LATERAL EPITAXIAL GROWTH BY SEEDED SOLIDIFICATION

Abstract: An improved method and apparatus for crystallizing amorphous or polycrystalline material. In this invention, a material which is to be crystallized is formed on the substrate (10) and single crystalline seed material (18) is disposed in contact and/or adjacent to or with at least a portion of the material which is to be crystallized. A layer of material (20) which serves as a "wetting agent" is then formed over the material (18) to be crystallized. The structure thus formed is subjected to a heat treatment which melts the material (18) being crystallized and when the material solidifies its crystalline structure is substantially epitaxial based on the seed material. The "wetting agent" layer (20) serves to prevent deleterious balling up of the material during crystallization.

Description: LATERAL EPITAXIAL GROWTH BY SEEDED SOLIDIFICATION Technical Field This invention is in the field of materials, and more particularly relates to the conversion of amorphous 5or polycrystalline materials, such as sheets of semicon¬ ductor material, to sheets of substantially single- crystal semiconductor material. Background Art Much of modern technology makes use of thin solid films on the surfaces of solid substrates. A number of methods have been used to deposit such thin films in-- . eluding thermal evaporation, DC sputtering, rf sputter¬ ing, ion beam deposition, chemical vapor deposition, plating, molecular- beam deposition and deposition from the liquid phase. The structure of thin films can be amorphous (that is, the atoms of the film are not arranged in any crys¬ talline order), polycrystalline (that is, the film is composed of many small regions, in each of which the atoms are arranged in a regular crystalline order, but the small regions have no mutual alignment of their crystallographic axes), preferred orientation (that is, the film is " composed of many small regions, in each of OMPI which the atoms are arranged in a regular crystalline order, and one or more of the crystalline axes of the majority of said regions are parallel) , or epitaxial (that is, the film is predominantly of a single crystal- lographic orientation) . An epitaxial or single crystal film is a special case of a preferred orientation film in which corresponding crystallographic axes of all the small regions are essentially oriented in the same directions. A thin film can be the same material (that is, the same element or compound) as the substrate, or it can differ in chemical composition from the substrate. If the film is epitaxial, the former is called "homo- epitaxy" and the latter "heteroepitaxy". In many solid state electronic devices, the active volume of the device comprises or lies within a thin sheet, film or layer of crystalline semiconductor mat¬ erial, preferably in the single crystal or monocrystal- line form. This active volume is formed on an insula- tive substrate. This is particularly true of integrated circuits fo ' rmed from semiconductors such as gallium arsenide, silicon, germanium, indium phosphide, cadmium telluride, etc. Present techniques for fabricating such devices, however, require that ' - the crystalline sheets or films be grown mainly " by chemical vapor depo- sition from the surface of relatively thick substrates of high-purity, single crystal semiconductor material, such as sapphire. The use of such substrates for each sheet produced tends to inordinately increase the cost of producing the thin sheets. Furthermore, the high defect density of the epitaxial sheets or films thus formed and the high dielectric constant of the sapphire limits the performance of the resulting device. OM -3- Another alternative has been to form large grain sheets or films using a scanned laser beam to heat an amorphous or polycrystalline sheet or film of semicon¬ ductor material, such as Si, which has been deposited 5 on sapphire or fused silica- (Si0 2 ) - See, for example, U. S. Patent 4,059,461. Small grains, less than 50 microns in size, are obtained by this process and the film when overlayed on Si0 2 has a tendency to crack. W processed on sapphire, the Si film may interact detrime 0 tally with the sapphire. Another recent innovation in the growth of epit¬ axial films is described in a paper entitled "Silicon Graphoepitaxy Using a Strip-Heater Oven" by M. W. Geis, D. A. Antoniadis, D. J. Silversmith, R. . Mountain and 5 Henry I. Smith. Appl. Phys. Lett. ^7(5) 1 September_ 1980 which relates to the conversion of amorphous silicon to a silicon mosaic film by graphoepitaxy with a film or "cap" of SiO- over the silicon film. This process is also described in copending U. S. Patent Application Serial No. -181,102 filed August 25, 198D and entitled "Graphoepitaxy by Encapsulation n . The graphoepitaxy process requires the intentional creation of artificial surface relief steps or point defects in a geometric pattern on a substrate to control in a predetermined way the process of film formation and growth on the substrate. The geometric pattern is gen¬ erally a simple grating or grid, oriented to promote cry¬ stal growth in a predetermined manner. In the graphoepitaxy process, the substrate crystal orientation plays a passive role in the formation of the crystal orientation and growth which is determined pri¬ marily by the surface relief structure. As reported on ' page 455 of the referenced Appl. Phys. Lett, even with a "cap", if the silicon film is fully melted in a graphoepitaxial process, neither tex¬ ture or orientation of the crystallized film is observed. Apparently, the function of the SiO_ cap in the grapho¬ epitaxy process is to produce a shear stress as a result of thermal expansion differences between Si and SiO- which leads to anisotropy in the Si such that upon cry¬ stallization a (100) texture and uniform orientation rela- 0 tive to the relief gratings occurs. Also, recently, in copending U. S. Patent Appli¬ cation Serial No. 138,891 filed April 10, 1980, there is disclosed a method of achieving lateral epitaxial growth by seeded solidification (melting and refreezing of 5amprphous Si) through openings in an insulator formed on a crystallization substrate. After the growth is discontinued , '* the sheet of crystalline material is cleaved or otherwise separated from its substrate which may optionally be reused. This process we shall refer to for the sake of convenience as the CLEFT process and the application, as the CLEFT application. While the CLEFT process is believed to represent a significant