# US 10,312,077 B2 · Method for forming aluminum-containing dielectric layer

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- Number: US 10,312,077 B2
- Document ID: US10312077B2
- Status: Granted
- Kind: B2
- Application number: 14/878,016
- Filed: 2015-10-08
- Published: 2017-04-13
- Granted: 2019-06-04
- Earliest claimed: 2015-10-08
- Assignees: Taiwan Semiconductor Manufacturing Company, Ltd.
- Applicants: Taiwan Semiconductor Manufacturing Company, Ltd.
- Inventors: Peter Ramvall
- Web page: https://patentgrep.com/patent/US10312077B2

## CPC

- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- C23C 16/40: Oxides
- C23C 16/45531: {specially adapted for making ternary or higher compositions}
- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- H10P 14/69391: {the material containing aluminium, e.g. Al2O3}
- 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

The present disclosure provides a method of forming an aluminum-containing layer. The method includes providing a substrate in an atomic layer deposition (ALD) process chamber; and performing a cycle of a first step and a second step one or more times in the ALD process chamber to provide a composite layer, wherein performing the first step of the cycle includes: applying a first precursor that includes a non-aluminum-based component having a first molecular weight onto the substrate; and applying a second precursor that that includes an aluminum-based component having a second molecular weight onto the substrate, wherein the second molecular weight is lower than the first molecular weight; and wherein performing the second step of the cycle includes applying the first precursor onto the substrate.

## Claims

### Claim 1

A method comprising:
providing a substrate in an atomic layer deposition (ALD) process chamber; and
performing a cycle of a first step and a second step one or more times in the ALD process chamber to provide a composite layer,
wherein performing the first step of the cycle includes:
applying an oxygen-based precursor to the substrate to form an oxygen treated surface on the substrate;
after applying the oxygen-based precursor, applying a first precursor that includes a non-aluminum-based component having a first molecular weight onto the substrate such that the non-aluminum-based component is directly bonded to the oxygen treated surface of the substrate; and
after applying the oxygen-based precursor, applying a second precursor that that includes an aluminum-based component having a second molecular weight over the first precursor and the substrate such that the aluminum-based component is directly bonded to the oxygen treated surface of the substrate, wherein the second molecular weight is lower than the first molecular weight; and
wherein performing the second step of the cycle includes applying the first precursor onto the substrate.

### Claim 2 (depends on 1)

The method of claim 1, wherein after performing the cycle of the first step and the second step the composite layer has a concentration of aluminum that is about 5% atomic ratio.

### Claim 3 (depends on 1)

The method of claim 1, wherein the non-aluminum-based component includes either TetrakisDiMethylAminoHafnium (TDMAHf) or TetrakisEthylMethylAmidoZirconium (TEMAZr), and
wherein the aluminum-based component includes TriMethylAluminium (TMAl).

### Claim 4 (depends on 1)

The method of claim 1, wherein after performing the first step of the cycle a first layer of the composite layer is formed on the substrate having a concentration of aluminum that is about 10% atomic ratio.

### Claim 5 (depends on 4)

The method of claim 4, wherein the first layer of the composite layer includes a thickness that is about 1 angstrom.

### Claim 6 (depends on 1)

The method of claim 1, wherein the first molecular weight is greater than the second molecular weight by about 80%.

### Claim 7 (depends on 1)

The method of claim 1, wherein performing the first step of the cycle that includes applying the first precursor that includes the non-aluminum-based component having the first molecular weight onto the substrate includes applying the first precursor for a period of about 0.1 seconds to about 2 seconds, and
wherein performing the first step of the cycle that includes applying the second precursor that includes the aluminum-based component having the second molecular weight onto the substrate includes applying the second precursor for a period of about 0.1 seconds to about 0.5 seconds.

