US3201209A - Hydrothermal growth of zinc oxide crystals - Google Patents

Hydrothermal growth of zinc oxide crystals Download PDF

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Publication number
US3201209A
US3201209A US268326A US26832663A US3201209A US 3201209 A US3201209 A US 3201209A US 268326 A US268326 A US 268326A US 26832663 A US26832663 A US 26832663A US 3201209 A US3201209 A US 3201209A
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United States
Prior art keywords
growth
zinc oxide
molal
crystals
nutrient
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Expired - Lifetime
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US268326A
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English (en)
Inventor
Anthony J Caporaso
Ernest D Kolb
Robert A Laudise
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AT&T Corp
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Bell Telephone Laboratories Inc
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Priority to DENDAT1251294D priority Critical patent/DE1251294B/de
Application filed by Bell Telephone Laboratories Inc filed Critical Bell Telephone Laboratories Inc
Priority to US268326A priority patent/US3201209A/en
Priority to NL6401340A priority patent/NL6401340A/xx
Priority to BE645214D priority patent/BE645214A/xx
Priority to GB11609/64A priority patent/GB1061831A/en
Application granted granted Critical
Publication of US3201209A publication Critical patent/US3201209A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • 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
    • C30B29/16—Oxides
    • 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
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T117/00—Single-crystal, oriented-crystal, and epitaxy growth processes; non-coating apparatus therefor
    • Y10T117/10—Apparatus
    • Y10T117/1024—Apparatus for crystallization from liquid or supercritical state
    • Y10T117/1096—Apparatus for crystallization from liquid or supercritical state including pressurized crystallization means [e.g., hydrothermal]

