US3896765A - Apparatus for liquid-phase epitaxial growth - Google Patents

Apparatus for liquid-phase epitaxial growth Download PDF

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US3896765A
US3896765A US295554A US29555472A US3896765A US 3896765 A US3896765 A US 3896765A US 295554 A US295554 A US 295554A US 29555472 A US29555472 A US 29555472A US 3896765 A US3896765 A US 3896765A
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bore
solution
inner member
substrate
recess
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US295554A
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Kozo Ariga
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Priority claimed from JP7905271A external-priority patent/JPS5137142B2/ja
Priority claimed from JP46100523A external-priority patent/JPS5137144B2/ja
Priority claimed from JP9153672A external-priority patent/JPS531036B2/ja
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    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B19/00Liquid-phase epitaxial-layer growth
    • C30B19/06Reaction chambers; Boats for supporting the melt; Substrate holders
    • C30B19/064Rotating sliding boat system
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B19/00Liquid-phase epitaxial-layer growth
    • C30B19/06Reaction chambers; Boats for supporting the melt; Substrate holders
    • C30B19/061Tipping system, e.g. by rotation
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B19/00Liquid-phase epitaxial-layer growth
    • C30B19/06Reaction chambers; Boats for supporting the melt; Substrate holders
    • C30B19/065Multiple stacked slider system

