Method for crystal growth of a metal-nonmetal compound using a metallophobic-metallophilic surfactant and a thin metal wetting layer

• US 8,945,302 B2
• Filed: 03/04/2012
• Issued: 02/03/2015
• Est. Priority Date: 03/04/2011
• Status: Active Grant

• Current Assignee: Mosaic Crystals Ltd.
• Original Assignee: Mosaic Crystals Ltd.
• Inventors: Einav, Moshe
• Primary Examiner(s): Kornakov, Michael
• Application Number:
  US14/002,820
• Publication Number:
  US 20130333613A1
• Time in Patent Office: 1,066 Days
• Field of Search: 117/11, 117 53- 56, 117/58, 117 63- 65, 117/67, 117/84, 117 88- 90, 117 92- 94, 117102-103, 117105-106, 117/108, 117/937, 117951-952, 438/507, 438/509, 438761-763, 438/765, 438/767
• US Class Current: 117/58
• CPC Class Codes: C30B 19/00 Liquid-phase epitaxial-layer growth
• CPC Class Codes: C30B 19/068 Substrate holders
• CPC Class Codes: C30B 19/10 Controlling or regulating controlling or regulating in general G05
• CPC Class Codes: C30B 23/00 Single-crystal growth by condensing evaporated or sublimed materials
• CPC Class Codes: C30B 23/002 Controlling or regulating
• CPC Class Codes: C30B 23/02 Epitaxial-layer growth
• CPC Class Codes: C30B 25/00 Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 25/16 Controlling or regulating controlling or regulating in general G05
• CPC Class Codes: C30B 29/40 AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
• CPC Class Codes: C30B 7/005 Epitaxial layer growth
• CPC Class Codes: C30B 9/00 Single-crystal growth from melt solutions using molten solvents by normal or gradient freezing C30B11/00; by zone-melting C30B13/00; by crystal pulling C30B15/00; on immersed seed crystal C30B17/00; by liquid phase epitaxial growth C30B19/00; under a protective fluid C30B27/00

Abstract

Method for crystal growth from a surfactant of a metal-nonmetal (MN) compound, including the procedures of providing a seed crystal, introducing atoms of a first metal to the seed crystal thus forming a thin liquid metal wetting layer on a surface of the seed crystal, setting a temperature of the seed crystal below a minimal temperature required for dissolving MN molecules in the wetting layer and above a melting point of the first metal, each one of the MN molecules being formed from an atom of a second metal and an atom of a first nonmetal, introducing the MN molecules which form an MN surfactant monolayer, thereby facilitating a formation of the wetting layer between the MN surfactant monolayer and the surface of the seed crystal, and regulating a thickness of the wetting layer, thereby growing an epitaxial layer of the MN compound on the seed crystal.

Claims

1. A method for crystal growth from a surfactant of a metal-nonmetal (MN) compound, comprising the procedures of:

providing a seed crystal;

setting a temperature of said seed crystal below a minimal temperature required for dissolving MN molecules in a thin liquid metal wetting layer and above a melting point of a first metal, each one of said MN molecules being formed from at least one atom of a second metal and at least one atom of a first nonmetal;

introducing atoms of said first metal to said seed crystal in order to form said thin liquid metal wetting layer on at least one surface of said seed crystal, said thin liquid metal wetting layer having at least two monolayers and being spread over substantially the whole surface of said at least one surface of said seed crystal;

introducing said MN molecules which form an MN surfactant monolayer, thereby facilitating a formation of said thin liquid metal wetting layer between said MN surfactant monolayer and said at least one surface of said seed crystal; and

regulating a thickness of said thin liquid metal wetting layer such that at least some of said MN molecules of said MN surfactant monolayer couple with said at least one surface of said seed crystal, thereby growing an epitaxial layer of said MN compound on said seed crystal,

wherein said MN surfactant monolayer has a metallophilic side facing said thin liquid metal wetting layer and a metallophobic side facing away from said thin liquid metal wetting layer.

2. The method according to claim 1, further comprising the procedure of sputtering an MN compound target for introducing said MN molecules which form said MN surfactant monolayer.

