US3341359A - Process for pyrolytically precipitating elemental semiconductor substance - Google Patents

Process for pyrolytically precipitating elemental semiconductor substance Download PDF

Info

Publication number
US3341359A
US3341359A US300587A US30058763A US3341359A US 3341359 A US3341359 A US 3341359A US 300587 A US300587 A US 300587A US 30058763 A US30058763 A US 30058763A US 3341359 A US3341359 A US 3341359A
Authority
US
United States
Prior art keywords
temperature
carrier
precipitation
substance
reaction gas
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
Application number
US300587A
Other languages
English (en)
Inventor
Rummel Theodor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens and Halske AG
Siemens Corp
Original Assignee
Siemens Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Siemens Corp filed Critical Siemens Corp
Application granted granted Critical
Publication of US3341359A publication Critical patent/US3341359A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • 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
    • 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
    • C30B29/02—Elements
    • C30B29/08—Germanium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32082—Radio frequency generated discharge
    • H01J37/321—Radio frequency generated discharge the radio frequency energy being inductively coupled to the plasma
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/32—Processing objects by plasma generation
    • H01J2237/33—Processing objects by plasma generation characterised by the type of processing
    • H01J2237/332—Coating
    • H01J2237/3321—CVD [Chemical Vapor Deposition]
    • 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
    • Y10S438/935—Gas flow control

