US3615203A - Method for the preparation of groups iii{14 v single crystal semiconductors - Google Patents
Method for the preparation of groups iii{14 v single crystal semiconductors Download PDFInfo
- Publication number
- US3615203A US3615203A US805626A US3615203DA US3615203A US 3615203 A US3615203 A US 3615203A US 805626 A US805626 A US 805626A US 3615203D A US3615203D A US 3615203DA US 3615203 A US3615203 A US 3615203A
- Authority
- US
- United States
- Prior art keywords
- temperature
- vapor pressure
- single crystal
- gallium
- crucible
- 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
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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
- C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
- C30B11/04—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt
- C30B11/06—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method adding crystallising materials or reactants forming it in situ to the melt at least one but not all components of the crystal composition being added
-
- 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
- Y10S438/00—Semiconductor device manufacturing: process
- Y10S438/971—Stoichiometric control of host substrate composition
Definitions
- the melting point of a typical intermetallic compound semiconductor, gallium phosphide is approximately 1,450 C. and its decomposition pressure is measured in ls of atmospheres. It has been proposed to achieve single crystal growth of this intermetallic compound by means of high temperatures, but this method is defective because impurities are likely to contaminate the compound.
- the present invention provides a method for the manufacture of a single crystal intermetallic compound semiconductor wherein the constituent having the relatively low vapor pressure is fused in a confined zone, after which a temperature differential is applied along the fused mass such that one portion of the fused mass is at a significantly higher temperature than another portion of the same fused mass. While these conditions of temperature are maintained in the fused mass, the more volatile, higher vapor pressure element is vaporized and the higher temperature portion of the fused mass is exposed to the vapors of this element. This results in a reaction between the two to form the intermetallic compound which then grows as a single crystal from the lower temperature portion of the confined zone.
- FIGURE of the drawing shows somewhat schematically a furnace assembly which can be used for the purpose of the present invention, alongside of which there is a graphical representation of the temperatures existing at various portions of the furnace.
- reference numeral 1 indicates a vacuum container composed, for example, of quartz.
- the particular crucible shown in the drawing is generally conical in shape and has a pointed lower end 2a as shown in the drawing.
- the relatively low vapor pressure material, gallium in the example given is fused in the crucible 2 to provide a melt 3.
- a supply of red phosphorous 6 is placed at the bottom of the vacuum container 1. Heating of the gallium and of the phosphorous may be conducted independently by providing separate electric furnaces 4a and 4b, respectively for each of the two materials.
- the temperature of the upper surface 3a of the molten gallium is held, for example, at about 1,200 C. which is below the melting point of the desired intermetallic compound, gallium phosphide.
- the temperature at the lower-end 2a of the crucible 2 is held at a temperature which is lower than that of the upper end by 20 to 300 C. Eypically, the temperature at the lower end 2a is about i, 1 50
- the temperature of the phosphorous 6 is such that it has a vapor pressure which exceeds the decomposition pressure of the gallium phosphide to be produced. As shown in the graph which forms part of the figure, the temperature of the phosphorous may be about 450 C., while the temperature of the molten gallium may range from l,l50 C. near the bottom of the crucible to l,200 C. at the top of the crucible.
- EXAMPLE 1 With the type of assembly illustrated in the drawing, red phosphorous was heated up to 1,450 C. to provide a vapor pressure of phosphorous in the container 1 of 1,400 mm. of mercury.
- the temperature on the surface 34 of the gallium 3 was l,l00 C., and at the lower end 2a of the crucible, the temperature was 1,060 C.
- the distance between the lower end 2a of the crucible 2 and the surface 30 of the gallium 3 was about 10 mm.
- a single crystal of gallium phosphide having a diameter of 12 mm. and a height of 12 mm. was obtained.
