Method for etching high dielectric constant materials and for cleaning deposition chambers for high dielectric constant materials

• US 7,357,138 B2
• Filed: 11/26/2003
• Issued: 04/15/2008
• Est. Priority Date: 07/18/2002
• Status: Expired due to Fees

• Current Assignee: Versum Materials US Inc.
• Original Assignee: Air Products and Chemicals Incorporated (Linde Plc)
• Inventors: Ji, Bing, Karwacki, Eugene Joseph Jr., Pearlstein, Ronald Martin, Wu, Dingjun, Motika, Stephen Andrew
• Primary Examiner(s): Goudreau; George A.
• Application Number:
  US10/723,714
• Publication Number:
  US 20040129671A1
• Time in Patent Office: 1,602 Days
• Field of Search: 134/1.1, 134/1.2, 134/22.1, 216/67, 216/76, 438/714, 438/720, 156/345.29, 156/345.33, 156/345.43, 252/79.1, 252/79.2, 252/79.3
• US Class Current: 134/22.1
• CPC Class Codes: B08B 7/00 Cleaning by methods not provided for in a single other subclass or a single group in this subclass
• CPC Class Codes: B08B 7/0035 by radiant energy, e.g. UV, laser, light beam or the like
• CPC Class Codes: C23C 16/4405 Cleaning of reactor or parts inside the reactor by using reactive gases

Abstract

A process for the removal of a substance from a substrate for etching and/or cleaning applications is disclosed herein. In one embodiment, there is provided a process for removing a substance having a dielectric constant greater than silicon dioxide from a substrate by reacting the substance with a reactive agent that comprises at least one member from the group consisting a halogen-containing compound, a boron-containing compound, a hydrogen-containing compound, nitrogen-containing compound, a chelating compound, a carbon-containing compound, a chlorosilane, a hydrochlorosilane, or an organochlorosilane to form a volatile product and removing the volatile product from the substrate to thereby remove the substance from the substrate.

Claims

1. A process for removing a substance from at least a portion of the surface of a reaction chamber, said process comprising:

providing a reactor chamber wherein at least a portion of the surface is at least partially coated with the substance and wherein the substance has a dielectric constant of 4.1 or greater and is at least one member of the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, or a laminate comprising at least one layer of the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing Group 13 metal oxide, a nitrogen containing Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate;

introducing a reactive agent into the reaction chamber wherein the reactive agent comprises at least one fluoride containing compound and at least one other compound comprising BCl₃ wherein the amount of fluorine-containing compound is less than 50% by volume of an amount of the at least one other compound;

exposing the reactive agent to one or more energy sources sufficient to react the substance with the reactive agent and form a volatile product; and

removing the volatile product from the reaction chamber.

2. The process of claim 1 wherein the at least one other compound further comprises at least one member selected from the group consisting of a boron-containing compound, a carbon-containing compound, a hydrogen-containing compound, a nitrogen-containing compound, a chelating compound, a chlorosilane compound, a hydrochlorosilane compound, and an organochlorosilane compound.

3. The process of claim 1 wherein the reactive agent is exposed to one or more energy sources and the exposing step is conducted prior to the introducing step.

4. The process of claim 1 wherein the reactive agent is exposed to one or more energy sources and the exposing step is conducted during at least a portion of the introducing step.

5. The process of claim 1 wherein a temperature of the exposing step is at least 150°

C.

6. The process of claim 1 wherein a pressure of the exposing step is at least 10 mTorr.

7. The process of claim 1 wherein the reactor is an atomic layer deposition reactor.

8. The process of claim 1 wherein the substance is at least one member selected from the group consisting of Al₂O₃, HfO₂, ZrO₂, HfSi_xO_y, ZrSi_xO_y wherein x is greater than 0 and y is 2x+2, Al₂Si_wO_z, where w is greater than 0 and z is 2w+3, and any of the aforementioned compounds containing nitrogen.

9. The process of claim 1 wherein the substance is a laminate comprising layers of at least one material selected from the group consisting of a transition metal oxide, a transition metal silicate, a Group 13 metal oxide, a Group 13 metal silicate, a nitrogen containing transition metal oxide, a nitrogen containing transition metal silicate, a nitrogen containing Group 13 metal oxide, or a nitrogen containing Group 13 metal silicate.

10. The process of claim 1 wherein the at least one other compound further comprises a carbon-containing compound having the formula C_xH_yCl_z, wherein x is a number ranging from 1 to 6, y is a number ranging from 0 to 13, and z is a number ranging 1 from 14.

11. The process of claim 1 wherein the reactive agent is conveyed to the substance from a gas cylinder, a safe delivery system or a vacuum delivery system.

12. The process of claim 1 wherein the reactive agent is formed in situ by a point-of-use generator.

13. The process of claim 1 wherein the substance is contacted with the reactive agent diluted with an inert gas diluent.

14. A process for cleaning a substance from a reactor surface, said process comprising:

providing a reactor wherein the reactor surface is at least partially coated with the substance and wherein the substance has a dielectric constant of 4.1 or greater and is at least one member of the group consisting of Al₂O₃, HfO₂, ZrO₂, HfSi_xO_y, ZrSi_xO_y wherein x is a number greater than 0 and y is 2x+2, Al₂Si_wO_z wherein w is greater than 0 and z is 2w+3 and any of the aforementioned compounds containing nitrogen;

reacting the substance with a reactive agent to form a volatile product, wherein the reactive agent comprises at least one fluorine-containing compound comprising NF₃ and at least one other compound comprising BCl₃ wherein the amount of fluorine-containing compound is less than 50% by volume of an amount of the at least one other compound; and

removing the volatile product from the reactor to thereby remove the substance from the surface.