advance over the state-όf-the-art at the time the invention was made; certain problems have arisen in the application of the CLEFT invention to the consistent production of high quality, defect free, epitaxial films. More specifically, if for any reason, the lateral epi¬ taxial growth is discontinuous, then further epitaxial growth is precluded since the further growth has no crystalline orientation to start from and will therefore grow in random polycrystalline fashion. Accordingly, a need exists for a method and apparatus for minimizing OM discontinuities in epitaxial films laterally grown throug openings in an insulative mask formed on a crystalliza¬ tion substrate. We have also found that where lateral growths meet, 5 i.e., when lateral growth in one direction encounters lateral growth from another direction, dislocation de¬ fects are apt to occur; presumably caused by the strain or stress created when two crystallization fronts meet. For thes≤ and other reasons / it would be highly ° desirable to have a process and apparatus for producing lateral epitaxial growth in amorphous semiconductor material wherein discontinuities in growth and crystal dislocations are minimized and which is relatively sim¬ ple in operation and low in cost. • Disclos re of the Invention In the apparatus of the present invention, trans¬ formation of amorphous or polycrystalline semiconductor material to epitaxial material is achieved using a layer of wetting agent material which preferably has a melting 0 point higher than the crystallization temperature of the material being transformed. This wetting agent layer is disposed in contact ' with the semiconductor material to be transformed._ The semiconductor material is also in contact and/or adjacent . ith a sinqle crystal seed material. By "wetting agent" is meant a substance or composition that causes the spreading of the semiconductor material out and over an underlying or overlying intimately contacting surface. While the precise nature of the phenomena associated with this wetting agent layer is not entirely understood, at present, we are of the opinion that this layer serves to prevent the semiconductor material from agglomerating (beading or balling up) as the crystalline front propa ¬ gates laterally during epitaxial growth. Agglomeration or "balling up" of the semiconductor 5 material during the growth process is to be avoided since it results in voids or discontinuities in the film or layer. Once a " void occurs, epitaxial growth; which is predicated on continuity with the seed, is interrupted. 1-- It should be emphasized that the function of the wetting agent layer of the present invention is funda¬ mentally different and distinct from the "cap" referenced in the prior art graphoepitaxy process. In the present invention, the primary purpose of the wetting agent 51ayer is to wet the surfaces between the material to be. crystallized and the seed material. The seed material is the principle determinant of the resultant crystal¬ line properties. On the other hand, the graphoepitaxy "cap" is intended, not as a "wetting agent 1* , but to 0 actively contribute to the crystalline orientation and textural properties of the grown material. In one embodiment of the invention, the growth is achieved from a seed which is not a part of the substrate as in the aforementioned CLEFT process. A "seed" is a 5body of single-crystal semiconductor material from which the epitaxial growth, originates . However, unlike the embedded or buried single crystal material in the CLEFT process, an externally seeded growth is .achieved from a body of single-crystal growth material which is pro- vided on an external face or surface of the amorphous material which is being transformed to single-crystal material. In the external seed eπ-bodiment it is unneces- OMPI sary to make openings in insulative layers to reach the underlying single crystal seed material. Furthermore, growth can be achieved by starting at the external seed and propogating the crystallization front in one directio along the surface of the amorphous material. In this and other embodiments to be described, the crystallizatio front does not encounter -a crystallization front propa¬ gating from the opposite direction, as in the case of parallel adjacent stripe openings,, and potential 0 crystal dislocations caused by such an encounter are avoided. Brief Description of the Drawings Fig. 1 is a process flow diagram for one embodi¬ ment of a process according to this invention; 5 Fig. 2 presents a series of schematic views illustrating a first embodiment of the invention accord ¬ ing to the process shown in Fig. 1; Fig. 3 presents a schematic illustrating a prior art structure made without a wetting agent layer; Fig. 4 presents a schematic perspective view illustrating a technique of this invention, in simpli¬ fied form, a stationary single heater embodiment for.. thermally heating a sample to produce lateral epit¬ axial growth from a crystallization substrate; Fig. 4a " is a plot which shows the thermal profile to which the sample in Fig. 4 is subjected; Fig. 4b is a schematicized cross-section of a portion of the sample in Fig. 4; Fig. 5 is a perspective of a ual heater embodi- ment of the invention; OMP Fig. 6 is an exploded perspective showing the apparatus of Fig. 5 in more detail; Fig. 7 is a perspective as in Fig. 6 except that the heater is located parallel to the stripe opening; Fig. 8 is a schematic perspective view of an exter ¬ nal seed embodiment which is suitable for.growing sheets which are substantially single crystal; Fig. 9 is a schematic perspective view of an external seed embodiment with an overlayer of Si0 2 - Fig. 10 is a schematic perspective view of an external seed embodiment with both the Si0 2 wetting agent layer and Si layer over the seed; Fig. 11 is, a schematic perspective view of a com¬ posite wetting agent embodiment; Fig. 11a is a schematic perspective view of an embodiment in which the wetting agent is located on the mask surface. Fig. 12 is a series of schematic perspective views illustrating the steps in forming a planar embodiment of the invention. Figs. 13A and 13B show the construction in partial schematic form of a three terminal semiconduc¬ tor device fabricated on a SiO substrate manufactured in accordance with the process described herein. Fig. 14 is a process flow diagram of an alternate embodiment of a process in accordance with the invention. Fig. 15 is a perspective view of a further embodi¬ ment of the invention utilizing a simplified scribing technique to induce seeded solidification- Fig. 16 is an enlarged partial cross-sectional view of Fig. 15 taken along lines 16-16. Best Mode of Carrying Out the Invention The following description generally relates to silicon semiconductor • epitaxial growth and silicon is selected since silicon is the most important semicon- 5 ductor material in use today. However, the invention is in no way intended to be limited thereby. In fact, the invention will have beneficial application in the epitaxial growth ' of other well known semiconductor material such as gallium arsenide and germanium to name 10 a few. A variety of specific embodiments of this inven¬ tion will now be illustrated with reference to the Fig¬ ures. In these Figures, like elements have been given like numerals. 