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
  • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
  • C30B25/02—Epitaxial-layer growth
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
  • C07F5/06—Aluminium compounds
  • C07F5/061—Aluminium compounds with C-aluminium linkage
  • C07F5/064—Aluminium compounds with C-aluminium linkage compounds with an Al-Halogen linkage
• • 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
  • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
  • C30B29/10—Inorganic compounds or compositions
  • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02367—Substrates
  • H01L21/0237—Materials
  • H01L21/02387—Group 13/15 materials
  • H01L21/02392—Phosphides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02367—Substrates
  • H01L21/0237—Materials
  • H01L21/02387—Group 13/15 materials
  • H01L21/02395—Arsenides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02518—Deposited layers
  • H01L21/02521—Materials
  • H01L21/02538—Group 13/15 materials
  • H01L21/02543—Phosphides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02518—Deposited layers
  • H01L21/02521—Materials
  • H01L21/02538—Group 13/15 materials
  • H01L21/02546—Arsenides
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
  • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
  • H01L21/02104—Forming layers
  • H01L21/02365—Forming inorganic semiconducting materials on a substrate
  • H01L21/02612—Formation types
  • H01L21/02617—Deposition types
  • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
• • 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
  • Y10S148/00—Metal treatment
  • Y10S148/119—Phosphides of gallium or indium

