# US 12,015,092 B2 · Physical forms of MXene materials exhibiting novel electrical and optical characteristics

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- Number: US 12,015,092 B2
- Document ID: US12015092B2
- Status: Granted
- Kind: B2
- Application number: 17/678,120
- Filed: 2022-02-23
- Published: 2022-06-09
- Granted: 2024-06-18
- Earliest claimed: 2014-09-25
- Assignees: Drexel University
- Applicants: Drexel University
- Inventors: Michael J Ghidiu; Michel W Barsoum; Yury Gogotsi; Aaron Thomas Fafarman; Andrew DeVries Dillon
- Web page: https://patentgrep.com/patent/US12015092B2

## CPC

- H10F 77/244: {made of transparent conductive layers, e.g. transparent conductive oxide [TCO] layers}
- C01B 32/914: Carbides of single elements
- C01B 32/921: Titanium carbide
- C01B 32/949: Tungsten or molybdenum carbides
- C04B 35/56: based on carbides {or oxycarbides (containing free metal binder C22C29/00)}
- C04B 35/5607: {based on refractory metal carbides}
- C04B 35/5618: {based on titanium aluminium carbides}
- C04B 35/58: based on borides, nitrides, {i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides} or silicides {(containing free binder metal C22C29/00)}
- C04B 35/58007: {based on refractory metal nitrides}
- H10H 20/833: Transparent materials
- C04B 2235/3201: Alkali metal oxides or oxide-forming salts thereof
- C04B 2235/3203: Lithium oxide or oxide-forming salts thereof
- C04B 2235/3205: Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B 2235/445: Fluoride containing anions, e.g. fluosilicate
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- H10H: INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS

## Abstract

The present invention(s) is directed to novel conductive Mn+1Xn(Ts) compositions exhibiting high volumetric capacitances, and methods of making the same. The present invention(s) is also directed to novel conductive Mn+1Xn(Ts) compositions, methods of preparing transparent conductors using these materials, and products derived from these methods.

## Claims

### Claim 1

An article, comprising:
a substrate,
the substrate having disposed thereon a coating that comprises a Mn+1Xn(Ts) composition having multiple layers, each layer having a first and second surface,
each layer comprising
a substantially two-dimensional array of crystal cells,
each crystal cell having an empirical formula of Mn+1Xn, such that each X is positioned within an octahedral array of M,
wherein M is at least one Group 3, 4, 5, 6, or 7 metal,
wherein each X is C, N, or a combination thereof and
n=1, 2, or 3;
wherein at least one of said surfaces of the layers has surface terminations, Ts, independently comprising alkoxide, alkyl, carboxylate, halide, hydroxide, hydride, oxide, sub-oxide, nitride, sub-nitride, sulfide, sulfonate, thiol, or a combination thereof,
said coating being electrically conductive and exhibiting:
(i) a resistivity in a range of from about 0.01 to about 1000 micro-ohm-meters;
(ii) an ability to transmit at least about 50% of incident light of at least one wavelength in a range of from about 300 nm to about 2000 nm
(iii) a ratio of DC conductivity, measured in Siemens/meter, to light absorbance, (including visible light absorbance), measured as a decadic absorbance per meter, of at least 0.1 Siemens measured at least one wavelength in the range of 300 to 2500 nm;
(iv) a value of the real dielectric permittivity less than negative one for wavelengths greater than a threshold wavelength; or
(v) a combination of any two or more of (i), (ii), (iii), and (iv),
wherein the substrate is comprised in a plasmonic device, wherein the plasmonic device comprises an optical-to-electrical signal transducer a surface-plasmon polariton transmitter, or an infrared-reflecting window.