Definitions

  • ABSTRACT An apparatus for liquid-phase epitaxial growth of a semiconductor including a crucible comprising an outer member having a cylindrical large bore at the upper end thereof and at least one substrate-carrying recess at the bottom wall of the large bore, and a cylindrical basic inner member snugly and slidably accommodated in the bore and having a solutioncontaining bore at the lower end wall thereof which contacts with the bottom of the bore.
  • a method for liquid-phase epitaxial growth of a hetero-epitaxial layer comprising: holding at least two solutions each containing at least one material in containers, respectively; placing a substrate in a chamber filled with an inert gas or evacuated; heating the solutions and the substrate; contacting one of the solutions on the upper surface of the other solution so that one solution diffuses into the other solution toward the lower surface of the other solution; contacting the substrate to the lower surface of the other solution; and cooling the solutions and substrate, whereby a hetero-epitaxial layer is formed on the substrate.
  • the present invention relates to apparatus for epitaxial growth of semiconductor material and more particularly to a method and an apparatus for liquid-phase epitaxial growth of semiconductor material.
  • liquid-phase epitaxial growth method which were developed by Nelson in 1964 has been highly utilized for producing semiconductive crystallines for electron devices. The particular method is especially effective for manufacturing wafers for a photoemissive diode or the like which is susceptible to the property of the wafer.
  • Various improved methods and apparatus of liquid-phase epitaxial growth of semiconductive material have been developed, one of which method is disclosed in US. Pat. No. 3,565,702 for producing an epitaxial multi-layer. Another method is disclosed in US. Pat. No. 3,560,276 for growing an epitaxial GaAlAs layer on an n-type GaAs substrate. More recently, an improved apparatus was disclosed in Applied Physics Letters, volume 17, page 109, which epitaxially grows a multi-layer. However, these methods and apparatus are not, in practice, fully acceptable.
  • FIG. 1 is a sectional view of a crucible according to the invention.
  • FIGS. 2A through 2C are respectively top end, perspective and sectional views of an outer member of the crucible of FIG. 1.
  • FIGS. 3A through 3C are respectively top end, perspective and sectional views of an inner member of the crucible of FIG. 1.
  • FIG. 4 is a sectional view of the crucible of FIG. 1 the members of which are upset and decoupled for the sake of explanation of assembling the crucible.
  • FIG. 5 is a sectional view of another crucible according to the invention.
  • FIGS. 6A through 6D are sectional, top end, bottom end and perspective views of a part of the crucible of FIG. 5.
  • FIG. 7 is a bottom end views of another part corresponding to the part shown in FIGS. 6A through 6D.
  • FIG. 8 is a sectional view of another crucible according to the invention.
  • FIGS. 9A and 9B, 9C and 9D, and 9E and 9F are sectional and top end views of parts of the crucible of FIG. 8, respectively.
  • FIGS. 10A and 10B are sectional views of another crucible according to the invention.
  • FIGS. 11A and 11B are sectional views of another crucible according to the invention.
  • FIG. 12 is a sectional view of another crucible according to the invention.
  • FIGS. 13A through 13F are side views and sectional views of parts of the crucible of FIG. 12 which is disassembled.
  • FIG. 14 is a cross sectional views of another crucible according to the invention.
  • the crucible 10 comprises an outer member 11 preferably formed cylindrical and having at the upper end thereof a cylindrical large bore 12 with a clear and flat bottom 13.
  • a substrate-carrying recess 14 having, for example, a deepness of about 1 mm is formed at a portion of the bottom 13 excluding the central point.
  • a substrate 15 on which an epitaxial layer is to be grown is accommodated in the recess 14.
  • the substrate-carrying recess 14 may have a form suitable for receiving the substrate 15.
  • the inner member 17 has a solution-containing bore 18 at a portion of the lower end wall thereof excluding the central axis thereof. Although the bore 18 is formed at such portion as abovestated, it is sufficient that the bore 18 is formed at such a portion of the lower end wall of the inner member 17 that the bore shut by the remaining portion of the bottom 13 other than the recess 14.
  • the bore 18 preferably has a diameter larger than that of the recess 14.
  • a solution 19 containing one or more semiconductive materials to be grown on the substrate 15 is carried in the bore 18.
  • a small passageway 20 is formed in the inner member 17, communicating the upper portion of the bore 18 with the lower end of the inner member 17.
  • the passageway 20 is convenient for relieving an inert gas substituting air in the bore 18 when the inert gas expands due to the heating up of the crucible 10.
  • a small rectangular recess 21 is formed at the upper end of the inner member 17 for the rotation or locking of the member 17. The surfaces of the bottom 13 and the lower end wall of the inner member 17 should be so clear as to fluid-tightly contact with each other thereby to prevent the solution contained in the bore 18 to unwantedly contact with the substrate 15.
  • the inner member 17 When the crucible is heated up to the desired temperature, the inner member 17 is rotated through about 180 relative to the outer support member 11 so that the solution 19 is brought into contact with the substrate 15 and, thereupon, the temperature of the furnace is reduced so as to make the semiconductive materials in the solution 19 deposits on the substrate 15 as an epitaxial layer.
  • the furnace tube since the crucible only rotates but does not move axially of the furnace, it is sufficient for the furnace tube to have such a short constant temperature zone that the constant temperature zone can be readily maintained by a relatively small heater. Further, since the solution 19 hermetically confined in the bore 18, the composition of the solution 19 is desiredly maintained. Furthermore, although the inner member 17 is shown to have only one solution-containing bore 18, the inner member 17 may have a plurality of solution containing bores so as to make a epitaxial multi layer on the substrate 15.
  • FIGS. 5, and 6A through 6D illustrate another crucible 30 according to the invention, which comprises an outer support member 11 having at the upperend a large bore of, in this case, a relatively large depth, a cylindrical basic inner member 17 accommodated in the large bore 12, and additional members 17a, 17b, 17c, and 17d which are piled up with one another in the order named, are slidably accommodated in the large bore 12 and interposed between the bottom 13 of the large bore 12 and the basic inner member 17.
  • the outer support member 1 1 has the same construction as that of the outer member of the crucible 10 except that the outer member 11 further has a stop projection 31 at an edge portion of the bottom 13.
  • the basic inner member 17 has the same construction as that of the inner member of the crucible 10 except that the member 17 has an arcuated guide groove 32 extending through an edge portion of the lower end wall thereof.
  • a solution 19 containing a source material is carried by the solution-containing bore 18 of the inner member 17.
  • the additional inner members 17a, 17b, 17c and 17d respectively have the same constructions as that of the basic inner member 17 except that these members respectively have stop projections 31a, 31b, 31c and 31d at edge portions thereof.
  • the stop projections 31, 31a through 31d engage with the guide grooves 32a, 32b, 32c 32d and 32.
  • Solutions 19a, l9b, 19c and 19d each containing a source material are carried by bores 18a, l8b, 18c and 18d of the additional members 17a, 17b, 17c and 17d. It should be understood that the upper and lower ends of the additional members 17a through 1711 are finished so as to make intimate contacts between neighbouring ones of the inner members.
  • the crucible 30 is assembled in the same manner as the crucible 10 as explained with reference to FIG. 4.
  • the assembled crucible 30 is then placed in a suitable furnace tube such as a quartz furnace tube, which is heated up by a heater.
  • a suitable furnace tube such as a quartz furnace tube
  • the inner members 17, 17a, 17b, 17c and 17d are rotated through the recess 21 so that the exposed face of the substrates 15, a, 15b, 15c and 15d are flooded with the solutions 19a, 19b, 19c, 19d and 19.
  • the crucible 30 is cooled, so that the source materials in the solutions respectively grow on the flooded faces of the substrates 15, 15a, 15b, 15c and 15d.
  • this crucible 30 can produce a plurality of epitaxial layers at one time, the crucible 30 is useful for mass-production process of the epitaxial wafers.
