US3647389A - Method of group iii-v semiconductor crystal growth using getter dried boric oxide encapsulant - Google Patents
Method of group iii-v semiconductor crystal growth using getter dried boric oxide encapsulant Download PDFInfo
- Publication number
- US3647389A US3647389A US36367A US3647389DA US3647389A US 3647389 A US3647389 A US 3647389A US 36367 A US36367 A US 36367A US 3647389D A US3647389D A US 3647389DA US 3647389 A US3647389 A US 3647389A
- Authority
- US
- United States
- Prior art keywords
- boric oxide
- getter
- gallium
- growth
- crystal growth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-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
- C30B27/00—Single-crystal growth under a protective fluid
- C30B27/02—Single-crystal growth under a protective fluid by pulling from a melt
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S148/00—Metal treatment
- Y10S148/06—Gettering
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S148/00—Metal treatment
- Y10S148/107—Melt
Definitions
- the boric oxide is maintained for a time together with a getter substance under vacuum at a temperature at which both are molten.
- some suitable getter substances are boron-palladium alloy, boron-platinum alloy and the pure metals or alloy combination of gallium, aluminum and silicon.
- Field of the Invention The invention lies in the field of semiconductor crystal growth.
- Boric oxide however is highly hygroscopic and even most high-purity materials contain sufficient quantities of water to cause the boric oxide to froth and spatter when melted.
- a treatment has been developed to decrease the amount of water present in boric oxide to be used in crystal growth.
- the material is subjected to a vacuum baking treatment in which the boric oxide is melted and maintained under vacuum at a temperature in excess of I,0O0 C. for times ranging from many hours to several days. Boric oxide produced by this rather extreme process has proven, generally, quite satisfactory for crystal growth and is widely used.
- the liquid encapsulation technique as described above does not solve all of the crystal growth problems.
- gallium arsenide under vacuum-baked boric oxide considerable bubbling is still observed and reaction products, which contaminate the crystal growth system, are produced.
- arsenic is deposited over the inside of the vacuum chamber at times obscuring the viewing ports. Considerable effort has gone into an attempt to locate the source of these problems and effect improvements.
- Volatile reaction products are substantially removed by the vacuum system and many solid and liquid reaction products and other impurities are dissolved in the getter substance.
- This gettering step can also be incorporated in the vacuum baking procedure.
- suitable getter substances are boron-palladium alloy, boron-platinum alloy, gallium aluminum, silicon or alloys of these latter three metals.
- FIG. I is a plan view in section of a getter drying apparatus.
- FIG. 2 is a plan view in section of a Czochralski crystal growth apparatus using the liquid encapsulation technique.
- the proposed getter substance must be capable of reducing H (the high-temperature hydrated form of 8 0 at the drying temperature. Its oxide must be soluble in boric oxide and must be either volatile (hence removable by vacuum baking) or should not possess elements which would deleteriously contaminate the semiconductor melt.
- the getter substance should be a liquid at the temperature at which drying is carried out so as to be capable of dissolving nonvolatile impurities. It is also advantageous that the getter substances be more dense than boric oxide since the simplest way to separate the getter substance from the boric oxide after drying is to melt the boric oxide and pour it oft" of the getter substance. Although this is not a strict requirement.
- getter substances Considering these requirements as applied to the growth of gallium phosphide, gallium arsenide and mixed crystals thereof, a number of suitable getter substances have been found. Alloys of boron-platinum and boron-palladium possess a steep eutectic, melting in the neighborhood of 830 to 850 C. Alloys of these substances in the neighborhood of eutectic composition are suitable as getter substances.
- the oxide produced by the reduction of water is boric oxide and thus does not introduce any new species into the boric oxide encapsulant.
- the platinum or palladium are nonreacting in this system.
- Gallium as a getter substance, introduces a new species into the boron oxide in that some gallium oxide remains after the drying treatment.
- gallium is not a contaminant in the growth of gallium phosphide and gallium arsenide and the oxygen levels are reduced below the levels produced by the presence of H 0.
- Oxygen is a deep trap in gallium arsenide and-an important dopant in gallium phosphide which must be carefully controlled.
- Aluminum appearing just above gallium in the periodic table of the elements, is not an electrically active contaminant. It is thus an acceptable material. Also aluminum oxide is more stable than gallium oxide or boric oxide and, therefore, leads to even less oxygen contamination of the semiconductor melt.
- the gettering process should take place at a temperature above which both the boric oxide and the getter substance are molten in order to promote the chemical drying process and the solution of other impurities in the getter substance.
