WO2016164791A1 - Metal phosphide nanomaterials prepared from single source metal amides - Google Patents

Metal phosphide nanomaterials prepared from single source metal amides Download PDF

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Publication number
WO2016164791A1
WO2016164791A1 PCT/US2016/026743 US2016026743W WO2016164791A1 WO 2016164791 A1 WO2016164791 A1 WO 2016164791A1 US 2016026743 W US2016026743 W US 2016026743W WO 2016164791 A1 WO2016164791 A1 WO 2016164791A1
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precursor
metal
group
solution processing
element selected
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French (fr)
Inventor
Richard Alan Kemp
Diane DICKIE
Bernadette A. Hernandez-Sanchez
Timothy N. LAMBERT
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National Technology and Engineering Solutions of Sandia LLC
UNM Rainforest Innovations
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STC UNM
Sandia Corp
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/08—Other phosphides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/08—Other phosphides
    • C01B25/082—Other phosphides of boron, aluminium, gallium or indium
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/50—Organo-phosphines
    • C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • 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
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
    • 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
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/81—Of specified metal or metal alloy composition
    • 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
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/813—Of specified inorganic semiconductor composition, e.g. periodic table group IV-VI compositions
    • Y10S977/825—Heterojunction formed between semiconductor materials that differ in that they belong to different periodic table groups
    • 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
    • Y10S977/00—Nanotechnology
    • Y10S977/84—Manufacture, treatment, or detection of nanostructure
    • Y10S977/895—Manufacture, treatment, or detection of nanostructure having step or means utilizing chemical property
    • Y10S977/896—Chemical synthesis, e.g. chemical bonding or breaking

Definitions

  • MP X metal phosphide
  • the present invention provides a novel solution or route for metal phosphide (MP X ) nanomaterials from the thermal decomposition of metal bis[bis(diisopropylphosphino)amide], M[N(PPr' 2 ) 2 ]2, and/or single-source precursors.
  • MP X metal phosphide
  • the present invention provides a novel route to MP X that avoids high temperature solid-state reactions, high temperature solution processing, and detrimental halide contamination products.
  • Nano MP x were generated by solution precipitation/solvothermal processing routes using
  • MP X can be produced from almost all the metals found in the periodic table.
  • the present invention provides a novel route to MP X that avoids high temperature solid-state reactions wherein the solution processing route and precursor lower the processing temperature as compared to a solid state reaction.
  • the present invention provides a novel route to MP X that avoids high temperature solid-state reactions wherein the solution processing route and precursor lower the processing temperature by converting a metal amide to a metal or metal phosphide nanoparticle.
  • the present invention provides a novel route to MP X that avoids high temperature solid-state reactions wherein the solution processing route and precursor lower the processing temperature by decomposing a metal amide to a metal or metal phosphide nanoparticle.
  • the present invention provides a process that is halide free.
  • the present invention provides a process where nanomaterials are obtained from a halide free process.
  • the present invention provides one or more processes where more than one metal amide is used during synthesis.
  • the processes may be used in the production of metal alloys or core- shells nanomaterials comprised of alloys or metal phosphides.
  • FIG. 1 illustrates a substituent that may be used with an embodiment of the present invention.
  • FIG. 2 illustrates different metal/ligands and ratios that may be used with embodiments of the present invention.
  • FIG. 3 illustrates a substituent that may be used with an embodiment of the present invention.
  • FIG. 4 illustrates another substituent that may be used with an embodiment of the present invention.
  • FIG. 5A is a TEM image an embodiment of the present invention.
  • FIG. 5B is a TEM image of another embodiment of the present invention.
  • FIG. 6A shows an x-ray diffraction pattern of the embodiment of the present invention shown in FIG. 5A.
  • FIG. 6B shows an x-ray diffraction pattern of the embodiment of the present invention shown in FIG. 5B.
  • the present invention provides a general solution synthetic route for the production of metal phosphides (nanoscale to bulk) materials.
  • the present invention does not require high processing temperatures (> 350 °C) or additional thermal treatments, and avoids halide contamination in the final product.