  • FIG. 7 illustrates another form of additional inner member 17x which has the same construction as that of each additional inner member of the crucible 30 except that the additional member 17x has two solution containing bores 18x and 18y.
  • a plurality of such additional members 17x are assembled with one another in the same manner as the crucible 30 of FIG. 5.
  • the resultant crucible including the additional inner members 17x is heated in the same manner so that epitaxial multi layer are grown on the substrates place in the recesses 14x.
  • an improved method of epitaxially growing a heteroepitaxial layer on a substrate comprises, holding at least two solutions each containing at least one source material in containers, respectively; placing a substrate in a chamber evacuated or filled with an inert gas; heating the solutions and said substrate up to a desired temperature; contacting one of the solutions on the upper surface of other solution so that one solution diffuses into the other solution toward the lower surface of the other solution; contacting the substrate to the lower surface of the other solution; and cooling the solutions and substrate, whereby a hetero-epitaxial layer is formed on the substrate.
  • the resultant hetero-epitaxial layer has a preferred crystal structure without crystal lattice defect and has continuously varying concentrations of source materials.
  • FIGS. 8, and 9A through 9F there is shown a preferred crucible 40 carrying out the above-stated method, which comprises an outer support member 41 preferably formed cylindrical and having at the upper end thereof a cylindrical large bore 42 with a clear and flat bottom 43.
  • a substrate-carrying recess 44 having, for example, a deepness of 1 mm is formed at a portion of the bottom 43 excluding the central point.
  • a substrate 45 on which an epitaxial layer is to be deposited is placed in the recess 44.
  • the recess 44 may have a form appropriate for carrying the substrate 45.
  • a small rectangular recess 46 At the lower end wall of the outer support member 41 is formed a small rectangular recess 46 to be engaged with a drive rod (not shown) for the rotation or locking of the outer support member 41.
  • An inner member 47 is snugly and slidably accommodated in the large bore 42.
  • the inner member 47 has a first solution containing bore 48a at a portion of the lower end thereof excluding the central axis thereof.
  • the inner member 47 further has a second solution containing bore 48b at another portion of the lower end thereof excluding the central point of the end wall.
  • Each of the bore 480 and 48b preferably has generally the same largeness as that of the recess 44.
  • the second solution containing bore 48b is shut by a barrier plate 50 having a plurality of small openings.
  • a small rectangular recess 51 is formed at the upper end wall of the inner member 47 for the rotation or locking of the member 47.
  • a cylindrical intermediate inner member 60 is snugly and slidably accommodated in the large bore 42 of the outer support member 41 and interposed between the bottom wall 43 and the lower end of the inner member 47.
  • the intermediate member 60 has a bore 61 extending from the upper to lower end walls.
  • the communication bore 61 extends through a portion excluding the central axis of the intermediate inner member 60.
  • the diameter of the bore 61 is preferably the same as that of the recess 44. It should be understood the surfaces of the members 41, 47 and 60 contacting other members are clearly finished so as to make fluid-tight contact between those members.
  • a stopper projection is formed at an edge portion of the bottom 43, an arcuate guide recess to be engaged with the stop projection is formed at an edge portion of the lower end of the intermediate member 60.
  • a stopper projection is formed at an edge portion of the upper end of the intermediate member 60 and an arcuate guide recess to be engaged with the stopper projection of the intermediate member 60 is formed at the lower end of the member 47.
  • a substrate 45 on which a heteroepitaxial layer is to be grown is placed in the recess 44 and first and second solutions 49a and 49b respectively containing different source materials are carried 49a and 49b in the bores 48a and 48b through a similar procedure as explained with reference toFIG. 5.
  • the intermediate inner member 60 is so positioned that the lower open end of the bore 48a is shut by the bottom 43 and the inner member 47 is so positioned that the first solution containing bore 48a communicates with the communication bore 61 as shown in FIG. 10A, whereby the communication bore 61 is filled with the first solution 49a.
  • the second solution containing bore 48b is shut by the upper end wall of the intermediate inner member 60.
  • the outer support member 41 is, for example, rotated through a certain angle so that the substrate carrying recess 44 confronts the lower open end of the communication bore 61, whereby the exposed surface of the substrate 45 flooded with the solution 49a.
  • the inner member 47 is rotated through a certain angle for example about 180 so that the lower open end of the second bore 48b communicates by way of the plate 50 with the communication bore 61, whereby the second solution contacts through the plate 50 with the first solution.
  • the crucible 40 is gradually cooled by reducing the temperature of the furnace tube, while the second solution diffuse through the openings of the plate 50 into the first solution, whereby concentration gradient is established in the solution in the communication bore 61.
  • concentration gradient is established in the solution in the communication bore 61.
  • the barrier plate 50 with small openings suppresses the diffusion rate of the second solution into the first solution whereby the resultant epitaxial layer has desired composition rates.
  • the largeness of the openings of the barrier plate 50 is desiredly selected in dependence on the diffusion rate of one solution into another.
  • the members 41, 47 and 60 are formed to have stop projections and guide grooves similar to those of the members of the crucible 30 of FIG. 5, so as to make easy the above-stated positioning of the members 41, 47 and 60.
  • FIG. 11A there is shown another crucible according to the invention, which has the same construction as the crucible 40 of FIG. 8 except that the crucible 70 does not includes a barrier plate corresponding to the plate 50 of the crucible 40.
  • the crucible 70 is placed in a suitable furnace tube (not shown) and heated up to a desired temperature. Thereafter, the members of the crucible are positioned as shown in FIG. 11B, and cooled so as to grow the source materials contained in the first and second solutions on the substrate 45.
  • This crucible 70 is useful when the first and second solutions have generally the same specific gravities. This is because the second solution gradually diffuses into the first solution even if the solutions contact direct with each other. Solutions having generally the same specific gravities are, for example, GaP containing In or In? containing In.
  • an apparatus including a crucible of FIG. 10A or 11A is advantageous 1. That, when a signal epitaxial layer is grown, the remaining source material floating on the upper surface of the solution is preferably removed through the rotation of the intermediate member 60 thereby to avoid unwanted influence by the remaining source material, and the thickness of the epitaxial layer can be controlled by changing the thickness of the intermediate member. It is possible to obtain an epitaxial layer of a thickness less than I micron-meter by reducing the thickness of the intermediate member in spite of such a layer temperature change as several tens degrees in Centigrade.
  • the resultant epitaxial layer is composed of the composition where the parameters x and/or y varies along the direction of depth of the epitaxial layer.
  • the apparatus is capable of producing a hetero-epitaxial layer of high quality even ifthe source materials have largelydifferent lattice coefficients.
  • That the mixing rate of the solutions can be desiredly selected by selecting the largeness of the openings of the barrier plate.
  • That the invention apparatus is capable of producing any junction or an epitaxial layer of a ternary or compound consisting of 4 elements by forming a third solution-containing bore in the basic inner member 47.
  • FIGS. 12, and 13A through 13F show another crucible according to the invention, which is generally designated by a reference numeral 80 and comprises an outer support member 81 having a cylindrical bore 82 with a bottom wall 83.
  • the outer support member 81 has in the side wall thereof solution-containing chamber 84 for carrying a solution 85 containing one or more source materials.
  • the chamber 84 communicates with the cylindrical bore 82 through a plurality of openings 86 formed in the inner side wall of the bore 82 at a predetermined pitch.
  • a rectangular locking emboss 87 is formed at a portion of the bottom 83.
  • a cylindrical inner bottom member 88 is snugly and slidably accommodated in the deepest portion of the bore 82.
