible comprising @ bottom a side wall and con- tained within a crucible holder, ‘eating the crncible with heating elements located adjacent the erucible older side wall, surrounding the erucible on at least the erucible bottom ‘with a moveable het shield: molting th silicon in the erucible; and cooling the melted stieon in the erucible in a controlled manner to achieve controlled solidification by changing the position of theheat shield with expect to the erveible bot, 17, The method oF claim 16, wherein the enuible inelides {oursice walls and the crucible bottom comprises four mem- bers adapted to move so that an opening having a similar shape tothe erucible boom can be Formed 18, The method of claim 16, wherein a muli-erystalline silicon ingot is produced whee the gran size inthe center of ‘he ingot is substantially uniform with the grain size at the ccdge of the ing. 19. A multi-rystllne silicon ingot made prepared using the apparatus of ela 16, the ingot having a top surface, four sides, and an interlace being defined asthe soli-Higuidinter- Tie. 720. The multi-crystalin silicon ingot of lai 19, wherein the interface curls downward atthe intersection of the solid- liquid interfuce withthe walls ofthe crucible 21. The multi-crystaline silicon ingot of lai 19, wherein ‘he interface is perpendicular tothe ingot side.