# US 10,319,586 B1 · Methods comprising an atomic layer deposition sequence

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,319,586 B1
- Document ID: US10319586B1
- Status: Granted
- Kind: B1
- Application number: 15/860,388
- Filed: 2018-01-02
- Published: 2019-07-04
- Granted: 2019-06-11
- Earliest claimed: 2018-01-02
- Assignees: Micron Technology, Inc.
- Applicants: Micron Technology, Inc.
- Inventors: John A. Smythe; Woohee Kim; Stefan Uhlenbrock
- Web page: https://patentgrep.com/patent/US10319586B1

## CPC

- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- C23C 16/345: {Silicon nitride}
- C23C 16/401: {containing silicon}
- 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 16/46: characterised by the method used for heating the substrate (C23C16/48, C23C16/50 take precedence)
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane}
- H10P 14/69215: {the material being a silicon oxide, e.g. SiO2}
- H10P 14/6927: {the material being a silicon oxynitride, e.g. SiON or SiON:H}
- H10P 14/6938: {the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides}
- H10P 14/69433: {the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- 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

An example method comprises an ALD sequence including contacting an outer substrate surface at a temperature T1 with a first precursor to form a monolayer onto the outer substrate surface. Temperature of the outer substrate surface and the monolayer thereon is increased to a temperature T2 that is at least 200° C. greater than a maximum of the temperature T1. The temperature-increasing is at a temperature-increasing rate that takes no more than 10 seconds to get the outer substrate surface and the monolayer thereon at least 200° C. above the maximum temperature T1. At the temperature T2, the monolayer is contacted with a second precursor that reacts with the monolayer to form a reaction product and a new outer substrate surface that each comprise a component from the monolayer and a component from the second precursor. With the monolayer not having been allowed to be at least 200° C. above the maximum temperature T1 for more than 10 seconds, temperature of the new outer substrate surface is decreased from the temperature T2 to a lower temperature TL that is at least 200° C. lower than a minimum of the temperature T2.

## Claims

### Claim 1

A method comprising the following ALD sequence:
contacting an outer substrate surface at a temperature T1 at or below 650° C. with a Si-comprising precursor to form a monolayer comprising Si from the Si-comprising precursor onto the outer substrate surface;
increasing temperature of the outer substrate surface and the Si-comprising monolayer thereon to a temperature T2 that is at least 100° C. greater than a maximum of the temperature T1 and is greater than 650° C., the temperature-increasing being at a temperature-increasing rate that takes no more than 10 seconds to get the outer substrate surface and the Si-comprising monolayer thereon above 650° C.;
at the temperature T2, contacting the Si-comprising monolayer with an O and/or N-comprising precursor that reacts with the Si-comprising monolayer to form a reaction product and a new outer substrate surface that each comprise an insulative material comprising silicon from the monolayer and at least one of O and N from the O and/or N-comprising precursor; and
with the Si-comprising monolayer not having been allowed to be above 650° C. for more than 10 seconds, decreasing temperature of the new outer substrate surface from the temperature T2 to a lower temperature TL that is at least 50° C. lower than a minimum of the temperature T2 and is lower than or equal to 650° C.

### Claim 2 (depends on 1)

The method of claim 1 being devoid of contacting the outer substrate surface with any Si-comprising precursor at a temperature above 650° C.

### Claim 3 (depends on 1)

The method of claim 1 wherein the temperature T1 is no lower than 20° C.

### Claim 4 (depends on 1)

The method of claim 1 comprising repeating said sequence and until no more than a total of 100 Angstroms of the insulative material is formed.

### Claim 5 (depends on 4)

The method of claim 4 comprising repeating said sequence until the total of the insulative material is no less than 10 Angstroms.

### Claim 6 (depends on 4)

The method of claim 4 wherein an outermost region of the substrate when beginning said method comprises elemental-form Si, all of the repeating consuming no more than 2 Angstroms, if any, of said elemental-form Si.