  • metal phosphide nanomaterials which may be M x Py, may be prepared from the thermal decomposition of a single source precursor such as a metal bis[bis(diisopropylphosphino)amide], M[N(PPr' 2 )2]2, M[N(PR 2 )2]x, or [M[N(PR 2 ) 2 ]x] y , in high boiling coordinating or non-coordinating solvents .
  • the precursor may be from several sources.
  • the precursor converts to particles having a size in the range of 5-100 nm.
  • the precursor is used to produce SnP or Sn 4 P 3 , which may be in the size range of 5-1 00 nm.
  • the particles may be formed by a solution precipitation processing route using Sn[N(PPr' 2 )2]2 in trioctylphosphine.
  • the particle size and phase may be controlled.
  • M may be a metallic element selected from the group consisting of Groups 1 - 15 in the Period Table of the Elements, Lanthanide elements (numbers 58-71 ), Actinide elements (numbers 90-92) or any transition metal which is a member of Group 3.
  • M is a metallic element selected from the group consisting of Mg, Ca, Sr, Sn, Al, Ga, In, Ti, Ge, Pb, Sb, Bi, Th, Pa, U, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Ba.
  • R may be Pr'.
  • R may also equal H, or be any linear or branched alkyl group and substituted analogs, any aryl or substituted aryl, any silyl alkyl or silyl aryl group, or any other group that serves essentially the same purpose, or mixtures thereof.
  • x may vary from 1 to 5 depending on the valent state of the metal, where x is chosen to balance the charges of the precursor such as M[N(PPr' 2 )2]2, M[N(PR 2 ) 2 ]x, or [M[N(PR 2 ) 2 ]x] y .
  • the present invention provides nanoparticle precursors other than isopropyls.
  • the present invention provides a mixture of isopropyl and phenyl substituents that may be used as the nanoparticle precursors as shown in FIG. 1 , including any salt, stereoisomer, or adduct thereof.
  • the present invention may also provide a 1 :1 metal/ligand ratio as well as other stoichiometries as shown in FIG. 2 including any salt, stereoisomer, or adduct thereof.
  • FIGS. 3 and 4 illustrate other substituents that may be used with the embodiments of the present invention, including any salt, stereoisomer, or adduct thereof, wherein each R can be the same or different and each M can be the same or different.
  • FIG. 5A and FIG. 5B show TEM images of nanomaterials made in accordance with the teachings of the present invention.
  • FIG. 6A shows an x-ray diffraction pattern of the nanomaterial shown in FIG. 5A.
  • FIG. 6B shows an x-ray diffraction pattern of the nanomaterial shown in FIG. 5B.

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Abstract

The present invention provides a novel solution or route for metal phosphide (MPx) nanomaterials from the thermal decomposition of metal bis[bis(diisopropylphosphino)amide], M[N(PPri2)2]2, and/or single-source precursors. Synthetic routes to MPx nanomaterials may be used in energy applications including batteries, semiconductors, magnets, catalyst, lasers, inks, electrocatalysts and photodiodes.

Description

Metal Phosphide Nanomaterials Prepared from Single Source Metal Amides
RELATED APPLICATIONS
[0001 ] This application claims the benefit of U.S. Provisional Application No. 62/145927 filed April 10, 2015 and herein incorporated by reference.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH & DEVELOPMENT
[0002] This invention was made with government support under Department of Energy Contract Number DE-AC04-94AL85000 and National Science Foundation Contract Number CHE1213529. The government has certain rights in the invention.
INCORPORATION BY REFERENCE OF MATERIAL SUBMITTED ON A COMPACT DISC
[0003] Not applicable.
BACKGROUND OF THE INVENTION
[0004] Various metal phosphide (MPX) nanomaterials have shown promise as high capacity anodes in ceramic/air batteries, as electrocatalysts and in other
applications. However, there is a need to produce such namomaterials using processes that avoid high temperature solid-state reactions, high temperature solution processing, and detrimental halide contamination products.
BRIEF SUMMARY OF THE INVENTION
[0005] In one embodiment, the present invention provides a novel solution or route for metal phosphide (MPX) nanomaterials from the thermal decomposition of metal bis[bis(diisopropylphosphino)amide], M[N(PPr'2)2]2, and/or single-source precursors. Synthetic routes to MPX nanomaterials are of interest for energy applications including: batteries, semiconductors, magnets, catalysts, lasers, and photodiodes.