5 Figure 1 is a process flow sheet presenting the steps for one embodiment of this invention. In the first step of this process, a crystal growth mask is formed on a crystallization substrate to cover portions of the substrate and to leave a pattern of exposed sub- 0strate areas The crystallization substrate "can be a single crystal substrate, such as a single crystal of silicon, germanium, gallium arsenide or other semi¬ conductor, or any other, substrate capable of supporting crystal growth on at least some exposed area of the 5surface. The growth mask is formed from a material which will inhibit nucleation on the growth mask itself but will permit crystalline growth laterally from exposed areas. In the next step of this embodiment, amorphous or polycrystalline semiconductor material is deposited over the mask and exposed areas of the substrate. This might be done, for example, by placing the masked substrate in a -chemical vapor deposition reactor. OMP After the first layer of amorphous semiconductor material has been formed, a second layer is formed of a suitable wetting agent material. This second layer should preferably have a higher melting temperature than the first 5 layer. For example, if the first layer is amorphous sili¬ con, the second layer may comprise Si0 2 . The respective melting points of these materials are Si " -^ 1430 C C and for Si0 2 1700°C. Next, the structure is subjected to a heating 10 cycle by any of several methods to be described in detail later whereby the first layer is caused to melt and then solidify. As it solidifies, single crystal growth is initiated at areas exposed by the mask and lateral epitaxial overgrowth occurs. 15 Figure 2 presents a series of views which schema¬ tically illustrate the production of a continuous thin sheet of mono-crystalline material on a crystallization substrate according to the process of Figure " 1. In Figure 2A, relatively thick crystallization sub- 20 strate 10 is shown. This substrate can be any material capable of supporting crystal growth --thereon. As a typical example of a substrate suitable for growing single crystal silicon thereon, substrate 10 might be a ' slab of single crystal Si in the range of 5-50 mils 25 thick and might be doped or undoped. If the crystalline film produced is to.be separated by cleavage, it is pre¬ ferred, although not essential, that substrate 10 have an orientation so -" that the ' surface of substrate 10 lies in a plane, which is a preferential cleavage plane for - ■" .Q the substrate material. - * * OM As shown in Figure 2B, crystal growth mask 12 is then applied to substrate 10. Mask 12 has a pattern of openings through which substrate 10 is exposed. One typical pattern found to be suitable is a pattern of slits or stripes 14 as shown in Figure 2B. The ratio of width to spacing for slits 14 can be widely varied depending upon the materials, growth conditions, ' required layer thickness, separation techniques employed, etc., and the optimum ratio, which depends on the par- 0 ticular application, can be determined by methods des ¬ cribed in detail in the CLEFT application. Of course, growth masks having patterns of exposed areas other than slits can also be employed. Next, as shown in Figure 2C, a layer 18 of amor- 5 phous or polycrystalline semiconductor material, such as Si, is formed over the mask a.nd extending into the stripes 14, as shown at 16, to contact the exposed single-crystal substrate 10. This layer may be formed by well known means such as by chemical vapor ceposi- tion. Finally, as shown in Figure 2D, a second layer 20 of SiO_, for example, is formed, such . . * * as by Chemical vapor deposition or thermal oxidation, over the first amorphous Si layer._ The structure shown in Figure 2D is then subjected to a heat treatment as will be described in detail, which melts the silicon _ layer 18. The layer 18 then solidifies and single crystal growth is initiated from the interface 16 with ' the epitaxial substrate 10. In other words, epitaxial growth is "seeded" by substrate 10. This growth proceeds laterally from the interfaces 16 until the lateral growths meet to form a continuous layer.. OMP c / Hj IP The function of the second layer 20 may be appre¬ ciated after a consideration of Figure 3 which shows in simplified form the problems encountered with the prior art CLEFT process. In the CLEFT process, no second layer 20 is used, thus when the amorphous silicon layer 18' is melted, the layer tends to agglomerate or "ball-up" as shown in schematic form in Figure 3. In some cases, dis¬ continuities are created between "balls" of material creating islands at 19 of amorphous or polycrystalline material resulting from the interruption of the seeded epitaxial growth from substrate 10. The initial growth at 21 is satisfactory since here the interface is between compatible surface structure, Si to Si, so no agglomera¬ tion occurs. With the addition of a wetting agent layer 20 over layer 18, as in Figure 2, such tendency to agglomerate has been minimized and substantially defect free lateral epitaxial growth has been repeatedly- achieved. Depending on the selection of thermal treatment and other parameters, lateral growths in excess of 1 cm have been achieved and further extension is expected. Apparatus for subjecting the sample prepared in *" » accordance with the invention to an appropriate heat cycle will now be described in connection with Figure 4. In the apparatus of Figure 4 , a 1 x 2 cm sample 34, an exploded section of which is shown schematically in Figure 4b, cut from a wafer prepared in accordance, with Figure 2A-D having the following constituents and dimensions; ' is placed on a graphite cloth strip heater 30, with the Si substrate 10 facing down: OM