# US 10,121,699 B2 · Selective deposition of aluminum and nitrogen containing material

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- Number: US 10,121,699 B2
- Document ID: US10121699B2
- Status: Granted
- Kind: B2
- Application number: 15/432,263
- Filed: 2017-02-14
- Published: 2017-06-01
- Granted: 2018-11-06
- Earliest claimed: 2015-08-05
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Han Wang; Qi Xie; Delphine Longrie; Jan Willem Maes; David de Roest; Julian Hsieh; Chiyu Zhu; Timo Asikainen; Krzysztof Kachel; Harald Profijt
- Web page: https://patentgrep.com/patent/US10121699B2

## CPC

- H10W 20/038: {covering conductive structures (H10W20/037 takes precedence)}
- C23C 16/00: Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes (reactive sputtering or vacuum evaporation C23C14/00)
- C23C 16/04: Coating on selected surface areas, e.g. using masks
- C23C 16/34: Nitrides {(C23C16/303 takes precedence)}
- 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 16/56: After-treatment
- 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 14/6514: {by exposure to a plasma}
- H10P 14/6532: {by exposure to a plasma}
- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- H10P 14/69391: {the material containing aluminium, e.g. Al2O3}
- H10P 50/285: {of materials not containing Si, e.g. PZT or Al2O3}
- H10P 50/73: {using masks for insulating materials}
- H10W 20/069: {by forming self-aligned vias or self-aligned contact plugs}
- H10W 20/077: {on sidewalls or on top surfaces of conductors (H10W20/076 takes precedence)}
- H10W 20/425: {Barrier, adhesion or liner layers}
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

Methods are provided for selectively depositing Al and N containing material on a first conductive surface of a substrate relative to a second, dielectric surface of the same substrate. In some aspects, methods of forming an Al and N containing protective layer or etch stop layer for use in integrated circuit fabrication are provided.

## Claims

### Claim 1

A process for selectively forming AlN on a first surface of a substrate relative to a second different surface of the substrate, the process comprising one or more super-cycles comprising:
selectively depositing AlN on the first surface of the substrate relative to the second different surface of the substrate by one or more selective deposition sub-cycles;
etching the deposited AlN by one or more thermal etching sub-cycles;
wherein the super-cycle further comprises exposing the substrate to a pretreatment reactant prior to the selectively depositing AlN; and
wherein AlN is selectively formed on the first surface of the substrate relative to the second different surface of the substrate with a selectivity greater than about 99%.

### Claim 2 (depends on 1)

The process of claim 1, wherein in the one or more super-cycles the one or more selective deposition sub-cycles and the one or more thermal etching sub-cycles are repeated until an AlN thin film of a desired thickness has been formed on the first surface.

### Claim 3 (depends on 1)

The process of claim 1, wherein the pretreatment reactant comprises plasma.

### Claim 4 (depends on 3)

The process of claim 3, wherein the plasma is generated from a gas comprising H2.

### Claim 5 (depends on 1)

The process of claim 1, wherein the one or more selective deposition sub-cycles comprise:
contacting the substrate with a first vapor phase precursor comprising aluminum; and
contacting the substrate with a second vapor phase precursor comprising nitrogen.

### Claim 6 (depends on 5)

The process of claim 5, wherein the one or more selective deposition sub-cycles are repeated until AlN of a desired thickness is deposited on the first surface.

### Claim 7 (depends on 5)

The process of claim 5, wherein the one or more selective deposition sub-cycles are repeated until the one or more selective deposition sub-cycles are no longer selective.

### Claim 8 (depends on 5)

The process of claim 5, wherein the first vapor phase precursor comprising aluminum comprises one of tritertbutylaluminum (TTBA), trimethylaluminum (TMA) or triethylaluminum (TEA).

### Claim 9 (depends on 5)

The process of claim 5, wherein the second vapor phase precursor comprising nitrogen comprises NH3.

### Claim 10 (depends on 1)

The process of claim 1, wherein the one or more thermal etching sub-cycles comprise:
contacting the substrate with a first vapor phase halide etch reactant; and
contacting the substrate with a second vapor phase etch reactant comprising aluminum.

### Claim 11 (depends on 10)

The process of claim 10, wherein the first vapor phase halide etch reactant comprises NF3 or NbF5.

### Claim 12 (depends on 10)

The process of claim 10, wherein the second vapor phase etch reactant comprising aluminum comprises trimethylaluminum (TMA) or triethylaluminum (TEA).

### Claim 13 (depends on 10)

The process of claim 10, wherein the one or more etching sub-cycles are carried out at a process temperature of about 300° C.

### Claim 14 (depends on 1)

The process of claim 1, wherein the first surface comprises W and the second surface comprises SiO2.

### Claim 15 (depends on 1)

The process of claim 1, wherein the first surface comprises TiN and the second surface comprises SiO2.

### Claim 16 (depends on 1)

The process of claim 1, wherein the one or more selective deposition sub-cycles are repeated from 1 to about 300 times; and
wherein the one or more thermal etching sub-cycles comprise an atomic layer etching (ALE) process and are repeated from 1 to about 150 times.

### Claim 17

A process for selectively forming AlN on a first surface of a substrate relative to a second different surface of the same substrate, the process comprising a super-cycle comprising:
a selective deposition sub-cycle comprising:
alternately and sequentially contacting the substrate with a first vapor phase precursor comprising aluminum and a second vapor phase precursor comprising nitrogen such that the AlN is deposited on the first surface of the substrate relative to the second different surface of the same substrate with a selectivity greater than about 5%; and
an atomic layer etch sub-cycle comprising:
alternately and sequentially contacting the substrate with a first vapor phase halide etch reactant and a second vapor phase etch reactant comprising aluminum.

### Claim 18 (depends on 17)

The process of claim 17, wherein the super-cycle is repeated one or more times.

### Claim 19 (depends on 17)

The process of claim 17, the super-cycle further comprising exposing the substrate to a plasma generated from a gas comprising H2 prior to the selective deposition sub-cycle.

### Claim 20 (depends on 17)

The process of claim 17, wherein the first vapor phase precursor comprising aluminum comprises trimethylaluminum (TMA), the second vapor phase precursor comprising nitrogen comprises NH3, the first vapor phase halide etch reactant comprises NF3, and the second vapor phase etch reactant comprising aluminum comprises TMA.

### Claim 21 (depends on 17)

The process of claim 17, wherein the first surface is a conductive surface and the second surface is a dielectric surface.