[0006] In another embodiment, the present invention provides a novel route to MPX that avoids high temperature solid-state reactions, high temperature solution processing, and detrimental halide contamination products. Nano MPx were generated by solution precipitation/solvothermal processing routes using
M[N(PPr2)2]2 at considerably lower temperatures and times. MPX can be produced from almost all the metals found in the periodic table. [0007] In another embodiment, the present invention provides a novel route to MPX that avoids high temperature solid-state reactions wherein the solution processing route and precursor lower the processing temperature as compared to a solid state reaction.
[0008] In another embodiment, the present invention provides a novel route to MPX that avoids high temperature solid-state reactions wherein the solution processing route and precursor lower the processing temperature by converting a metal amide to a metal or metal phosphide nanoparticle.
[0009] In another embodiment, the present invention provides a novel route to MPX that avoids high temperature solid-state reactions wherein the solution processing route and precursor lower the processing temperature by decomposing a metal amide to a metal or metal phosphide nanoparticle.
[00010] In another embodiment, the present invention provides a process that is halide free.
[0001 1 ] In another embodiment, the present invention provides a process where nanomaterials are obtained from a halide free process.
[00012] In another embodiment, the present invention provides one or more processes where more than one metal amide is used during synthesis. In this embodiment, the processes may be used in the production of metal alloys or core- shells nanomaterials comprised of alloys or metal phosphides.
[00013] Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.
[00014] It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[00015] In the drawings, which are not necessarily drawn to scale, like numerals may describe substantially similar components throughout the several views. Like numerals having different letter suffixes may represent different instances of substantially similar components. The drawings illustrate generally, by way of example, but not by way of limitation, a detailed description of certain embodiments discussed in the present document.
[00016] FIG. 1 illustrates a substituent that may be used with an embodiment of the present invention.
[00017] FIG. 2 illustrates different metal/ligands and ratios that may be used with embodiments of the present invention.
[00018] FIG. 3 illustrates a substituent that may be used with an embodiment of the present invention.
[00019] FIG. 4 illustrates another substituent that may be used with an embodiment of the present invention.
[00020] FIG. 5A is a TEM image an embodiment of the present invention.
[00021 ] FIG. 5B is a TEM image of another embodiment of the present invention.
[00022] FIG. 6A shows an x-ray diffraction pattern of the embodiment of the present invention shown in FIG. 5A.
[00023] FIG. 6B shows an x-ray diffraction pattern of the embodiment of the present invention shown in FIG. 5B. DETAILED DESCRIPTION OF THE INVENTION
[00024] Detailed embodiments of the present invention are disclosed herein;
however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed method, structure or system. Further, the terms and phrases used herein are not intended to be limiting, but rather to provide an understandable description of the invention.
[00025] The present invention provides a general solution synthetic route for the production of metal phosphides (nanoscale to bulk) materials. In a preferred embodiment, the present invention does not require high processing temperatures (> 350 °C) or additional thermal treatments, and avoids halide contamination in the final product. [00026] In one preferred embodiment, metal phosphide nanomaterials, which may be MxPy, may be prepared from the thermal decomposition of a single source precursor such as a metal bis[bis(diisopropylphosphino)amide], M[N(PPr'2)2]2, M[N(PR2)2]x, or [M[N(PR2)2]x]y, in high boiling coordinating or non-coordinating solvents. In other embodiments of the present invention, the precursor may be from several sources.
[00027] In another preferred embodiment of the present invention, the precursor converts to particles having a size in the range of 5-100 nm. In one embodiment, the precursor is used to produce SnP or Sn4P3, which may be in the size range of 5-1 00 nm. The particles may be formed by a solution precipitation processing route using Sn[N(PPr'2)2]2 in trioctylphosphine. In addition, depending on the conditions used (e.g.; solvent, time, temperature) the particle size and phase may be controlled.