- the melting point of boric oxide is approximately 460 C. although because of its viscosity a preferred lower temperature for the gettering process is 600 C.
- the temperature of the gettering process should be kept below l,500 C. because of excessive boric oxide evaporation above this temperature.
- the drying process In order to remove the volatile reaction products. the drying process must take place under reduced pressure.
- the time occupied by this process varies from about an hour to several days. 0ne reason for this large time variation is the variation of the viscosity of boric oxide with temperature.
- the molten boric oxide is extremely viscous so that the pressure above the melt must be reduced slowly in order to avoid excessive frothing produced by the volatile reaction products.
- the boric oxide is much less viscous and the pressure can be more rapidly reduced (within one hour or more preferably within 5 hours) to as low as the l micron level without causing excessive loss of boric oxide due to frothing.
- Experiments which have been performed during the investigation of this process have generally taken place in the neighborhood of 900 to 1,100 C. Enough of the getter material must be used in order to react with all of the water in the boric oxide. However, much more than this quantity is generally employed since the speed of the reaction depends in part on the surface area of the molten getter substance.
- FIG. 1 shows the elements of an exemplary getter drying apparatus.
- the boric oxide 11 and the getter substance 12 are contained within a crucible 13 which is situated in a chamber 14, connected through an orifice 15 to a vacuum system 19.
- the required treatment temperature is maintained by heating coils 16.
- Fig. 2 shows some of the elements of a Czochralski crystal growing apparatus making use of the liquid encapsulation technique.
- This is one of the many crystal growing techniques known in the art which can make use of liquid encapsulation where this proves advantageous.
- the semiconductor melt 27 and the boron oxide encapsulant 21 are contained within a crucible 23 and maintained at the proper growing temperature by means of the heating element 26.
- a rotating rod 29 with a seed crystal attached to its lowest end is lowered to make contact with the free surface 22 of the semiconductor melt 27 and initiate crystalization. It is then slowly raised pulling" crystal 28 from the melt through the encapsulant 21 which usually provides a coating over the crystal 28.
- the pressure-regulating system 31 maintains the required overpressure of inert gas.
- boric oxide can be produced by the disclosed process with less than 0.0] weight percent water. Water contents a factor 10 less than this and lower have been attained in boric oxide produced by a gettering process such as produced by an apparatus shown in FIG. 1.
- Crystal growth'by an apparatus such as shown in FIG. 2 is greatly facilitated since the bubbling of the liquid encapsulant 21 is greatly reduced and the deposition of reaction products on the walls of the vacuum chamber 24 and the consequent obscuration of the viewing port 30 are greatly reduced.
- the effects of the disclosed techniques can also be observed in the electrical properties of the pulled crystal 28. Exemplary crystals produced by this technique have shown such electrical improvements as increase of carrier mobility which can be traced to a lowering of the impurity content of the semiconductor material 28.
- said getter substance consists essentially of at least one substance selected from the group consisting of gallium, boron-platinum alloy, boron-palladium alloy, aluminum and silicon.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
- Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US3636770A | 1970-05-11 | 1970-05-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3647389A true US3647389A (en) | 1972-03-07 |
Family
ID=21888223
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US36367A Expired - Lifetime US3647389A (en) | 1970-05-11 | 1970-05-11 | Method of group iii-v semiconductor crystal growth using getter dried boric oxide encapsulant |
Country Status (9)
Country | Link |
---|---|
US (1) | US3647389A (de) |
JP (1) | JPS5026422B1 (de) |
BE (1) | BE766750A (de) |
CA (1) | CA952413A (de) |
CH (1) | CH569514A5 (de) |