  • the bottom member 88 has at one end wall thereof a rectangular locking recess 89 which then engages with the locking emboss 87 and at a central portion of the other end wall thereof a cylindrical coupling emboss 90.
  • a cylindrical substrate-carrying recess 91 At a portion of the other end wall of the bottom member 88 other than the central portion is formed a cylindrical substrate-carrying recess 91, which may be otherwise formed so as to favourably receive a substrate 92 on which one or more epitaxial layers are to be grown.
  • One or more cylindrical inner intermediate members 93 are slidably and snugly accommodated in the bore 82, each of which has a coupling recess 94 at the left end wall thereof and a coupling emboss 95 at the right end wall thereof.
  • the intermediate members 92 are coupled with one another through the coupling recess and emboss 94 and 95, and the leftmost one of the intermediate members 93 is coupled with bottom member 88.
  • Each intermediate members 93 has a cylindrical solution-containing recess 96 at the left end wall and a cylindrical substrate-carrying recess 97 at the right end wall thereof.
  • the solution-containing and substrate-carrying recesses 96 and 97 may be otherwise formed, if desired.
  • the solution containing recess 96 communicates with an opening 98 formed at the peripheral wall of the member 93.
  • a cylindrical inner cap member 99 is snugly and slidably accommodated in the bore 82 and disposed on the rightmost one of the intermediate members 93.
  • the cap member 99 has at the light end wall a coupling recess 100 which couples with the coupling emboss 95 of the rightmost intermediate member.
  • the cap member 99 has at the left end wall a cylindrical solution containing recess 101 which communicates with an opening 102 formed in the peripheral wall of the cap member 99 as seen more clearly in FIG. 13E.
  • the cap member 99 has at the right end wall thereof a rectangular drive recess 103 for receiving a drive rod (not shown) which is rotated desiredly.
  • the thicknesses of the bottom, intermediate and cap members 88, 93 and 99 are so selected that the openings 98 and 102 confront and communicated with the openings 86 of the inner wall of the bore 82. It should be understood that a suitable locking mechanism (not shown) for limiting rotation angles of the inner members 93 relative to neighbouring ones is provided.
  • the thus assembled crucible is positioned in a suitable furnace tube (not shown) which is horizontally positioned.
  • the outer support member 81 is first so positioned that the chamber 84 locates at the lower most position and a solution containing one or more source suitable is poured into the chamber 84.
  • the inner members 88, 93 and 99 are, on the other hand, so positioned through the drive rod engaged with the recess 103 that the inner members hermetically contact with one another and the openings 98 and 102 confront and communicate with the opening 86.
  • the heated solution 85 enters the solution containing recesses 96 and 101 of the inner members 93 and 99 through the openings 86, 98 and 102. Thereupon, the intermediate members 93 and the cap member 99 are respectively rotated at certain angles so that the solution containing recess of the inner members confront the corresponding substrate carrying recess, respectively, whereby the substrates are flooded with the solution carried by the corresponding solution containing recess.
  • the crucible 80 is then cooled at a certain rate with the result that source materials contained in the solution 85 epitaxially grows on every substrate.
  • FIG. 14 illustrates another crucible according to the invention, which is generally designated by a reference numeral and comprises an outer support member 111 having a cylindrical bore 112 formed therein, and inner member assembly snugly and slidably accommodated the bore 112 and constituted by the same inner bottom, intermediate and cap members as those of the crucible 80 shown in FIGS. 12, and 13A through 13F.
  • the outer support member 111 has a plurality of solution-containing members 1 14 formed in the side wall of the outer support member 111 and each having the same construction as that of the chamber 84 of the crucible 80. Inlets of chambers 114 are shutted by the closure member 115 surrounding the outer support member 111, so that the solutions carried in the chambers 114 are prevented to flow out of the chambers 114.
  • the crucible 110 is placed in a furnace tube and desiredly heated.
  • the chambers 114 contain different solutions of different source materials and similar operation in the case of the crucible 80 are repeated so as to grow epitaxial multi-layers.
  • the crucible 80 and 110 are capable of growing a plurality of epitaxial layers of uniform properties since the layers grow at the same time in the same crucible.
  • An outer member having therein a cylindrical large bore opened at the upper end thereof and at least one substrate-carrying recess at the bottom wall of said large bore;
  • a cylindrical basic inner member snugly and slidably accommodated in said large bore and having at least two solution-containing bores at the lower end portion thereof excluding the central axis thereof, and opening toward said bottom wall of said large bore;
  • a barrier plate with a plurality of openings mounted at the open end of one of said solution containing bores.
  • said means includes a first stopper projection formed on the bottom wall of said large bore, an arcuate recessed portion formed at the edge of the lower end of said intermediate inner member and engaged with said first stopper projection, a second stopper projection formed at the upper end of said intermediate inner member, and an arcuate recessed portion formed at the edge of the lower end of said basic inner member and engaged with said second stopper projection.
  • an outer member having therein a cylindrical large bore opened at the upper end thereof and at least one substrate-carrying recess at the bottom wall of said bore;
  • At least one cylindrical additional inner member having upper and lower end walls, snugly slidably accommodated in said large bore and interposed between said basic inner member and said bottom wall of said large bore, said additional inner member having at least one solution-containing bore at said lower end wall thereof and opening toward said bottom wall of said large bore, and a substratecarrying recess at said upper end wall thereof and opening toward said lower end wall of said basic inner member.
  • said means includes a first stopper projection formed on said bottom wall of said large bore, an arcuate recessed portion formed at the edge of said lower end wall of said additional inner member and engaged with said first stopper projection, a second stopper projection formed at the upper end wall of said additional inner member, and an arcuate recess portion formed at the edge of the lower end wall of said basic inner member and engaged with said second stopper projection.
  • an outer support member having therein a cylindrical large bore opened at one end thereof and at least one solution containing chamber in the side wall of said bore, said chamber communicating with said bore through at least two openings formed in said side wall;
  • a cylindrical bottom member snugly and slidably accommodated in the deepest portion of said large bore and having at one end wall thereof opposite to the bottom of said large bore a substratecarrying recess for carrying therein a substrate;
  • a cylindrical inner cap member snugly and slidably accommodated in said bore and contacted through one end wall thereof with the other end wall of said intermediate inner member, said cap member having at said one end wall a solution-containing recess communicating through the other of said openings with said solution-containing recess.
  • said outer support member has at the bottom wall of said bore a rectangular locking emboss
  • said bottom member has at the other end thereof a rectangular locking recess engagable with said locking emboss
  • said bottom member has a coupling emboss at said one end wall
  • said intermediate member has on said one end wall a coupling recess engageable with said coupling emboss of said bottom member
  • said intermediate member has an coupling emboss on said other end wall thereof
  • said cap member has on said one end thereof a coupling recess engageable with said coupling emboss of the intermediate member.
  • an outer member having therein a cylindrical large bore opened at the upper end thereof and at least one substrate-carrying recess at said bottom wall of said bore;
  • a cylindrical basic inner member snugly and slidably accommodated in said bore and having a solutioncontaining bore at a lower wall thereof and opening toward said bottom wall and with an end wall, said inner member including a small passageway extending therethrough from a portion near to the end wall of said solution-containing bore to said lower wall of said inner member.

