US3810794A - Preparation of gap-si heterojunction by liquid phase epitaxy - Google Patents

Preparation of gap-si heterojunction by liquid phase epitaxy Download PDF

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Publication number
US3810794A
US3810794A US00075001A US7500170A US3810794A US 3810794 A US3810794 A US 3810794A US 00075001 A US00075001 A US 00075001A US 7500170 A US7500170 A US 7500170A US 3810794 A US3810794 A US 3810794A
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United States
Prior art keywords
gap
solution
substrate
solvent
saturated
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Expired - Lifetime
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US00075001A
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English (en)
Inventor
G Antypas
F Rosztoczy
W Stein
Szeremy S Von
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Varian Medical Systems Inc
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Varian Associates Inc
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Priority to US00075001A priority Critical patent/US3810794A/en
Priority to GB4114571A priority patent/GB1332389A/en
Priority to DE19712144828 priority patent/DE2144828A1/de
Priority to NL7113128A priority patent/NL7113128A/xx
Priority to FR7134385A priority patent/FR2108499A5/fr
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Publication of US3810794A publication Critical patent/US3810794A/en
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/29—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by the substrates
    • H10P14/2901—Materials
    • H10P14/2902—Materials being Group IVA materials
    • H10P14/2905—Silicon, silicon germanium or germanium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/26—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using liquid deposition
    • H10P14/263—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using liquid deposition using melted materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/26—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using liquid deposition
    • H10P14/265—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using liquid deposition using solutions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
    • H10P14/34—Deposited materials, e.g. layers
    • H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
    • H10P14/3414—Deposited materials, e.g. layers characterised by the chemical composition being group IIIA-VIA materials
    • H10P14/3418—Phosphides
    • 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
    • Y10S148/059—Germanium on silicon or Ge-Si on III-V
    • 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
    • Y10S148/072—Heterojunctions
    • 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
    • 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
    • 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
    • Y10S438/933—Germanium or silicon or Ge-Si on III-V

Definitions

  • the molten, saturated solution was brought into contact with a Si single crystal substrate and cooled, causing the GaP to form an epitaxial layer on the Si surface.
  • the crystal lattice structure and dimensions of Si and GaP crystals are very similar.
  • the preferred physical properties of the solvent are: a relatively high solubility for GaP; a relatively low solubility for Si; and a relatively low solubility of the selected solvent in the epitaxially grown GaP.
  • This invention relates to the epitaxial growth of GaP on Si by liquid phase epitaxy and more particularly to the use of Pb and/or Sn as solvents for that purpose.
  • FIG. 1 is a sectional view of a tiltable furnace tube in the standby position showing the saturated solution and the silicon substrate before contact;
  • FIG. 2 is a sectional view of the tiltable furnace in the growing position showing the saturated solution covering the Si substrate during epitaxy;
  • FIG. 3 is a plot of temperature versus time depicting the thermal cycle employed by the apparatus of FIG. 1 and 2.
  • FIG. 1 there is shown a tiltable furnace tube 10 in a first or standby position, containing a boat 12.
  • Boat 12 is made of a refractory material, for example,
  • a solution 14 of GaP and Si in a solvent is shown at the lower end of boat 12.
  • the solution is preferably saturated with GaP to expedite epitaxial growth later.
  • Solution 14 is maintained in the molten state by a furnace (not shown).
  • Excess GaP 15 on solution 14 assures that the solution is saturated.
  • a Si wafer or substrate 16 is mounted at the upper end of boat 12 by means of a refractory hold down screw 18 which is also a refractory material. It is preferable that Si substrate 16 be a single crystal having a crystal orientation of (111) or A flow of inert gas, preferably H is maintained through furnace tube 10 to prevent oxidation of molten solution 14.
  • FIG. 1 Contact between solution 14 and substrate 16 is established by tilting furnace tube 10 into a second or growing position as shown in FIG. 2.
  • Solution 14 rolls to the opposite end of furnace tube 10' and covers substrate 16 causing a GaP crystal 20 to form.
  • the apparatus of FIG. 1 is similar in design to the H. Nelson apparatus described in RCSA Review, vol. 24, page 603 (1963). Clearly other types of solution-substrate contacting apparatus may be employed.
  • FIG. 3 depicts the thermal cycle employed in growing GaP layer 20 on substrate 16 using the apparatus of FIG. 1.
  • the temperature is elevated with furnace tube 10 in the standby position.
  • time t furnace is maintained at a preselected constant temperature Thigh to melt the initial charge and form saturated solution 14.
  • Thigh a preselected constant temperature
  • the temperature is slowly decreased to T causing GaP to form an epitaxial layer onto substrate 16.
  • the lattice constant of GaP is 5.4505 and the lattice constant of Si is 5.43072, sufficiently matched to permit GaP to epitaxially grow on the surface of Si substrate 16.
  • a scraper apparatus not shown.
  • the solvent or carrier material in saturated solution 14 may be formed by more than one material, and is selected on the basis of the following physical properties:
  • Pb solvent embodiment Pb is a suitable solvent for the present technique.
  • Pb has a low solubility coefficient for Si (about 0.1 mol percent at 950 C.) and a high solubility coeflicient of GaP (about 2 mol percent at 950 C.).
  • saturated solution 14 was prepared by thoroughly mixing 13 grams of Pb and 0.3 gram of GaP. The amount of GaP is more than can be dissolved in 13 grams of Pb at the Thigh involved which guaranteed that the solution was saturated. The mixture was placed in boat 12 and maintained at 950 C. for 60 minutes. A small portion of the Ga? remained undissolved. The system was quenched and subsequently saturated with Si at 950 C. for 60 minutes to prevent Si substrate 16 from dissolving into solution 14 during the FIG.
  • Thigh (in this case preferably 950 C.) is not critical and is a function of the solubility coefficients of the materials and the desired composition of solution 14.
  • solution 14 should be about 1% by weight of GaP.
  • the concentration of GaP can be as low as .1% by weight, in which case the epitaxial growth proceeds very slowly.
  • the concentration of GaP may be as high as 20% or even higher.
  • T in this case preferably 800 C.
  • time periods described above are representative of the time required for the solution to reach equilibrium without external agitation. Atomic diffusion was the primary means through which equilibrium was obtained. The time periods may be shortened considerably by agitating solution 14 or rocking boat 12. In any event the time periods are not generally critical.
  • Sn is also a suitable solvent having a relatively low solubility coefiicient for Si and a relatively high solubility coefiicient of GaP.
  • a saturated solution of GaP in Sn was prepared by placing grams of Sn and 0.5 gram of GaP in boat 12 (more than sufiicient GaP for the temperature involved) and maintaining the temperature at 850 C. for a period of 60 minutes.
  • Solution 14 was quenched and Si saturated as described in the Pb embodiment and brought into contact with substrate 16. The temperature was lowered to 650 C. over a period of 3 hours, resulting in a micron GaP layer epitaxially grown on Si.
  • the quenching steps can be eliminated by initially placing all of solution 14 constituents (GaP, Pb and/or Sn, Si) at the lower end of the boat in the standby position. Si substrate 16 is then mounted at the upper end of boat 12. The temperature of the system is cycled only once as depicted in FIG. 3.
  • the resulting GaP-Si heterojunction has a low cost Si base.
  • the price of the Si substrate is approximately 1000 4 times less than the price of suitable GaP substrates.
  • the uncoated side of the Si substrate is also suitable for use as part of the integrated circuit employed in conjunction with the GaP layer.
  • a vertical structure may be employed wherein the substrate is dipped into the solution (see F. E. -Rosztoczy, Varian Technical Journal, No. 3, page 1 (Spring 1970).
  • a steady state-temperature gradient technique may be employed which does not employ a thermal cycle as depicted in FIG. 3. Instead, the substrate is maintained at a constant temperature slightly lower than the source of GaP causing a gradient across the solution.
  • concentration by weight of GaP in the solution is from about 0.1% to about 20%.

