US3094388A - Method of producing gallium or aluminum arsenides and phosphides - Google Patents

Method of producing gallium or aluminum arsenides and phosphides Download PDF

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Publication number
US3094388A
US3094388A US859060A US85906059A US3094388A US 3094388 A US3094388 A US 3094388A US 859060 A US859060 A US 859060A US 85906059 A US85906059 A US 85906059A US 3094388 A US3094388 A US 3094388A
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United States
Prior art keywords
gallium
halide
arsenic
hydrogen
aluminum
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Expired - Lifetime
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US859060A
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English (en)
Inventor
Rowland E Johnson
Edward W Mehal
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Texas Instruments Inc
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Texas Instruments Inc
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Publication date
Priority to NL121550D priority Critical patent/NL121550C/xx
Priority to NL258863D priority patent/NL258863A/xx
Application filed by Texas Instruments Inc filed Critical Texas Instruments Inc
Priority to US859060A priority patent/US3094388A/en
Priority to FR846592A priority patent/FR1275902A/fr
Priority to GB42709/60A priority patent/GB967185A/en
Application granted granted Critical
Publication of US3094388A publication Critical patent/US3094388A/en
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/007—Preparing arsenides or antimonides, especially of the III-VI-compound type, e.g. aluminium or gallium arsenide
    • A—HUMAN NECESSITIES
    • A21—BAKING; EDIBLE DOUGHS
    • A21D—TREATMENT, e.g. PRESERVATION, OF FLOUR OR DOUGH, e.g. BY ADDITION OF MATERIALS; BAKING; BAKERY PRODUCTS; PRESERVATION THEREOF
    • A21D2/00—Treatment of flour or dough by adding materials thereto before or during baking
    • A21D2/08—Treatment of flour or dough by adding materials thereto before or during baking by adding organic substances
    • A21D2/14—Organic oxygen compounds
    • A21D2/16—Fatty acid esters
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/06—Hydrogen phosphides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/04—Metal borides
    • 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
    • Y10S148/049—Equivalence and options
    • 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
    • Y10S148/056—Gallium arsenide
    • 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
    • Y10S148/065—Gp III-V generic compounds-processing
    • 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
    • Y10S420/00—Alloys or metallic compositions
    • Y10S420/903—Semiconductive