Si Substrate 10 - 5 cm diameter <100> wafer Si0 2 Mask 12 - 0.2 micron thick formed by thermal oxidation Amorphous Si 18 - 0.8 - 1.0 micron thick deposited 5 in CVD reactor at 610°C Si0 2 Layer 20 - 2 micron thick CVD deposited at 625°C Stripes - 3.5 microns wide and _ to the (11 plane opened in the mask 12 by 0 . photolithographic process. A graphite sheet 32 about 2.5 cm by 2.5 cm is inter- . posed between the cloth heater 30 and the sample to reduce surface morphology defects induced by the weave in the cloth heater. A thermocouple 36 is embedded in . the 5cloth heater 30. The graphite sheet 32 is coated with an insulator (Al- j O--,) -to prevent electrical current- from passing through the sheet. The heating is performed in an inert gas (Argon) environment. The thermal cycle profile, as measured by the 0 thermocouple 36 is shown in Figure 4a (which is a plot of the temperature in- egrees Centigrade versus time in seconds.) The measured temperature is the temperature at the graphite cloth heater 30 and the actual sample temperatures may be different. Still, by maintaining this profile, repeatable results may be attained. Excellent results have also been achieved using the two-step heater approach shown in Figures 5 and 6; in place of the single, stationary heater described in connection with Figure 4. Figure 5 is a schematic diagram of the two-step heater apparatus.. A device to be processed, sample . 34, a portion of which is shewn in the perspective Figure 6, which has been made in accor¬ dance with the previous description; is placed on a lower OMPI strip heater 30 similar to the graphite heater des¬ cribed in connection with Figure 4. The lower heater is energized by means (not shown) and brought to a tem ¬ perature close to the melting point of silicon. Next, the upper strip heater 38, which is movable, in accor¬ dance with well known means not shown is energized to induce melting of a strip zone 36 of silicon 18 under ¬ neath the Si0 2 layer 20. Next, the upper heater 38 is translated past the top surface of sample 34 to cause melting zone 36 to move in unison with the heater 38 to induce zone melting then solidification of the amor¬ phous ' Si layer 18 to achieve lateral epitaxial growth transforming layer 18 into single crystal material. For example, the- lower graphite strip heater may be- resistively heated to 1100-1300°C in about 20 seconds. The upper strip heater is then rapidly heated by apply¬ ing power at a level of about 1 kW. Due to the addi¬ tional heating of the sample 32 by radiation from this upper strip heater, in 20-40 seconds , a portion of the Si film 18 and a portion of the upper surface of the Si substrate 10 are melted in a narrow zone located below the narrow upper strip heater 38. The strip heater may then be manually moved over the sample 34 at a velocity of about 0.5 cm/sec. This rate should be slow enough for the molten zone to traverse the sample at the same rate, as determined by visual observation. When the strip heater and molten zone reach the .far end of the sample, the power to both heaters is switched off. In the apparatus of Figures 5 and 6, the strip heater is scanned in a direction parallel to the stripe openings 16. In some applications, it may be desirable OMPI to scan in a direction perpendicular to a single open ¬ ing 16 and grow a continuous sheet in one direction, as shown in Figure 7; to avoid any problems associated with the intersection of two opposing growth fronts. In the apparatus of Figure 7, the sample is brought close to the melting point of Si, by a lower heater (not shown) . Melting is then induced at the single stripe opening 16 by the upper heater 38 which is aligned parallel to the opening and which moves in the direction of the arrows. *- elting is induced in the stripe opening 16 and then solidification and epitaxial growth of layer 18 continues in the same direction, as the heater 38 traverses the surface of sample 34. It should be noted that the apparatus of Figure 7 5 results in a single continuous insulator over a sub¬ stantial area underlying the single crystal and this is advantageous in the production of integrated circuits. The crystalline orientation of the growth layer 18 is determined by the orientation of the substrate 16. For example, if the substrate 16 is aligned in the (100) plane then the layer 18 will grow oriented in the (100) plane. Figure 8 shows an external seed embodiment of the invention. In this embodiment no stripe 16 is required in insulative mask layer 12. Instead, there is a single continuous substrate 10. Since the substrate 10 is not used for seeding, it need not be a single crystal sub¬ strate but may be amorphous or polycrystalline silicon, or any suitable material for supporting a subsequent active semiconductor layer. After the polycrystalline or amorphous Si layer 18 is formed on SiO~ layer 12 by any of the many well known means, an SiO layer 20 is formed on top of Si layer 18 to serVe as a wetting agent layer, as previously described. However, at a-convenient location on the surface of the top layer 20 of Si0 2 , such as at the edge, a portion of layer 20 is removed leaving a convoluted edge 82 on the layer 20. An external seed 80 in the form of a volume of single crystal silicon is disposed on top of layer 20 so as to partly overlie the convoluted edge 82. The sample 34 is heated up as in previous disclosed embodiments to a temperature near the melting point of silicon by a lower strip heater (not shown) . Next, the, upper strip heater 38 is energiz.ed to bring the sample 34 to a temperature which will cause melting of the Si layer 18 in the zone adjacent to the heater .38. The - convolutions at this edge permit the radiant energy from the heater 38 to more readily pass to the Si .layer 18 beneath layer 20, thus making it easier to start melting layer 18. Next, the heater 38 is translated past the sample, in the direction of the arrows, by mov ¬ ing either the heater or sample with respect to one another. This causes the melted zone to move across the sample causing melting and solidification of layer 18. - The layer 18 solidifies in a single crystalline state derived from external seed 80. "- It should be noted that with an external seed, the n ecessity for the single crystal Si substrate is obviated. Accordingly, Figures 9 and 10, show alternative embodi¬ ments of an externally seeded lateral epitaxially grown structure on a insulative layer, such as Si0 2 layer 12'. In the Figure 9 embodiment, the wetting agent layer 20 is formed over the