- EXAMPLE 2 In this example, the distance between the surface 30 of the gallium and the lower end 2a of the crucible was about 14 mm. The temperature on the surface 3a was 1,1 15 C. and that at the lower end 2a of the crucible was 1,060 C. After 5 days reaction time, a single crystal having a diameter of 15 mm. and a height of 10 mm. was produced.
- EXAMPLE 3 The temperature of the phosphorous was 430 C., and its vapor pressure was 700 mm. of mercury. The temperature on the surface 3a of the gallium was 1,170 C., and the temperature at the lower end 2a of the crucible 2 was l,l 15 C. The distance between the surface 3a of the gallium 3 and the lower end 2a of the crucible 2 was 12 mm. After 5 days, a polycrystal having a diameter of 12 mm. and a height of 13 mm. was obtained.
- EXAMPLE 4 In this example, the temperature on the surface 3a of the fused gallium 3 was l,l70 C., and the temperature at the lower end 2a of the crucible was l,l30 C. The distance between the surface 3a and the lower end 20 of the crucible 2 was l2 mm. Otherwise, the conditions were those specified in example 3. In this case also, a polycrystal was produced.
- the temperature on the surface 3a of the gallium should be high enough to provide for efficient reaction speed, but not so high as to exceed the melting temperature of the gallium phosphide. Furthermore, if the temperature is too high the vapor pressure in the container is so high as to necessitate the use of an expensive high pressure container. For example, at l,450 C., the container 1 is required to withstand a vapor pressure of about 30 atmospheres. Consequently, it is desirable that the temperature on the surface 3a of the fused gallium be no higher than about l,300 C. n the other hand, too low a temperature requires an excessively long reaction time and therefore the temperature should be at least l,l00 C.
- the diffusion velocity of the product increases with an increase in the temperature differential between the upper and lower portions of the crucible 2 and as a result increases the reaction speed.
- the reaction speed is related to the vapor pressure of the phosphorous, too great a temperature differential is not desirable, and the temperature differential should not normally exceed 300 C.
- the reaction speed is substantially decreased. Accordingly, it is desirable that there be a temperature differential at least 20 C. to provide practical reaction speeds.
- vapor pressure of the phosphorous As far as vapor pressure of the phosphorous is concerned, the use of an excessively high vapor pressure provides a problem of container design, as mentioned previously, while too low a vapor pressure reduces the reaction velocity. It is accordingly preferred to use a vapor pressure in the enclosure of from l/lO to 30 atmospheres. The pressure should, however, be greater than the decomposition pressure of the gallium phosphide on the surface 3a of the gallium.
- the heating of the crucible took place by means of an electric resistance furnace. It can also be accomplish'ed in the following manner.
- a carbon crucible can be [Oil used instead of the quartz crucible 2, or a carbon susceptor is disposed outside of the crucible 2 and a coil is placed around the container 1. The carbon is then heated by high frequency heating currents to heat the crucible.
- the crucible may also be made of boron nitride to eliminate the possibility that oxygen or silicon from the quartz could enter the resulting crystal. In order to diffuse suitable impurities into the crystal such as zinc, oxygen, cadmium, tellurium or the like, these elements may be added to the fused gallium 3. In order to maintain a temperature distribution in the crucible at desired values, the crucible or the electric furnaces may be axially shifted.
- a vaporous atmosphere of phosphorous is produced in the sealed container but it is also possible that the crucible can be placed in a nonsealed tube and phosphorous containing gases such as phosphine, phosphorous chloride and the like passed over the surface of the fused gallium using hydrogen as a carrier gas.
