# US 10,767,112 B2 · Methods of producing metal sulfides, metal selenides, and metal sulfides/selenides having controlled architectures using kinetic control

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- Number: US 10,767,112 B2
- Document ID: US10767112B2
- Status: Granted
- Kind: B2
- Application number: 15/541,937
- Filed: 2016-01-15
- Published: 2017-12-28
- Granted: 2020-09-08
- Earliest claimed: 2015-01-15
- Assignees: The Trustees of Columbia University in the City of New York
- Applicants: The Trustees of Columbia University In the City of New York; Gregory T. Cleveland; Ilan Jen-La Plante; Leslie Sachiyo Hamachi
- Inventors: Jonathan S. Owen; Mark P. Hendricks; Michael P. Campos; Gregory T. Cleveland; Ilan Jen-La Plante; Leslie Sachiyo Hamachi
- Web page: https://patentgrep.com/patent/US10767112B2

## CPC

- C09K 11/883: {with zinc or cadmium}
- C01B 19/007: {Tellurides or selenides of metals (C01B19/002 takes precedence)}
- C01B 19/04: Binary compounds {including binary selenium-tellurium compounds (C01B19/004, C01B19/005, C01B19/007 take precedence)}
- C01G 1/12: Sulfides
- C01G 3/12: Sulfides
- C01G 9/08: Sulfides
- C01G 11/02: Sulfides
- C01G 19/00: Compounds of tin
- C01G 19/006: {Compounds containing tin, with or without oxygen or hydrogen, and containing two or more other elements}
- C01G 21/21: Sulfides
- C01G 53/11: Sulfides; Oxysulfides
- C09K 11/565: {with zinc cadmium}
- C09K 11/582: {Chalcogenides}
- C09K 11/602: {Chalcogenides}
- C09K 11/661: {Chalcogenides}
- C09K 11/881: {Chalcogenides}
- B82Y 20/00: Nanooptics, e.g. quantum optics or photonic crystals
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram
- C01P 2002/84: by UV- or VIS- data
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C01P 2004/16: Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
- C01P 2004/24: Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
- C01P 2004/32: Spheres
- C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer
- C01P 2004/80: Particles consisting of a mixture of two or more inorganic phases
- H10H 20/811: having quantum effect structures or superlattices, e.g. tunnel junctions
- Y10S 977/774: Exhibiting three-dimensional carrier confinement, e.g. quantum dots
- Y10S 977/824: Group II-VI nonoxide compounds, e.g. CdxMnyTe
- Y10S 977/825: Heterojunction formed between semiconductor materials that differ in that they belong to different periodic table groups
- Y10S 977/892: Liquid phase deposition
- Y10S 977/896: Chemical synthesis, e.g. chemical bonding or breaking
- Y10S 977/95: Electromagnetic energy
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- H10H: INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

The present invention is directed to methods of preparing metal sulfide, metal selenide, or metal sulfide/selenide nanoparticles and the products derived therefrom. In various embodiments, the nanoparticles are derived from the reaction between precursor metal salts and certain sulfur- and/or selenium-containing precursors each independently having a structure of Formula (I), (II), or (III), or an isomer, salt, or tautomer thereof, where Q1, Q2, Q3, R1, R2, R3, R5, and X are defined within the specification.

