Method and apparatus for anisotropic tungsten etching
Methods for anisotropically etching a tungsten-containing material (such as doped or undoped tungsten metal) include cyclic treatment of tungsten surface with Cl 2 plasma and with oxygen-containing radicals. Treatment with chlorine plasma is performed while the substrate is electrically biased resulting in predominant etching of horizontal surfaces on the substrate. Treatment with oxygen-containing radicals passivates the surface of the substrate to etching, and protects the vertical surfaces of the substrate, such as sidewalls of recessed features, from etching. Treatment with Cl 2 plasma and with oxygen-containing radicals can be repeated in order to remove a desired amount of material. Anisotropic etching can be performed selectively in a presence of dielectric materials such as silicon oxide, silicon nitride, and silicon oxynitride.
1. A method of anisotropically etching a tungsten-containing material on a semiconductor substrate in a plasma etching apparatus, the method comprising:
(a) providing a semiconductor substrate comprising a tungsten-containing material to a plasma etching process chamber;
(b) introducing a first process gas to the plasma etching process chamber, wherein the first process gas consists essentially of Cl 2 , and forming a plasma to react the tungsten-containing material with a plasma-activated chlorine, etch the tungsten-containing material and expose a new surface of the tungsten-containing material;
(c) removing the first process gas from the plasma etching process chamber after (b);
(d) directly after removing the first process gas from the plasma etching process chamber, introducing a second process gas comprising an oxygen radical source and a hydrofluorocarbon to the plasma etching process chamber and forming a plasma comprising oxygen radicals to react the plasma with the new exposed surface of the tungsten-containing material and thereby form a passivation layer comprising a compound that includes tungsten and oxygen, wherein the oxygen radical source is a gas selected from the group consisting of O 2 , O 3 , CO, CO 2 and mixtures thereof; and
(e) removing the second process gas from the plasma etching process chamber after (d), wherein the method predominantly etches the tungsten-containing material in a selected direction.
2. The method of claim 1 , wherein forming a plasma in (b) comprises providing a bias of at least about 500 V to a substrate-holding support.
3. The method of claim 1 , wherein the hydrofluorocarbon is CH 3 F.
4. The method of claim 1 , wherein (b) comprises pulsing the plasma.
5. The method of claim 1 , wherein the source of oxygen radicals is O 2 .
6. The method of claim 1 , wherein operations (b) (e) are repeated.
7. The method of claim 1 , wherein the semiconductor substrate further comprises an exposed layer of a dielectric material selected from the group consisting of silicon oxide, silicon nitride, and silicon oxynitride.
8. The method of claim 1 , wherein the semiconductor substrate further comprises an exposed layer of a dielectric material selected from the group consisting of silicon oxide, silicon nitride, and silicon oxynitride, and wherein the tungsten-containing material is etched with an etch selectivity of at least about 2:1.
9. The method of claim 1 , wherein the semiconductor substrate comprises a recessed feature comprising an exposed layer of tungsten-containing material at the bottom of the recessed feature, and wherein the etching removes the tungsten-containing material from the bottom of the recessed feature without substantially altering the width or diameter of the recessed feature.
10. The method of claim 1 , wherein the method comprises etching a layer of tungsten-containing material having a thickness of between about 1000-7000 Å.
11. The method of claim 1 , wherein the semiconductor substrate comprises a recessed feature comprising an exposed layer of tungsten-containing material at the bottom of the recessed feature, wherein the width or diameter of the recessed feature is less than about 150 nm.
12. The method of claim 1 , wherein a single sequence of operations (b)-(e) removes between about 10-50 nm of the tungsten-containing material.
13. The method of claim 1 , wherein the compound that includes tungsten and oxygen is selected from the group consisting of WO x and WOCl x .