### Claim 7 (depends on 6)

The method of claim 6 wherein all of the repeating consumes no measurable quantity of said elemental-form Si.

### Claim 8 (depends on 1)

The method of claim 1 comprising at least one of before and after the contacting with the O and/or N-comprising precursor, contacting the substrate with a metal-comprising precursor and forming the reaction product and the new outer surface to comprise the metal from the metal-comprising precursor.

### Claim 9 (depends on 8)

The method of claim 8 wherein the contacting with the metal-comprising precursor occurs before the contacting with the O and/or N-comprising precursor and at the temperature T1 such that the new outer surface comprises the metal immediately upon formation of the reaction product having the new outer surface.

### Claim 10 (depends on 8)

The method of claim 8 wherein the contacting with the metal-comprising precursor occurs after the contacting with the O and/or N-comprising precursor such that the reaction product having the new outer surface comprises the metal after and not before formation of the reaction product having the new outer surface.

### Claim 11 (depends on 10)

The method of claim 10 wherein,
the contacting with the metal-comprising precursor occurs at the temperature T1 and forms a monolayer comprising metal from the metal-comprising precursor onto the new outer substrate surface;
thereafter, increasing temperature of the new outer substrate surface and the metal-comprising monolayer thereon to the temperature T2, the temperature-increasing of the new outer substrate surface and the metal-comprising monolayer thereon being at a temperature-increasing rate and taking no more than 10 seconds to get the new outer substrate surface and the metal-comprising monolayer thereon above 650° C.; and
at the temperature T2, contacting the metal-comprising monolayer with the O and/or N-comprising precursor that reacts with the metal-comprising monolayer to form another reaction product and another new outer substrate surface that each comprise the insulative material comprising the metal from the metal-comprising monolayer and at least one of O and N from the O and/or N-comprising precursor.

### Claim 12 (depends on 8)

The method of claim 8 wherein the contacting with the metal-comprising precursor occurs before and after the contacting with the O and/or N-comprising precursor.

### Claim 13 (depends on 1)

The method of claim 1 wherein the temperature T1 is no greater than 500° C.

### Claim 14 (depends on 13)

The method of claim 13 wherein the temperature T1 is no less than 350° C. during at least some of the contacting the outer substrate surface with the Si-comprising precursor to form the monolayer.

### Claim 15 (depends on 13)

The method of claim 13 wherein the temperature T1 is no less than 350° C. during all of the contacting the outer substrate surface with the Si-comprising precursor to form the monolayer.

### Claim 16 (depends on 14)

The method of claim 14 wherein the lower temperature TL is at least 200° C. lower than the minimum of the temperature T2.

### Claim 17 (depends on 13)

The method of claim 13 wherein the temperature T1 is at least 100° C. during all of the contacting the outer substrate surface with the Si-comprising precursor to form the monolayer.

### Claim 18 (depends on 1)

The method of claim 1 wherein the lower temperature TL is at least 150° C. lower than the minimum of the temperature T2.

### Claim 19 (depends on 1)

The method of claim 1 wherein the temperature T1 is constant during all of the contacting of the outer substrate surface with the Si-comprising precursor.

### Claim 20 (depends on 1)

The method of claim 1 wherein the temperature T1 is not constant during all of the contacting of the outer substrate surface with the Si-comprising precursor.

### Claim 21 (depends on 20)

The method of claim 20 wherein the maximum and a minimum of the temperature T1 during most of the contacting of the outer substrate surface with the Si-comprising precursor are each more than 10% in degrees C. from the middle value between the maximum and the minimum of the temperature T1.

### Claim 22 (depends on 1)

The method of claim 1 wherein the maximum and a minimum of the temperature T1 during all of the contacting of the outer substrate surface with the Si-comprising precursor are each within 10% in degrees C. from the middle value between the maximum and the minimum of the temperature T1.

### Claim 23 (depends on 1)

The method of claim 1 wherein the temperature T2 is at least 200° C. above the maximum of the temperature T1.