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

An apparatus for liquid-phase epitaxial growth of a semiconductor including a crucible comprising an outer member having a cylindrical large bore at the upper end thereof and at least one substrate-carrying recess at the bottom wall of the large bore, and a cylindrical basic inner member snugly and slidably accommodated in the bore and having a solutioncontaining bore at the lower end wall thereof which contacts with the bottom of the bore. A method for liquid-phase epitaxial growth of a hetero-epitaxial layer, comprising: holding at least two solutions each containing at least one material in containers, respectively; placing a substrate in a chamber filled with an inert gas or evacuated; heating the solutions and the substrate; contacting one of the solutions on the upper surface of the other solution so that one solution diffuses into the other solution toward the lower surface of the other solution; contacting the substrate to the lower surface of the other solution; and cooling the solutions and substrate, whereby a hetero-epitaxial layer is formed on the substrate.

Description

United States Patent [191 Ariga July 29, 1975 APPARATUS FOR LIQUID-PHASE EPlTAXIAL GROWTH [75] Inventor: Kozo Ariga, Kadoma, Japan [73] Assignee: Matsushita Electric Industrial Co.,
Ltd., Kadoma, Japan [22] Filed: Oct. 6, 1972 [21] Appl. No.: 295,554
[30] Foreign Application Priority Data om. 6, 1971 Japan 46-79052 Dec. 10, 1971 Japan..... 46-100523 Sept. 11, 1972 Japan 47-91536 [52] US. Cl. 118/412; 118/415; 118/421; 118/426; 148/171 [51] Int. Cl. B05c 3/18 [58] Field of Search 118/412, 415, 421, 422, 118/426; 148/171, 172; 206/5 A [56] References Cited UNITED STATES PATENTS 3,115,146 12/1963 Erwin 206/5 A X 3,690,965 9/1972 Bergh et a1. 118/415 X 3,765,959 10/1973 Unno et a1. 118/415 X OTHER PUBLICATIONS IBM Technical Disclosure Bulletin, Vol. 13, No. 11, April 1971, Blum et a1.
Primary ExaminerJohn P. McIntosh [57] ABSTRACT An apparatus for liquid-phase epitaxial growth of a semiconductor including a crucible comprising an outer member having a cylindrical large bore at the upper end thereof and at least one substrate-carrying recess at the bottom wall of the large bore, and a cylindrical basic inner member snugly and slidably accommodated in the bore and having a solutioncontaining bore at the lower end wall thereof which contacts with the bottom of the bore.
A method for liquid-phase epitaxial growth of a hetero-epitaxial layer, comprising: holding at least two solutions each containing at least one material in containers, respectively; placing a substrate in a chamber filled with an inert gas or evacuated; heating the solutions and the substrate; contacting one of the solutions on the upper surface of the other solution so that one solution diffuses into the other solution toward the lower surface of the other solution; contacting the substrate to the lower surface of the other solution; and cooling the solutions and substrate, whereby a hetero-epitaxial layer is formed on the substrate.
9 Claims, 33 Drawing Figures PATENTEUJULZSIQYS 3.896.765
SHEET PATENTEI] JUL29 1975 SW 3 3. 8 9 6 76 5 PATENTEUJULZQISYS 3,896,765
SHEET 6 Fig. /2
PATENTED JUL 2 9 I975 SHEET APPARATUS FOR LIQUID-PHASE EPITAXIAL GROWTH The present invention relates to apparatus for epitaxial growth of semiconductor material and more particularly to a method and an apparatus for liquid-phase epitaxial growth of semiconductor material.
The liquid-phase epitaxial growth method which were developed by Nelson in 1964 has been highly utilized for producing semiconductive crystallines for electron devices. The particular method is especially effective for manufacturing wafers for a photoemissive diode or the like which is susceptible to the property of the wafer. Various improved methods and apparatus of liquid-phase epitaxial growth of semiconductive material have been developed, one of which method is disclosed in US. Pat. No. 3,565,702 for producing an epitaxial multi-layer. Another method is disclosed in US. Pat. No. 3,560,276 for growing an epitaxial GaAlAs layer on an n-type GaAs substrate. More recently, an improved apparatus was disclosed in Applied Physics Letters, volume 17, page 109, which epitaxially grows a multi-layer. However, these methods and apparatus are not, in practice, fully acceptable.
It is therefore a primary object of the present invention to provide an improved apparatus for liquid-phase epitaxial growth of semiconductive material which has a so short controlled temperature zone that a favourable epitaxial layer or wafer is produced.
It is another object of the invention to provide an apparatus for liquid-phase epitaxial growth which is suitable for mass-productive process.
It is a further object of the invention to provide an apparatus for liquid-phase epitaxial growth each of which are desirable for growing a hetero-epitaxial layer.
It is a still further object of the invention to provide an apparatus for liquid-phase epitaxial growth which is compact and simple in construction.
These and other objects and the attendant advantages of the invention will become more readily appreciated as the same becomes better understood by reference to the following detailed description when taken in conjunction with the accompanying drawings in which:
FIG. 1 is a sectional view of a crucible according to the invention.
FIGS. 2A through 2C are respectively top end, perspective and sectional views of an outer member of the crucible of FIG. 1.
FIGS. 3A through 3C are respectively top end, perspective and sectional views of an inner member of the crucible of FIG. 1.
FIG. 4 is a sectional view of the crucible of FIG. 1 the members of which are upset and decoupled for the sake of explanation of assembling the crucible.
FIG. 5 is a sectional view of another crucible according to the invention.
FIGS. 6A through 6D are sectional, top end, bottom end and perspective views of a part of the crucible of FIG. 5.
FIG. 7 is a bottom end views of another part corresponding to the part shown in FIGS. 6A through 6D.
FIG. 8 is a sectional view of another crucible according to the invention.
FIGS. 9A and 9B, 9C and 9D, and 9E and 9F are sectional and top end views of parts of the crucible of FIG. 8, respectively.
FIGS. 10A and 10B are sectional views of another crucible according to the invention.
FIGS. 11A and 11B are sectional views of another crucible according to the invention.
FIG. 12 is a sectional view of another crucible according to the invention.
FIGS. 13A through 13F are side views and sectional views of parts of the crucible of FIG. 12 which is disassembled.
FIG. 14 is a cross sectional views of another crucible according to the invention.
Like numerals refer to like or corresponding parts in the views.
Referring now to the drawings and more specifically to FIGS. 1 and 3A through 3C, there is shown a crucible 10 of an apparatus for liquid-phase epitaxial growth according to the invention. The crucible 10 comprises an outer member 11 preferably formed cylindrical and having at the upper end thereof a cylindrical large bore 12 with a clear and flat bottom 13. A substrate-carrying recess 14 having, for example, a deepness of about 1 mm is formed at a portion of the bottom 13 excluding the central point. A substrate 15 on which an epitaxial layer is to be grown is accommodated in the recess 14. The substrate-carrying recess 14 may have a form suitable for receiving the substrate 15. At the lower end wall of the outer member 11 is formed a small rectangular recess 16 for receiving a drive rod (not shown) for the rotation or locking of the outer support member 11. An inner member 17 is snugly and slidably accommodated in the large bore 12. The inner member 17 has a solution-containing bore 18 at a portion of the lower end wall thereof excluding the central axis thereof. Although the bore 18 is formed at such portion as abovestated, it is sufficient that the bore 18 is formed at such a portion of the lower end wall of the inner member 17 that the bore shut by the remaining portion of the bottom 13 other than the recess 14. The bore 18 preferably has a diameter larger than that of the recess 14. A solution 19 containing one or more semiconductive materials to be grown on the substrate 15 is carried in the bore 18. A small passageway 20 is formed in the inner member 17, communicating the upper portion of the bore 18 with the lower end of the inner member 17. The passageway 20 is convenient for relieving an inert gas substituting air in the bore 18 when the inert gas expands due to the heating up of the crucible 10. A small rectangular recess 21 is formed at the upper end of the inner member 17 for the rotation or locking of the member 17. The surfaces of the bottom 13 and the lower end wall of the inner member 17 should be so clear as to fluid-tightly contact with each other thereby to prevent the solution contained in the bore 18 to unwantedly contact with the substrate 15.
Before coupling the outer support member 11 and the inner member 17, these members 11 and 17 are upset as shown in FIG. 4. The solution 19 is poured into the bore 18 and the substrate 15 is placed on a portion of the end wall of the member 17 corresponding to the recess 14 and thereafter the members 11 and 17 are coupled with each other. The coupled members 11 and 17 are again upset so that the members 11 and 17 serve as the crucible 10 shown in FIG. 1. The crucible 10 is then placed in a suitable furnace (not shown) such as .a quartz furnace tube and heated up to a desired temperature. When the crucible is heated up to the desired temperature, the inner member 17 is rotated through about 180 relative to the outer support member 11 so that the solution 19 is brought into contact with the substrate 15 and, thereupon, the temperature of the furnace is reduced so as to make the semiconductive materials in the solution 19 deposits on the substrate 15 as an epitaxial layer.
It should be, in this instance, noted that since the crucible only rotates but does not move axially of the furnace, it is sufficient for the furnace tube to have such a short constant temperature zone that the constant temperature zone can be readily maintained by a relatively small heater. Further, since the solution 19 hermetically confined in the bore 18, the composition of the solution 19 is desiredly maintained. Furthermore, although the inner member 17 is shown to have only one solution-containing bore 18, the inner member 17 may have a plurality of solution containing bores so as to make a epitaxial multi layer on the substrate 15.
FIGS. 5, and 6A through 6D illustrate another crucible 30 according to the invention, which comprises an outer support member 11 having at the upperend a large bore of, in this case, a relatively large depth, a cylindrical basic inner member 17 accommodated in the large bore 12, and additional members 17a, 17b, 17c, and 17d which are piled up with one another in the order named, are slidably accommodated in the large bore 12 and interposed between the bottom 13 of the large bore 12 and the basic inner member 17. The outer support member 1 1 has the same construction as that of the outer member of the crucible 10 except that the outer member 11 further has a stop projection 31 at an edge portion of the bottom 13. The basic inner member 17 has the same construction as that of the inner member of the crucible 10 except that the member 17 has an arcuated guide groove 32 extending through an edge portion of the lower end wall thereof. A solution 19 containing a source material is carried by the solution-containing bore 18 of the inner member 17. The additional inner members 17a, 17b, 17c and 17d respectively have the same constructions as that of the basic inner member 17 except that these members respectively have stop projections 31a, 31b, 31c and 31d at edge portions thereof. The stop projections 31, 31a through 31d engage with the guide grooves 32a, 32b, 32c 32d and 32. Solutions 19a, l9b, 19c and 19d each containing a source material are carried by bores 18a, l8b, 18c and 18d of the additional members 17a, 17b, 17c and 17d. It should be understood that the upper and lower ends of the additional members 17a through 1711 are finished so as to make intimate contacts between neighbouring ones of the inner members.