[00028] In other embodiments, M may be a metallic element selected from the group consisting of Groups 1 - 15 in the Period Table of the Elements, Lanthanide elements (numbers 58-71 ), Actinide elements (numbers 90-92) or any transition metal which is a member of Group 3. In yet other embodiments, M is a metallic element selected from the group consisting of Mg, Ca, Sr, Sn, Al, Ga, In, Ti, Ge, Pb, Sb, Bi, Th, Pa, U, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Ba.
[00029] In other embodiments, R may be Pr'. R may also equal H, or be any linear or branched alkyl group and substituted analogs, any aryl or substituted aryl, any silyl alkyl or silyl aryl group, or any other group that serves essentially the same purpose, or mixtures thereof.
[00030] In yet other embodiments, x may vary from 1 to 5 depending on the valent state of the metal, where x is chosen to balance the charges of the precursor such as M[N(PPr'2)2]2, M[N(PR2)2]x, or [M[N(PR2)2]x]y.
[00031 ] In other embodiments, the present invention provides nanoparticle precursors other than isopropyls. For example, in yet another preferred embodiment, the present invention provides a mixture of isopropyl and phenyl substituents that may be used as the nanoparticle precursors as shown in FIG. 1 , including any salt, stereoisomer, or adduct thereof.
[00032] In yet other embodiments, besides providing a metal with two ligands (i.e. M[N(P'Pr2)2]2), the present invention may also provide a 1 :1 metal/ligand ratio as well as other stoichiometries as shown in FIG. 2 including any salt, stereoisomer, or adduct thereof. FIGS. 3 and 4 illustrate other substituents that may be used with the embodiments of the present invention, including any salt, stereoisomer, or adduct thereof, wherein each R can be the same or different and each M can be the same or different.
[00033] FIG. 5A and FIG. 5B show TEM images of nanomaterials made in accordance with the teachings of the present invention. FIG. 6A shows an x-ray diffraction pattern of the nanomaterial shown in FIG. 5A. FIG. 6B shows an x-ray diffraction pattern of the nanomaterial shown in FIG. 5B.
[00034] While the foregoing written description enables one of ordinary skill to make and use what is considered presently to be the best mode thereof, those of ordinary skill will understand and appreciate the existence of variations, combinations, and equivalents of the specific embodiment, method, and examples herein. The disclosure should therefore not be limited by the above described embodiments, methods, and examples, but by all embodiments and methods within the scope and spirit of the disclosure.

Claims

WHAT IS CLAIMED IS:
1 . A method of making nanomaterials comprising the steps of: solution
processing a [M[N(PR2)2]x]y precursor to synthesize nanomaterials.
2. The method of claim 1 wherein R equals H.
3. The method of claim 1 wherein R is a linear alkyl group.
4. The method of claim 1 wherein R is a branched alkyl group.
5. The method of claim 1 wherein R is an aryl.
6. The method of claim 1 wherein R is a substituted aryl.
7. The method of claim 1 wherein R is a silyl alkyl.
8. The method of claim 1 wherein R is a silyl aryl.
9. The method of claim 1 wherein R is a linear or branched alkyl group and
substituted analogs, an aryl or substituted aryl, a silyl alkyl or silyl aryl, or mixtures thereof.
10. The method of claim 1 wherein said nanomaterials are MPX.
1 1 . The method of claim 1 wherein said nanomaterials are MxPy.
12. The method of claim 1 wherein R is Pr'.
13. The method of claim 1 wherein x can vary from 1 to 5 depending on the valent state of the metal, where x is chosen to balance the charges of said
[M[N(PR2)2]x]y molecule; and/or wherein y can vary from about 1 to about 5.
14. The method of claim 1 wherein M is a metallic element selected from the
group consisting of Groups 1 - 1 5 in the Period Table of the Elements.
15. The method of claim 1 wherein M is a Lanthanide element (numbers 58-71 ).
16. The method of claim 1 wherein M is an Actinide element (numbers 90-92).
17. The method of claim 1 wherein M is any transition metal which is a member of Group 3.
18. The method of claim 1 wherein M is Mg, Ca, Sr, Sn, Al, Ga, In, Ti, Ge, Pb, Sb, Bi, Th, Pa, U, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and/or Ba.
19. The method of claim 1 wherein M is a metallic element selected from the group consisting of Mg, Ca, Sr, and Ba.
20. The method of claim 1 wherein M is a metallic element selected from the
group consisting of Al, Ga, In, and TI.