Definitions

  • This invention relates to a new method of producing compound semiconductors and in particular to the production of gallium arsenide.
  • gallium arsenide is customarily produced by reacting liquid gallium with arsenic in the vapor stage at a tempera-ture at least as high as the melting point of gallium arsenide.
  • this method has the disadvantage of requiring a relatively high temperature which increases the susceptibil-ity toward contamination.
  • this method i-s not readily adaptable as la continuous production process.
  • gallium arsenide be prepared by reducing gallium oxide with a gaseous stream of heated hydrogen and arsenic vapors.
  • Another suggested technique has been to volatilize gallium and arsenic ⁇ and thereafter codeposit on a relatively cooled surface to form the gallium arsenide.
  • the object of the instant invention is to provide an improved process for production of compound semiconductors and especially gallium arsenide.
  • FIGURES 1 to 3 schematically illustrate the best modes for performing the method tof the invention.
  • the instant invention involves the process of simultaneous reduction of a halide of a group III element and a halide of a groupy V element.
  • the invention involves producing the compound semi-conductor by the vapor phase reduction of karsenic halide by hydrogen in the presence of gallium halide or metallic gallium under conditions whereby the gallium arsenide is stoichiometrically produced.
  • a mixture of arsenic trichloride and gallium trichloride is introduced into a stream of hydrogen in excess of that required for complete reduction ⁇ of the chlorides. 'Ihe gaseous mixture is then passed through -a hot reaction zone, at for example about 1,000 C. It is theorized that in the hot reaction zone the hydrogen reduces the arsenic trichloride to free arsenic. The combination of high temperatures and low partial pressure keep the arsenic in the vapor phase. It is thought that the gallium trichloride reacts with the hydrogen to form gallium dichloride. An important feature of this invention is that free gallium is not formed in the hot reaction zone.
  • Any free gallium produced immediately reacts with the various chlorides present 'to form a chloride of gallium which is reduced to the more stable gallium dichloride. There is no gallium arsenide deposited because under these conditions, any gallium arsenide produced would be unstable.
  • the gases are passed into contact with a relatively cool surface maintained at la .temperature of from about 200 to 900 C.
  • the gallium dichloride disproportionates and the gallium combines with the free arsenic to form gallium arsenide which deposits in solid form.
  • the deposition temperature is still high enough to maintain the other components of the gas stream in Vapor phase, namely, hydrogen and hydrogen chloride which are gaseous even at room temperature, and unreacted gallium and arsenic chlorides as well.
  • pure gallium arsenide is deposited.
  • the temperature of the crystals is maintained high enough to also keep any excess arsenic from depositing on the crystal product.
  • gallium trichloride as van initial constituent presents problems in thatrgallium trichloride readily hydrolyzes with moisture and is very corrosive.
  • problems are minimized by forming the galliumtrichloride in the reaction chamber.
  • the gaseous stream which contains only the hydrogen and ⁇ arsenic trichloride is passed into Contact with liquid gallium heated to 900- 11t00 C.
  • the arsenic trichloride is reduced by the hydrogen to elemental arsenic vapors yand HCl.
  • the HC1 produced when the AsCl3 is reduced reacts with the liquid gallium to produce gallium trichloride. This reaction continues until all of' the galtliumlium is converted to gallium trichloride. Gallium arsenide is then produced by the same mechanism described in the rst embodiment of the invention.
  • Example I Apparatus as shown in FIGURE 1 is used.
  • the apparatus consists of a quartz tube 10 (25 mm. OD.; 22 mm. LD.) having an inlet 11 connected to a suitable hydrogen supply and lan exhaust Outlet 12. Heaters 14 and 15 are provided to maintain the temperatures noted in the legend.
  • a flask 18 terminating in a dripper 20 is positioned in a branch tube 22 adjacent one end of tube 10.
  • hydrogen is admitted through inlet "11 at about 100 cc./ min. (0.0045 mole/min.).
  • the flask 18 contains a mixture of GaCl3 and AsCl3 in the weight ratio of 37.5 to
  • the dripper 20 is controlled to give ⁇ a drip rate of about 0.2 ze/min. corresponding to about 0.44 g./min. (average specific gravity 2.2) and about 0.00244 mole/ min., ⁇ assuming an average molecular weight of 180. This gives a mole ratio in the reaction zone of where x equals GaCl3 and AsC13. Galliutn arsenide is deposited in the region of tube within heater 15.
  • Example III Apparatus las shown in FIGUR-E 3 is used.
  • a tube 40 like tubes 10 and A30 is employed.
  • a flask 42 is attached at one end of tube 40 and contains AsC13.
  • a boat 44 of liquid gallium is located in tube 40.
  • Hydro gen is bubbled through the AsCl3 and Yalsoadmitted to the vvend of tube 40.
  • Hydrogen llow is about l liter/min.
  • the mole ratio of H2 to AsCl3 is about 76 to l.
  • Gallium arsenide is deposited at the right end of tube 40.
  • the present ⁇ invention has been shown and phase mixture of hydrogen, halide of aluminum and phosphorus into a high temperature zone maintained at a temperature in the range of from about 900 C. to about 1l00 C. to cause the hydrogen to react with the halide producing a reactant stream vcomprising the halide of aluminum as a lower order halide and phosphorus in the elemental state, passing the reactant stream produced into contact with a relatively cool surface maintained at a temperature of from ⁇ about 200 C. to 900 C.
  • a method of producing the compound semiconductor gallium phosphide which comprises passing a vapor phase mixture of hydrogen, halide of gallium-and phosphorus in a high temperature Zone maintained at a ternperature in the range of .from about 900 .C.to about 1l00 C. to cause the hydrogen to react with the halide producing a .reactant stream comprising the halide of gallium as -a lower order halide ⁇ and phosphorus in the elemental state, passing the reactant stream produced into contact with a relatively cool surface maintained at a temperature of from about 200 C. to 900 C.
  • a method of producing the compound semiconductor gallium arsenide which comprises passing ⁇ a vapor phase mixture of hydrogen and halides of gallium and t arsenic .into a high temperature Zone maintained at a temperature in the range of from about 900 C. -to about 1100 C. to cause the hydrogen to react with the halides producing a reactant stream comprising vthe halide of galliumV as a lower 'order halide and arsenic in the elemental state, passing the reactant stream produced into contact with a relatively ⁇ cool surface maintained at a y temperature of from about 200 C. 'to about 900 C.
  • a method of producing the compound semiconductor aluminum arsenide which comprises passing a vapor phase mixture of hydrogen and halides of aluminum and arsenic into a high temperature zone maintained at a temperature in the range of from about 900 C. to about 1l00 to vcause the hydrogen to react with the halide producing a reactant stream comprising the halide of aluminum as a lower order halide and arsenic in the elemental state, passing the reactant stream ⁇ produced into contact with a relatively cool surface rmaintained at a temperature of from about 200 C. to 900 C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Food Science & Technology (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US859060A 1959-12-11 1959-12-11 Method of producing gallium or aluminum arsenides and phosphides Expired - Lifetime US3094388A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL121550D NL121550C (US07816562-20101019-C00012.png) 1959-12-11
NL258863D NL258863A (US07816562-20101019-C00012.png) 1959-12-11
US859060A US3094388A (en) 1959-12-11 1959-12-11 Method of producing gallium or aluminum arsenides and phosphides
FR846592A FR1275902A (fr) 1959-12-11 1960-12-10 Procédé de fabrication de composés semi-conducteurs
GB42709/60A GB967185A (en) 1959-12-11 1960-12-12 Method of producing specified ó¾í¬v compounds