## Claims

### Claim 1

A method of preparing metal sulfide, metal selenide, metal sulfide/selenide, mixed metal sulfide, mixed metal selenide, or mixed metal sulfide/selenide nanoparticles, the method comprising:
(a) contacting at least two precursor metal salts with a sulfur-containing precursor, a selenium-containing precursor, or a combination or mixture of the sulfur- and selenium-containing precursors, or
(b) contacting a precursor metal salt with a sulfur-containing precursor, a selenium-containing precursor, or a mixture of sulfur- and selenium-containing precursors,
in each case where plural precursor metal salts and/or sulfur-/seleno-containing precursors are employed, the contacting being done simultaneously or sequentially in either order in a solution, each precursor metal salt being capable of reacting with each sulfur- and selenium-containing precursor to form the corresponding metal sulfide and metal selenide, the contacting giving rise to reaction conditions sufficient to control at least one parameter of particle size, particle distribution, and particle composition of the nanoparticles to-a predetermined architecture, the sulfur- or selenium-containing precursor each independently having a structure of Formula (I), Formula (II), or Formula (III), or an isomer, salt, or tautomer thereof,
wherein
Q1 is independently —O—, —S—, Se—, —CR3R4—, —N(R4)— or P(R4)—;
Q2 is independently —O—, —S—, Se—, —CR3R4—, —N(R3)— or P(R3)—;
Q3 is an optionally substituted aryl or optionally substituted heteroaryl;
R1, R2, R3, and R4 are independently at each occurrence H, optionally substituted C1-24 alkyl, optionally substituted C3-12 cycloalkyl, optionally substituted C2-24 alkenyl, optionally substituted C3-12 cycloalkenyl, optionally substituted aryl, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroaralkyl;
or any two of R1, R2, R3, and R4 are, within the same structure, linked to form a 5- to 10-membered heterocycle comprising an optionally substituted alkylene or an optionally substituted and/or conjugated alkenylene linkage;
or optionally one or more of R1, R2, and R3 is not H;
R5 is halogen, —CN, —NO2, C1-6 alkoxy, C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroaralkyl;
q is 0, 1, 2, or 3;
X is S or Se; and
Y is a bond —O—, —S—, or —N(R3)—;
with the provisos that, in Formula (I):
when Q1R1 is NH2, then Q2R2 is not CH3;
when Q2R2 is NH2, then Q1R1 is not CH3; and
when Q1 is —N(R4)— and Q2 is —N(R3)—, then R1 and R2 are linked to form a 5- or 6-membered heterocycle comprising an optionally substituted alkylene linkage or a 6-membered heterocycle comprising an optionally substituted alkenylene linkage.

### Claim 2 (depends on 1)

The method of claim 1, comprising contacting two precursor metal salts with the sulfur-containing precursor, the selenium-containing precursor, or a combination of the sulfur- and selenium-containing precursors to form the nanoparticles.

### Claim 3 (depends on 1)

The method of claim 1 comprising contacting a precursor metal salt with a combination of a sulfur-containing precursor and a selenium-containing precursor to form the nanoparticles.

### Claim 4 (depends on 1)

The method of claim 1 comprising contacting a precursor metal salt with a sulfur-containing precursor, a selenium-containing precursor, or a mixture of sulfur-containing and selenium-containing precursors, each sulfur-containing or selenium-containing precursor independently having a structure of Formula (IA), Formula (II), or Formula (III), or an isomer, salt, or tautomer thereof, in solution under controlled nucleation and growth conditions for the formation of the monodispersed nanoparticles:
wherein
Q1 is independently —O—, —S—, Se—, —CR3R4—, —N(R4) or P(R4)—;
Q2 is independently —O—, —S—, Se—, —CR3R4—, —N(R3) or P(R3)—;
Q3 is optionally substituted aryl or optionally substituted heteroaryl;
R1 and R2 are independently at each occurrence optionally substituted C1-24 alkyl, optionally substituted C3-12 cycloalkyl, optionally substituted C2-24 alkenyl, optionally substituted C3-12 cycloalkenyl, optionally substituted aryl, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroaralkyl;
R3 and R4 are independently at each occurrence H, optionally substituted C1-24 alkyl, optionally substituted C3-12 cycloalkyl, optionally substituted C2-24 alkenyl, optionally substituted C3-12 cycloalkenyl, optionally substituted aryl, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroaralkyl;
or any two of R1, R2, R3, and R4 are, within the same structure, linked to form an optionally substituted 5- to 10-membered heterocycle comprising an optionally substituted alkylene or an optionally substituted and/or conjugated alkenylene linkage;
or optionally one or more of R1, R2, and R3 is not H;
R5 is halogen, —CN, —NO2, C1-6 alkoxy, C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroaralkyl;
q is 0, 1, 2, or 3;
X is S or Se; and
Y is a bond —O—, —S— or —N(R3)—;
with the provisos that, in Formula (IA):
when Q1R1 is NH2, then Q2R2 is not CH3;
when Q2R2 is NH2, then Q1R1 is not CH3; and
when Q1 is —N(R4)— and Q2 is —N(R3)—, then R1 and R2 are linked to form a 5- or 6-membered heterocycle comprising an optionally substituted alkylene linkage or a 6-membered heterocycle comprising an optionally substituted alkenylene linkage.