### Claim 2

An article, comprising:
a substrate,
the substrate having disposed thereon a coating that comprises a Mn+1Xn(L) composition having multiple layers, each layer having a first and second surface,
each layer comprising
a substantially two-dimensional array of crystal cells,
each crystal cell having an empirical formula of Mn+1Xn, such that each X is positioned within an octahedral array of M,
wherein M is at least one Group 3, 4, 5, 6, or 7 metal,
wherein each X is C, N, or a combination thereof and
n=1, 2, or 3;
wherein at least one of said surfaces of the layers has surface terminations, Ts, independently comprising alkoxide, alkyl, carboxylate, halide, hydroxide, hydride, oxide, sub-oxide, nitride, sub-nitride, sulfide, sulfonate, thiol, or a combination thereof,
said coating being electrically conductive and exhibiting:
(i) a resistivity in a range of from about 0.01 to about 1000 micro-ohm-meters;
(ii) an ability to transmit at least about 50% of incident light of at least one wavelength in a range of from about 300 nm to about 2000 nm
(iii) a ratio of DC conductivity, measured in Siemens/meter, to light absorbance, (including visible light absorbance), measured as a decadic absorbance per meter, of at least 0.1 Siemens measured at least one wavelength in the range of 300 to 2500 nm;
(iv) a value of the real dielectric permittivity less than negative one for wavelengths greater than a threshold wavelength; or
(v) a combination of any two or more of (i), (ii), (iii), and (iv),
wherein the substrate is comprised in a metamaterial, wherein the metamaterial comprises cloaking material, transformational optic component, or a superlens.

### Claim 3 (depends on 1)

The article of claim 1, wherein the coating exhibits a resistivity in a range of from about 0.01 to about 1000 micro-ohm-meters.

### Claim 4 (depends on 1)

The article of claim 1, wherein the coating exhibits an ability to transmit at 50% of incident light of at least one wavelength in a range of from about 300 nm to about 2000 nm.

### Claim 5 (depends on 1)

The article of claim 1, wherein the coating exhibits a ratio of DC conductivity, measured in Siemens/meter, to light absorbance, (including visible light absorbance), measured as a decadic absorbance per meter, of at least 0.1 Siemens measured at at least one wavelength in the range of 300 to 2500 nm.

### Claim 6 (depends on 1)

The article of claim 1, wherein the coating exhibit a value of the real dielectric permittivity less than negative one for wavelengths greater than a threshold wavelength.

### Claim 7

An article, comprising:
a substrate,
the substrate having disposed thereon a coating that comprises a Mn+1Xn(Ts) composition having multiple layers, each layer having a first and second surface,
each layer comprising
a substantially two-dimensional array of crystal cells,
each crystal cell having an empirical formula of Mn+1Xn, such that each X is positioned within an octahedral array of M,
wherein M is at least one Group 3, 4, 5, 6, or 7 metal,
wherein each X is C, N, or a combination thereof and
n=1, 2, or 3;
wherein at least one of said surfaces of the layers has surface terminations, Ts, independently comprising alkoxide, alkyl, carboxylate, halide, hydroxide, hydride, oxide, sub-oxide, nitride, sub-nitride, sulfide, sulfonate, thiol, or a combination thereof,
said coating being electrically conductive and exhibiting:
(i) a resistivity in a range of from about 0.01 to about 1000 micro-ohm-meters;
(ii) an ability to transmit at least about 50% of incident light of at least one wavelength in a range of from about 300 nm to about 2000 nm
(iii) a ratio of DC conductivity, measured in Siemens/meter, to light absorbance, (including visible light absorbance), measured as a decadic absorbance per meter, of at least 0.1 Siemens measured at least one wavelength in the range of 300 to 2500 nm;
(iv) a value of the real dielectric permittivity less than negative one for wavelengths greater than a threshold wavelength; or
(v) a combination of any two or more of (i), (ii), (iii), and (iv),
wherein the Mn+iXn(Ts) composition comprises a plurality of Mn+1Xn(Ts) platelets having at least one mean lateral dimension in a range or from about 0.1 micron to about 50 microns.

### Claim 8 (depends on 1)

The article of claim 1, wherein M is at least one of Hf, Cr, Mn, Mo, Nb, Sc Ta, Ti, V, W or Zr.