The crucible 30 is assembled in the same manner as the crucible 10 as explained with reference to FIG. 4. The assembled crucible 30 is then placed in a suitable furnace tube such as a quartz furnace tube, which is heated up by a heater. When the crucible 30 is heated up to a desired temperature through the furnace tube, the inner members 17, 17a, 17b, 17c and 17d are rotated through the recess 21 so that the exposed face of the substrates 15, a, 15b, 15c and 15d are flooded with the solutions 19a, 19b, 19c, 19d and 19. Thereupon, the crucible 30 is cooled, so that the source materials in the solutions respectively grow on the flooded faces of the substrates 15, 15a, 15b, 15c and 15d.
It is, in this instance, to be noted that since this crucible 30 can produce a plurality of epitaxial layers at one time, the crucible 30 is useful for mass-production process of the epitaxial wafers.
FIG. 7 illustrates another form of additional inner member 17x which has the same construction as that of each additional inner member of the crucible 30 except that the additional member 17x has two solution containing bores 18x and 18y. A plurality of such additional members 17x are assembled with one another in the same manner as the crucible 30 of FIG. 5. The resultant crucible including the additional inner members 17x is heated in the same manner so that epitaxial multi layer are grown on the substrates place in the recesses 14x.
In accordance with the present invention, an improved method of epitaxially growing a heteroepitaxial layer on a substrate is provided. The particular method comprises, holding at least two solutions each containing at least one source material in containers, respectively; placing a substrate in a chamber evacuated or filled with an inert gas; heating the solutions and said substrate up to a desired temperature; contacting one of the solutions on the upper surface of other solution so that one solution diffuses into the other solution toward the lower surface of the other solution; contacting the substrate to the lower surface of the other solution; and cooling the solutions and substrate, whereby a hetero-epitaxial layer is formed on the substrate.
It is to be noted that since the solutions are contact with each other, the solutions are gradually and continuously mixed with each other, thereby causing a desired hetero-epitaxial layer is grown on the substrate. The resultant hetero-epitaxial layer has a preferred crystal structure without crystal lattice defect and has continuously varying concentrations of source materials.
In FIGS. 8, and 9A through 9F, there is shown a preferred crucible 40 carrying out the above-stated method, which comprises an outer support member 41 preferably formed cylindrical and having at the upper end thereof a cylindrical large bore 42 with a clear and flat bottom 43. A substrate-carrying recess 44 having, for example, a deepness of 1 mm is formed at a portion of the bottom 43 excluding the central point. A substrate 45 on which an epitaxial layer is to be deposited is placed in the recess 44. The recess 44 may have a form appropriate for carrying the substrate 45. At the lower end wall of the outer support member 41 is formed a small rectangular recess 46 to be engaged with a drive rod (not shown) for the rotation or locking of the outer support member 41. An inner member 47 is snugly and slidably accommodated in the large bore 42. The inner member 47 has a first solution containing bore 48a at a portion of the lower end thereof excluding the central axis thereof. The inner member 47 further has a second solution containing bore 48b at another portion of the lower end thereof excluding the central point of the end wall. Each of the bore 480 and 48b preferably has generally the same largeness as that of the recess 44. The second solution containing bore 48b is shut by a barrier plate 50 having a plurality of small openings. A small rectangular recess 51 is formed at the upper end wall of the inner member 47 for the rotation or locking of the member 47. A cylindrical intermediate inner member 60 is snugly and slidably accommodated in the large bore 42 of the outer support member 41 and interposed between the bottom wall 43 and the lower end of the inner member 47. The intermediate member 60 has a bore 61 extending from the upper to lower end walls. The communication bore 61 extends through a portion excluding the central axis of the intermediate inner member 60. The diameter of the bore 61 is preferably the same as that of the recess 44. It should be understood the surfaces of the members 41, 47 and 60 contacting other members are clearly finished so as to make fluid-tight contact between those members. Although not illustrated in FIGS. 8 through 9F for the simplicity of illustration, a stopper projection is formed at an edge portion of the bottom 43, an arcuate guide recess to be engaged with the stop projection is formed at an edge portion of the lower end of the intermediate member 60. A stopper projection is formed at an edge portion of the upper end of the intermediate member 60 and an arcuate guide recess to be engaged with the stopper projection of the intermediate member 60 is formed at the lower end of the member 47.
In operation, a substrate 45 on which a heteroepitaxial layer is to be grown is placed in the recess 44 and first and second solutions 49a and 49b respectively containing different source materials are carried 49a and 49b in the bores 48a and 48b through a similar procedure as explained with reference toFIG. 5. Firstly, the intermediate inner member 60 is so positioned that the lower open end of the bore 48a is shut by the bottom 43 and the inner member 47 is so positioned that the first solution containing bore 48a communicates with the communication bore 61 as shown in FIG. 10A, whereby the communication bore 61 is filled with the first solution 49a. In this condition, the second solution containing bore 48b is shut by the upper end wall of the intermediate inner member 60.
When the crucible 40 and the solutions 49a and 49b are desiredly heated up, the outer support member 41 is, for example, rotated through a certain angle so that the substrate carrying recess 44 confronts the lower open end of the communication bore 61, whereby the exposed surface of the substrate 45 flooded with the solution 49a. Thereafter, the inner member 47 is rotated through a certain angle for example about 180 so that the lower open end of the second bore 48b communicates by way of the plate 50 with the communication bore 61, whereby the second solution contacts through the plate 50 with the first solution. Thereupon, the crucible 40 is gradually cooled by reducing the temperature of the furnace tube, while the second solution diffuse through the openings of the plate 50 into the first solution, whereby concentration gradient is established in the solution in the communication bore 61. When this condition is maintained, a hetero-epitaxial layer grows on the substrate 45 having a gradually varied composition rate.
It should be noted that the barrier plate 50 with small openings suppresses the diffusion rate of the second solution into the first solution whereby the resultant epitaxial layer has desired composition rates. In addition, the largeness of the openings of the barrier plate 50 is desiredly selected in dependence on the diffusion rate of one solution into another.
It may be apparent that when the solution 49a and 49b contain the same source materials, respectively, a homo-epitaxial layer grows on the substrate 45.
It should be now understood that the members 41, 47 and 60 are formed to have stop projections and guide grooves similar to those of the members of the crucible 30 of FIG. 5, so as to make easy the above-stated positioning of the members 41, 47 and 60.
In FIG. 11A, there is shown another crucible according to the invention, which has the same construction as the crucible 40 of FIG. 8 except that the crucible 70 does not includes a barrier plate corresponding to the plate 50 of the crucible 40. The crucible 70 is placed in a suitable furnace tube (not shown) and heated up to a desired temperature. Thereafter, the members of the crucible are positioned as shown in FIG. 11B, and cooled so as to grow the source materials contained in the first and second solutions on the substrate 45. This crucible 70 is useful when the first and second solutions have generally the same specific gravities. This is because the second solution gradually diffuses into the first solution even if the solutions contact direct with each other. Solutions having generally the same specific gravities are, for example, GaP containing In or In? containing In.
It should be now appreciated that an apparatus including a crucible of FIG. 10A or 11A is advantageous 1. That, when a signal epitaxial layer is grown, the remaining source material floating on the upper surface of the solution is preferably removed through the rotation of the intermediate member 60 thereby to avoid unwanted influence by the remaining source material, and the thickness of the epitaxial layer can be controlled by changing the thickness of the intermediate member. It is possible to obtain an epitaxial layer of a thickness less than I micron-meter by reducing the thickness of the intermediate member in spite of such a layer temperature change as several tens degrees in Centigrade.
2. That since the barrier plates restricts the contact area between the first and second solutions so as to suppress the diffusion rate of one into another, the liquidphase epitaxial growth of either a ternary composition expressed by a general form A B M such as Ga A1,,As, In Ga Cd I-Ig Te and Pb Sn Te or a composition consisting of 4 elements expressed by a general form A B M Ny. The resultant epitaxial layer is composed of the composition where the parameters x and/or y varies along the direction of depth of the epitaxial layer. The apparatus is capable of producing a hetero-epitaxial layer of high quality even ifthe source materials have largelydifferent lattice coefficients. Furthermore, it is easy in the invention apparatus to regulate the proportions of the source materials in the epitaxial layer even in the care of Ga Al As or cd Hg Te, although it has been difficult'in the conventional apparatus to regulate the proportions of the components in the epitaxial layer when the source materials have lattice coefficients slightly different from each other.
3. That it is impossible to obtain p-n junction, p -p junction or n -n junction either by selecting the thickness of the intermediate member 60 or by changing the concentration or kind of dopant of the source material to be contained in the solution, and to obtain any type of junction, for example, graded, abrupt and step junctrons.
4. That the mixing rate of the solutions can be desiredly selected by selecting the largeness of the openings of the barrier plate.
5. That the invention apparatus is capable of producing any junction or an epitaxial layer of a ternary or compound consisting of 4 elements by forming a third solution-containing bore in the basic inner member 47.
6. That it is possible to pile up a plurality of crucibles the same as the crucible 70 so as to produce a plurality of epitaxial layers at one time, since the height of the crucible 70 is, in practice, smaller than mm because of such a small depth of the solution as 5 to 8 mm.