### Claim 24 (depends on 23)

The method of claim 23 wherein the temperature T2 is at least 300° C. above the maximum of the temperature T1.

### Claim 25 (depends on 1)

The method of claim 1 wherein the temperature T2 is at least 750° C.

### Claim 26 (depends on 1)

The method of claim 1 wherein the temperature T2 is no more than 1,000° C.

### Claim 27 (depends on 1)

The method of claim 1 wherein the temperature T2 is constant during all of the contacting of the monolayer with the O and/or N-comprising precursor.

### Claim 28 (depends on 1)

The method of claim 1 wherein the temperature T2 is not constant during all of the contacting of the monolayer with the O and/or N-comprising precursor.

### Claim 29 (depends on 28)

The method of claim 28 wherein the minimum and a maximum of the temperature T2 during most of the contacting of the monolayer with the O and/or N-comprising precursor are each more than 10% in degrees C. from the middle value between the maximum and the minimum of the temperature T2.

### Claim 30 (depends on 1)

The method of claim 1 wherein the maximum and a minimum of the temperature T2 during all of the contacting of the monolayer with the O and/or N-comprising precursor are each within 10% in degrees C. from the middle value between the maximum and the minimum of the temperature T2.

### Claim 31 (depends on 1)

The method of claim 1 comprising contacting the monolayer with the O and/or N-comprising precursor when it is at or below 650° C.

### Claim 32 (depends on 1)

The method of claim 1 comprising only contacting the monolayer with the O and/or N-comprising precursor when it is above 650° C.

### Claim 33 (depends on 1)

The method of claim 1 comprising contacting the monolayer with the O and/or N-comprising precursor all of the time it is at the temperature T2.

### Claim 34 (depends on 1)

The method of claim 1 comprising contacting the monolayer with the O and/or N-comprising precursor only some of the time it is at the temperature T2.

### Claim 35 (depends on 1)

The method of claim 1 wherein the temperature-increasing rate is constant.

### Claim 36 (depends on 1)

The method of claim 1 wherein the temperature-increasing rate is at least 40° C./second.

### Claim 37 (depends on 36)

The method of claim 36 wherein the temperature-increasing rate is no more than 75° C./second.

### Claim 38 (depends on 1)

The method of claim 1 wherein the temperature-increasing takes no more than 6 seconds.

### Claim 39 (depends on 38)

The method of claim 38 wherein the temperature T2 is at least 700° C., and the temperature-increasing taking no more than 6 seconds is to the temperature T2.

### Claim 40 (depends on 1)

The method of claim 1 wherein the temperature-increasing takes no less than 3 seconds.

### Claim 41 (depends on 40)

The method of claim 40 wherein the temperature T2 is at least 700° C., and the temperature-increasing taking no more than 3 seconds is to the temperature T2.

### Claim 42 (depends on 1)

The method of claim 1 wherein the temperature-decreasing occurs with the monolayer not having been allowed to be above 650° C. for more than 5 seconds.

### Claim 43 (depends on 42)

The method of claim 42 wherein the temperature-decreasing occurs with the monolayer not having been allowed to be above 650° C. for more than 2 seconds.

### Claim 44 (depends on 1)

The method of claim 1 wherein,
the temperature T1 is within 10% in degrees C. of the maximum and a minimum of the temperature T1 during all of the contacting of the outer substrate surface with the Si-comprising precursor; and
the lower temperature TL is the same as the temperature T1.

### Claim 45 (depends on 1)

The method of claim 1 wherein,
the temperature T1 is within 10% in degrees C. of the maximum and a minimum of the temperature T1 during all of the contacting of the outer substrate surface with the Si-comprising precursor; and
the lower temperature TL is lower than the temperature T1.

### Claim 46 (depends on 1)

The method of claim 1 wherein,
the temperature T1 is within 10% in degrees C. of the maximum and a minimum of the temperature T1 during all of the contacting of the outer substrate surface with the Si-comprising precursor; and
the lower temperature TL is greater than the temperature T1.