Definitions

  • Zinc oxide has recentlybeen found to be strongly piezoelectric with a coupling coefficient significantly larger than quartz.
  • Zinc oxide characteristically grows most rapidly in the 000l direction. As the growth proceeds, the growth plane, (0001), typically becomes rough or cobbled due to nucleation of new growth steps before completion of old steps on the (0001) growth plane. The peaks of the cobbles begin to grow more rapidly than the valleys due to the existing supersaturation gradient. Ultimately dendritic growth begins and the resulting crystal becomes heavily flawed.
  • the premature nucleation of aditional growth steps during the planar growth is retarded so that growth proceeds uniformly along successive growth planes. This is achieved by the addition of a specified amount of lithium ion to the hydro-' thermal solution.
  • the figure is a perspective view, partly cut away, of an apparatus appropriate for carrying out the process of this invention.
  • the apparatus of the figure is basically a pressuretemperature bomb and is generally known in the art as a Morey autoclave. It consists of a casing 10 which is constructed of high strength steel alloy such as Inconel or Timken1722 A(S). The casing is sealed by cover 11 which includes a plunger 12. Within the casing is a liner 13. Sealing the liner is seal disk 14 and the lower portion of the plunger 12. The liner consists of a noble metal. Silver is particularly suitable since it is resistant to corrosive attack by the hot alkaline hydrothermal solution.
  • the interior of the casing is made free of imperfections and machine marks.
  • the bottom of the cavity is machined to be flat with a /8 radius which blends smoothly with the wall and the bottom.
  • a weep hole (not shown) is formed in the bottom of the casing.
  • the liner is made of 0.045" anode silver with 0.075" sterling silver lip 15.
  • the liner is deep drawn with intermediate half hour anneals at 400 C. in a helium atmosphere. Stress and grain growth during drawing are minimized by using lubricants and by Patented Aug. 17, 1965 drawing slowly.
  • the lip 15 is welded on the liner with a helium arc torch.
  • Seeds for the hydrothermal growth may be obtained by the flux growth technique described in Journal of Physical Chemistry, vol. 64, page 688 (1960).
  • the seeds are appropriately of the order of 0.3 mm. thick and 10 mm. x 10 mm. in the longer dimensions.
  • the constituents of the solution should be of at least reagent purity.
  • the furnace and controllers (not depicited) must be capable of maintaining a reasonable temperature control such as to Within i3 C.
  • the temperatures are measured by thermocouple units installed at various points on the autoclave.
  • the interior portion of the autoclave, shown in the figure, indicates the position of the growth seeds 16 with respect to the nutrient mass 17.
  • a battle 18 which serves to maintain a temperature differential between the growth region and the nutrient region of the hydrothermal solution while permitting the flow of zinc oxide rich solution to the growth region.
  • the baflie may be of the order of 2 to 20% open.
  • a convenient baffle construction is 5% open with one-half of the space in a central opening and the remainder distributed about the periphery.
  • the seeds are suspended by silver wire 19.
  • the hydrothermal solution 20 which fills the autoclave at the operating temperature, consists of a solution of 2 to 8 molal alkali or alkaline earth metal hydroxide and a lithium ion concentration of 0.1 to 4.0 molal.
  • Appropriate alkali compounds are NaOH, KOH, CsOH, RbOI-l, Sr(OH) Ba(OH) and mixtures thereof.
  • ⁇ reasonably soluble lithium compound is adequate for contributing the desired amount of lithium ion.
  • the anion is not important. However, certain combinations are obviously to be preferably avoided such as Ba(OH) and Li SO since barium sulfate will precipitate and may interfere with the crystal quality.
  • Suggested lithium salts are lithium acetate, lithium tetraborate, lithium citrate, lithium for-mate, lithium hydroxide, lithiumnitrate, lithium oxalate, lithium sulfate and the halide salts.
  • the bottom of the autoclave is charged with nutrient zinc oxide particles.
  • the effect of nutrient size on rate and perfection can be understood in terms of its effect on the dissolving step.
  • Small size nutrient packs tightly in the autoclave and prevents circulation of the solution through it. Its efiective surface area for dissolving in the limiting case is the cross-sectional area of the autoclave. Under such conditions, dissolving is rate limiting and the growth rate falls off.
  • the small particles are easily swept about by the convection currents and act as nucleation sites for spontaneous nucleation and as sites for flawed growth on the seeds. circulation through the nutrient is easier making the effective surface area for dissolving larger, so that dissolving is not rate limiting and the rate increases.
  • seed crystals may be prepared by flux growth techniques.
  • useful seeds may also be obtained by the hydrothermal technique of this invention. In either case it is found that the surface As the particle size is increased,
  • the pressure condition within the autoclave will be determined by the degree of fill and the temperature. However, a useful pressure range can be stated as 3200 psi. to 8000 psi. The upper limit reflects, in part, the capabilities of the particular container which was used in the present investigation. Higher pressures may become practical with improved apparatus designs. The lower limit coincides approximately with the critical pressure of the solution which, it has been found, should be exceeded.
  • Example I The autoclave was charged with 6 molal KOI-I and 0.1 molal LiF. The amount of solution was sufiicient to fill 83% of the total volume of the autoclave at room temperature excluding the seed and nutrient volume.
  • the seed crystals were 0.05 mm. in thickness with their major faces in the (0001) and (000i) planes. The seeds were suspended in the upper region of the autoclave, as in the figure and were held by silver wires.
  • the nutrient material was sintered, recrystallized ZnO. The particles were of a size which was retained by a US. #10 sieve and generally smaller than A.
  • the autoclave was sealed and heated slowly to 353 C.
  • the baffie used was 5% open and was effective in maintaining an operating temperature differential between the growth region and nutrient of C.
  • the growth proceeded for days.
  • vAt the termination Q 7t g owth period crystals were The previous example was re-run with a reduced amount of lithium ion.
  • the autoclave was charged with 6.4 molal KOH and 0.01 molal LiF and filled to 83% of capacity.
  • the autoclave was sealed and heated slowly to 353 C. A temperature difference of 15 C. was established between the growth region and the nutrient region. Under these conditions the growth proceeds rather fast and the crystals obtained were heavily flawed and substantially inferior to those obtained in the previous example. Since only one variable was changed, this was due to the insufiicient amount of lithium ion present in the growth solution. Consequently, it is considered essential that the operating concentration of lithium ion reach at least 0.1 molal.
  • Example 111 Example I was repeated using a temperature difference of 14 C. and a hydrothermal solution consisting of 6.4 molal KOH, and 0.3 molal LiF. The growth rate was 9.0 mils/day and the crystal quality remained excellent.
  • Example IV The growth conditions of Example 111 were followed this time using 6.4 molal KOH and 0.2 molal LiOH. The results were essentially unchanged.
  • Example V In this example the autoclave was charged to of fill with 6.4 molal KOH and 0.3 molal LiOH. The growth temperature was 340 C. and the temperature difference was 8 C. The growth rate under these conditions was 15.7 mils/day and the crystals were again of high quality.
  • Example VI Example V was repeated without the inclusion of lithium ion. The crystals obtained were heavily flawed and were generally undesirable for device use.
  • Example VII This example followed the growth conditions of Example V except that the lithium addition was in the form of 0.9 molal LiOH. The crystals obtained were of high quality with a lower growth rate.
  • Example VIII In this example the solution was 6.4 molal KOH and 0.2 molal Li B O with an 85% fill. The growth temperature was 340 C. and the nutrient temperature was 327 C. Again the crystals were of exceptional quality. The rate of growth was 9.2 mils/day.
  • Example 1X The procedure of Example I was repeated using NaOH in place of KOH. Essentially the same results were obtained.
  • Example X To determine how much Li+ can be tolerated consistent with the results desired, a run was made following the conditions of Example V except that the lithium was present in a4 molal concentration. Essentially the same crystals were obtained except, as might be suggested by Example VII, the growth rate was somewhat reduced.
  • a method of growing zinc oxide crystals from a hydrothermal solution which comprises maintaining a zinc oxide crystal seed and a mass of nutrient zinc oxide in an aqueous medium comprising lithium ions and a metal hydroxide selected from the group consisting of alkali metal hydroxides, strontium hydroxide and barium hydroxide and mixtures thereof, the lithium ion and the metal hydroxide having concentrations of 0.1 to 4.0 molal and 2 to 8 molal, respectively at a temperature of at least 300 C. at a pressure of at least 3200 p.s.i. While rnaintaining a temperature difference between said seed and said nutrient mass of from 5 to 100 C. without the nutrient hotter than the seed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US268326A 1963-03-27 1963-03-27 Hydrothermal growth of zinc oxide crystals Expired - Lifetime US3201209A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
DENDAT1251294D DE1251294B (de) 1963-03-27 Ernest Denicke KoIb New Providence, N J , Robert Alfred Iaudise Berkeley Heights N] (V St A ) I Verfahren zum Zuchten von Zink oxyd Einkristallen
US268326A US3201209A (en) 1963-03-27 1963-03-27 Hydrothermal growth of zinc oxide crystals
NL6401340A NL6401340A (US07714131-20100511-C00038.png) 1963-03-27 1964-02-14
BE645214D BE645214A (US07714131-20100511-C00038.png) 1963-03-27 1964-03-13
GB11609/64A GB1061831A (en) 1963-03-27 1964-03-19 Hydrothermal growth of zinc oxide crystals

