# US 10,309,011 B2 · Method for manufacturing two-dimensional transition metal dichalcogemide thin film

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- Number: US 10,309,011 B2
- Document ID: US10309011B2
- Status: Granted
- Kind: B2
- Application number: 15/562,545
- Filed: 2016-07-28
- Published: 2018-04-19
- Granted: 2019-06-04
- Earliest claimed: 2015-07-29
- Assignees: Korea Research Institute of Standards and Science
- Applicants: Korea Research Institute of Standards and Science
- Inventors: Sang Woo Kang; Ji Hun Mun
- Web page: https://patentgrep.com/patent/US10309011B2

## CPC

- C23C 16/305: {Sulfides, selenides, or tellurides}
- C01B 17/20: Methods for preparing sulfides or polysulfides, in general (ammonium sulfides or polysulfides C01C; sulfides or polysulfides of metals, other than alkali metals, magnesium, calcium, strontium and barium, see the relevant groups of subclasses C01F or C01G, according to the metal)
- C01G 39/06: Sulfides
- C23C 16/0227: {by cleaning or etching}
- C23C 16/45527: {characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C23C 16/45555: {applied in non-semiconductor technology}
- C23C 16/52: Controlling or regulating the coating process {(C23C16/45557, C23C16/279 take precedence)}
- C30B 25/16: Controlling or regulating (controlling or regulating in general G05)
- C30B 25/186: {being specially pre-treated by, e.g. chemical or physical means}
- C30B 29/46: Sulfur-, selenium- or tellurium-containing compounds
- C30B 29/64: Flat crystals, e.g. plates, strips or discs
- C01P 2002/82: by IR- or Raman-data
- C01P 2002/85: by XPS, EDX or EDAX data
- C01P 2004/03: obtained by SEM
- C01P 2004/04: obtained by TEM, STEM, STM or AFM
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- 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)
- C30B: SINGLE-CRYSTAL GROWTH (by using ultra-high pressure, e.g. for the formation of diamonds, B01J3/06); UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL (zone-refining of metals or alloys C22B); PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (casting of metals, casting of other substances by the same processes or devices B22D; working of plastics B29; modifying the physical structure of metals or alloys C21D, C22F); SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (for producing semiconductor devices or parts thereof H10); APPARATUS THEREFOR
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

The present invention relates to a method for preparing a two-dimensional transition metal dichalcogenide and, more particularly, to a method for preparing a highly uniform two-dimensional transition metal dichalcogenide thin film. More specifically, the present invention is directed to a preparation method for a highly uniform two-dimensional transition metal dichalcogenide thin film at low temperature of 500° C. or below.

## Claims

### Claim 1

A method for preparing a two-dimensional transition metal dichalcogenide, comprising:
pre-treating a substrate in a deposition chamber; and
introducing a chalcogen-containing precursor and a transition-metal-containing precursor into the deposition chamber to deposit a two-dimensional transition metal dichalcogenide on the substrate,
wherein the deposition step includes further adding an inhibitor for preventing the creation of a two-dimensional transition metal dichalcogenide bilayer.

### Claim 2 (depends on 1)

The method as claimed in claim 1, wherein the transition-metal-containing precursor comprises a transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Nb, Ta, Mo, W, Tc, Re, Ru, Os, Rh, Ir, Pt, Ag, Au, Cd, In, Tl, Sn, Pb, Sb, Bi, Zr, Te, Pd, Hf, and a combination thereof.

### Claim 3 (depends on 1)

The method as claimed in claim 1, wherein a partial pressure ratio of the chalcogen-containing precursor to the transition-metal-containing precursor is 1:2 or greater.

### Claim 4 (depends on 1)

The method as claimed in claim 1, wherein the chalcogen-containing precursor comprises an S-containing organic compound or an S-containing inorganic compound.

### Claim 5 (depends on 1)

The method as claimed in claim 1, wherein the deposition is performed at a low temperature of 600° C. or below.

### Claim 6 (depends on 1)

The method as claimed in claim 1, wherein the deposition is performed according to a chemical vapor deposition method.

### Claim 7 (depends on 6)

The method as claimed in claim 6, wherein the chemical vapor deposition method comprises low pressure chemical vapor deposition, atmospheric pressure chemical vapor deposition, metal organic chemical vapor deposition, plasma-enhanced chemical vapor deposition, inductively coupled plasma chemical vapor deposition, atomic-layer chemical vapor deposition, or plasma-enhanced atomic layer deposition.

### Claim 8 (depends on 1)

The method as claimed in claim 1, wherein the pretreatment of the substrate is performed to control a nucleation site of the transition metal dichalcogenide to be deposited on the substrate.