3. The method according to claim 1, wherein said seed crystal is formed from a third metal and a second nonmetal.

4. The method according to claim 3, wherein said first metal, said second metal and said third metal are identical.

5. The method according to claim 3, wherein said first nonmetal and said second nonmetal are identical.

6. The method according to claim 1, wherein said first metal and said second metal are each metal elements from the periodic table of elements classified as a metal selected from the list consisting of:

an alkali metal;

an alkaline earth metal;

a transition metal;

a lanthanide element;

an actinide element; and

an other metal.

7. The method according to claim 1, wherein said first nonmetal is a nonmetal element from the periodic table of elements classified as a nonmetal selected from the list consisting of:

a nonmetal; and

a halogen.

8. The method according to claim 1, wherein said seed crystal is selected from the list consisting of:

a homogeneous crystal in relation to said MN compound;

a heterogeneous crystal in relation to said MN compound;

a small crystallite grown on an amorphous substrate; and

a small crystallite grown on a crystalline substrate.

9. The method according to claim 1, wherein said procedure of regulating said thickness comprises a sub procedure selected from the list consisting of:

regulating said thickness using an evaporation controller for controlling a rate of evaporation of said MN molecules;

regulating said thickness using a gas inlet manometer and a photo spectrometer; and

regulating said thickness using a droplet criterion and a reflection high energy electron diffraction (RHEED) technique.

10. The method according to claim 1, wherein said procedure of setting said temperature comprises the sub-procedure of determining an optimal temperature for said seed crystal wherein an incorporation rate of said MN molecules is maximized and a stoichiometric balance point of a MN precursor material can be regulated.

11. The method according to claim 1, further comprising the procedures of:

ceasing the introduction of said atoms of said first metal such that said thin liquid metal wetting layer dries up; and

growing a crystal layer of said MN compound exhibiting a polycrystalline structure over said epitaxial layer of said MN compound on said seed crystal.

12. The method according to claim 1, further comprising the procedures of:

slowing an introduction of atoms of said first nonmetal until ceased, thereby leaving a thin layer of said atoms of said first metal on said epitaxial layer of MN compound; and

removing said thin layer of said atoms of said first metal.

13. The method according to claim 12, wherein said procedure of removing comprises a sub-procedure selected from the list consisting of:

evaporating said thin layer by heating said seed crystal;

etching said thin layer using wet chemistry techniques; and

etching said thin layer using plasma chemistry techniques.

14. The method according to claim 1, wherein said thin liquid metal wetting layer is a portion of a metal solution surrounding said seed crystal.

15. The method according to claim 1, wherein said thin liquid metal wetting layer has a thickness of up to 3 nanometers.

16. The method according to claim 1, wherein said MN surfactant monolayer comprises up to three monolayers, each one of said three monolayers having a thickness of substantially 0.3 nanometers.

22. The method according to claim 1, further comprising the procedure of vaporizing said at least one atom of said first nonmetal until said MN surfactant monolayer is formed.

23. The method according to claim 1, further comprising the procedure of vaporizing an MN precursor for introducing said MN molecules which form said MN surfactant monolayer.

24. The method according to claim 3, wherein said first metal, said second metal and said third metal are different.

25. The method according to claim 3, wherein at least two of said first metal, said second metal and said third metal are identical.

26. The method according to claim 3, wherein said first nonmetal and said second nonmetal are different.

27. The method according to claim 1, wherein said seed crystal exhibits a crystallographic structure selected from the list consisting of:

a terraced structure;

a Manhattan structure;

a nanowire structure;

a flat geometrical structure; and

a pyramidal structure.

28. The method according to claim 1, wherein said procedure of introducing said MN molecules comprises the sub procedure of introducing a precursor material in a growth environment required to grow said MN compound using a crystal growth technique.

29. The method according to claim 1, wherein said procedure of introducing atoms of said first metal comprises a sub procedure selected from the list consisting of:

introducing said atoms as a vapor which will eventually condense on said at least one surface of said seed crystal;

introducing said atoms as a liquid metal which surrounds said at least one surface of said seed crystal; and

introducing a compound comprising said first metal and a nonmetal element, in which said compound is dissociated in a vicinity of said seed crystal.