DE (1) | DE2122192C3 (de) |
FR (1) | FR2088484B1 (de) |
GB (1) | GB1311048A (de) |
IT (1) | IT942100B (de) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3857679A (en) * | 1973-02-05 | 1974-12-31 | Univ Southern California | Crystal grower |
US3974002A (en) * | 1974-06-10 | 1976-08-10 | Bell Telephone Laboratories, Incorporated | MBE growth: gettering contaminants and fabricating heterostructure junction lasers |
US4196171A (en) * | 1977-09-05 | 1980-04-01 | Tokyo Shibaura Denki Kabushiki Kaisha | Apparatus for making a single crystal of III-V compound semiconductive material |
WO1981001016A1 (en) * | 1979-10-12 | 1981-04-16 | Western Electric Co | Minimization of strain in single crystals |
US4277303A (en) * | 1978-08-07 | 1981-07-07 | The Harshaw Chemical Company | Getter for melt-grown scintillator ingot and method for growing the ingot |
US4431476A (en) * | 1981-01-17 | 1984-02-14 | Tokyo Shibaura Denki Kabushiki Kaisha | Method for manufacturing gallium phosphide single crystals |
US4537652A (en) * | 1983-06-10 | 1985-08-27 | Sumitomo Electric Industries, Ltd. | Process for preparing single crystal |
US4704257A (en) * | 1983-08-31 | 1987-11-03 | Research Development Corporation Of Japan | Apparatus for growing single crystals of dissociative compounds |
US4721539A (en) * | 1986-07-15 | 1988-01-26 | The United States Of America As Represented By The United States Department Of Energy | Large single crystal quaternary alloys of IB-IIIA-SE2 and methods of synthesizing the same |
US4824520A (en) * | 1987-03-19 | 1989-04-25 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Liquid encapsulated crystal growth |
US5183767A (en) * | 1991-02-14 | 1993-02-02 | International Business Machines Corporation | Method for internal gettering of oxygen in iii-v compound semiconductors |
US5186784A (en) * | 1989-06-20 | 1993-02-16 | Texas Instruments Incorporated | Process for improved doping of semiconductor crystals |
US5272373A (en) * | 1991-02-14 | 1993-12-21 | International Business Machines Corporation | Internal gettering of oxygen in III-V compound semiconductors |
WO2010053960A1 (en) * | 2008-11-07 | 2010-05-14 | The Regents Of The University Of California | Using boron-containing compounds, gasses and fluids during ammonothermal growth of group-iii nitride crystals |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5914440B2 (ja) * | 1981-09-18 | 1984-04-04 | 住友電気工業株式会社 | CaAs単結晶への硼素のド−ピング方法 |
US4637854A (en) * | 1983-01-18 | 1987-01-20 | Agency Of Industrial Science And Technology | Method for producing GaAs single crystal |
-
1970
- 1970-05-11 US US36367A patent/US3647389A/en not_active Expired - Lifetime
-
1971
- 1971-01-15 CA CA102,847A patent/CA952413A/en not_active Expired
- 1971-05-05 DE DE2122192A patent/DE2122192C3/de not_active Expired
- 1971-05-05 BE BE766750A patent/BE766750A/xx unknown
- 1971-05-07 GB GB1375671*[A patent/GB1311048A/en not_active Expired
- 1971-05-10 FR FR7116785A patent/FR2088484B1/fr not_active Expired
- 1971-05-11 CH CH689971A patent/CH569514A5/xx not_active IP Right Cessation
- 1971-05-11 JP JP46030887A patent/JPS5026422B1/ja active Pending
- 1971-05-11 IT IT50249/71A patent/IT942100B/it active
Non-Patent Citations (3)
Title |
---|
Goetzherger et al.: Metal Precipitates in Silicon PN Junctions J. of Applied Physics Vol. 31 (1960), pp. 1821 1824 * |
Mullin et al.: Liquid Encapsulation Techniques, J. Phys. Chem. Solids, Vol. 26 (1965), pp. 782 784 * |
Pock: Glastechnische Berichte, Vol. 37 (1964), pp. 533 535 * |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3857679A (en) * | 1973-02-05 | 1974-12-31 | Univ Southern California | Crystal grower |
US3974002A (en) * | 1974-06-10 | 1976-08-10 | Bell Telephone Laboratories, Incorporated | MBE growth: gettering contaminants and fabricating heterostructure junction lasers |
US4196171A (en) * | 1977-09-05 | 1980-04-01 | Tokyo Shibaura Denki Kabushiki Kaisha | Apparatus for making a single crystal of III-V compound semiconductive material |
US4277303A (en) * | 1978-08-07 | 1981-07-07 | The Harshaw Chemical Company | Getter for melt-grown scintillator ingot and method for growing the ingot |
WO1981001016A1 (en) * | 1979-10-12 | 1981-04-16 | Western Electric Co | Minimization of strain in single crystals |
US4299650A (en) * | 1979-10-12 | 1981-11-10 | Bell Telephone Laboratories, Incorporated | Minimization of strain in single crystals |