Definitions

• the present invention relates to a method for vapor phase growth of an epitaxial layer of a compound of group llla Va elements (in the mendelejeffs periodic table) using an alkyl compound of group llla element as a source for the group llla element.
• a method for vapor phase growth of an epitaxial layer of a compound of group llla Va elements on a surface of a substrate which comprises reacting triethylaluminum which is prepared by specific synthesis methods and of which the silicon content is 4 ppm or lower (in accordance with the analysis method specified hereinafter) as a source for group Illa element with a halogenated gallium or indium to produce triethylgallium or triethylindium and then mixing, in vapor phase, thus obtained triethylgallium or triethylindium alone, a mixture thereof or a mixture of said compound and an alkyl compound of aluminum with a group Va element, a hydride of this element or an alkyl compound of this element.
• the group llla Va element compound semiconductors such as GaP, GaAs, GaAs P Ga A] AS, lnP, etc. are extremely useful as materials for Gunn diode, superhigh frequency devices and electro-luminescent devices and demands therefor have recently been markedly increased.
• the halogen transport method it is necessary that a reaction zone and a deposition zone are provided and the method is carried out under such condition as a slow gradient of temperature of 7 12C/cm being provided near substrate. Therefore, the area suitable for growth is limited to extremely narrow area. Furthermore, usually only several 30 pieces can be produced at one time and productivity is low. Furthermore, it is difficult to produce mixed crystals of two or more such as (Ga, Al)As, (Ga, ln)P, etc.
• the thermal decomposition method growth of epitaxial layer can be attained by heating only the substrate, area of growth zone can be optionally selected, productivity can be increased and moreover, since group llla Va element compound is deposited by thermal decomposition of an alkyl compound of Group llla element, mixed crystals such as (Ga, Al)P, (Ga, ln)P, etc. can easily be produced.
• group llla Va element compound is deposited by thermal decomposition of an alkyl compound of Group llla element, mixed crystals such as (Ga, Al)P, (Ga, ln)P, etc. can easily be produced.
• the drawbacks encountered in the halogen transport method as mentioned above can be overcome.
• epitaxial layers having practically usable electron carrier concentration and mobility for electron devices have not been able to be produced by the thermal decomposition method and the thermal decomposition method has not yet been industrialized.
• the inventors in an attempt to produce an epitaxial layer having practically usable electron concentration and mobility by thermal decomposition method, synthesized alkylgallium by reaction of (a) Grignards reagent and a gallium halide, (b) dialkylmercury and metallic gallium and (c) dialkylzinc and a gallium halide which are generally known as methods for synthesis of an alkyl compound of a group lIIa element and they purifled thus obtained alkylgallium to find that this alkylgallium inevitably contains Mg, Hg and Zn.
• the inventors have made an intensive research as to the reason why epitaxial layers produced using alkylgallium or alkylindium prepared with use of an alkylaluminum as an alkylating agent cannot be practically utilized and they found that the epitaxial layer produced from said starting material contains silicon.
• the inventors supposed that this incorporation of silicon into the epitaxial layer was caused by the alkylaluminum used for synthesis of alkylgallium or allkylindium.
• no method for determination of a slight amount of silicon compound in alkylaluminum has been proposed, they firstly established a method for determination of amount of silicon compound in alkylaluminum and then made a detailed research.
• silicon compound is incorporated due to aluminum which is a starting material for synthesis of alkylaluminum and is present as various organosilicon compounds in a wide range of boiling point and that some of said silicon compounds are difficultly separatable from alkylgallium or alkylindium by distillation, but the silicon compounds can easily be separated from alkylaluminum compounds by distillation.
• an epitaxial layer is produced using alkylgallium or alkylindium synthesized from alkylaluminum compound from which silicon compound has been removed and gallium halide or indium halide, in case of the alkyl being methyl a large amount of carbides are incorporated into epitaxial layer to cause reduction of crystalgroup Va element. Based on these discoveries, the present invention was accomplished.
• the object of the present invention is to provide a method for vapor phase growth of a high purity epitaxial layer having practicable electron concentration and mobility, such as those GaAs, namely, less than 1 X l/cm at room temperature and higher than 6,000 cm /V-sec, respectively from an alkyl compound of group Illa element.
• the above object of the present invention to produce an epitaxial layer of group Illa Va element compound on a surface of a substrate by mixing an alkyl com pound of a group Illa element and a group Va element or a compound thereof in vapor phase and contacting the reaction product with the substrate is attained as follows:
• I Triethylaluminum which is synthesized by (i) reaction of triethylaluminum, diethylaluminum hydride or a mixture thereof, aluminum, hydrogen and ethylene, (ii) reaction of an alkylaluminum compound, aluminum and hydrogen or aditionally an olefin to produce an alkylaluminum compound, which is then subjected to alkyl substitution with ethylene or (iii) reaction or reducing ethylaluminum sesquihalide obtained by reaction of aluminum and an ethyl halide and in which silicon content is made 4 ppm or lower is reacted with 11 gallium halide or indium halide to