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US859060A US3094388A (en) 1959-12-11 1959-12-11 Method of producing gallium or aluminum arsenides and phosphides

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US3094388A true US3094388A (en) 1963-06-18

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GB (1) GB967185A (US07816562-20101019-C00012.png)
NL (2) NL258863A (US07816562-20101019-C00012.png)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3224911A (en) * 1961-03-02 1965-12-21 Monsanto Co Use of hydrogen halide as carrier gas in forming iii-v compound from a crude iii-v compound
US3249473A (en) * 1961-08-30 1966-05-03 Gen Electric Use of metallic halide as a carrier gas in the vapor deposition of iii-v compounds
US3269878A (en) * 1962-03-29 1966-08-30 Siemens Ag Method of producing iii-v semiconductor compounds in crystalline form
US3310425A (en) * 1963-06-28 1967-03-21 Rca Corp Method of depositing epitaxial layers of gallium arsenide
US3361530A (en) * 1966-12-09 1968-01-02 Texas Instruments Inc Process for purifying gallium arsenide
US3364084A (en) * 1959-06-18 1968-01-16 Monsanto Co Production of epitaxial films
US3391017A (en) * 1963-08-26 1968-07-02 Int Standard Electric Corp Formation of aluminum, gallium, arsenic, and phosphorous binary conatings
US3947549A (en) * 1973-03-15 1976-03-30 British Secretary of State for Defence Preparation of indium phosphide
CN107902695A (zh) * 2017-11-21 2018-04-13 红河砷业有限责任公司 一种高效制备高纯砷化铝的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2501908B2 (fr) * 1981-03-11 1990-08-17 Labo Electronique Physique Croissance epitaxiale acceleree en phase vapeur, sous pression reduite

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2313410A (en) * 1939-03-31 1943-03-09 Bell Telephone Labor Inc Preparation of boron compositions
US2798989A (en) * 1951-03-10 1957-07-09 Siemens Schuckertwerke Gmbh Semiconductor devices and methods of their manufacture
US2938816A (en) * 1957-06-08 1960-05-31 Siemens Ag Vaporization method of producing thin layers of semiconducting compounds

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2313410A (en) * 1939-03-31 1943-03-09 Bell Telephone Labor Inc Preparation of boron compositions
US2798989A (en) * 1951-03-10 1957-07-09 Siemens Schuckertwerke Gmbh Semiconductor devices and methods of their manufacture
US2938816A (en) * 1957-06-08 1960-05-31 Siemens Ag Vaporization method of producing thin layers of semiconducting compounds

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3364084A (en) * 1959-06-18 1968-01-16 Monsanto Co Production of epitaxial films
US3224911A (en) * 1961-03-02 1965-12-21 Monsanto Co Use of hydrogen halide as carrier gas in forming iii-v compound from a crude iii-v compound
US3249473A (en) * 1961-08-30 1966-05-03 Gen Electric Use of metallic halide as a carrier gas in the vapor deposition of iii-v compounds
US3269878A (en) * 1962-03-29 1966-08-30 Siemens Ag Method of producing iii-v semiconductor compounds in crystalline form
US3310425A (en) * 1963-06-28 1967-03-21 Rca Corp Method of depositing epitaxial layers of gallium arsenide
US3391017A (en) * 1963-08-26 1968-07-02 Int Standard Electric Corp Formation of aluminum, gallium, arsenic, and phosphorous binary conatings
US3361530A (en) * 1966-12-09 1968-01-02 Texas Instruments Inc Process for purifying gallium arsenide
US3947549A (en) * 1973-03-15 1976-03-30 British Secretary of State for Defence Preparation of indium phosphide
CN107902695A (zh) * 2017-11-21 2018-04-13 红河砷业有限责任公司 一种高效制备高纯砷化铝的方法

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GB967185A (en) 1964-08-19
NL258863A (US07816562-20101019-C00012.png)
NL121550C (US07816562-20101019-C00012.png)

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