### Claim 5 (depends on 4)

The method of claim 4, wherein a mixture of a sulfur- and a selenium-containing precursor is used, the sulfur- and selenium-containing precursors exhibiting pseudo first order kinetics with respect to the metal precursor salt, the pseudo first kinetics of each having an associated pseudo first order rate constant, the ratio of the pseudo first order rate constants being in a range of from 1 to 10, under the reaction conditions employed.

### Claim 6 (depends on 5)

The method of claim 5, wherein the pseudo-first order rate constants, kobs (s−1) associated with at least one of the sulfur- or selenium-containing precursors with the metal containing precursor salt is in a range from 1×10−4 to 1×10−1.

### Claim 7 (depends on 1)

The method of claim 1, wherein at least one of the sulfur- or selenium-containing precursors has a structure according to
or an isomer, salt, or tautomer thereof.

### Claim 8 (depends on 1)

The method of claim 1, wherein R1 and R2 are, within the same structure, linked to form a 5- to 10-membered heterocycle comprising an optionally substituted alkylene or an optionally substituted and/or conjugated alkenylene linkage.

### Claim 9 (depends on 1)

The method of claim 1, wherein at least one of the sulfur- or selenium-containing precursors has a structure according to:
or an isomer, salt, or tautomer thereof, wherein m is 0, 1, 2, 3, or 4; and
R5 is halogen, —CN, —NO2, C1-6 alkoxy, C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroaralkyl.

### Claim 10 (depends on 1)

The method of claim 1, wherein at least one of the sulfur- or selenium-containing precursors has a structure according to:
or an isomer, salt, or tautomer thereof,
wherein n is 0, 1, or 2; and
R5 is halogen, —CN, —NO2, C1-6 alkoxy, C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroaralkyl.

### Claim 11 (depends on 1)

The method of claim 1, wherein at least one of the sulfur- or selenium-containing precursors has a structure according to:
or an isomer, salt, or tautomer thereof,
wherein p is 0, 1, 2, 3, 4, 5, or 6; and
R5 is halogen, —CN, —NO2, C1-6 alkoxy, C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroaralkyl.

### Claim 12 (depends on 1)

The method of claim 1, wherein at least one of the sulfur- or selenium-containing precursors has a structure according to:
or an isomer, salt, or tautomer thereof,
wherein m is 0, 1, 2, 3, or 4; and
R5 is halogen, —CN, —NO2, C1-6 alkoxy, C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroaralkyl.

### Claim 13 (depends on 1)

The method of claim 1, wherein at least one of the sulfur- or selenium-containing precursors has a structure according to:
or an isomer, salt, or tautomer thereof,
wherein q is 0, 1, 2, or 3; and
R5 is halogen, —CN, —NO2, C1-6 alkoxy, C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, optionally substituted aryl, optionally substituted aryloxy, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroaralkyl.

### Claim 14 (depends on 1)

The method of claim 1, wherein at least one of the sulfur- or selenium-containing precursors has a structure according to:

### Claim 15 (depends on 14)

The method of claim 14, wherein Q3 is phenyl or pyridinyl, optionally substituted with 0, 1, 2, 3, or 4 halogen, —CN, —NO2, C1-6 alkoxy, C1-6 alkyl, C3-6 cycloalkyl, C2-6 alkenyl, optionally substituted aryl, optionally substituted aralkyloxy, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroaralkyl.

### Claim 16 (depends on 1)

The method of claim 1, wherein R3 and R4 are independently optionally substituted alkyl, optionally substituted aryl, or optionally substituted aralkyl.

### Claim 17 (depends on 1)

The method of claim 1, wherein R5 in Formula (III) is an optionally substituted alkyl, optionally substituted aryl, or optionally substituted aralkyl.

### Claim 18 (depends on 1, 4)

The method of claim 1 or claim 4, wherein Xis S.

### Claim 19 (depends on 1, 4)

The method of claim 1 or claim 4, wherein X is Se.

### Claim 20 (depends on 1, 4)

The method of claim 1 or claim 4, wherein at least one of the precursor metal salts comprises Cd, Cu, Fe, Ga, Hg, In, Mn, Mo, Ni, Pb, or Zn.

### Claim 21 (depends on 1)

The method of claim 1, wherein at least one of the precursor metal salts comprises a C2-30 carboxylate, thiocarboxylate, (alkyl)phosphonate, alkylsulfonate, alkylphosphate, alkyl sulfate, alkylphosphonamide, or halide.

### Claim 22 (depends on 1)

The method of claim 1, wherein at least one precursor metal salts comprises Cd, Cu, Fe, Ga, Hg, In, Mn, Mo, Ni, Pb, or Zn.