Definitions

  • My invention relates of elemental semiconductor substance, preferably silicon or germanium, from a reaction gas containing a compound of the substance, upon a monocrystalline rodshaped carrier.
  • a monocrystalline carrier rod mounted only at its ends, is subjected to a flow of a reaction gas consisting of hydrogen and silicon halogenide and is heated to incandescent, pyrolytic temperature.
  • a reaction gas consisting of hydrogen and silicon halogenide
  • the halogen compound of silicon is dissociated and the evolving free silicon precipitates upon the carrier rod where it forms a growing monocrystalline layer.
  • the resulting jacket portion of monocrystalline silicon can be grown, in principle, up to any desired thick ness. Since the carrier body can be heated to a high and uniform surface temperature, for example by passing electric current from the rod holders through the carrier rod, the entire carrier surface with the exception of the mounted ends is available for the precipitation thereon so that the silicon content of the reaction gas is well utilized.
  • a particular prerequisite for trouble-free monocrystalline growth is the maintenance of the carrier surface at a temperature below the melting temperature of the carrier because otherwise the precipitated silicon would accumulate in droplets which would interfere with the uniformity and precipitation required for monocrystalline growth on the semiconductor surface. Nevertheless, even if the formation of molten or fused localities at the carrier surface is avoided, considerable difliculties are encountered in growing monocrystalline silicon and other elemental semiconductor substances from the gaseous phase.
  • the carrier rod is heated by directly passing electric current therethrough.
  • the carrier is disposed on the axis of an induction winding which concentrically surrounds the carrier and is energized with alternating current, particularly of high-frequency.
  • the axial length of the coil is preferably so dimensioned that the peripheral carrier surface on which the precipitation is to take place becomes inductively heated to the pyrolytic temperature as uniformly as posto the pyrolytic precipitation sible.
  • I maintain the monocrystalline rod-shaped carrier or core during the entire pyrolytic precipitation process at a proper temperature below the melting point of the elemental semiconductor substance by subjecting the carrier surface to induction heating by means of an electromagnetic field preferably of high-frequency, along the entire length that is to receive the precipitate.
  • I further adjust the composition of the reaction gas during the entire precipitation process in such a manner that the precipitation rate of the elemental semiconductor substance has a maximal value at a temperature T which is below the pyrolytic operating temperature T, that is maintained inductively and substantially uniformly at the carrier surface, the precipitation rate having upwardly from the temperature T at its maximum a monotonously or continuously declining range which includes the chosen pyrolytic precipitation temperature T,, of the carrier surface, so that the actually effective precipitation rate is appreciably smaller than that obtaining at the lower temperature T
  • FIG. 1 is a coordinate diagram of precipitation rate against carrier temperature
  • FIG. 2 shows schematically and in section an apparatus for performing the process according to the invention.
  • the curve shown in the diagram of FIG. 1 is typical of the precipitation characteristic required of a reaction gas suitable for performing the process according to the invention.
  • the abscissa indicates the temperature T at the carrier surface.
  • the ordinate indicates the quantity m of the elemental semiconductor substance, here silicon, which is precipitated upon each cm. of the carrier surface per minute. Consequently, the m-values indicate the rate of precipitation.
  • the values shown in the diagram are conditioned upon maintaining a constant flowing speed of the reaction gas through the reaction vessel.
  • the precipitation of silicon begins to be noticeable at a threshold temperature T As the carrier surface temperature increases to a temperature T the precipitation rate also increases.
  • the precipitation rate monotonously or continuously declines through a range of temperatures which includes the chosen pyrolytic working temperature T at the carrier surface.
  • This pyrolytic working or reaction temperature T should be higher than the temperature T of maximum precipitation, but must remain lower than the melting temperature T of the carrier.
  • the reaction temperature at the carrier surface must be lower than 1415 C.
  • the temperature T is higher than 1100 C., and even more particularly higher than 1150 C.
  • the composition of the reaction gas decisively determines whether in a particular case the curve of precipitation rate against carrier temperature possesses the characteristic exemplified in FIG. 1 which is necessary for the process performed in accordance with the invention.
  • An example of an unsuitable reaction gas is one in which the semiconductor compound to be dissociated is a silane. Silanes or other pure gaseous hydrogen compounds of semiconducting elements, when used in the process, become increasingly dissociated at increasing temperature during the formation of the semiconducting element, and the precipitation curve, if plotted in accordance with the principles of FIG. 1, does not exhibit a maximum value followed by a range descending toward higher temperature values.
  • the necessary precipitation-temperature characteristic can be produced and regulated by employing semiconductor-halogen compounds.
  • the quantity of the precipitation silicon also depends upon the pressure of the reaction gas and amounts at normal atmospheric pressure to about 2 mg. silicon per minute and per cm. of carrier surface. If the carrier temperature is increased above 1400" C., the precipitation rate decreases.
  • the value of the temperature T greatly depends upon the hydrogen content of the reaction gas. For example with molar ratio of 7 mole percent SiHCl and 93 mole percent hydrogen, the temperature T of maximum precipitation is considerably above the melting point of silicon.
  • silicon tetrachloride SiCl is used instead of silicochloroform SiHCl analogous temperature and composition ratios are applicable, except that the quantity of silicon precipitating during unit time for a given gas pressure and a given temperature is smaller than when using SiHCl under the otherwise same conditions.