seed after the seed 80 has been disposed on the amorphous Si layer 18"; so the entire seed is encapsulated. In Figure 10, both the amorphous Si layer 18* and the Si0 2 wetting agent layer 20 are forr ** .ed over - URE OMP the seed 80 after the seed has been placed on the SiO-, insulating substrate 12'. It is to be understood that the samples described in Figures 9 and 10 are then sub¬ jected to a heat treatment as described in connection 5 with the previous embodiments to convert the amorphous Si layer 18' to an epitaxial silicon layer seeded by single crystal seed 80. In the apparatus thus far described, only a single wetting agent layer of Si0 2 has been utilized. In the embodiment shown in Figure 11 an additional layer 40 of silicon nitride , Si,N. has been formed, such as by CVD, over the Si0 2 layer 20, In all other respect ' s, the sample 42 is identical to the sample in Figure 2D and is heat treated in the same fashion. The added Si, ^ 5 layer appears to further enhance the wetting properties of the composite structure as compared to a- single layer of SiO-,. This additional Si-^N, layer may be located as shown in Figure 2D on top of the Si0 2 layer or it may be located below the SiO-, layer adjacent the Si p layer 18. Optionally, it may be found desirable in some appli¬ cations, to form the wetting agent on top of- the Siθ2 insulating mask as shown in Figure 11a, wherein parts corresponding to those in Figure 11 are similarly . numbered. Thus, there is shown in Figure 11a, a sili¬ con substrate 10 of single crystal material from which is formed an oxide insulative mask of silicon dioxide 12 and on top of silicon dioxide mask 12 is formed a layer of silicon nitride which may serve as a wetting agent during the transformation of silicon amorphous or polycrystalline silicon layer 18 to an epitaxial crystalline layer. The silicon nitride may be formed on layer 12 b any of the well known means, such as chamical vapor deposition, sputtering, etc. On top of amorphous or polycrystalline- silicon 5 layer 18, "a first we ' tting agent layer of silicon dio is formed as in previous embodiments. The sample, as shown in Figure 11a, is then subjected to a heat trea ment process, as previously described, which converts the amorphous or polycrystalline silicon layer 18 to 0 an epitaxial silicon layer in accordance with the cry talline structure of silicon substrate 10 by lateral, epitaxial growth from seeded solidi ication. A recessed SiO_ lateral epitaxy by seeded solidi¬ fication embodiment is shown in Figures 12A-E. This 5produces a planar epitaxial structure as contrasted to ' prior embodiments which, although shown in planar fashi actually form sligh plateaus" at the stripes where the axial growth is initiated. In this embodiment, a stri of silicon nitride 52 is formed by well known means on a single crystal silicon substrate 50 as shown in " Figure 12A. Next, the sample 60 is subjected to a the mal oxidation process to form a layer 54 " of Si0 2 over the Si substrate 50 as shown in Figure 12B. Then the Si3 N 4 is selectively etched by ion beam or chemical * etching, leaving channels 56 of exposed Si between a l 54 of Si0 2 , as shown in Figure 12C. Now the sample 60 is subjected " to a surface etch to remove the oxide unt the surface becomes flat as shown in Figure 12D. Fin¬ ally, as shown in Figure 12E, an amorphous Si layer 56 is formed on the sample 60 and a cap of Si0 2 is formed over layer 56 to produce the planar structure shown in O Figure 12E. The sample is then ready for heat treatment as previously described, to convert the amorphous Si laye 56 to epitaxy. In addition to the advantage of the planar epitaxial structure offered by the process and apparatus of Figure 12, it should be noted that melting only has to proceed down to the top surface of Si0 2 layer 54 since the single crystal substrate interface is co-extensive with the top of the Si0 2 layer 54. This is in contrast to the Figure 2 embodiment wherein the Si substrate interface is co ¬ extensive with the bottom of Si0 2 layer 12. Thus, less power can be employed. Also, there may be a lesser tendency for crystal defects to occur because the growth occurs at the planar surface rather than at the recessed surface of Figure 2D. Figure 13B shows a partial schematic of a three ele- ment semiconductor device fabricated on an Si0 2 substrate manufactured in accordance with the process described herein. The device of Figure 13B is a MOSFET with LOCOS oxide isolation. MOSFET stands for Metal Oxide Semi¬ conductor Field Effect Transistor. LOCOS stands for Local Oxidation of Silicon. A MOSFET is a well known device which is made in large quantities in the United States and elsewhere. Figure 13A illustrates how to form a MOSFET in accordance with the present invention. First a silicon substrate 8p of single crysatlline silicon is oxidized forming a silicon dioxide mask 82. A layer of amorphous or polycrystalline silicon material 83 is then formed on the Si0 2 mask 82 and wetting agent layer 90 of Si0 2 is formed on first layer 83. The amorphous or polycrystal¬ line layer 83 is then transformed by heat treatment sub¬ stantially to an epitaxial layer or film 83 in accordance with the previously described embodiments. The Si0 2 wetting agent layer is then removed, for example, by chemical etching. Next, as shown in Figure 13B, the active region 83 of the device is isolated from other active ' regions (not shown) by the LOCOS oxide 84 formed in a well known manner. A thermal oxide layer 85 is then formed on the surface of the active Si layer 83. A polysilicon gate 89 is formed by chemical vapor deposition on the oxide layer 85. This gate 89 is defined by photolithography 0 and etching techniques. Windows are then opened on the gate oxide layer 85 for the introduction of suitable dopants by ion implantation into the source region 94 and drain region 92 of the active region 83. Finally, contacts for the source, gate and drain elements are formed by aluminum metallization. It should be emphasized that the Figure 13B device is only one of many type integrated circuit or semi¬ conductor structures that could be formed using the process herein disclosed. Referring now to Figures 14-16, a further embodi¬ ment of the invention will be described which siσni-r_ ficantly differs from the previously described embodi¬ ments in that the layer being recrystallized does not have to be in physical contact with the crystallization seed during the commencement of the application of a melting temperature. In this