• triethylgallium or triethylindium is synthesized using triethylaluminum of which the silicon contant is at most 4 ppm determined in accordance with the method of analysis as specified hereinafter.
• the triethylaluminum of which the silicon content is at most 4 ppm is synthesized by either one of the following methods: (i) triethylaluminum, diethylaluminum hydride or a mixture thereof, aluminum, hydrogen and ethylene are reacted, (ii) alkylaluminum compound, aluminum and hydrogen are reacted or these are further reacted with an olefin to obtain an alkylaluminum compound, which is then subjected to alkyl substitution with ethylene and (iii) aluminum and ethyl halide are reacted to obtain ethylaluminum sesquihalide, which is then reduced.
• Said reactions (i) and (ii) may be accomplished by the methods disclosed in Japanese Patent Publications No. 57l0/57, No. 927/58 and US. Pat. No. 2,835,689 and the reaction (iii) also may be accomplished by the known reaction conditions.
• alkylaluminum compounds for example, trialkylaluminum or dialkylaluminum hydride having alkyl group of 3 20 carbon atoms such as tripropylaluminum, triisobutylaluminium, tri-2- ethylhexylaluminum, trioctylaluminum or hydrides thereof may be used.
• ethyl halides ethyl chloride, ethyl bromide and ethyl iodide may be used.
• the silicon compound which has become a problem in the present invention results from a slight amount of silicon contained in aluminum which is a starting material for synthesis of triethylaluminum and which is extracted as an organo silicone compound during synthesis of triethylaluminum and is incorporated therein.
• the commercially available triethylaluminum usually contains more than l0 ppm (in terms of silicon) of silicon compound determined by the analysis method of the present invention.
• the form of the silicon compound present in the alkylaluminum compound is not known and it is difficult to remove said silicon compound from triethylgallium or triethylindium synthesized using triethylaluminum containing the silicon compound.
• Triethylaluminum whose silicon content is 4 ppm or lower may be obtained by purification of triethylaluminum synthesized by the method (i), alkylaluminum compound or triethylaluminum synthesized by the method (ii) or ethylaluminumsesquihalide or triethylaluminum synthesized by the method (iii) by the known purification means such as rectification, recrystallization, etc. It is preferred to conduct filtration and the like prior to the purification to reduce load in purification. It is essential in the present invention that the alkylaluminum compound used for synthesis of triethylgallium or triethylindium is triethylaluminum and the reason therefor will be given hereinafter.
• the high purity triethylaluminum which is synthe sized by said specific methods and of which the silicon content is made 4 ppm or lower is then reacted with gallium halide or indium halide by the known method to synthesis triethylgallium or triethylindium.
• gallium halides gallium chloride, gallium bromide or gallium iodide is used and as the indium halides, indium chloride, indium bromide or indium iodide is used.
• the gallium halides and the indium halides commercially available high purity products may be used or these may be purified by sublimation. Furthermore, they may be synthesized by blowing a halogen into molten gallium or indium metal and then purified by sublimation.
• the synthesis reaction may be generally carried out at a temperature of 0 150C and under a pressure of normal pressure, but if necessary, under reduced pressure or higher pressure. Furthermore, the reaction may also be carried out in the presence of a solvent having a boiling point of 30 C such as petroleum ether, pentane, hexane, etc.
• a solvent having a boiling point of 30 C such as petroleum ether, pentane, hexane, etc.
• triethylgallium or triethylindium is vacuum distilled or is maintained at 0 C. for about 10 minutes 2 hours with addition of potassium chloride, sodium fluoride or a mixture thereof before or after the vacuum distillation to fix by-product diethylaluminum halide as a complex and thereafter is rectified to obtain purified triethylgallium or triethylindium.
• alkyl group of alklylgallium of alkylindium is ethyl and in case alkyl group is methyl, carbides in a large amount are incorporated into the obtained epitaxial layer to cause reduction in crystallinity of the group Illa Va element compound and in case alkyl group is propyl or higher alkyls, vapor pressure is low and such alkylgallium and alkylindium are not suitable as starting materials for growth of crystal.
• many methods for synthesis of triethylgallium or triethylindium have been known other than the method of the present invention, but in accordance with these known methods, group II element is inevitably incorporated and practically usable product cannot be obtained.
• the triethylgallium or triethylindium obtained from triethylaluminum whose silicon content is 4 ppm or lower as mentioned above alone or in a form of a mixture thereof or in admixture with an alkylaluminum compound is mixed with a group Va element, a hydride thereof or an alkyl compound thereof in vapor phase by known method to form an epitaxial layer on a surface of a substrate.
• arsenic or phosphorus may be used.
• phosphine As the group Va element, arsenic or phosphorus may be used.
• alkylphosphine As the hydride or alkyl compound of the group Va element, phosphine; alkylphosphines such as triethylphosphine, diethylphosphine, monoethylphosphine, tripropylphosphine, etc.; arsine; alkylarsines such as triethylarsine, diethylarsine, monoethyl arsine, monopropylarsine, etc.; or ammonia may be used.