### Claim 8 (depends on 1)

The method of claim 1, wherein performing the first step of the cycle that includes applying the first precursor that includes the non-aluminum-based component having the first molecular weight onto the substrate includes applying the first precursor at a flow rate of about 100 to about 300 standard cubic centimeters per minute (sccm), and
wherein performing the first step of the cycle that includes applying the second precursor that includes the aluminum-based component having the second molecular weight onto the substrate includes applying the second precursor at a flow rate of about 50 to about 300 sccm.

### Claim 9 (depends on 1)

The method of claim 1, wherein the first precursor and the second precursor respectively includes a first size and a second size, and the first size is substantially greater than the second size.

### Claim 10 (depends on 1)

The method of claim 1, wherein performing the cycle of the first step and the second step one or more times in the ALD process chamber includes maintaining a temperature of the ALD process chamber in a range of temperature from about 100° C. to about 150° C.

### Claim 11

A method comprising:
providing a substrate in an atomic layer deposition (ALD) process chamber;
applying an oxygen-based precursor to the substrate to form an oxygen treated surface on the substrate;
after applying the oxygen based precursor, injecting a first precursor that includes a first molecule with a first molecular weight into the ALD chamber for a first interval such that the first molecule bonds directly to the oxygen treated surface of the substrate; and
after applying the oxygen based precursor, injecting a second precursor that includes a second molecule containing aluminum and having a second molecular weight into the ALD chamber for a second interval thereby forming a first aluminum layer on the substrate, wherein the second molecular weight is less than the first molecular weight and the second molecule bonds directly to the oxygen treated surface of the substrate after the injecting of the second precursor.

### Claim 12 (depends on 11)

The method of claim 11, further comprising injecting a third precursor into the ALD chamber thereby forming a second layer on the first layer, after forming the first layer on the substrate.

### Claim 13 (depends on 12)

The method of claim 12, wherein the third precursor is formed of the same material as the first precursor.

### Claim 14 (depends on 11)

The method of claim 11, wherein the percentage of aluminum in the first layer is not greater than 10% atomic ratio and a thickness of the first layer is about 1 angstrom.

### Claim 15 (depends on 11)

The method of claim 11, wherein the first precursor includes either TetrakisDiMethylAminoHafnium (TDMAHf) or TetrakisEthylMethylAmidoZirconium (TEMAZr), and
wherein the second precursor includes TriMethylAluminium (TMAl).

### Claim 16 (depends on 11)

The method of claim 11, wherein the first molecular weight is greater than the second molecular weight by about 80%.

### Claim 17 (depends on 11)

The method of claim 11, wherein injecting the first precursor into the ALD chamber includes flowing the first precursor at a flow rate of about 100 to about 300 standard cubic centimeters per minute (sccm), and
wherein injecting the second precursor into the ALD chamber includes flowing the second precursor at a flow rate of about 50 to about 300 sccm.

### Claim 18 (depends on 11)

The method of claim 11, wherein injecting the first precursor into the ALD chamber and injecting the second precursor into the ALD chamber includes maintaining temperature of the ALD chamber in a temperature range of about 100° C. to about 150° C.

### Claim 19

A method comprising:
providing a substrate in an atomic layer deposition (ALD) process chamber;
applying an oxygen-based precursor to the substrate to form an oxygen treated surface on the substrate;
after applying the oxygen based precursor, injecting a first precursor that includes a first molecule with a first molecular weight into the ALD process chamber such that the first molecule bonds directly to the oxygen treated surface of the substrate;
after applying the oxygen based precursor, injecting a second precursor that includes a second molecule containing aluminum and having a second molecular weight into the ALD process chamber thereby forming a first aluminum-containing layer on the substrate, wherein the second molecular weight is less than the first molecular weight by about 80% and the second molecule bonds directly to the oxygen treated surface of the substrate after the injecting of the second precursor; and
injecting the first precursor into the ALD process chamber thereby forming a second non-aluminum-containing layer over the first aluminum-containing layer.

### Claim 20 (depends on 1)

The method of claim 1, wherein after applying the first precursor and the second precursor a layer is formed having a 2:1 ratio of the non-aluminum-based component to the aluminum-based component.