### Claim 9 (depends on 1)

The article of claim 1, wherein Mn+1Xn comprises Sc2C, Sc2N, Ti2C, Ti2N, V2C, V2N, Cr2C, Cr2N, Zr2C, Zr2N, Nb2C, Nb2N, Hf2C, Hf2N, Ta2C, Mo2C, Ti3C2, Ti3N2, V3C2, Ta3C2, Ta3N2, Mo3C2, (Cr2/3Ti1/2)3C2, Ti4C3, Ti4N3, V4C3, V4N3, Ta4C3, Ta4N3, Nb4C3, or a combination thereof.

### Claim 10

An article, comprising:
a substrate,
the substrate having disposed thereon a coating that comprises a Mn+1Xn(Ts) composition having multiple layers, each layer having a first and second surface,
each layer comprising
a substantially two-dimensional array of crystal cells,
each crystal cell having an empirical formula of Mn+1Xn, such that each X is positioned within an octahedral array of M,
wherein M is at least one Group 3, 4, 5, 6, or 7 metal,
wherein each X is C, N, or a combination thereof and
n=1, 2, or 3;
wherein at least one of said surfaces of the layers has surface terminations, Ts, independently comprising alkoxide, alkyl, carboxylate, halide, hydroxide, hydride, oxide, sub-oxide, nitride, sub-nitride, sulfide, sulfonate, thiol, or a combination thereof, said coating being electrically conductive and exhibiting:
(i) a resistivity in a range of from about 0.01 to about 1000 micro-ohm-meters;
(ii) an ability to transmit at least about 50% of incident light of at least one wavelength in a range of from about 300 nm to about 2000 nm
(iii) a ratio of DC conductivity, measured in Siemens/meter, to light absorbance, (including visible light absorbance), measured as a decadic absorbance per meter, of at least 0.1 Siemens measured at least one wavelength in the range of 300 to 2500 nm;
(iv) a value of the real dielectric permittivity less than negative one for wavelengths greater than a threshold wavelength; or
(v) a combination of any two or more of (i), (ii), (iii), and (iv),
wherein M comprises at least two Group 4, 5, 6, or 7 metals, and Mn+iXn(Ts) composition is represented by a formula M′2M″mXm+1(Ts), where m=n−1,
where M′ is a first metal from Group 4, 5, 6, or 7 and where M″ is a second metal from Group 4, 5, 6, or 7.

### Claim 11 (depends on 10)

The article of claim 10, wherein M′ comprises Ti, V, Cr, or Mo.

### Claim 12 (depends on 10)

The article of claim 10, wherein M″ comprises Ti, V, Nb, or Ta, and M′ is different than M″.

### Claim 13 (depends on 10)

The article of claim 10, wherein M′2M″mXm+1, comprises Mo2TiC2, Mo2VC2, Mo2TaC2, Mo2NbC2, Mo2Ti2C3, Cr2TiC2, Cr2VC2, Cr2TaC2, Cr2NbC2, Tia bC2, Ti2TaC2, V2TaC2, V2TiC2, or a combination thereof.

### Claim 14

The article of 10, wherein comprises M′2M″mXm+1, comprises Mo2TiC3, Mo2V2C3, Mo2Nb2C3, Mo2Ta2C3, Cr2Ti2C3, Cr2V2C3, Cr2Nb2C3, Cr2Ta2C3, Nb2Ta2C3, Ti2Nb2C3, Ti2Ta2C3, V2Ta2C3, V2 b2C3, V2Ti2C3, or a combination thereof.

### Claim 15 (depends on 10)

The article, of claim 10, wherein M′2M″mXm+1, comprises Nb2VC2, Ta2TiC2, Ta2VC2, Nb2TiC2 or a combination thereof.

### Claim 16 (depends on 10)

The article of claim 10, wherein the crystal cells have an empirical formula Ti3C2 or Ti2C and wherein at least one of said surfaces of each layer is coated with surface terminations, Ts, comprising alkoxide, fluoride, hydroxide, oxide, sub-oxide, sulfonate, or a combination thereof.

### Claim 17 (depends on 1)

A method, wherein incident light is reflected by an article according to claim 1.