• Use of phosphorus trichloride and arsenic trichloride is not preferred as the compound of group Va element because in this case, growth of crystal is difficult.
• alkylaluminum compound to be used in admixture with triethylgallium or triethylindium triethylaluminum, diethylaluminum hydride, tripropylaluminum, dipropylaluminum hydride, dibutylaluminum hydride, etc. may be used and preferably silicon content in these compounds is less than 1 ppm per aluminum atom.
• the growth of crystal may be carried out by the known method and known apparatus.
• Gas of alkyl compound of group llla element is introduced into crystal growing zone at a rate of (0.05 X 10' mol/min and group Va element, or hydride or alkyl compound thereof is introduced into the crystal growing zone at a rate of (0.05 50) X 10' mol/min.
• hydrogen, argon or a mixture thereof may be introduced as a carrier together with the alkyl compound of group Illa element and group Va element or a compound thereof.
• the same crystal as the growing layer, silicon, sapphire, spine], etc. may be used as the substrate. Growth of crystal is generally effected at a temperature of 500 1,300C.
• a reactor made of the usual refractories such as quartz, porcelain, carborundum, graphite, etc. may be used.
• the gaseous reagents are introduced in individual stream or in a mixture stream into the reactor.
• Heating of substrate in the reactor is generally carried out by induction heating so that the group Illa Va element compound is deposited on only the surface of the substrate.
• the method of the present invention has been explained with reference to growth of a high purity crystal, but donor or acceptor may be added to the growing layer by the conventional method at the time of growth of crystal.
• Semiconductors having the epitaxial layer produced by the method of the present invention can sufficiently be used for Gunn diode, superhigh frequency devices and electro-luminescent devices.
• the solution was transferred to a polyethylene beaker of 200 ml. Said platinum dish was washed with 1 cc of 8N nitric acid with warm and the washing solution was transferred to said beaker. Then, 20 ml of 8N nitric acid was further added to the content of the beaker. The beaker was covered with a polyethylene watch glass and the content was warmed to completely dissolve the precipitate. The solution was cooled and then transferred into a polyethylene measuring flask to attain predetermined volume. This was employed as a sample solution. 30 ml of this sample solution was taken and charged in a polyethylene beaker of ml.
• the pH of this solution was adjusted to 0.8 with ammonia water (if necessary, nitric acid is used) and was transferred into a polyethylene measuring flask of 50 ml.
• the solution was added 2.5 ml of an ammonium molybdate solution prepared by dissolving 10 g of ammonium molybdate in 100 ml of water and they were stirred and allowed to stand for 5 minutes.
• A Amount of silicon in the sample solution (g)
• B Amount of silicon in the blank test solution (g)
• C Amount of the sample solution used (m)
• W Amount of aluminum hydroxide (g)
• F Conversion factor of triethylaluminum and dried aluminum hydroxide In case of the above method, F 0.6.
• the following reagents were used in the above analysis.
• Water This was prepared by distilling an ion exchanged water in a quartz still to obtain water having a specific resistance of 1,500,000 wcm (30C).
• l-lexane This was prepared by treating a guaranteed grade hexane with sulfuric acid and then distilling it.
• Ammonium molybdate, sodium sulfite and l-amino-2-naphthol-4-sulfonic acid Commercially available guaranteed reagents ln carrying out the crystal growth of group Illa Va element compound using an alkyl compound ofa group llla element in accordance with the present invention, it is natural that purity of group Va element or a hydride of this element is also very important, but in the Examples hereinafter, raw materials commercially available as those for semiconductors were used.
• EXAMPLE 1 30 atm., 70 75C) were alternately charged and 7 they were reacted to obtain triethylaluminum.
• triethylaluminum was filtered and distilled and furthermore rectified through a packed column having theoretical plates to obtain triethylaluminum containing 0.5 ppm of silicon.
• gallium chloride was purified with sublimation.
• triethylgallium To the separated triethylgallium were added 20 parts of potassium chloride and 18 parts of sodium fluoride and they were stirred at C for 1 hour to fix triethylaluminum and diethylaluminum chloride present in a slight amount as a complex. Thereafter, they were rectified through a borosilicate glass (Pyrex glass) of 15 mm X 1,000 mm packed with a Pyrex glass spiral rings to obtain 162 parts of high purity triethylgallium. ii. 800 Parts of triisobutylaluminum, 250 parts of aluminum and 1,800 parts of isobutylene were charged in an autoclave and hydrogen was charged therein until 200 atm reached.
• borosilicate glass Pyrex glass
• triisobutylaluminum was allowed to contact with ethylene at 100C to cause alkyl exchange reaction to produce triethylaluminum.
• This triethylaluminum was filtered and distilled and furthermore was rectified through a packed column having 70 theoretical plates to obtain triethylaluminum containing 2.4 ppm of silicon. Then, triethylgallium was prepared in the same manner as in (i). iii. 43 Parts of aluminum and 2 parts of ethylaluminum sesquibromide were dissolved in methylcyclohexane.
• Triethylgallium was prepared in the same manner as in (i). iv. Metallic indium was placed in a transparent quartz reactor and chlorine was blown thereinto at 200C to produce indium chloride. This indium chloride was purified with sublimation.