  • FIG. 2 An example of the process performed according to the invention will be best described with reference to FIG. 2 in which there is shown a rod-shaped carrier 'body 3 of hyperpure silicon mounted in vertical position in a cylindrical quartz reaction vessel 1 by means of coaxially spaced holders 2 and 2 also consisting of quartz.
  • the reaction vessel has an inlet opening 4 and an outlet opening 5 for the reaction gas.
  • a tightly wound induction coil 6 serving to heat the carrier is mounted in the outer surface of the reaction vessel and is sufficiently long enough to extend along the entire length of the carrier 3 between the two holders. During operation, the coil is energized by alternating current supplied from a high-frequency generator 7.
  • the reaction gas consists of 2 mole percent SiHCl and 98 mole percent H
  • the gaseous mixture is produced by passing a current of hydrogen in the direction of the arrow as shown in FIG. 2 through an evaporator vessel 8 filled With liquid SiHCl whose temperature is kept constant by means of a temperature bath 10.
  • the hydrogen and the liquid SiHCl used are available in highly pure condition.
  • a gas-flow speed measuring instrument 9 is provided for determining the quantity of reaction gas entering per unit time into the reaction vessel. Also provided is a bypass 11 for the evaporator vessel 8 which is controllable by valves 11a, 11b, to permit further dilution of the gas coming from the evaporator by adding pure hydrogen. For example, flow through valve 1112 can be suitably reduced while the flow through valve 11a can be increased as required.
  • the quantity of SiHCl entering per unit time into the reaction vessel 1 is dependent upon the temperature of the evaporator vessel 8 and the flow speed of the hydrogen gas passing through the evaporator vessel.
  • the amount of SiHCl in the reaction gas can be regulated.
  • This amount also depends upon the size and shape of the evaporator vessel, and it is, therefore, not possible to make definite and broadly applicable statements with respect to the temperature of the evaporator vessel and flow speed of the gas.
  • the gas-flow meter 9 the amount of hydrogen consumed within a given time can be measured and the hydrogen flow can then be regulated at will.
  • the precipitation vessel can be substituted in preliminary tests by a cooling trap in which the entire SiI-lCl entrained by the hydrogen current is caused to freeze out. In this manner, the SiHCl content in the reaction gas which is entrained by the hydrogen at a given evaporator temperature and at a given flow speed of the hydrogen gas, can readily be determined.
  • the carrier 3 is heated to the desired precipitation temperature.
  • the induction field at the coil 6 is switched on and the carrier is thus heated up to the glowing temperature corresponding to the chosen value.
  • the temperature is then controlled and kept constant in known manner.
  • the reaction gas is introduced into the reaction vessel in accordance with the composition determined by the preliminary tests, for example in the manner heretofore explained.
  • the carrier surface Since the growth of the carrier by precipitation takes place in the radial direction, the carrier surface gradually approaches the inner periphery of the induction heater coil as the precipitation process progresses. Consequently, the inductive coupling between the coil and the carrier surface increases during the precipitation process.
  • the temperature of the carrier surface consequently likewise increases when the power supply to the heater coil is kept constant. Similar results are produced by the socalled skin effect resulting from eddy currents induced in the surface zone of the carrier and heating the carrier. Any parts protruding at the carrier surface, for example bosses or other protuberances, are therefore hotter than the normal carrier surface or even any recesses in the surface. These conditions are just the opposite from those existing when the carrier is heated by means of alternating current or direct current supplied by electrodes or termina s.
  • the reaction gas employed in accordance with the invention is selected with due regard to the pyrolytic precipitation temperature adjusted at the carrier surface, so that a reduction in precipitation takes place when the surface temperature is increased, and so that the rate of precipitation is augmented when the carrier temperature decreases. Consequently, any protruding and therefore hotter localities of the carrier surface encounter a reduced amount of precipitation, and any recessed and therefore cooler localities of the carrier surface receive an increased amount of precipitation.
  • the semiconducting compound employed in the process according to the invention is greatly diluted with hydrogen and since, furthermore, precipitation takes place either under normal atmospheric pressure or at negative pressure, supersaturation of the carrier with precipitating semiconductor material generally does not occur.
  • the doping element may be added to the reaction gas either in pure condition or in the form of a halogen or hydrogen compound, if it is desired to build the dopant int-o the semiconductor during the pyrolytic production process. Since the fraction of the dopant in the reaction gas must be fundamentally set at a very small value, the configuration of the precipitation curve of the semiconducting element from the reaction gas is not appreciably influenced thereby.
  • said substance being silicon
  • said reaction gas being fugitive halogen silane
  • said pyrolytic reaction temperature being between 1100 and 1415 C.
  • reaction gas comprises, as another component thereof, hydrogen intermixed with the halogen silane thereof.
  • reaction-gas mixture consisting substantially of about 98 mole percent hydrogen and about 2 mole percent of said silicon compound, and said reaction temperature at the carrier surface being above 1150 C. but less than 1415 C.
  • reaction temperature at the carrier surface being about 1250 C.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Chemical Vapour Deposition (AREA)
US300587A 1962-08-24 1963-08-07 Process for pyrolytically precipitating elemental semiconductor substance Expired - Lifetime US3341359A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DES0081093 1962-08-24