### Claim 47 (depends on 1)

The method of claim 1 wherein the temperature-decreasing is at a temperature-decreasing rate that is at least 40° C./second.

### Claim 48 (depends on 47)

The method of claim 47 wherein the temperature-decreasing rate is no more than 75° C./second.

### Claim 49 (depends on 1)

The method of claim 1 wherein the temperature-decreasing is at a temperature-decreasing rate that is less than the temperature-increasing rate.

### Claim 50 (depends on 49)

The method of claim 49 wherein the temperature-decreasing to the lower temperature TL takes no more than 30 seconds.

### Claim 51 (depends on 50)

The method of claim 50 wherein the temperature-decreasing to the lower temperature TL takes no less than 6 seconds.

### Claim 52 (depends on 1)

The method of claim 1 wherein the O and/or N-comprising precursor comprises O and the insulative material of the reaction product and the new outer substrate surface comprises O from the O-comprising precursor.

### Claim 53 (depends on 1)

The method of claim 1 wherein the O and/or N-comprising precursor comprises N and the insulative material of the reaction product and the new outer substrate surface comprises N from the N-comprising precursor.

### Claim 54 (depends on 1)

The method of claim 1 wherein the O and/or N-comprising precursor comprises O and N, the insulative material of the reaction product and the new outer substrate surface comprise O and N from the O and N-comprising precursor.

### Claim 55 (depends on 1)

The method of claim 1 further comprising an inert-gas purge of a chamber in which the ALD sequence occurs, the inert-gas purge occurring at least in part during the temperature-increasing.

### Claim 56 (depends on 1)

The method of claim 1 further comprising an inert-gas purge of a chamber in which the ALD sequence occurs, the inert-gas purge occurring at least in part during the temperature-decreasing.

### Claim 57

A method comprising the following ALD sequence:
contacting an outer substrate surface at a temperature T1 with a Si-comprising precursor to form a monolayer comprising Si from the Si-comprising precursor onto the outer substrate surface;
increasing temperature of the outer substrate surface and the Si-comprising monolayer thereon to a temperature T2 that is at least 200° C. greater than a maximum of the temperature T1, the temperature-increasing being at a temperature-increasing rate that takes no more than 10 seconds to get the outer substrate surface and the Si-comprising monolayer thereon at least 200° C. above the maximum temperature T1;
at the temperature T2, contacting the Si-comprising monolayer with an and/or N-comprising precursor that reacts with the Si-comprising monolayer to form a reaction product and a new outer substrate surface that each comprise an insulative material comprising silicon from the monolayer and at least one of O and N from the O and/or N-comprising precursor; and
with the Si-comprising monolayer not having been allowed to be at least 200° C. above the maximum temperature T1 for more than 10 seconds, decreasing temperature of the new outer substrate surface from the temperature T2 to a lower temperature TL that is at least 200° C. lower than a minimum of the temperature T2.

### Claim 58

A method comprising the following ALD sequence:
contacting an outer substrate surface at a temperature T1 with a first precursor to form a monolayer onto the outer substrate surface;
increasing temperature of the outer substrate surface and the monolayer thereon to a temperature T2 that is at least 200° C. greater than a maximum of the temperature T1, the temperature-increasing being at a temperature-increasing rate that takes no more than 10 seconds to get the outer substrate surface and the monolayer thereon at least 200° C. above the maximum temperature T1;
at the temperature T2, contacting the monolayer with a second precursor that reacts with the monolayer to form a reaction product and a new outer substrate surface that each comprise a component from the monolayer and a component from the second precursor; and
with the monolayer not having been allowed to be at least 200° C. above the maximum temperature T1 for more than 10 seconds, decreasing temperature of the new outer substrate surface from the temperature T2 to a lower temperature TL that is at least 200° C. lower than a minimum of the temperature T2.