# US 12,180,586 B2 · Apparatus and methods for roll-to-roll (R2R) plasma enhanced/activated atomic layer deposition (PEALD/PAALD)

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- Number: US 12,180,586 B2
- Document ID: US12180586B2
- Status: Granted
- Kind: B2
- Application number: 17/402,205
- Filed: 2021-08-13
- Published: 2023-02-16
- Granted: 2024-12-31
- Earliest claimed: 2021-08-13
- Assignees: NanoMaster, Inc.
- Applicants: Nano-Master, Inc.
- Inventors: Birol Kuyel
- Web page: https://patentgrep.com/patent/US12180586B2

## CPC

- C23C 16/45536: {Use of plasma, radiation or electromagnetic fields}
- C23C 16/45551: {for relative movement of the substrate and the gas injectors or half-reaction reactor compartments}
- C23C 16/46: characterised by the method used for heating the substrate (C23C16/48, C23C16/50 take precedence)
- C23C 16/482: {using incoherent light, UV to IR, e.g. lamps}
- C23C 16/545: {for coating elongated substrates}
- H01J 37/32082: {Radio frequency generated discharge (H01J37/32357, H01J37/32366, H01J37/32394 and H01J37/32403 take precedence)}
- H01J 37/32596: {Hollow cathodes}
- H01J 37/3277: {of continuous material}
- 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)
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)

## Abstract

Techniques are disclosed for roll-to-roll (R2R) atomic layer deposition (ALD). R2R ALD is accomplished by arranging precursor nozzles in A/B pairs while a flexible web substrate moves underneath the A/B pairs at a uniform speed. Nozzles A of the A/B pairs continuously flow a precursor A into the process volume of the R2R ALD chamber. The plasma enhanced/activated ALD (PEALD/PAALD) embodiments utilize electron cyclotron resonance or rotation (ECR)-enhanced hollow cathode plasma sources (HCPS) where nozzles B flow activated neutrals of precursor B into the process volume. As the flexible web moves in an R2R motion, nucleates from precursor A deposited on the surface of the substrate, and neutrals of precursor B undergo a self-limiting reaction to deposit a single atomically sized ALD film/layer. In this manner, multiple ALD layers may be deposited by each successive A/B pair in a single pass of the web. There is also a heat source underneath the web to further facilitate the ALD reaction, or to support thermal ALD embodiments.

## Claims

### Claim 1

A roll-to-roll vacuum deposition chamber comprising:
(a) a first plurality of nozzles A for continuously flowing a precursor A into said roll-to-roll vacuum deposition chamber;
(b) a second plurality of nozzles B for continuously flowing a precursor B into said roll-to-roll vacuum deposition chamber;
(c) said first plurality of nozzles A and said second plurality of nozzles B arranged linearly in A/B pairs in a direction perpendicular to a motion of a flexible web of a substrate, said motion occurring at a constant speed from a first roll to a second roll of said roll-to-roll vacuum deposition chamber, and said motion occurring underneath said A/B pairs, wherein a first spacing between each of said first plurality of nozzles A in each of said A/B pairs is approximately half of a distance between the lower ends of said A/B pairs and said flexible web, and wherein a second spacing between each of said second plurality of nozzles B in each of said A/B pairs is also approximately half of said distance between the lower ends of said A/B pairs and said flexible web;
(d) an evacuation pump underneath an end of said flexible web near said second roll for evacuating unused quantities of said precursor A and said precursor B;
(e) said second plurality of nozzles comprising a plurality of corresponding electron cyclotron resonance (ECR)-enhanced hollow cathode plasma sources (HCPSes) for producing a plasma of said precursor B, wherein said plurality of corresponding ECR-enhanced HCPSes comprise a plurality of corresponding cylindrical and aligned magnets around a plurality of corresponding hollow cathodes; and
(f) a ceramic plug with a pinhole placed underneath each of said second plurality of nozzles for allowing said activated neutrals of said precursor B to pass into said roll-to-roll vacuum deposition chamber while preventing said plasma to pass into said roll-to-roll vacuum deposition chamber and to come in contact with said flexible web;
wherein nucleates from said precursor A and said activated neutrals of precursor B undergo a self-limiting reaction on a surface of said flexible web and consequently deposit one or more atomically sized layers of uniform thickness on said surface by atomic layer deposition (ALD) without requiring intervening purge and exhaust operations, and wherein:
(g) a distance between the lower ends of said first plurality and said second plurality of nozzles and said flexible web is substantially in the range of 1 inch to 2 inches;
(h) a spacing between each of said first plurality of nozzles is substantially in the range of 0.5 inch to 1 inch;
(i) a spacing between each of said second plurality of nozzles is substantially in the range of 0.5 inch to 1 inch; and
(j) a spacing between said first plurality of nozzles and said second plurality of nozzles is greater than 2 inches.

### Claim 2 (depends on 1)

The roll-to-roll vacuum deposition chamber of claim 1, wherein said uniform atomically sized layer is deposited across an entire width of said flexible web.

### Claim 3 (depends on 1)

The roll-to-roll vacuum deposition chamber of claim 1, wherein a heat source underneath said flexible web is used to heat said flexible web for further facilitating said self-limiting reaction.

### Claim 4 (depends on 1)

The roll-to-roll vacuum deposition chamber of claim 1 having a temperature of said flexible web substantially in the range of 20° C. to 300° C.

### Claim 5 (depends on 1)

The roll-to-roll vacuum deposition chamber of claim 1 utilizing one pair amongst said one or more pairs to deposit one of said one or more atomically sized layers of uniform thickness in a single pass of said flexible web.

### Claim 6 (depends on 1)

The roll-to-roll vacuum deposition chamber of claim 1, wherein said precursor A and said activated neutrals of said precursor B do not stick to said surface once said surface is saturated by said self-limiting reaction.

### Claim 7 (depends on 1)

The roll-to-roll vacuum deposition chamber of claim 1, wherein a diameter of said pinhole in said ceramic plug is substantially 20 mills.

### Claim 8 (depends on 1)

The roll-to-roll vacuum deposition chamber of claim 1 having an inside pressure substantially in the range of 0.1 Torr to 0.5 Torr.