US4431476A (en) * | 1981-01-17 | 1984-02-14 | Tokyo Shibaura Denki Kabushiki Kaisha | Method for manufacturing gallium phosphide single crystals |
US4684515A (en) * | 1983-06-10 | 1987-08-04 | Sumitomo Electric Industries, Ltd. | Single crystal article |
US4537652A (en) * | 1983-06-10 | 1985-08-27 | Sumitomo Electric Industries, Ltd. | Process for preparing single crystal |
US4704257A (en) * | 1983-08-31 | 1987-11-03 | Research Development Corporation Of Japan | Apparatus for growing single crystals of dissociative compounds |
US4721539A (en) * | 1986-07-15 | 1988-01-26 | The United States Of America As Represented By The United States Department Of Energy | Large single crystal quaternary alloys of IB-IIIA-SE2 and methods of synthesizing the same |
US4824520A (en) * | 1987-03-19 | 1989-04-25 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Liquid encapsulated crystal growth |
US5186784A (en) * | 1989-06-20 | 1993-02-16 | Texas Instruments Incorporated | Process for improved doping of semiconductor crystals |
US5183767A (en) * | 1991-02-14 | 1993-02-02 | International Business Machines Corporation | Method for internal gettering of oxygen in iii-v compound semiconductors |
US5272373A (en) * | 1991-02-14 | 1993-12-21 | International Business Machines Corporation | Internal gettering of oxygen in III-V compound semiconductors |
WO2010053960A1 (en) * | 2008-11-07 | 2010-05-14 | The Regents Of The University Of California | Using boron-containing compounds, gasses and fluids during ammonothermal growth of group-iii nitride crystals |
US20110223092A1 (en) * | 2008-11-07 | 2011-09-15 | The Regents Of The University Of California | Using boron-containing compounds, gasses and fluids during ammonothermal growth of group-iii nitride crystals |
US8574525B2 (en) * | 2008-11-07 | 2013-11-05 | The Regents Of The University Of California | Using boron-containing compounds, gasses and fluids during ammonothermal growth of group-III nitride crystals |
Also Published As
Publication number | Publication date |
---|---|
CA952413A (en) | 1974-08-06 |
IT942100B (it) | 1973-03-20 |
FR2088484A1 (de) | 1972-01-07 |
DE2122192C3 (de) | 1974-06-06 |
BE766750A (fr) | 1971-10-01 |
FR2088484B1 (de) | 1976-04-16 |
DE2122192B2 (de) | 1973-10-18 |
JPS5026422B1 (de) | 1975-09-01 |
CH569514A5 (de) | 1975-11-28 |
DE2122192A1 (de) | 1971-11-25 |
GB1311048A (en) | 1973-03-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3647389A (en) | Method of group iii-v semiconductor crystal growth using getter dried boric oxide encapsulant | |
USRE41551E1 (en) | Method of preparing group III-V compound semiconductor crystal | |
EP0417843A2 (de) | Verfahren zur Herstellung von Einkristallen aus II-V- oder III-V-Gruppenverbindungen und die erhaltenen Produkte | |
US3741817A (en) | Process for producing monocrystals from iii-v compound melts with a boron oxide rim | |
US3649193A (en) | Method of forming and regularly growing a semiconductor compound | |
JP4120016B2 (ja) | 半絶縁性GaAs単結晶の製造方法 | |
EP0036891B1 (de) | Minimieren der spannung in monokristallen | |
Weiner et al. | Liquid encapsulated Czochralski growth of GaAs | |
EP0104741A1 (de) | Verfahren zum Wachsen von kristallinem Material | |
US3290181A (en) | Method of producing pure semiconductor material by chemical transport reaction using h2s/h2 system | |
JPH06219900A (ja) | Siドープn型ガリウム砒素単結晶の製造方法 | |
JPH10259100A (ja) | GaAs単結晶の製造方法 | |
US3649192A (en) | Method of manufacturing semiconductor compounds | |
US3615205A (en) | Method for the synthesis and growth of high purity iii{14 v semiconductor compositions in bulk | |
US3480472A (en) | Method of growing epitaxial layers from binary semiconductor compounds | |
US3591347A (en) | Encapsulating a seed crystal for producing monocrystals | |
US3353912A (en) | Preparation of high-purity materials | |
JPH07300385A (ja) | 化合物半導体結晶の製造方法及び製造用るつぼ | |
US3615928A (en) | Growth of pb1-xsnxte from nonstoichiometric melts | |
JP2527718B2 (ja) | 液体カプセル引き上げ法用封止剤及び単結晶の成長方法 | |
US4371420A (en) | Method for controlling impurities in liquid phase epitaxial growth | |
US6635323B2 (en) | Raw material for production of GaAs crystals | |
JP3627255B2 (ja) | Iii−v族化合物半導体単結晶の育成方法 | |
US3573108A (en) | Purification of germanium | |
JPH0446097A (ja) | 化合物半導体単結晶成長におけるドーピング方法 |