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BE (1) BE645214A (US07714131-20100511-C00038.png)
DE (1) DE1251294B (US07714131-20100511-C00038.png)
GB (1) GB1061831A (US07714131-20100511-C00038.png)
NL (1) NL6401340A (US07714131-20100511-C00038.png)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3271114A (en) * 1964-06-15 1966-09-06 Bell Telephone Labor Inc Crystal growth container
US3353926A (en) * 1965-09-29 1967-11-21 Bell Telephone Labor Inc Hydrothermal growth of zinc oxide crystals with ammonium ion additives
US3377209A (en) * 1964-05-01 1968-04-09 Ca Nat Research Council Method of making p-n junctions by hydrothermally growing
US3440025A (en) * 1966-06-20 1969-04-22 Bell Telephone Labor Inc Hydrothermal growth of potassium tantalate-potassium niobate mixed crystals and material so produced
US3615264A (en) * 1967-12-21 1971-10-26 Owens Illinois Inc Hydrothermal method of growing zinc oxide crystals
US4579622A (en) * 1983-10-17 1986-04-01 At&T Bell Laboratories Hydrothermal crystal growth processes
US4654111A (en) * 1985-12-02 1987-03-31 At&T Laboratories Hydrothermal growth of potassium titanyl phosphate
US4762588A (en) * 1985-11-12 1988-08-09 Seiko Instruments & Electronics Ltd. Method of manufacturing calcium carbonate single crystal
US4961823A (en) * 1985-11-12 1990-10-09 Shinichi Hirano Method of manufacturing calcium carbonate single crystal
US20070178039A1 (en) * 2005-03-18 2007-08-02 General Electric Company Crystals for a semiconductor radiation detector and method for making the crystals
WO2009122974A1 (ja) 2008-04-04 2009-10-08 株式会社福田結晶技術研究所 酸化亜鉛単結晶およびその製造方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2508208A (en) * 1945-10-31 1950-05-16 Hazeltine Research Inc Method of producing quartz crystal
US2697737A (en) * 1954-03-31 1954-12-21 Monroe B Goldberg Rechargeable cadmium dry cell