21 . The method of claim 1 wherein M is a metallic element selected from the group consisting of Ge, Sn, and Pb.
22. The method of claim 1 wherein M is a metallic element selected from the group consisting of Sb and Bi.
23. The method of claim 1 wherein M is a metallic element selected from the group consisting of Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
24. The method of claim 1 wherein M is a metallic element selected from the group consisting of Th, Pa, and U.
25. The method of claim 1 wherein said processing uses a coordinating solvent.
26. The method of claim 1 wherein said processing uses a non-coordinating solvent.
27. The method of claim 1 wherein said solution processing is less than 350 degrees C.
28. The method of claim 1 wherein said solution processing route and said
precursor lower the processing temperature.
29. The method of claim 1 wherein said solution processing route and said
precursor lower the processing temperature by converting a metal amide to a metal or metal phosphide nanomaterial.
30. The method of claim 1 wherein said solution processing route and precursor lower the processing temperature by decomposing a metal amide to a metal or metal phosphide nanomaterial.
31 . The method of claim 1 wherein said solution processing route and said
precursor lower the processing temperature and said solution processing is less than 350 degrees C.
32. The method of claim 1 wherein said solution processing route and said
precursor lower the processing temperature by converting a metal amide to a metal or metal phosphide nanomaterial and said solution processing is less than 350 degrees C.
33. The method of claim 1 wherein said solution processing route and precursor lower the processing temperature by decomposing a metal amide to a metal or metal phosphide nanomaterial and said solution processing is less than 350 degrees C.
34. The method of claim 1 wherein said [M[N(PR2)2]x]y is halide free.
35. The method of claim 1 wherein said [M[N(PR2)2]x]y is obtained from a halide free process.
36. The method of claim 1 wherein said precursor converts to SnP.
37. The method of claim 1 wherein said precursor converts to Sn4P3.
38. The method of claim 1 wherein changing solvent boiling temperature changes the particle size of said nanomaterial.
39. The method of claim 1 wherein said precursor is
Figure imgf000009_0001
, or a salt, stereoisomer, or adduct thereof.
40. The method of claim 1 wherein said precursor is
Figure imgf000009_0002
, or a salt, stereoisomer, or adduct thereof.
41 . The method of claim 1 wherein said precursor comprises a structure of:
Figure imgf000010_0001
, or a salt, stereoisomer, or adduct thereof, wherein each R can be the same or different and each M can be the same or different.
42. The method of claim 1 wherein said precursor comprises a structure of:
Figure imgf000010_0002
, or a salt, stereoisomer, or adduct thereof, wherein each R can be the same or different.
43. The method of claim 1 wherein said precursor converts to particles having a size in the range of 5-100 nm.
44. The method of claim 1 wherein said nanomaterials are used in batteries, semiconductors, magnets, catalysts, lasers, inks, electrocatalysts or photodiodes.
45. A method of making nanomaterials comprising the steps of: solution
processing a [M[N(PR2)2]x]y precursor to synthesize nanomaterials.
46. The method of claim 45 wherein R equals H.
47. The method of claim 45 wherein R is a linear alkyl group.
48. The method of claim 45 wherein R is a branched alkyl group.
49. The method of claim 45 wherein R is an aryl.
50. The method of claim 45 wherein R is a substituted aryl.
51 . The method of claim 45 wherein R is a silyl alkyl.
52. The method of claim 45 wherein R is an silyl aryl.
53. The method of claim 45 wherein R is a linear or branched alkyl group and substituted analogs, an aryl or substituted aryl, an silyl alkyl or silyl aryl, or mixtures thereof.
54. The method of claim 45 wherein said nanomaterials are MPX.
55. The method of claim 45 wherein said nanomaterials are MxPy.
56. The method of claim 45 wherein R is Pr'.
57. The method of claim 45 wherein x can vary from 1 to 5 depending on the
valent state of the metal, where x is chosen to balance the charges of said M[N(PR2)2]x molecule; and/or wherein y can vary from about 1 to about 5.
58. The method of claim 45 wherein M is a metallic element selected from the group consisting of Groups 1 - 1 5 in the Period Table of the Elements.