- phosphorous containing gases such as phosphine, phosphorous chloride and the like
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 |
---|---|---|---|
JP43015116A JPS4820106B1 (de) | 1968-03-08 | 1968-03-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3615203A true US3615203A (en) | 1971-10-26 |
Family
ID=11879844
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US805626A Expired - Lifetime US3615203A (en) | 1968-03-08 | 1969-03-10 | Method for the preparation of groups iii{14 v single crystal semiconductors |
Country Status (4)
Country | Link |
---|---|
US (1) | US3615203A (de) |
JP (1) | JPS4820106B1 (de) |
DE (1) | DE1911715B2 (de) |
GB (1) | GB1251251A (de) |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3899572A (en) * | 1969-12-13 | 1975-08-12 | Sony Corp | Process for producing phosphides |
US3947548A (en) * | 1970-10-01 | 1976-03-30 | Semiconductor Research Foundation | Process of growing single crystals of gallium phosphide |
US3966881A (en) * | 1972-05-11 | 1976-06-29 | Sony Corporation | Method of making a single crystal intermetallic compound semiconductor |
DE2510612A1 (de) * | 1975-03-11 | 1976-09-23 | Siemens Ag | Verfahren zur herstellung von kompaktem einphasigem galliumphosphid stoechiometrischer zusammensetzung |
US4040894A (en) * | 1967-06-13 | 1977-08-09 | Huguette Fumeron Rodot | Process of preparing crystals of compounds and alloys |
US4169727A (en) * | 1978-05-01 | 1979-10-02 | Morgan Semiconductor, Inc. | Alloy of silicon and gallium arsenide |
US4181515A (en) * | 1974-09-24 | 1980-01-01 | The Post Office | Method of making dielectric optical waveguides |
US4190486A (en) * | 1973-10-04 | 1980-02-26 | Hughes Aircraft Company | Method for obtaining optically clear, high resistivity II-VI, III-V, and IV-VI compounds by heat treatment |
US4521272A (en) * | 1981-01-05 | 1985-06-04 | At&T Technologies, Inc. | Method for forming and growing a single crystal of a semiconductor compound |
US20090095713A1 (en) * | 2004-10-26 | 2009-04-16 | Advanced Technology Materials, Inc. | Novel methods for cleaning ion implanter components |
US20110021011A1 (en) * | 2009-07-23 | 2011-01-27 | Advanced Technology Materials, Inc. | Carbon materials for carbon implantation |
US20120260848A1 (en) * | 2011-04-12 | 2012-10-18 | Xiao-Yu Hu | Single crystal growth method for vertical high temperature and high pressure group III-V compound |
US20130330917A1 (en) * | 2005-06-22 | 2013-12-12 | Advanced Technology Materials, Inc | Apparatus and process for integrated gas blending |
US9455147B2 (en) | 2005-08-30 | 2016-09-27 | Entegris, Inc. | Boron ion implantation using alternative fluorinated boron precursors, and formation of large boron hydrides for implantation |
US9685304B2 (en) | 2009-10-27 | 2017-06-20 | Entegris, Inc. | Isotopically-enriched boron-containing compounds, and methods of making and using same |
US9960042B2 (en) | 2012-02-14 | 2018-05-01 | Entegris Inc. | Carbon dopant gas and co-flow for implant beam and source life performance improvement |
US9991095B2 (en) | 2008-02-11 | 2018-06-05 | Entegris, Inc. | Ion source cleaning in semiconductor processing systems |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS51113903U (de) * | 1975-03-12 | 1976-09-16 | ||
US4083748A (en) * | 1975-10-30 | 1978-04-11 | Western Electric Company, Inc. | Method of forming and growing a single crystal of a semiconductor compound |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1063084A (en) * | 1962-03-29 | 1967-03-30 | Siemens Ag | The production of a b -compounds in crystalline form |
US3366454A (en) * | 1954-09-18 | 1968-01-30 | Siemens Ag | Method for the production and remelting of compounds and alloys |
-
1968