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2508208A (en) * 1945-10-31 1950-05-16 Hazeltine Research Inc Method of producing quartz crystal
US2697737A (en) * 1954-03-31 1954-12-21 Monroe B Goldberg Rechargeable cadmium dry cell

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3377209A (en) * 1964-05-01 1968-04-09 Ca Nat Research Council Method of making p-n junctions by hydrothermally growing
US3271114A (en) * 1964-06-15 1966-09-06 Bell Telephone Labor Inc Crystal growth container
US3353926A (en) * 1965-09-29 1967-11-21 Bell Telephone Labor Inc Hydrothermal growth of zinc oxide crystals with ammonium ion additives
US3440025A (en) * 1966-06-20 1969-04-22 Bell Telephone Labor Inc Hydrothermal growth of potassium tantalate-potassium niobate mixed crystals and material so produced
US3615264A (en) * 1967-12-21 1971-10-26 Owens Illinois Inc Hydrothermal method of growing zinc oxide crystals
US4579622A (en) * 1983-10-17 1986-04-01 At&T Bell Laboratories Hydrothermal crystal growth processes
US4961823A (en) * 1985-11-12 1990-10-09 Shinichi Hirano Method of manufacturing calcium carbonate single crystal
US4762588A (en) * 1985-11-12 1988-08-09 Seiko Instruments & Electronics Ltd. Method of manufacturing calcium carbonate single crystal
US4654111A (en) * 1985-12-02 1987-03-31 At&T Laboratories Hydrothermal growth of potassium titanyl phosphate
US20070178039A1 (en) * 2005-03-18 2007-08-02 General Electric Company Crystals for a semiconductor radiation detector and method for making the crystals
US20070181056A1 (en) * 2005-03-18 2007-08-09 General Electric Company Crystals for a semiconductor radiation detector and method for making the crystals
WO2009122974A1 (ja) 2008-04-04 2009-10-08 株式会社福田結晶技術研究所 酸化亜鉛単結晶およびその製造方法
US20110117349A1 (en) * 2008-04-04 2011-05-19 Fukuda Crystal Laboratory Zinc oxide single crystal and method for producing the same

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BE645214A (US07714131-20100511-C00038.png) 1964-07-01
DE1251294B (de) 1967-10-05
GB1061831A (en) 1967-03-15
NL6401340A (US07714131-20100511-C00038.png) 1964-09-28

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