Thermal etching of ruthenium
Embodiments of methods are provided for thermal dry etching of a ruthenium (Ru) metal layer. In the disclosed embodiments, a substrate containing a Ru metal layer formed thereon is exposed to a gas pulse sequence, while the substrate is held at a relatively high substrate temperature (e.g., a temperature greater than or equal to about 160° C.), to provide thermal etching of the Ru metal layer. As described further herein, the gas pulse sequence may generally include a plurality of gas pulses, which are supplied to the substrate sequentially with substantially no overlap between gas pulses. The gas pulses supplied to the substrate form: (i) volatile reaction products that are vaporized from the Ru surface, and (ii) non-volatile oxide surface layers that are removed from the Ru surface by the next gas pulse, resulting in atomic layer etching (ALE) of the Ru metal layer.
1 . A method of etching, the method comprising:
providing a substrate containing a ruthenium metal layer thereon, the ruthenium metal layer having a ruthenium surface exposed on the substrate; and
exposing the substrate to a gas pulse sequence to etch the ruthenium metal layer, wherein said exposing the substrate to the gas pulse sequence includes:
a) exposing the substrate to a first gas pulse comprising an oxygen-containing gas to form a first non-volatile oxide surface layer on the ruthenium metal layer, wherein the first non-volatile oxide surface layer is not removed by the oxygen-containing gas;
b) exposing the substrate to a second gas pulse comprising a chlorine-containing gas to convert the first non-volatile oxide surface layer into a second non-volatile oxide surface layer, wherein the second non-volatile oxide surface layer is not removed by the chlorine-containing gas; and
c) exposing the substrate to a third gas pulse comprising a fluorine-containing gas to remove the second non-volatile oxide surface layer from the ruthenium surface to etch the ruthenium metal layer.
2 . The method of claim 1 , further comprising repeating said exposing the substrate to the gas pulse sequence at least once to achieve a predetermined etch amount of the ruthenium metal layer.
3 . The method of claim 1 , wherein steps b) and c) are performed without plasma excitation.
4 . The method of claim 1 , wherein the oxygen-containing gas comprises ozone (O 3 ), and wherein step a) further includes:
forming the ozone in a remote plasma source, and
flowing the ozone to the substrate.
5 . The method of claim 1 , wherein a temperature of the substrate is between about 160° C. and about 400° C. during said exposing the substrate to the gas pulse sequence.
6 . The method of claim 1 , wherein the oxygen-containing gas comprises oxygen (O 2 ), ozone (O 3 ), water or hydrogen peroxide (H 2 O 2 ).
7 . The method of claim 1 , wherein the chlorine-containing gas comprises boron trichloride (BCl 3 ), chlorine (Cl 2 ), tungsten chloride (WCl 5 ), hydrochloric acid (HCl), trans-dichloroethylene (C 2 H 2 Cl 2 ), chlorine trifluoride (ClF 3 ) or titanium tetrachloride (TiCl 4 ).
8 . The method of claim 1 , wherein the fluorine-containing gas comprises hydrogen fluoride (HF), tungsten hexafluoride (WF 6 ), chlorine trifluoride (ClF 3 ), fluorine (F 2 ), xenon difluoride (XeF 2 ), boron trifluoride (BF 3 ), carbon tetrafluoride (CF 4 ), or nitrogen trifluoride (NF 3 ).
9 . The method of claim 1 , wherein the oxygen-containing gas comprises ozone (O 3 ), wherein the chlorine-containing gas comprises boron trichloride (BCl 3 ), and wherein the fluorine-containing gas comprises hydrogen fluoride (HF).
10 . The method of claim 9 , wherein:
a) exposing the substrate to the first gas pulse comprising ozone (O 3 ) forms a ruthenium oxide surface layer on the ruthenium metal layer, wherein the ruthenium oxide surface layer is non-volatile and not removed by the ozone;
b) exposing the substrate to the second gas pulse comprising boron trichloride (BCl 3 ) forms a boron oxide surface layer on the ruthenium metal layer, wherein the boron oxide surface layer is non-volatile and not removed by the boron trichloride; and
c) exposing the substrate to the third gas pulse comprising hydrogen fluoride (HF) removes the boron oxide surface layer from the ruthenium surface without etching the ruthenium metal layer underlying the boron oxide surface layer.
11 . A method of etching, the method comprising:
providing a substrate containing a ruthenium metal layer thereon, the ruthenium metal layer having a ruthenium surface exposed on the substrate;
exposing the substrate to a gas pulse sequence to etch the ruthenium metal layer, wherein said exposing the substrate to the gas pulse sequence includes sequentially:
a) exposing the substrate to a first gas pulse comprising ozone (O 3 ) to form: (i) volatile ruthenium oxide reaction products that are removed from the ruthenium surface, and (ii) a non-volatile ruthenium oxide surface layer on the ruthenium metal layer, wherein the non-volatile ruthenium oxide surface layer is not removed by the ozone;
b) exposing the substrate to a second gas pulse comprising boron trichloride (BCl 3 ) to react with the non-volatile ruthenium oxide surface layer and form: (i) volatile ruthenium oxychloride reaction products that are removed from the ruthenium surface, and (ii) a non-volatile boron oxide surface layer on the ruthenium metal layer, wherein the non-volatile boron oxide surface layer is not removed by the boron trichloride; and
c) exposing the substrate to a third gas pulse comprising hydrogen fluoride (HF) to remove the non-volatile boron oxide surface layer from the ruthenium surface to etch the ruthenium metal layer; and
repeating the gas pulse sequence at least once to achieve a predetermined etch amount of the ruthenium metal layer.
12 . The method of claim 11 , wherein a temperature of the substrate is between about 160° C. and about 400° C. during said exposing the substrate to the gas pulse sequence.
13 . The method of claim 11 , wherein step a) further includes:
forming the ozone in a remote plasma source, and
flowing the ozone to the substrate.
14 . The method of claim 11 , wherein steps b) and c) are performed without plasma excitation.
15 . A method of etching, the method comprising:
providing a substrate containing a ruthenium metal layer thereon, the ruthenium metal layer having a ruthenium surface exposed on the substrate;
exposing the substrate to a gas pulse sequence to etch the ruthenium metal layer, wherein a temperature of the substrate is greater than about 160° C. while exposing the substrate to the gas pulse sequence, and wherein said exposing the substrate to the gas pulse sequence includes sequential and alternating exposures of:
a) exposing the substrate to a first gas pulse comprising ozone to form a non-volatile ruthenium oxide surface layer on the ruthenium metal layer, wherein the non-volatile ruthenium oxide surface layer is not removed by the ozone; and
b) exposing the substrate to a second gas pulse comprising a chlorine-containing gas to remove the non-volatile ruthenium oxide surface layer from the ruthenium surface and etch the ruthenium metal layer; and
repeating the gas pulse sequence at least once to achieve a predetermined etch amount of the ruthenium metal layer.
16 . The method of claim 15 , wherein step b) is performed without plasma excitation.
17 . The method of claim 15 , wherein step a) further includes:
forming the ozone in a remote plasma source, and
flowing the ozone to the substrate.
18 . The method of claim 15 , wherein the temperature of the substrate is between about 160° C. and about 400° C.
19 . The method of claim 15 , wherein the chlorine-containing gas further comprises hydrogen.
20 . The method of claim 19 , wherein the chlorine-containing gas is hydrogen chloride (HCl), chloroform (CHCl 3 ), chloromethane (CH 3 Cl), dichloromethane (CH 2 Cl 2 ) or trichloroethylene (C 2 HCl 3 ).