### Claim 23 (depends on 1)

The method of claim 1, wherein the method comprises contacting a first and second precursor metal salt with a sulfur-containing precursor or a selenium-containing precursor in solution under controlled nucleation and growth conditions.

### Claim 24 (depends on 23)

The method of claim 23, wherein the first and second precursor metal salts are contacted with the sulfur-containing precursor or the selenium-containing precursor at the same time.

### Claim 25 (depends on 23)

The method of claim 23, wherein the first and second precursor metal salts are contacted with the sulfur-containing precursor or the selenium-containing precursor sequentially in either order.

### Claim 26 (depends on 1)

The method of claim 1, wherein the method comprises contacting a precursor metal salt with a sulfur-containing precursor and a selenium-containing precursor in solution under controlled nucleation and growth conditions.

### Claim 27 (depends on 26)

The method of claim 26, wherein the precursor metal salt is contacted with the sulfur-containing precursor and the selenium-containing precursor, at the same time.

### Claim 28 (depends on 26)

The method of claim 26, wherein the precursor metal salt is contacted with the sulfur-containing precursor and the selenium-containing precursor sequentially in either order.

### Claim 29 (depends on 26)

The method of claim 26, wherein the resulting nanoparticles having different amounts of metal sulfide and metal selenide therewithin.

### Claim 30 (depends on 1, 4)

The method of claim 1 or claim 4, resulting in a plurality of monodispersed nanoparticles, each nanoparticle exhibiting a variable composition of metal sulfide/metal selenide throughout its structure.

### Claim 31 (depends on 28)

The method of claim 28, wherein the nanoparticles produced by the method comprise continuously varying graded metal sulfide/metal selenide structures.

### Claim 32 (depends on 28)

The method of claim 28, wherein the nanoparticles produced by the method comprise discontinuously varying core-shell metal sulfide/metal selenide varies discontinuously core-shell structures.

### Claim 33 (depends on 1, 4)

The method of claim 1 or claim 4, wherein the solution is non-aqueous.

### Claim 34 (depends on 1, 4)

The method of claim 1 or claim 4, wherein the solution is or comprises an alkane, alkene, aromatic hydrocarbon, ether or a polyether, or a trialkyl- or triaylphosphine or trialkylphosphine oxide.

### Claim 35 (depends on 1)

The method of claim 1, wherein the nanoparticles prepared by the method are substantially spherical, the nanoparticles having an average mean diameter in a range of from about 1 nm to about 10 nm.

### Claim 36 (depends on 1)

The method of claim 1, wherein the nanoparticles prepared by the method are cylindrical having at least one dimension in a range of from about 1 nm to about 25 nm.

### Claim 37 (depends on 1)

The method of claim 1, wherein nanoparticles prepared by the method exhibit a monodispersity characterized by a standard deviation variance of particle size of less than 5%, relative to the mean particle size of the nanoparticle, as measured by statistical samples of TEM micrographs.

### Claim 38 (depends on 1)

The method of claim 1, wherein the metal sulfide, metal selenide, or mixed metal sulfide/selenide nanoparticles prepared by the method are crystalline.

### Claim 39 (depends on 1)

The method of claim 1, wherein the metal sulfide, metal selenide, metal sulfide/selenide, mixed metal sulfide, mixed metal selenide, or mixed metal sulfide/selenide nanoparticles prepared by the method exhibit the characteristics of quantum dots.

### Claim 40 (depends on 1)

The method of claim 1, wherein the nanoparticles prepared by the method comprise CdS, CdSe, CuS, CuSe, GaS, GaSe, InS, InSe, NiS, NiSe, PbS, PbSe, ZnS, ZnSe or a combination thereof.

### Claim 41 (depends on 1)

The method of claim 1, wherein the size of each nanoparticle prepared by the method is greater than the Exciton Bohr radius of that material.

### Claim 42 (depends on 1)

The method of claim 1, wherein the nanoparticles prepared by the method exhibit:
(a) quantum yields of at least 80%;
(b) less than 5% thermal droop at operating temperatures of 100° C.;
(c) less than 10% flux density saturation at a flux of 100 mW/mm2;
(d) emission wavelengths within 5 nm precision while maintaining a linewidth in a range of 25 nm to 35 nm;
(e) or any combination of two or more of (a)-(d).