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  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US00075001A 1970-09-24 1970-09-24 Preparation of gap-si heterojunction by liquid phase epitaxy Expired - Lifetime US3810794A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US00075001A US3810794A (en) 1970-09-24 1970-09-24 Preparation of gap-si heterojunction by liquid phase epitaxy
GB4114571A GB1332389A (en) 1970-09-24 1971-09-03 Preparation of gap-si heterojunction by liquid phase epitaxy
DE19712144828 DE2144828A1 (de) 1970-09-24 1971-09-08 Verfahren zur Bildung einer GaP Schicht auf einem Si-Träger
NL7113128A NL7113128A (enExample) 1970-09-24 1971-09-23
FR7134385A FR2108499A5 (enExample) 1970-09-24 1971-09-24

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US00075001A US3810794A (en) 1970-09-24 1970-09-24 Preparation of gap-si heterojunction by liquid phase epitaxy

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US (1) US3810794A (enExample)
DE (1) DE2144828A1 (enExample)
FR (1) FR2108499A5 (enExample)
GB (1) GB1332389A (enExample)
NL (1) NL7113128A (enExample)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4128440A (en) * 1978-04-24 1978-12-05 General Electric Company Liquid phase epitaxial method of covering buried regions for devices
US4591408A (en) * 1982-11-16 1986-05-27 Stauffer Chemical Company Liquid phase growth of crystalline polyphosphide
WO1987007313A1 (en) * 1986-05-28 1987-12-03 Massachusetts Institute Of Technology Epitaxial growth
US4764350A (en) * 1986-10-08 1988-08-16 The United States Of America As Represented By The Secretary Of The Air Force Method and apparatus for synthesizing a single crystal of indium phosphide
US5057287A (en) * 1988-11-01 1991-10-15 Sfa, Inc. Liquid encapsulated zone melting crystal growth method and apparatus
US5278452A (en) * 1991-02-13 1994-01-11 Koito Manufacturing Co., Ltd. Lighting apparatus for vehicular discharge lamp

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4310612C1 (de) * 1993-03-31 1994-11-10 Max Planck Gesellschaft Flüssigphasen-Heteroepitaxieverfahren

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4128440A (en) * 1978-04-24 1978-12-05 General Electric Company Liquid phase epitaxial method of covering buried regions for devices
US4591408A (en) * 1982-11-16 1986-05-27 Stauffer Chemical Company Liquid phase growth of crystalline polyphosphide
WO1987007313A1 (en) * 1986-05-28 1987-12-03 Massachusetts Institute Of Technology Epitaxial growth
US4764350A (en) * 1986-10-08 1988-08-16 The United States Of America As Represented By The Secretary Of The Air Force Method and apparatus for synthesizing a single crystal of indium phosphide
US5057287A (en) * 1988-11-01 1991-10-15 Sfa, Inc. Liquid encapsulated zone melting crystal growth method and apparatus
US5278452A (en) * 1991-02-13 1994-01-11 Koito Manufacturing Co., Ltd. Lighting apparatus for vehicular discharge lamp

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Publication number Publication date
FR2108499A5 (enExample) 1972-05-19
NL7113128A (enExample) 1972-03-28
DE2144828A1 (de) 1972-03-30
GB1332389A (en) 1973-10-03

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