59. The method of claim 45 wherein M is a Lanthanide element (numbers 58-71 ).
60. The method of claim 45 wherein M is an Actinide element (numbers 90-92).
61 . The method of claim 45 wherein M is any transition metal which is a member of Group 3.
62. The method of claim 45 wherein M is Mg, Ca, Sr, Sn, Al, Ga, In, Ti, Ge, Pb, Sb, Bi, Th, Pa, U, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and/or Ba.
63. The method of claim 45 wherein M is a metallic element selected from the group consisting of Mg, Ca, Sr, and Ba.
64. The method of claim 45 wherein M is a metallic element selected from the group consisting of Al, Ga, In, and TI.
65. The method of claim 45 wherein M is a metallic element selected from the group consisting of Ge, Sn, and Pb.
66. The method of claim 45 wherein M is a metallic element selected from the group consisting of Sb and Bi.
67. The method of claim 45 wherein M is a metallic element selected from the group consisting of Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
68. The method of claim 45 wherein M is a metallic element selected from the group consisting of Th, Pa, and U.
69. The method of claim 45 wherein said processing uses a coordinating solvent.
70. The method of claim 45 wherein said processing uses a non-coordinating solvent.
71 . The method of claim 45 wherein said solution processing is less than 350 degrees C.
72. The method of claim 45 wherein said solution processing route and said
precursor lower the processing temperature.
73. The method of claim 45 wherein said solution processing route and said
precursor lower the processing temperature by converting a metal amide to a metal or metal phosphide nanomaterial.
74. The method of claim 45 wherein said solution processing route and precursor lower the processing temperature by decomposing a metal amide to a metal or metal phosphide nanomaterial.
75. The method of claim 45 wherein said solution processing route and said
precursor lower the processing temperature and said solution processing is less than 350 degrees C.
76. The method of claim 45 wherein said solution processing route and said
precursor lower the processing temperature by converting a metal amide to a metal or metal phosphide nanomaterial and said solution processing is less than 350 degrees C.
77. The method of claim 45 wherein said solution processing route and precursor lower the processing temperature by decomposing a metal amide to a metal or metal phosphide nanomaterial and said solution processing is less than 350 degrees C.
78. The method of claim 45 wherein said [M[N( PR2)2]x]y is halide free.
79. The method of claim 45 wherein said [ [N(PR2)2]x]y is obtained from a halide free process.
80. The method of claim 45 wherein said precursor converts to SnP.
81 . The method of claim 45 wherein said precursor converts to Sn4P3.
82. The method of claim 45 wherein changing solvent boiling temperature
changes the particle size of said nanomaterial.
83. The method of claim 45 wherein said precursor is
Figure imgf000013_0001
, or a salt, stereoisomer, or adduct thereof.
84. The method of claim 45 wherein said precursor is
Figure imgf000013_0002
or a salt, stereoisomer, or adduct thereof.
85. The method of claim 45 wherein said precursor comprises a structure of:
Figure imgf000013_0003
, or a salt, stereoisomer, or adduct thereof, wherein each R can be the same or different and each M can be the same or different.
86. The method of claim 45 wherein said precursor comprises a structure of:
Figure imgf000014_0001
, or a salt, stereoisomer, or adduct thereof, wherein each R can be the same or different.
87. The method of claim 45 wherein said precursor converts to particles having a size in the range of 5-100 nm.
88. The method of claim 45 wherein said nanomaterials are used in batteries, semiconductors, magnets, catalyst, lasers, inks, electrocatalysts or photodiodes.
89. The method of claim 1 wherein more than one precursor is used to
synthesize a metal alloy.
90. The method of claim 1 wherein more than one precursor is used to synthesize metal alloys.
91 . The method of claim 1 wherein more than one precursor is used to synthesize a core-shell nanomaterial comprised of alloys or metal phosphides.
92. The method of claim 45 wherein more than one precursor is used to
synthesize a metal alloy.
93. The method of claim 45 wherein more than one precursor is used to
synthesize metal alloys.
94. The method of claim 45 wherein more than one precursor is used to
synthesize a core-shell nanomaterial comprised of alloys or metal
phosphides.
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