- 1968-03-08 JP JP43015116A patent/JPS4820106B1/ja active Pending
-
1969
- 1969-03-06 GB GB1251251D patent/GB1251251A/en not_active Expired
- 1969-03-07 DE DE1911715A patent/DE1911715B2/de not_active Ceased
- 1969-03-10 US US805626A patent/US3615203A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3366454A (en) * | 1954-09-18 | 1968-01-30 | Siemens Ag | Method for the production and remelting of compounds and alloys |
GB1063084A (en) * | 1962-03-29 | 1967-03-30 | Siemens Ag | The production of a b -compounds in crystalline form |
Cited By (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4040894A (en) * | 1967-06-13 | 1977-08-09 | Huguette Fumeron Rodot | Process of preparing crystals of compounds and alloys |
US3899572A (en) * | 1969-12-13 | 1975-08-12 | Sony Corp | Process for producing phosphides |
US3947548A (en) * | 1970-10-01 | 1976-03-30 | Semiconductor Research Foundation | Process of growing single crystals of gallium phosphide |
US3966881A (en) * | 1972-05-11 | 1976-06-29 | Sony Corporation | Method of making a single crystal intermetallic compound semiconductor |
US4190486A (en) * | 1973-10-04 | 1980-02-26 | Hughes Aircraft Company | Method for obtaining optically clear, high resistivity II-VI, III-V, and IV-VI compounds by heat treatment |
US4181515A (en) * | 1974-09-24 | 1980-01-01 | The Post Office | Method of making dielectric optical waveguides |
DE2510612A1 (de) * | 1975-03-11 | 1976-09-23 | Siemens Ag | Verfahren zur herstellung von kompaktem einphasigem galliumphosphid stoechiometrischer zusammensetzung |
US4169727A (en) * | 1978-05-01 | 1979-10-02 | Morgan Semiconductor, Inc. | Alloy of silicon and gallium arsenide |
US4521272A (en) * | 1981-01-05 | 1985-06-04 | At&T Technologies, Inc. | Method for forming and growing a single crystal of a semiconductor compound |
US20090095713A1 (en) * | 2004-10-26 | 2009-04-16 | Advanced Technology Materials, Inc. | Novel methods for cleaning ion implanter components |
US9666435B2 (en) * | 2005-06-22 | 2017-05-30 | Entegris, Inc. | Apparatus and process for integrated gas blending |
US20130330917A1 (en) * | 2005-06-22 | 2013-12-12 | Advanced Technology Materials, Inc | Apparatus and process for integrated gas blending |
TWI552797B (zh) * | 2005-06-22 | 2016-10-11 | 恩特葛瑞斯股份有限公司 | 整合式氣體混合用之裝置及方法 |
US9455147B2 (en) | 2005-08-30 | 2016-09-27 | Entegris, Inc. | Boron ion implantation using alternative fluorinated boron precursors, and formation of large boron hydrides for implantation |
US9991095B2 (en) | 2008-02-11 | 2018-06-05 | Entegris, Inc. | Ion source cleaning in semiconductor processing systems |
US20110021011A1 (en) * | 2009-07-23 | 2011-01-27 | Advanced Technology Materials, Inc. | Carbon materials for carbon implantation |
US10497569B2 (en) | 2009-07-23 | 2019-12-03 | Entegris, Inc. | Carbon materials for carbon implantation |
US9685304B2 (en) | 2009-10-27 | 2017-06-20 | Entegris, Inc. | Isotopically-enriched boron-containing compounds, and methods of making and using same |
US20120260848A1 (en) * | 2011-04-12 | 2012-10-18 | Xiao-Yu Hu | Single crystal growth method for vertical high temperature and high pressure group III-V compound |
US9960042B2 (en) | 2012-02-14 | 2018-05-01 | Entegris Inc. | Carbon dopant gas and co-flow for implant beam and source life performance improvement |
US10354877B2 (en) | 2012-02-14 | 2019-07-16 | Entegris, Inc. | Carbon dopant gas and co-flow for implant beam and source life performance improvement |
Also Published As
Publication number | Publication date |
---|---|
GB1251251A (de) | 1971-10-27 |
DE1911715A1 (de) | 1969-10-09 |
JPS4820106B1 (de) | 1973-06-19 |
DE1911715B2 (de) | 1976-01-02 |
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