# US 9,040,372 B2 · Niobium and vanadium organometallic precursors for thin film deposition

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- Number: US 9,040,372 B2
- Document ID: US9040372B2
- Status: Granted
- Kind: B2
- Application number: 13/888,970
- Filed: 2013-05-07
- Published: 2013-11-07
- Granted: 2015-05-26
- Earliest claimed: 2008-10-07
- Assignees: L'Air Liquide, Societe Anonyme pour l'Etude et l'Exploitation des Procedes Georges
- Applicants: L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude
- Inventors: Nicolas Blasco; Antony Correia-Anacleto; Audrey Pinchart; Andreas Zauner
- Web page: https://patentgrep.com/patent/US9040372B2

## CPC

- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- C07F 9/00: Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- 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)

## Abstract

Disclosed are methods for forming a metal-containing layer on a substrate. The methods include providing a vapor and at least one reaction gas and reacting the vapor and the reaction gas with the substrate by a deposition process. The vapor may be selected from the group consisting of (Cp)V(═NtBu)(NEt2)2; (Cp)V(═NtBu)(NMe2)2; (Cp)V(═NtBu)(NEtMe)2; (Cp)V(═NiPr)(NEt2)2; (Cp)V(═NiPr)(NMe2)2; (Cp)V(═NiPr)(NEtMe)2; (Cp)V(═NC5H11)(NEt2)2; (Cp)V(═NC5H11)(NMe2)2; (Cp)V(═NC5H11)(NEtMe)2; (Cp)Nb(═NtBu)(NEt2)2; (Cp)Nb(═NtBu)(NMe2)2; (Cp)Nb(═NtBu)(NEtMe)2; (Cp)Nb(═NiPr)(NEt2)2; (Cp)Nb(═NiPr)(NMe2)2; (Cp)Nb(═NiPr)(NEtMe)2; (Cp)Nb(═NC5H11)(NEt2)2; (Cp)Nb(═NC5H11)(NMe2)2; and (Cp)Nb(═NC5H11)(NEtMe)2. The reaction gas may be selected from the group consisting of hydrogen, hydrogen sulfide, hydrogen selenide, hydrogen telluride, carbon monoxide, ammonia, organic amine, silane, disilane, higher silanes, silylamines, diborane, hydrazine, methylhydrazine, chlorosilane, chloropolysilane, metal alkyl, arsine, phosphine, trialkylboron, oxygen, hydrogen peroxide, nitrous oxide, nitrogen monoxide, nitrogen dioxide, alcohols, plasma comprising fragments of those species, and combinations thereof.

## Claims

### Claim 1

A method for forming a metal-containing layer on a substrate, the method comprising the steps of:
a) providing a vapor comprising at least one precursor compound selected from the group consisting of (Cp)V(═NtBu)(NEt2)2; (Cp)V(═NtBu)(NMe2)2; (Cp)V(═NtBu)(NEtMe)2; (Cp)V(═NiPr)(NEt2)2; (Cp)V(═NiPr)(NMe2)2; (Cp)V(═NiPr)(NEtMe)2; (Cp)V(═NC5H11)(NEt2)2; (Cp)V(═NC5H11)(NMe2)2; (Cp)V(═NC5H11)(NEtMe)2; (Cp)Nb(═NtBu)(NEt2)2; (Cp)Nb(═NtBu)(NMe2)2; (Cp)Nb(═NtBu)(NEtMe)2; (Cp)Nb(═NiPr)(NEt2)2; (Cp)Nb(═NiPr)(NMe2)2; (Cp)Nb(═NiPr)(NEtMe)2; (Cp)Nb(═NC5H11)(NEt2)2; (Cp)Nb(═NC5H11)(NMe2)2; and (Cp)Nb(═NC5H11)(NEtMe)2;
b) providing at least one reaction gas selected from the group consisting of hydrogen, hydrogen sulfide, hydrogen selenide, hydrogen telluride, carbon monoxide, ammonia, organic amine, silane, disilane, higher silanes, silylamines, diborane, hydrazine, methylhydrazine, chlorosilane, chloropolysilane, metal alkyl, arsine, phosphine, trialkylboron, oxygen, hydrogen peroxide, nitrous oxide, nitrogen monoxide, nitrogen dioxide, alcohols, plasma comprising fragments of those species, and combinations thereof; and
c) reacting the vapor and the reaction gas with the substrate, according to a deposition process, to form the metal-containing layer on at least one surface of the substrate.

### Claim 2 (depends on 1)

The method of claim 1, wherein the deposition process is an atomic layer deposition process.

### Claim 3 (depends on 1)

The method of claim 1, wherein the deposition process is a chemical vapor deposition process.