Publications (1)

Publication Number Publication Date
US3341359A true US3341359A (en) 1967-09-12

Family

ID=7509332

Family Applications (1)

Application Number Title Priority Date Filing Date
US300587A Expired - Lifetime US3341359A (en) 1962-08-24 1963-08-07 Process for pyrolytically precipitating elemental semiconductor substance

Country Status (6)

Country Link
US (1) US3341359A (enrdf_load_html_response)
CH (1) CH430665A (enrdf_load_html_response)
DE (1) DE1444526B2 (enrdf_load_html_response)
FR (1) FR1397154A (enrdf_load_html_response)
GB (1) GB998942A (enrdf_load_html_response)
SE (1) SE337973B (enrdf_load_html_response)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4426408A (en) 1978-07-19 1984-01-17 Siemens Aktiengesellschaft Method of deposition of silicon in fine crystalline form

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3444327B2 (ja) * 1996-03-04 2003-09-08 信越半導体株式会社 シリコン単結晶薄膜の製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1048638B (de) * 1957-07-02 1959-01-15 Siemens &. Halske Aktiengesellschaft, Berlin und München Verfahren zur Herstellung von Halbleitereinkristallen, insbesondere von Silizium durch thermische Zersetzung oder Reduktion
US3222217A (en) * 1959-09-23 1965-12-07 Siemens Ag Method for producing highly pure rodshaped semiconductor crystals and apparatus
US3232792A (en) * 1954-05-18 1966-02-01 Siemens Ag Method for producing hyperpure silicon
US3239372A (en) * 1960-01-15 1966-03-08 Siemens Ag Method of producing single crystal silicon

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3232792A (en) * 1954-05-18 1966-02-01 Siemens Ag Method for producing hyperpure silicon
DE1048638B (de) * 1957-07-02 1959-01-15 Siemens &. Halske Aktiengesellschaft, Berlin und München Verfahren zur Herstellung von Halbleitereinkristallen, insbesondere von Silizium durch thermische Zersetzung oder Reduktion
US3222217A (en) * 1959-09-23 1965-12-07 Siemens Ag Method for producing highly pure rodshaped semiconductor crystals and apparatus
US3239372A (en) * 1960-01-15 1966-03-08 Siemens Ag Method of producing single crystal silicon

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4426408A (en) 1978-07-19 1984-01-17 Siemens Aktiengesellschaft Method of deposition of silicon in fine crystalline form

Also Published As

Publication number Publication date
FR1397154A (fr) 1965-04-30
GB998942A (en) 1965-07-21
SE337973B (enrdf_load_html_response) 1971-08-23
DE1444526A1 (de) 1968-10-17
CH430665A (de) 1967-02-28
DE1444526B2 (de) 1971-02-04

Similar Documents

Publication Publication Date Title
US4659421A (en) System for growth of single crystal materials with extreme uniformity in their structural and electrical properties
US20100101485A1 (en) Manufacturing method of silicon single crystal
JP6202119B2 (ja) シリコン単結晶の製造方法
CA1178178A (en) Gas curtain continuous chemical vapor deposition production of semiconductor bodies
KR100204522B1 (ko) 단결정 성장방법 및 그 장치
US3341359A (en) Process for pyrolytically precipitating elemental semiconductor substance
US3351433A (en) Method of producing monocrystalline semiconductor rods
US5840116A (en) Method of growing crystals
JPS6156162B2 (enrdf_load_html_response)
US2890939A (en) Crystal growing procedures
JPS6156163B2 (enrdf_load_html_response)
US3099523A (en) Method of producing hyperpure silicon, silicon carbide and germanium
US3558376A (en) Method for controlled doping by gas of foreign substance into semiconductor materials
US3021198A (en) Method for producing semiconductor single crystals
JPH0317771B2 (enrdf_load_html_response)
US3293001A (en) Process and apparatus for producing elongated, particularly tape-shaped semiconductor bodies from a semiconductor melt
US3179593A (en) Method for producing monocrystalline semiconductor material
US3160476A (en) Process of producing compact boron, particularly in monocrystalline form
US3144357A (en) Preparation of semiconductor materials
EP0045600B1 (en) Improved method for producing semiconductor grade silicon
US4111742A (en) Process for producing crucible-drawn silicon rods containing volatile doping agents
JPS62501497A (ja) 連続して引き出される単結晶シリコンインゴット
JP2710433B2 (ja) 単結晶引上装置
JP2785623B2 (ja) 単結晶成長装置
CA1178180A (en) Method for producing semiconductor grade silicon