### Claim 9 (depends on 1)

The method as claimed in claim 1, wherein a partial pressure ratio of the chalcogen-containing precursor to the transition-metal-containing precursor is adjusted to control a surface energy and the size of a cluster formed by gas phase reaction during the deposition process of the transition metal dichalcogenide, thereby inducing a two-dimensional growth of the transition metal dichalcogenide.

### Claim 10 (depends on 1)

The method as claimed in claim 1, wherein in the deposition process, the internal pressure of the deposition chamber is adjusted to control the amounts of the chalcogen-containing precursor and the transition-metal-containing precursor to be introduced into the deposition chamber, thereby controlling a partial pressure ratio of the chalcogen-containing precursor to the transition-metal-containing precursor.

### Claim 11

A method for preparing a two-dimensional transition metal dichalcogenide thin film, comprising:
performing a surface treatment on a substrate in a deposition chamber to reduce the surface energy of the substrate; and
introducing a chalcogen-containing precursor, a transition-metal-containing precursor, and a precursor-decomposition-accelerating catalyst into the deposition chamber to deposit a two-dimensional transition metal dichalcogenide monolayer on the substrate,
wherein the deposition step includes further adding an inhibitor for preventing the creation of a two-dimensional transition metal dichalcogenide bilayer.

### Claim 12 (depends on 11)

The method as claimed in claim 11, wherein the inhibitor has an adsorption energy higher on the edge planes of the substrate and the transition metal dichalcogenide monolayer rather than on the basal plane of the two-dimensional transition metal dichalcogenide monolayer,
wherein the chalcogen has an adsorption energy higher on the basal planes of the substrate and the transition metal dichalcogenide monolayer than on the edge plane of the transition metal dichalcogenide monolayer.

### Claim 13 (depends on 11)

The method as claimed in claim 11, wherein the precursor-decomposition-accelerating catalyst speeds up the decomposition of the chalcogen-containing precursor to take the ligand off from the chalcogen atom in the chalcogen-containing precursor, and/or the decomposition of the transition-metal-containing precursor containing a ligand bonded to a transition metal atom to take the ligand off from the transition metal atom in the transition-metal-containing precursor.

### Claim 14 (depends on 11)

The method as claimed in claim 11, wherein the surface treatment of the substrate is performed by a wet surface treatment method selected from the group consisting of piranha solution treatment, sulfuric acid (H2SO4) solution treatment, hydrochloric acid (HCl) solution treatment, and alkali metal hydroxide solution treatment; or a dry surface treatment method selected from the group consisting of O2 plasma thermal treatment and water vapor thermal treatment.

### Claim 15 (depends on 11)

The method as claimed in claim 11, wherein the substrate is selected from the group consisting of SiO2, Al2O3, HfO2, LiAlO3, MgO, Si, Ge, GaN, AlN, GaP, InP, GaAs, SiC, glass, quartz, sapphire, graphite, graphene, plastic, polymer, boron nitride (h-BN), and a combination thereof.

### Claim 16 (depends on 11)

The method as claimed in claim 11, wherein the substrate is selected from the group consisting of SiO2, Al2O3, HfO2, LiAlO3, MgO, and a combination thereof,
wherein the surface treatment of the substrate is performed by a wet surface treatment method selected from the group consisting of piranha solution treatment, sulfuric acid (H2SO4) solution treatment, hydrochloric acid (HCl) solution treatment, and alkali metal hydroxide solution treatment; or a dry surface treatment method selected from the group consisting of O2 plasma thermal treatment and water vapor thermal treatment.

### Claim 17 (depends on 11)

The method as claimed in claim 11, wherein a partial pressure ratio of the chalcogen-containing precursor to the transition-metal-containing precursor is at least 2.

### Claim 18

A method for preparing a two-dimensional transition metal dichalcogenide thin film, comprising:
(1) performing a surface treatment on a substrate in a deposition chamber to reduce the surface energy of the substrate;
(2) introducing a chalcogen-containing precursor and a transition-metal-containing precursor into the deposition chamber at a temperature of 500° C. or below and a first pressure of 0.001 to 760 Torr to create crystals of the two-dimensional transition metal dichalcogenide on the substrate;
(3) introducing the chalcogen-containing precursor and the transition-metal-containing precursor into the deposition chamber at a second pressure higher than the first pressure of the step (2) to increase the crystal size of the two-dimensional transition metal dichalcogenide on the substrate; and
(4) introducing the chalcogen-containing precursor and the transition-metal-containing precursor into the deposition chamber at a third pressure higher than the second pressure of the step (3) to form a two-dimensional transition metal dichalcogenide monolayer on the substrate,
wherein an inhibitor for preventing the creation of a two-dimensional transition metal dichalcogenide bilayer is further added into the deposition chamber in the steps (2), (3) and (4).

### Claim 19 (depends on 18)

The method as claimed in claim 18, wherein a precursor-decomposition-accelerating catalyst is further added into the deposition chamber in the steps (2), (3) and (4).