embodiment of the inven¬ tion, the process may be generally described as follows, as shown in Figure 14. First, a crystallization substrate is formed. This crystallization substrate may be substantially similar to the previously described sinqle crystalline substrate of Fig. 10 of Figure 2. Next, an insulating layer, such as Si0 2 , is formed over the entire substrate. There is no necessity to use chemical etching to provide openings in this insu¬ lating layer, such as those provide in layer 12 of Fig. 2B previously described. After the insulating first layer is formed over the substrate, a second layer of polycrystalline or amorphous material is formed by well known means on the insulating layer. This second layer is the layer that is to be recrystallized to 0 form an epitaxial growt in accordance with the teach¬ ings of the invention. This layer may, for example, be amorphous silicon, such as the layer 18 described in connection with Fig. 2C. A third and fourth layer is then formed over the second layer of a material preferably having a higher melting temperature than the second layer. These third and fourth layers are the wetting agent layers, previously described, and may comprise an Si0 2 layer followed by an Si^N^ layer. The end result is a structure such as that described pre- viously in connection with Fig. 11, except that no openings are provided in the Si0 2 insulating layer 12. The next step is to fabricate an opening through the first, second, third and fourth layers down to the substrate, preferably this may be done by mechanically scribing the sample down to the substrate. It should be noted that for ease in fabrication, mechanical scrib¬ ing has been utilized for the preferred embodiment. However, the invention is not intended to be so limited and other means of forming openings, such as masking, etching, laser scribing, and other equivalents, are con¬ templated for use herein. Next, the sample is subjected to a temperature which causes the second layer to melt and solidify, co - mencing at the opening to the substrate and laterally epitaxially growing a crystalline structure along the second layer of single crystal material. As may be seen in Figure 15, the process apparatus is very much similar to that described in connection with Figure 5. A wafer 34, having a cross-sectional shape and construction, as shown in Figure 16, and fab¬ ricated in accordance with the method of Figure 14, is placed on a lower strip heater 30. The lower heater is 0energized by means (not shown) and brought to a tempera¬ ture close to the melting point of the silicon. Next, the upper strip heater 38, which is movable, in accordance with well known means (not shown) , is energized to induce melting of a strip zone 36 of sili- con 18 underneath the Si,N. and Si0 2 layers 40 and 20, respectively. Next, the upper heater.38 is translated pass the top surface of sample 34, commencing at or before the scribed area 100 to cause melting zone 36 to move in uni- son with the heater 38 to induce zone melting then solidi¬ fication of the amorphous silicon layer 18, thereby achieving lateral epitaxial growth and transforming layer 18 into single crystal material. Preferably, the heater apparatus is disposed in a stainless steel chamber with ports for access. The cham¬ ber may preferably be water cooled. The bottom graphite heater 30, in a typical application, is about 7 inches long by 4 inches wide and .04 inches thick. The upper heater is about 4.5 inches long by .04 inches wide and .1 inch thick. The wafer may be 2-3 inches in diameter and about .015 inches thick and rests in a circular depres¬ sion of either 2 or 3 inches diameter and about .01 inch deep at the center of the lower heater 30 (as shown in Figure 15) . The upper heater should be located about 1 " mm above the surface of wafer 34. OMPI A computer controller motor (not shown) , causes the upper heater to scan across the wafer. Both heaters are resistively heated by alternating currents of up to a few hundred amperes that are monitored and controlled by a microprocessor. Temperatures at the center and two edges of the wafer are monitored by well known thermocouples embedded in a lower heater. The silicon wafer 34, as shown in the cross-sectional view of Figure 16, are single crystal <10 > wafers 10 over- coated with a thermal Si0 2 layer about 1 micrometers thick, as indicated by the numeral 12. A silicon film of 0.5 micrometers thick 18 is deposited by chemical vapor deposition over the entire Si0 2 and Si layers. Next, a silicon nitrate and Si0 2 encapsulant is deposited by well known means on the silicon layer 18. The Si0 2 layer is labelled 20 and the Si3N. layer is labelled 40. After the wafer is constructed, as above, an opening down to -the single crystal substrate 10 is produced, preferably by mechanically scribing the wafer, as shown at 100 in Figures 15 and 16. The scribe may be either parallel to the <100> flat, as shown in Figure 16, or it may be disposed 45° with the flat along the <10Q> plane. The scribe has been measured to be about 5-8 micrometers deep with a cross-sectional shape, as shown in Figure 16. The scribe opening allows the single crystal sili¬ con substrate 10 to provide a convenient seed for the recrystallization of the amorphous silicon layer 18, as long as the zone-melting process is initiated from a surface of the wafer prior to the scribe opening. In other words., the zone-melting process should commence at or before the scribe opening 100 is reached. Then, as molten zone 36 reaches or occurs at the scribe open¬ ing 100, there is a certain amount of mass flow that moves down the scribe opening and upon solidification, the silicon substrate 10 is connected with the silicon film 18. Various geometries of scribe openings 100 have been found to be successful, including a semi¬ circular scribe opening around the edge of the wafer, thereby allowing a larger area of the wafer to be seeded. Using this seeding technique, lateral epitaxial seeded solidification films of over * 4 square inches have been obtained with no large angle grain boundaries. In summary, we have shown a method and apparatus for routine controllable recrystallization of Si films on Si0 2 coated silicon wafers of at least 3 inches in diameter. The method and apparatus of Figures 14-16 has the advantage that the resultant structure is planar with¬ out resorting to the complex recess process described in connection with Figures 12A-E. " Furthermore, if the scribing technique is used, it avoids the need for pho¬ tolithography, as required in the apparatus of Figures 2A-D. Note that as with previous embodiments, it may be preferable to etch away the wetting agent- layers 40 and 20 after the active Si epitaxial layer 18 has been formed, before further processing the body. As stated earlier, the present processes and apparatus of any of the previously related embodiments is not limited to silicon. For example, gallium arsenide may be converted by this process from an amorphous or polycrystalline state to an epitaxial state. Suitable wetting agent films or layers for gallium arsenide are silicon dioxide Si0 2 , silicon nitride Si 3 N., or tungsten or molybdinu . Similarly, " germanium may be converted from an amorphous or OMP - J . WΪF polycrystalline state to an epitaxial crystal film by the previously described process. In the germanium embodiment, a suitable wetting agent would comprise silicon nitride, molybdinum or tungsten. Also, in addition to the previously mentioned wetting agents useful in connection with silicon, either carbon or silicon carbide may be found useful as wetting agents in connection with the conversion of silicon from polycrystalline to an epitaxial film. 0 In general, we have found that suitable wetting agents are those with a high enough melting point to avoid being melted during the transformation process, and which have limited interaction with the film being transformed but have sufficient enough interaction to serve as a "wetting agent" as heretofore defined. Equivalents There are many equivalents to the embodiments specifically described herein and such equivalents are intended to be covered by the following claims. For example, although amorphous or polycrystalline ' films or layers are referred to in many instances, the terms films and layers are meant to be interchangeable. Also, the seed material need not comprise the entire portion of the substrate but only the areas in contact with the films or layers being crystallized. Indeed, the seed need not be a part of the substrate, but may be formed in the " film by local crystallization, such as, by local heat treatment. Additionally, the seed material need not be of identical composition with the material being crystallized. Thus, amorphous germanium may be seeded by single crystal silicon. OMPI Furthermore, while growth has been shown as propa¬ gating laterally based on perpendicular movement of the heating source, with respect to the stripe opening, it may be advantageous in some applications to move the heating element in an oblique direction with re¬ spect to the stripe opening. The heating elements heretofore described have comprised graphite elements; however, electron beam, laser beam or other radiant sources are contemplated for use herein.

Claims: Clai s 1. A method of forming a semiconductor body comprising: (a) forming an insulating first layer ' over a crystallization substrate; (b) forming a second layer of amorphous or poly¬ crystalline material over the first layer; (c) forming an opening in said first and second layer to expose a portion of said substrate; (d) heating said layers to melt a portion of the second layer; (e) solidifying the second layer to transform the second layer material to large grain substantially single crystal material, the crystallinity of said second layer being influenced by the crystallization substrate. 2. A method of forming a semiconductor body comprising: (a) forming an insulating first layer over a crystallization substrate; (b) forming a second layer of amorphous or polycrystalline material over the first layer; - . . . (c) forming a third layer over said first and second layers; (d) forming an opening in said first, second, and third layers to expose a portion of said substrate; (e) heating said layers to melt a portion of the second layer; (f) solidifying the second layer to transform the second layer material to large grain substantially single crystal material, the crystallinity of said second layer being influenced by the crystallization substrate. ' 3. A method of Claim 2 wherein the substrate is a single crystal material. 4. A method of Claim 2 wherein the opening is scribed. 5. A method of Claim 2 wherein a fourth layer is formed adjacent said third layer to enhance the wetting properties of the combined third and fourth layers. 6. A method Of Claim 2 wherein the first -layer is Si0 2 , the second layer is deposited Si, the third layer is Si0 2 and the substrate is single crystal Si. 7. The method of Claim 6 wherein the third layer is removed after step (f) . 8. The method of Claim 1 wherein the layers are heated to the melting temperature of the second layer .by an adjacent graphite strip heater. 9. The method of Claim 1 in which a first heater brings the body to a temperature slightly below the melting point of the second layer material and a second heater is translated across the surface OMF of the body commencing at an area prior to the opening to bring a zone of material in said second layer to its melting point and translating such melted zone along said layer whereby lateral epitaxial growth of the material in said layer is achieved by seeded solidification from the crystallization substrate. 10. A method of Claim .5 wherein the substrate is Si and the second layer is Si and the third and fourth layers are Si0 2 , Si 3 N 4 , C or SiC. 11. A method of Claim 2 wherein said third layer is formed of a material which is a wetting agent for said second layer. 12. A method of forming a semiconductor body - comprising: (a) forming a first layer of amorphous or polycrystalline material over but not in contact with a substrate; (b) said substrate comprising single crystal material; (c) providing an opening through said first layer to the substrate; (d) heating said first layer to melt the first layer; (e) solidifying the first layer to transform the layer material to large grain sub¬ stantially single crystal material seeded by said substrate. OMPI -so¬ ls. The method of Claim 12 including the step of (f) forming a second layer adjacent and in contact over a substantial portion of said first layer, said second layer com- prising material adapted to serve as a wetting agent with respect to said first layer and said substrate and wherein the opening in step (c) extends through both the first and second layers. 14. A semiconductor device made in accordance with the method of Claim 2 after removing said third layer and forming the active region of the semiconductor device in the epitaxial region thus exposed. 