30. The method according to claim 1, wherein said procedure of introducing said MN molecules comprises the sub procedure of co depositing metal particles and nonmetal particles which combine to form said MN molecules.

31. The method according to claim 1, wherein said seed crystal is selected from the list consisting of:

a nanometer sized crystalline seed;

a bulky millimeter sized seed;

a wafer with at least one flat surface;

a wafer with a tip of a crystalline fiber;

a seed crystal coupled with a crystalline material; and

a seed crystal coupled with an amorphous material.

32. The method according to claim 1, wherein said procedure of introducing said atoms of said first metal comprises introducing said atoms in the vicinity of said seed crystal.

33. The method according to claim 1, wherein said procedure of introducing said atoms of said first metal comprises introducing said atoms to contact with said seed crystal.

36. The method according to claim 28, wherein said crystal growth technique is selected from the list consisting of:

chemical vapor deposition (CVD);

molecular beam epitaxy (MBE);

liquid phase epitaxy (LPE);

vapor phase epitaxy (VPE); and

solution growth.

17. A method for crystal growth from a surfactant of a metal-nonmetal (MN) compound from a metal melt in a growth chamber, said growth chamber comprising a pedestal, located inside said growth chamber and a motor, coupled with said pedestal, for moving said pedestal in said growth chamber, comprising the procedures of:

placing a seed crystal on said pedestal such that a growth surface of said seed crystal faces opposite a direction of said pedestal;

filling said growth chamber with said metal melt such that said growth surface is covered by a thin layer of said metal melt, said thin layer of said metal melt having at least two monolayers;

introducing a nonmetal gas into said growth chamber above a surface of said metal melt, wherein particles of said nonmetal gas and particles of said metal melt interact, thereby forming a MN surfactant monolayer; and

regulating a distance between said growth surface and said MN surfactant monolayer such that molecules in said MN surfactant monolayer tunnel to said growth surface, thereby epitaxially growing at least one crystal layer on said growth surface,

wherein said MN surfactant monolayer has a metallophilic side facing said thin liquid metal wetting layer and a metallophobic side facing away from said thin liquid metal wetting layer.

18. The method according to claim 17, wherein said distance is regulated by said motor moving said pedestal such that said growth surface is covered by said thin layer of said metal melt.

34. The method according to claim 17, wherein said distance is regulated by adjusting an amount of said metal melt in said growth chamber such that said growth surface is covered by said thin layer of said metal melt.

19. A method for epitaxial crystal growth from a surfactant of a metal-nonmetal (MN) compound from a thin film in a growth chamber, said growth chamber comprising a metal source, coupled with said growth chamber, for introducing a metal vapor into said growth chamber, and an inlet, coupled with said growth chamber, for introducing a nonmetal vapor into said growth chamber, comprising the procedures of:

placing a seed crystal in said growth chamber;

simultaneously filling said growth chamber with said metal vapor and said nonmetal vapor, such that said metal vapor and said nonmetal vapor co-deposit on a growth surface of said seed crystal, thereby forming a thin liquid metal wetting layer from said metal vapor and a MN surfactant monolayer over said thin liquid metal wetting layer, said thin liquid metal wetting layer having at least two monolayers and being spread over substantially the whole surface of said growth surface of said seed crystal; and

regulating a thickness of said thin liquid metal wetting layer such that MN molecules in said MN surfactant monolayer tunnel to said growth surface, thereby epitaxially growing at least one crystal layer on said growth surface,

wherein a concentration of said metal vapor is initially higher than a concentration of said nonmetal vapor such that said thin liquid metal wetting layer is formed, and

wherein said MN surfactant monolayer has a metallophilic side facing said thin liquid metal wetting layer and a metallophobic side facing away from said thin liquid metal wetting layer.

20. The method according to claim 19, wherein said metal source is selected from the list consisting of:

a Knudsen cell; and

an evaporation crucible.

21. The method according to claim 19, wherein said inlet is selected from the list consisting of:

a gas inlet; and

a plasma inlet.

35. The method according to claim 19, wherein said concentration of said metal vapor is adjusted to regulate said thickness of said thin liquid metal wetting layer.