### Claim 4 (depends on 1)

The method of claim 1, further comprising the step:
d) reacting the metal-containing layer obtained in step c) with a reagent selected from the group consisting of another metal source, reducing reactants, nitriding reactants, oxidizing reactants, and combinations thereof.

### Claim 5 (depends on 1)

The method of claim 1, wherein the vapor provided in step a) further comprises at least one precursor compound containing a metal M2, and the metal-containing layer formed in step c) contains two metals M1 and M2, wherein M1 is Vanadium or Niobium.

### Claim 6 (depends on 1)

The method of claim 1, wherein a temperature of the substrate is 100° C. to 700° C. and wherein the deposition chamber containing the substrate has a pressure of 1.33 Pa to 100 kPa.

### Claim 7 (depends on 6)

The method of claim 6, wherein the temperature is 150° C. to 450° C. and the pressure is below 25 kPa.

### Claim 8 (depends on 1)

The method of claim 1, further comprising the step of purging excess vapor comprising the at least one precursor compound from the substrate with an inert gas selected from the group consisting of hydrogen, nitrogen, helium, argon, and mixtures thereof.

### Claim 9

A method of manufacturing a semiconductor structure, comprising the steps of:
forming a metal-containing layer on the semiconductor substrate by:
a) providing a vapor comprising at least one precursor compound selected from the group consisting of (Cp)V(═NtBu)(NEt2)2; (Cp)V(═NtBu)(NMe2)2; (Cp)V(═NtBu)(NEtMe)2; (Cp)V(═NiPr)(NEt2)2; (Cp)V(═NiPr)(NMe2)2; (Cp)V(═NiPr)(NEtMe)2; (Cp)V(═NC5H11)(NEt2)2; (Cp)V(═NC5H11)(NMe2)2; (Cp)V(═NC5H11)(NEtMe)2; (Cp)Nb(═NtBu)(NEt2)2; (Cp)Nb(═NtBu)(NMe2)2; (Cp)Nb(═NtBu)(NEtMe)2; (Cp)Nb(═NiPr)(NEt2)2; (Cp)Nb(═NiPr)(NMe2)2; (Cp)Nb(═NiPr)(NEtMe)2; (Cp)Nb(═NC5H11)(NEt2)2; (Cp)Nb(═NC5H11)(NMe2)2; and (Cp)Nb(═NC5H11)(NEtMe)2;
b) providing at least one reaction gas selected from the group consisting of hydrogen, hydrogen sulfide, hydrogen selenide, hydrogen telluride, carbon monoxide, ammonia, organic amine, silane, disilane, higher silanes, silylamines, diborane, hydrazine, methylhydrazine, chlorosilane, chloropolysilane, metal alkyl, arsine, phosphine, trialkylboron, oxygen, hydrogen peroxide, nitrous oxide, nitrogen monoxide, nitrogen dioxide, alcohols, plasma comprising fragments of those species, and combinations thereof; and
c) reacting the vapor and the reaction gas with the semiconductor substrate, according to a deposition process, to form the metal-containing layer on at least one surface of the semiconductor substrate.

### Claim 10 (depends on 9)

The method of claim 9, wherein the deposition process is an atomic layer deposition process.

### Claim 11 (depends on 9)

The method of claim 9, wherein the deposition process is a chemical vapor deposition process.

### Claim 12 (depends on 9)

The method of claim 9, further comprising the step:
d) reacting the metal-containing layer obtained in step c) with a reagent selected from the group consisting of another metal source, reducing reactants, nitriding reactants, oxidizing reactants, and combinations thereof.

### Claim 13 (depends on 9)

The method of claim 9, wherein the vapor provided in step a) further comprises at least one precursor compound containing a metal M2, and the metal-containing layer formed in step c) contains two metals M1 and M2, wherein M1 is Vanadium or Niobium.

### Claim 14 (depends on 9)

The method of claim 9, further comprising the step of purging excess vapor comprising the at least one precursor compound from the substrate with an inert gas selected from the group consisting of hydrogen, nitrogen, helium, argon, and mixtures thereof.

### Claim 15

A compound selected from the group consisting of:
(Cp)Nb(═NtBu)(NEt2)2
(Cp)Nb(═NtBu)(NMe2)2
(Cp)Nb(═NtBu)(N(EtMe)2.

### Claim 16 (depends on 15)

The compound of claim 15, wherein the compound is (Cp)Nb(═NtBu)(NEt2)2.

### Claim 17 (depends on 15)

The compound of claim 15, wherein the compound is (Cp)Nb(═NtBu)(NMe2)2.

### Claim 18 (depends on 15)

The compound of claim 15, wherein the compound is (Cp)Nb(═NtBu)(N(EtMe)2.