15. A device made in accordance with the method of Claim 2 after removing portions of said third layer and forming the active region of said device in the epitaxial layer exposed. 16. A semiconductor body comprising: (a) a first layer of amorphous or polycrystalline material adjacent a single crystal substrate but not in contact therewith; (b) an opening in said first layer exposing a portion of the substrate; (c) said first layer being adapted to melt and solidify thereby to transform the layer material to large grain substantially single crystal material seeded from the exposed region of the substrate. OMPI 82/00465 - 31- 17. The semiconductor body of Claim 16 wherein the first layer and the substrate is silicon. ' 18. The semiconductor body of Claim 16 in which the substrate and the first layer is GaAs. 19. The semiconductor body of Claim 16 in which the substrate and the first layer is Ge. 20. The semiconductor body of Claims 16, 17 or 18 in which a second wetting layer is added over the first layer and a third insulating layer is dis- posed intermediately the first layer and the substrate. 21. The body of Claim 19 in which the second and third layers are SiO-,. 22. A method of forming a semiconductor body comprisin (a) forming a first layer of amorphous or poly ¬ crystalline material over a substrate; (b) disposing a single crystalline seed material adjacent a surface of said layer; (c) forming a second layer over a substantial portion of said first layer; (d) heating said first layer to melt the first layer; - (e) solidifying the first layer to transform the first layer material to large grain substan- tially single crystal material, the crystal- Unity of said first layer being influenced by the- seed material. ' UHE —2H£ " -32- 23. A method of Claim 22 wherein the seed material is included in the substrate. 24. method of Claim 22 wherein the seed material is disposed in contact with a portion of said second layer and a portion of said first layer. 25. method of Claim 22 wherein a third layer is formed adjacent said second layer to enhance the wetting properties of the combined s ' econd and third layers. 26. A method of Claim 23 wherein a growth mask layer is formed between the substrate and the first layer and selectively exposed to permit the first layer to contact the seed material. 27. The method of Claim 22 wherein the layer is heated to its melting temperature by an adjacent graphite strip heater. 28. The method of Claim22 in which a first heater brings the body to a temperature slightly below the melt ¬ ing point of the first layer material and a second heater is translated across the surface of the body to bring a zone of material in said first layer to its melting point and translating such melted zone along said layer whereby lateral epitaxial growth of the material in said layer is achieved by seeded solidification from said seed material. i A 29. A method of Claim 26wherein the growth mask layer is recessed in the substrate such that the first layer forms a continuous planar sheet on the growth layer and seed material. 30. A method of Claim 22 wherein the seed material is Si aanndd the second layer is " SiO. Si 3 4 C or SiC. 31. A method of Claim 22 wherein the seed material is Ge and the second layer is Si^N,, tungsten or molybdenum. 32. A method of Claim 22wherein the seed material is GaAs and the second-layer is Si0 2 , Si.,N., tungsten or molybdenum. 33. A method of. Claim 22 wherein said second layer is formed of a material which is a wetting agent for said first layer. 34. A method of Claim 23 wherein a growth mask layer is formed between the substrate and the first layer and selectively exposed to permit the first layer to contact the seed material and a wetting agent material is incorporated in the second layer. - US^ OMP • WW • 34- 35. The method of Claim 33 in which a first heater brings the body to a temperature slightly below the melting point of the first layer material and a second heater is translated across the surface of the body to bring a zone of material in said first layer to its melting point and translating such melted zone along said layer whereby lateral epitaxial growth of the material in said layer is achieved by seeded solid ¬ ification from said seed material. 36- A method of Claim 34 wherein the growth mask layer is an insulator recessed in the substrate and the first layer forms a continuous planar sheet on the growth layer and seed material. 37. A semiconductor device made in accordance with the method of Claim 22 after removing portions of said second layer and forming the active region of the semiconductor device in the epitaxial region thus exposed. 38. A three element semiconductor device made in accor¬ dance with the method of Claim22 after removing por¬ tions of said second layer and forming the active region of said device in the epitaxial layer exposed. OMP 39. A semiconductor body comprising: (a) a first layer of amorphous or polycrystalline material formed over a substrate; (b) seed material disposed adjacent a surface of said layer; (c) a second layer over a substantial portion of said first layer; (d) said first layer being adapted to melt and solidify thereby to transform the layer mater¬ ial to large grain substantially single crystal material. 40. The semiconductor body of Claim 39 λvherein the first layer is silicon and the second layer is Si0 2 , Si--,N. , C or SiC. 41. The semiconductor body of Claim 39 in which the first layer is GaAs and the second layer is Si0 2 , Si-,N,, tungsten or molybdenum.. ' 42. The semiconductor body of Claim 39 in which the first layer is Ge and the second layer is Si-,N. , tungsten or molybdenum. 43. A method of forming a semiconductor body comprising: (a) forming a first layer of amorphous or poly ¬ crystalline material over a substrate; (b) disposing a single crystalline seed material adjacent a surface of said layer and in contact with at least a portion of said first layer; (c) . forming a second layer adjacent and in con¬ tact over a substantial portion of said first layer, said second layer comprising material adapted to serve as a wetting agent with respect to said first layer and said substrat (d) heating said first layer to melt the first layer; (e) solidifying the first layer to transform the" layer material to large grain substantially single crystal material.

Inventors: FAN JOHN C, GEIS MICHAEL W, TSAUR BOR YEU
Applicants: MASSACHUSETTS INST TECHNOLOGY, MASSACHUSETTS INST TECHN
Application year: 1982
Main classification: C30B13
IPC codes: C30B13, C30B27, H01L21