# US 11,443,919 B2 · Film formation via pulsed RF plasma

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- Number: US 11,443,919 B2
- Document ID: US11443919B2
- Status: Granted
- Kind: B2
- Application number: 16/785,331
- Filed: 2020-02-07
- Published: 2020-08-13
- Granted: 2022-09-13
- Earliest claimed: 2019-02-11
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Krishna Nittala; Diwakar N. Kedlaya; Karthik Janakiraman; Yi Yang; Rui Cheng
- Web page: https://patentgrep.com/patent/US11443919B2

## CPC

- H01J 37/32082: {Radio frequency generated discharge (H01J37/32357, H01J37/32366, H01J37/32394 and H01J37/32403 take precedence)}
- C23C 16/505: using radio frequency discharges
- C23C 16/515: using pulsed discharges
- H01J 37/3244: {Gas supply means}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane}
- H10P 72/0602: {Temperature monitoring}
- H01J 2237/3321: CVD [Chemical Vapor Deposition]
- H10P 72/0432: {mainly by conduction}
- H10P 72/0434: {mainly by convection}
- H10P 72/0436: {mainly by radiation}
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

Systems and methods of using pulsed RF plasma to form amorphous and microcrystalline films are discussed herein. Methods of forming films can include (a) forming a plasma in a process chamber from a film precursor and (b) pulsing an RF power source to cause a duty cycle on time (TON) of a duty cycle of a pulse generated by the RF power source to be less than about 20% of a total cycle time (TTOT) of the duty cycle to form the film. The methods can further include (c) depositing a first film interlayer on a substrate in the process chamber; (d) subsequent to (c), purging the process chamber; and (e) subsequent to (d), introducing a hydrogen plasma to the process chamber. Further in the method, (b)-(e) are repeated to form a film. The film can have an in-film hydrogen content of less than about 10%.

## Claims

### Claim 1

A method of forming a film, comprising:
ionizing a precursor gas to form a plasma in a process volume of a process chamber;
pulsing an RF power source coupled to the process chamber; and
in response to the pulsing, depositing a film on a substrate during the pulsing of the RF power source, the substrate being positioned on a substrate support inside of the process volume, wherein the substrate support is at a temperature from 350° C. to 450° C.; and
wherein the film includes a hydrogen content below about 5% and has a variation in thickness of less than 6%.

### Claim 2 (depends on 1)

The method of claim 1, wherein introducing the precursor gas comprises introducing the precursor gas via a gas distribution assembly opposite the substrate support, the gas distribution assembly being at a temperature from about 200° C. to about 350° C. during the depositing of the film.

### Claim 3 (depends on 1)

The method of claim 1, further comprising depositing the film at a deposition rate from 1 A/s to 8 A/s during the pulsing of the RF power source.

### Claim 4 (depends on 1)

The method of claim 1, wherein pulsing the RF power source comprises having a duty cycle on time (TON) of the RF power source of less than about 20%.

### Claim 5 (depends on 1)

The method of claim 1, wherein the precursor gas comprises silicon (Si) or germanium (Ge).

### Claim 6 (depends on 1)

The method of claim 1, wherein the precursor gas comprises hydrogen.

### Claim 7 (depends on 6)

The method of claim 6, wherein the precursor gas comprises C2H6, C2H2, or GeH4.

### Claim 8

A method of forming a film, comprising:
introducing a precursor gas to a process volume of a process chamber, the process chamber having a chamber lid, a chamber bottom, and a sidewall extending therebetween;
ionizing the precursor gas to form a plasma;
pulsing an RF power source to cause a duty cycle on time (TON) of a duty cycle of a pulse generated by the RF power source to be less than about 20% of a total cycle time (TTOT) of the duty cycle; and
depositing a film having a hydrogen content below about 5% onto a substrate positioned on a substrate support inside of the process volume, wherein the substrate support is at a temperature from 350° C. to 450° C., and wherein the thickness of the film has a variation of 6% or less.

### Claim 9 (depends on 8)

The method of claim 8, wherein the duty cycle on time (TON) of a duty cycle of a pulse generated by the RF power source to be less than about 10% of a total cycle time (TTOT) of the duty cycle.

### Claim 10 (depends on 8)

The method of claim 8, wherein the film is deposited on at least one of the chamber lid, the chamber bottom, and the sidewall of the process chamber.

### Claim 11 (depends on 8)

The method of claim 8, wherein the depositing of the film occurs at a deposition rate from about 1 Å/min to about 10 Å/min.

### Claim 12

A method of forming a film, comprising:
(a) forming a plasma in a process chamber from a film precursor;
(b) pulsing an RF power source to cause a duty cycle on time (TON) of a duty cycle of a pulse generated by the RF power source to be less than about 20% of a total cycle time (TTOT) of the duty cycle;
(c) depositing a first film interlayer on a substrate positioned on a substrate support inside of the process chamber, wherein the substrate support is at a temperature from 350° C. to 450° C.;
(d) subsequent to (c), purging the process chamber;
(e) subsequent to (d), introducing a hydrogen plasma to the process chamber; and
(f) repeating (b)-(e) to form a film including a hydrogen content below 5% and a variation in thickness less than 6%.

### Claim 13 (depends on 12)

The method of claim 12, wherein the substrate comprises at least one of a lid surface of the process chamber, a bottom surface of the process chamber, a sidewall of the process chamber, or a substrate positioned on a substrate support in the process chamber.

### Claim 14 (depends on 12)

The method of claim 12, wherein a film deposition rate at (c) is from about 1 Å/min to about 5 Å/min.

### Claim 15 (depends on 12)

The method of claim 12, wherein a thickness of the first film interlayer is from 2 Å-50 Å.

### Claim 16 (depends on 12)

The method of claim 12, wherein a thickness of the film is from about 100 Å to about 500 Å.