FIGS. 12, and 13A through 13F show another crucible according to the invention, which is generally designated by a reference numeral 80 and comprises an outer support member 81 having a cylindrical bore 82 with a bottom wall 83. The outer support member 81 has in the side wall thereof solution-containing chamber 84 for carrying a solution 85 containing one or more source materials. The chamber 84 communicates with the cylindrical bore 82 through a plurality of openings 86 formed in the inner side wall of the bore 82 at a predetermined pitch. A rectangular locking emboss 87 is formed at a portion of the bottom 83. A cylindrical inner bottom member 88 is snugly and slidably accommodated in the deepest portion of the bore 82. The bottom member 88 has at one end wall thereof a rectangular locking recess 89 which then engages with the locking emboss 87 and at a central portion of the other end wall thereof a cylindrical coupling emboss 90. At a portion of the other end wall of the bottom member 88 other than the central portion is formed a cylindrical substrate-carrying recess 91, which may be otherwise formed so as to favourably receive a substrate 92 on which one or more epitaxial layers are to be grown. One or more cylindrical inner intermediate members 93 are slidably and snugly accommodated in the bore 82, each of which has a coupling recess 94 at the left end wall thereof and a coupling emboss 95 at the right end wall thereof. The intermediate members 92 are coupled with one another through the coupling recess and emboss 94 and 95, and the leftmost one of the intermediate members 93 is coupled with bottom member 88. Each intermediate members 93 has a cylindrical solution-containing recess 96 at the left end wall and a cylindrical substrate-carrying recess 97 at the right end wall thereof. The solution-containing and substrate-carrying recesses 96 and 97 may be otherwise formed, if desired. As seen more clearly in FIG. 13C, the solution containing recess 96 communicates with an opening 98 formed at the peripheral wall of the member 93. A cylindrical inner cap member 99 is snugly and slidably accommodated in the bore 82 and disposed on the rightmost one of the intermediate members 93. The cap member 99 has at the light end wall a coupling recess 100 which couples with the coupling emboss 95 of the rightmost intermediate member. The cap member 99 has at the left end wall a cylindrical solution containing recess 101 which communicates with an opening 102 formed in the peripheral wall of the cap member 99 as seen more clearly in FIG. 13E. The cap member 99 has at the right end wall thereof a rectangular drive recess 103 for receiving a drive rod (not shown) which is rotated desiredly. The thicknesses of the bottom, intermediate and cap members 88, 93 and 99 are so selected that the openings 98 and 102 confront and communicated with the openings 86 of the inner wall of the bore 82. It should be understood that a suitable locking mechanism (not shown) for limiting rotation angles of the inner members 93 relative to neighbouring ones is provided.
In operation, the thus assembled crucible is positioned in a suitable furnace tube (not shown) which is horizontally positioned. The outer support member 81 is first so positioned that the chamber 84 locates at the lower most position and a solution containing one or more source suitable is poured into the chamber 84. The inner members 88, 93 and 99 are, on the other hand, so positioned through the drive rod engaged with the recess 103 that the inner members hermetically contact with one another and the openings 98 and 102 confront and communicate with the opening 86. When the crucible 80 is heated desiredly and the solution 85 and the substrate in the recess 97 are also heated sufficiently, the outer support member 81 together with the inner members are rotated until the chamber 84 moves up to the highest position as shown in FIG. 12. The heated solution 85 enters the solution containing recesses 96 and 101 of the inner members 93 and 99 through the openings 86, 98 and 102. Thereupon, the intermediate members 93 and the cap member 99 are respectively rotated at certain angles so that the solution containing recess of the inner members confront the corresponding substrate carrying recess, respectively, whereby the substrates are flooded with the solution carried by the corresponding solution containing recess. The crucible 80 is then cooled at a certain rate with the result that source materials contained in the solution 85 epitaxially grows on every substrate.
FIG. 14 illustrates another crucible according to the invention, which is generally designated by a reference numeral and comprises an outer support member 111 having a cylindrical bore 112 formed therein, and inner member assembly snugly and slidably accommodated the bore 112 and constituted by the same inner bottom, intermediate and cap members as those of the crucible 80 shown in FIGS. 12, and 13A through 13F. The outer support member 111 has a plurality of solution-containing members 1 14 formed in the side wall of the outer support member 111 and each having the same construction as that of the chamber 84 of the crucible 80. Inlets of chambers 114 are shutted by the closure member 115 surrounding the outer support member 111, so that the solutions carried in the chambers 114 are prevented to flow out of the chambers 114.
The crucible 110 is placed in a furnace tube and desiredly heated. The chambers 114 contain different solutions of different source materials and similar operation in the case of the crucible 80 are repeated so as to grow epitaxial multi-layers.
It is to be noted that the crucible 80 and 110 are capable of growing a plurality of epitaxial layers of uniform properties since the layers grow at the same time in the same crucible.
What is claimed is:
1. In an apparatus for liquid-phase epitaxial growth of a semiconductor, the improvement comprises:
An outer member having therein a cylindrical large bore opened at the upper end thereof and at least one substrate-carrying recess at the bottom wall of said large bore;
a cylindrical basic inner member snugly and slidably accommodated in said large bore and having at least two solution-containing bores at the lower end portion thereof excluding the central axis thereof, and opening toward said bottom wall of said large bore;
a cylindrical intermediate inner member accommodated in said large bore and interposed between said basic inner member and the bottom wall of said large bore, said intermediate inner member having a communication bore extending from upper to lower ends for establishing communication between one of said two solution-containing bores and said substrate-carrying recess; and
a barrier plate with a plurality of openings mounted at the open end of one of said solution containing bores.
2. The improvement as defined in claim 1, which further comprises means for defining relative rotation extent of said outer, basic and intermediate inner members with respect to one another.
3. The improvement as defined in claim 2, in which said means includes a first stopper projection formed on the bottom wall of said large bore, an arcuate recessed portion formed at the edge of the lower end of said intermediate inner member and engaged with said first stopper projection, a second stopper projection formed at the upper end of said intermediate inner member, and an arcuate recessed portion formed at the edge of the lower end of said basic inner member and engaged with said second stopper projection.
4. In an apparatus for liquid-phase epitaxial growth of a semiconductor, the improvement comprises:
an outer member having therein a cylindrical large bore opened at the upper end thereof and at least one substrate-carrying recess at the bottom wall of said bore;
a cylindrical basic inner member snugly and slidably accommodated in said bore and having a solutioncontaining bore at the lower end wall thereof and opening toward said bottom wall of said large bore;
at least one cylindrical additional inner member having upper and lower end walls, snugly slidably accommodated in said large bore and interposed between said basic inner member and said bottom wall of said large bore, said additional inner member having at least one solution-containing bore at said lower end wall thereof and opening toward said bottom wall of said large bore, and a substratecarrying recess at said upper end wall thereof and opening toward said lower end wall of said basic inner member.
5. The improvement as defined in claim 4 which further comprises:
means for defining relative rotation extent of said outer, basic inner and additional inner members with respect to one another.
6. The improvement as defined in claim 5, in which said means includes a first stopper projection formed on said bottom wall of said large bore, an arcuate recessed portion formed at the edge of said lower end wall of said additional inner member and engaged with said first stopper projection, a second stopper projection formed at the upper end wall of said additional inner member, and an arcuate recess portion formed at the edge of the lower end wall of said basic inner member and engaged with said second stopper projection.
7. In an apparatus for liquid-phase exitaxial growth of a semiconductor material, the improvement comprises:
an outer support member having therein a cylindrical large bore opened at one end thereof and at least one solution containing chamber in the side wall of said bore, said chamber communicating with said bore through at least two openings formed in said side wall;
a cylindrical bottom member snugly and slidably accommodated in the deepest portion of said large bore and having at one end wall thereof opposite to the bottom of said large bore a substratecarrying recess for carrying therein a substrate;
at least one cylindrical intermediate inner member snugly and slidably accommodated in said bore and placed on said bottom member, said intermediate member having at one end wall contacting with said bottom member a solution containing recess communicable through one of said openings with said solution-containing chamber, and having at the other end wall a substrate-carrying recess for carrying a substrate; and
a cylindrical inner cap member snugly and slidably accommodated in said bore and contacted through one end wall thereof with the other end wall of said intermediate inner member, said cap member having at said one end wall a solution-containing recess communicating through the other of said openings with said solution-containing recess.
8. The improvement as claimed in claim 7, in which said outer support member has at the bottom wall of said bore a rectangular locking emboss, said bottom member has at the other end thereof a rectangular locking recess engagable with said locking emboss, and said bottom member has a coupling emboss at said one end wall, said intermediate member has on said one end wall a coupling recess engageable with said coupling emboss of said bottom member, and said intermediate member has an coupling emboss on said other end wall thereof, and said cap member has on said one end thereof a coupling recess engageable with said coupling emboss of the intermediate member.
9. In an apparatus for liquid-phase epitaxial growth of a semiconductor, the improvement comprises:
an outer member having therein a cylindrical large bore opened at the upper end thereof and at least one substrate-carrying recess at said bottom wall of said bore; and
a cylindrical basic inner member snugly and slidably accommodated in said bore and having a solutioncontaining bore at a lower wall thereof and opening toward said bottom wall and with an end wall, said inner member including a small passageway extending therethrough from a portion near to the end wall of said solution-containing bore to said lower wall of said inner member.

