Process for fabricating conformal Ti-Si-N and Ti-B-N based barrier films with low defect density

• US 6,017,818 A
• Filed: 01/21/1997
• Issued: 01/25/2000
• Est. Priority Date: 01/22/1996
• Status: Expired due to Term

• Current Assignee: Texas Instruments, Inc.
• Original Assignee: Texas Instruments, Inc.
• Inventors: Lu, Jiong-Ping
• Primary Examiner(s): Niebling, John F.
• Assistant Examiner(s): Nguyen, Ha Tran
• Application Number:
  US08/784,657
• Time in Patent Office: 1,099 Days
• Field of Search: 438/653, 438/656, 438/658, 438/660, 438/680, 438/661, 257/763, 257/751
• US Class Current: 438/653
• CPC Class Codes: H01L 21/28556 by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD H01L21/28518 - H01L21/28537 and H01L21/28568 take precedence
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76856 by treatment in plasmas or gaseous environments, e.g. nitriding a refractory metal liner

Abstract

A CVD process for Ti--Si--N or Ti--B--N films wherein a single feed gas (preferably TDMAT) serves as the source for titanium and nitrogen, and another feed gas is used as the source for silicon or boron. This avoids gas-phase particulate nucleation while providing good conformality. When the required thickness has been deposited, the silicon or boron feed gas continues to flow for some time after the titanium/nitrogen or titanium/boron source gas has been turned off. This results in a Ti--N film with a Si-rich or B-rich surface, which is conformal and has a low defect density. In a second embodiment, a single feed gas, such as TDMAT, is thermally decomposed to form a Ti--N layer. A post-deposition anneal is performed in a gas which supplies silicon or boron, incorporating these materials into the layer. The incorporation of silicon or boron into the layer minimizes the absorption of oxygen into the films, and therefore stabilizes the resulting films. The Si-rich or boron-rich surfaces are also helpful in wetting Al and enhancing adhesion to Cu, therefore are advantageous for advanced metallization application. Compared with the sputtering method, this invention offers a process for depositing films with much better step coverage and easier control of Si/Ti ratio. Compared with the TDEAT+NH₃ +SiH₄ method, this invention eliminates the gas phase reaction between Ti source and NH₃.

Claims

1. A method of forming a thin film, comprising the steps of:

(a.) providing a substrate which includes at least one substantially monolithic body of semiconductor material;

(b.) depositing a conformal layer by CVD in an atmosphere which includes titanium and nitrogen;

(c.) after depositing said conformal layer, exposing said conformal layer to an atmosphere which contains silicon or boron at a temperature greater than or equal to 350 C. but less than 500 C.;

wherein said step (c.) produces a silicon- or boron-rich surface on said conformal layer.

2. The method of claim 1, wherein said step (c.) follows immediately after step (b.), with no intervening steps.

3. The method of claim 1, wherein said step (b.) utilizes an atmosphere which includes silicon or boron.

4. The method of claim 3, wherein said step (b.) utilizes an atmosphere which includes SiH₄.

5. The method of claim 1, wherein said step (b.) utilizes an atmosphere which contains a titanium source component selected from the group consisting of TDMAT, TMEAT, and TDEAT.

6. The method of claim 1, further comprising the subsequent step of rapid thermal annealing.

7. A method of forming a barrier layer over a substrate and abutting a contact/via, said method comprising the steps of:

providing a lower structure;

forming a dielectric layer over said substrate;

forming an opening in said substrate so as to expose at least a portion of said lower structure, said opening having side walls;

forming a film suing a metal-organic precursor, said film formed on said dielectric layer, on said side walls of said opening, and on said exposed portion of said lower structure; and

performing a heating step at a temperature greater than or equal to 350 C. but less than 500 C. in an active gas ambient such that silicon or boron is incorporated into said film.

8. The method of claim 7, wherein said metal-organic precursor is comprised of a material selected from the group consisting of:

[(CH₃)₂ N]₄ Ti, and [(C₂ H₅)₂ N]₄ Ti, and [(CH₃)(C₂ H₅)N]₄ Ti.

9. The method of claim 7, wherein said active gas is comprised of any gas which will incorporate silicon or boron in said metal-organic film.

10. The method of claim 7, wherein said active gas is selected from the group consisting of:

silane, disilane, diborane, or any combination thereof.

11. The method of claim 7, wherein said lower structure is a substrate.

12. The method of claim 7, wherein said lower structure is a conductive layer.