• Triethylindium was produced from said indium chloride and triethylaluminum containing 0.5 ppm of silicon obtained in (i) in the same manner as the method of production of triethylgallium in (i).
• the triethylaluminum produced in (i) was subjected to simple distillation to obtain triethylaluminum containing 10 ppm of silicon and triethylgallium was produced in the same manner as in EXAMPLE 2
• This Example illustrates epitaxial growth of GaAs using triethylgallium and arsine as starting materials.
• EXAMPLE 3 This Example illustrates epitaxial growth of GaP with use of triethylgallium and phosphine or phosphorus.
• a substrate for crystal growth a semi-insulating GaP crystal of (l( 0) direct io n in whichghromium was doped in a high concentration was heated to 810C.
• triethylgallium obtained in (i) of Example 1 and phosphine were flowed over said substrate at 0.5 X 10 mol/min and 2 X 10 mol/min and hydrogen was flowed at 2.5 l/min through this system, rate of the epitaxial growth of GaP was [.L/hl.
• EXAMPLE 4 This Example illustrates epitaxial growth of GaAlAs and application thereof to lightemitting diode.
• (100) GaAs crystal doped with Te and having an electron concentration of l X l0 /cm was heated to 800C and H Te diluted to 100 ppm was added to the system in such a manner that electron concentration of the grown layer was 1 X l0"/cm and at the same time, triethylgallium prepared in (i) of Example l, arsine and H were flowed through the system at 5 X 10' mol/min, 2 X 10* mol/min and 2.5 l/min, respectively to carry out epitaxial growth of GaAs on the GaAs substrate for 30 minutes.
• epitaxial layer contained aluminum in a concentration of x 0.39 in Ga Al As.
• P-N junction was formed by Zn diffusion method using the general sealed tube method and then a diode was produced.
• Luminance of red emission at 20 mA was 200 fL. This value is substantially the same as that of the commercially available GaAsP luminous diode.
• electron concentration of the epitaxial layer wax 3 X l0 /cm and sufficiently high purity crystal can be obtained by this method.
• EXAMPLE 5 This Example illustrates growth of lnGaP crystal and characteristics of a luminous diodle to which said crystal was applied.
• GaP crystal doped with l X lO /cm of Te was heated to 830C. While phospine was flowed through the system at a flow rate of 3 X 10 mol/min, 100 ppm of H Te was also flowed therethrough so that the electron concentration of the grown layer reached 7 X IO /cm and then triethylgallium obtained in (i) of Example 1 was supplied at a flow rate of 3 X 10 mol/min using hydrogen as a carrier to effect growth of GaP crystal for 30 minutes. The total amount of hydrogen which flowed through the system at this time was 2 l/min.
• a method for producing an epitaxial layer of a group IIIa Va element compound on surface of a substrate which comprises reacting an alkyl compound of a group IIIa element with a group Va element or a volatile compound thereof in vapor phase and contacting the reaction product with the substrate, the improvement which comprises reacting triethylaluminum which contains at most 4 ppm of silicon with a gallium halilde or an indium halide to produce triethylgallium or triethylindium and contacting thus obtained triethyl gallium or triethylindium alone, a mixture of them or a mixture of them and an alkyl compound of aluminum with a group Va element, a hydride of said element or an alkyl compound of said element.
• triethylaluminum is prepared by a reaction of triethylaluminum, diethylaluminum hydride or a mixture thereof, aluminum, hydrogen and ethylene.
• triethylaluminum is prepared by reacting an alkylaluminum compound, aluminum and hydrogen or reacting an alkylaluminum compound, aluminum, hydrogen and 1 1 an olefin and subjecting thus obtained alkylaluminum to alkyl exchange reaction with ethylene.
• triethylaluminum is prepared by reducing an ethylaluminum sesquihalide obtained by reaction of aluminum and'an ethyl halide.
• gallium halide is selected from gallium chloride, gallium bromide and gallium iodide.
• indium halide is selected from indium chloride, indium bromide and indium iodide.
• hydride or alkyl compound of the group Va element is selected from phosphine, triethylphosphine, diethylphosphine, monoethylphosphine, tripropylphosphine, arsine, triethylarsine, diethylarsine, monoethylarsine, monopropylarsine and ammonia.
• alkyl compound of aluminum mixed with triethylgallium or triethylindium is selected from triethyl aluminum, diethylaluminum hydride, tripropylaluminum, dipropylaluminum hydride and dibutylaluminum hydride.
• a method according to claim 1, wherein the growth of crystal is carried out at 500 1,300C.
• An epitaxial layer having an electron concentration at room temperature of less than 1 X IO /cm which is obtained by the method defined in claim 1.

Landscapes

• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• General Physics & Mathematics (AREA)
• Manufacturing & Machinery (AREA)
• Computer Hardware Design (AREA)
• Physics & Mathematics (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Crystallography & Structural Chemistry (AREA)
• Metallurgy (AREA)
• Inorganic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Crystals, And After-Treatments Of Crystals (AREA)
• Chemical Vapour Deposition (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=12309998

Family Applications (1)

Country Status (4)

Cited By (13)

Families Citing this family (2)

Citations (3)

• 1973
  • 1973-03-15 JP JP48030664A patent/JPS5129880B2/ja not_active Expired
• 1974
  • 1974-03-13 US US450682A patent/US3867202A/en not_active Expired - Lifetime
  • 1974-03-14 FR FR7408715A patent/FR2221183B1/fr not_active Expired
  • 1974-03-14 GB GB1151774A patent/GB1462471A/en not_active Expired

Patent Citations (3)

Also Published As

Similar Documents