Claims (9)

1. In an apparatus for liquid-phase epitaxial growth of a semiconductor, the improvement comprises: An outer member having therein a cylindrical large bore opened at the upper end thereof and at least one substrate-carrying recess at the bottom wall of said large bore; a cylindrical basic inner member snugly and slidably accommodated in said large bore and having at least two solution-containing bores at the lower end portion thereof excluding the central axis thereof, and opening toward said bottom wall of said large bore; a cylindrical intermediate inner member accommodated in said large bore and interposed between said basic inner member and the bottom wall of said large bore, said intermediate inner member having a communication bore extending from upper to lower ends for establishing communication between one of said two solution-containing bores and said substrate-carrying recess; and a barrier plate with a plurality of openings mounted at the open end of one of said solution containing bores.
2. The improvement as defined in claim 1, which further comprises means for defining relative rotation extent of said outer, basic and intermediate inner members with respect to one another.
3. The improvement as defined in claim 2, in which said means includes a first stopper projection formed on the bottom wall of said large bore, an arcuate recessed portion formed at the edge of the lower end of said intermediate inner member and engaged with said first stopper projection, a second stopper projection formed at the upper end of said intermediate inner member, and an arcuate recessed portion formed at the edge of the lower end of said basic inner member and engaged with said second stopper projection.
4. In an apparatus for liquid-phase epitaxial growth of a semiconductor, the improvement comprises: an outer member having therein a cylindrical large bore opened at the upper end thereof and at least one substrate-carrying recess at the bottom wall of said bore; a cylindrical basic inner member snugly and slidably accommodated in said bore and having a solution-containing bore at the lower end wall thereof and opening toward said bottom wall of said large bore; at least one cylindrical additional inner member having upper and lower end walls, snugly slidably accommodated in said large bore and interposed between said basic inner member and said bottom wall of said large bore, said additional inner member having at least one solution-containing bore at said lower end wall thereof and opening toward said bottom wall of said large bore, and a substrate-carrying recess at said uppeR end wall thereof and opening toward said lower end wall of said basic inner member.
5. The improvement as defined in claim 4 which further comprises: means for defining relative rotation extent of said outer, basic inner and additional inner members with respect to one another.
6. The improvement as defined in claim 5, in which said means includes a first stopper projection formed on said bottom wall of said large bore, an arcuate recessed portion formed at the edge of said lower end wall of said additional inner member and engaged with said first stopper projection, a second stopper projection formed at the upper end wall of said additional inner member, and an arcuate recess portion formed at the edge of the lower end wall of said basic inner member and engaged with said second stopper projection.
7. In an apparatus for liquid-phase exitaxial growth of a semiconductor material, the improvement comprises: an outer support member having therein a cylindrical large bore opened at one end thereof and at least one solution containing chamber in the side wall of said bore, said chamber communicating with said bore through at least two openings formed in said side wall; a cylindrical bottom member snugly and slidably accommodated in the deepest portion of said large bore and having at one end wall thereof opposite to the bottom of said large bore a substrate-carrying recess for carrying therein a substrate; at least one cylindrical intermediate inner member snugly and slidably accommodated in said bore and placed on said bottom member, said intermediate member having at one end wall contacting with said bottom member a solution containing recess communicable through one of said openings with said solution-containing chamber, and having at the other end wall a substrate-carrying recess for carrying a substrate; and a cylindrical inner cap member snugly and slidably accommodated in said bore and contacted through one end wall thereof with the other end wall of said intermediate inner member, said cap member having at said one end wall a solution-containing recess communicating through the other of said openings with said solution-containing recess.
8. The improvement as claimed in claim 7, in which said outer support member has at the bottom wall of said bore a rectangular locking emboss, said bottom member has at the other end thereof a rectangular locking recess engagable with said locking emboss, and said bottom member has a coupling emboss at said one end wall, said intermediate member has on said one end wall a coupling recess engageable with said coupling emboss of said bottom member, and said intermediate member has an coupling emboss on said other end wall thereof, and said cap member has on said one end thereof a coupling recess engageable with said coupling emboss of the intermediate member.
9. In an apparatus for liquid-phase epitaxial growth of a semiconductor, the improvement comprises: an outer member having therein a cylindrical large bore opened at the upper end thereof and at least one substrate-carrying recess at said bottom wall of said bore; and a cylindrical basic inner member snugly and slidably accommodated in said bore and having a solution-containing bore at a lower wall thereof and opening toward said bottom wall and with an end wall, said inner member including a small passageway extending therethrough from a portion near to the end wall of said solution-containing bore to said lower wall of said inner member.
US295554A 1971-10-06 1972-10-06 Apparatus for liquid-phase epitaxial growth Expired - Lifetime US3896765A (en)

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JP7905271A JPS5137142B2 (en) 1971-10-06 1971-10-06
JP46100523A JPS5137144B2 (en) 1971-12-10 1971-12-10
JP9153672A JPS531036B2 (en) 1972-09-11 1972-09-11

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3981764A (en) * 1974-08-12 1976-09-21 Hitachi, Ltd. III-V Compound semi-conductor crystal growth from a liquid phase on a substract including filtering liquid phase
US4028148A (en) * 1974-12-20 1977-06-07 Nippon Telegraph And Telephone Public Corporation Method of epitaxially growing a laminate semiconductor layer in liquid phase
US4160682A (en) * 1978-03-30 1979-07-10 Western Electric Co., Inc. Depositing materials on stacked semiconductor wafers
US4235191A (en) * 1979-03-02 1980-11-25 Western Electric Company, Inc. Apparatus for depositing materials on stacked semiconductor wafers
US20020114741A1 (en) * 2001-02-16 2002-08-22 Brandeis University Adhesive label for microcentrifuge tube

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3115146A (en) * 1960-12-01 1963-12-24 Weldon C Erwin Contact lens holder
US3690965A (en) * 1971-11-29 1972-09-12 Bell Telephone Labor Inc Semiconductor epitaxial growth from solution
US3765959A (en) * 1971-07-30 1973-10-16 Tokyo Shibaura Electric Co Method for the liquid phase epitaxial growth of semiconductor crystals

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3115146A (en) * 1960-12-01 1963-12-24 Weldon C Erwin Contact lens holder
US3765959A (en) * 1971-07-30 1973-10-16 Tokyo Shibaura Electric Co Method for the liquid phase epitaxial growth of semiconductor crystals
US3690965A (en) * 1971-11-29 1972-09-12 Bell Telephone Labor Inc Semiconductor epitaxial growth from solution

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3981764A (en) * 1974-08-12 1976-09-21 Hitachi, Ltd. III-V Compound semi-conductor crystal growth from a liquid phase on a substract including filtering liquid phase
US4028148A (en) * 1974-12-20 1977-06-07 Nippon Telegraph And Telephone Public Corporation Method of epitaxially growing a laminate semiconductor layer in liquid phase
US4160682A (en) * 1978-03-30 1979-07-10 Western Electric Co., Inc. Depositing materials on stacked semiconductor wafers
US4235191A (en) * 1979-03-02 1980-11-25 Western Electric Company, Inc. Apparatus for depositing materials on stacked semiconductor wafers
US20020114741A1 (en) * 2001-02-16 2002-08-22 Brandeis University Adhesive label for microcentrifuge tube

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DE2249144A1 (en) 1973-04-12
NL7213557A (en) 1973-04-10
DE2249144B2 (en) 1975-01-23
DE2249144C3 (en) 1975-09-04

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