Method of reducing carbon contamination of a thin dielectric film by using gaseous organic precursors, inert gas, and ozone to react with carbon contaminants

• US 6,124,158 A
• Filed: 06/08/1999
• Issued: 09/26/2000
• Est. Priority Date: 06/08/1999
• Status: Expired due to Term

• Current Assignee: Bell Semiconductor, LLC (Hilco Inc. (d/b/a Hilco Global))
• Original Assignee: Lucent Technologies, Inc. (Nokia Corporation)
• Inventors: Manchanda, Lalita, Dautartas, Mindaugas F.
• Primary Examiner(s): Fahmy, Wael
• Assistant Examiner(s): Brewster, William M.
• Application Number:
  US09/327,793
• Time in Patent Office: 476 Days
• Field of Search: 438/216
• US Class Current: 438/216
• CPC Class Codes: H01L 21/02178 the material containing aluminium, e.g. Al2O3
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/02304 formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
• CPC Class Codes: H01L 21/28185 with a treatment, e.g. annealing, after the formation of the gate insulator and before the formation of the definitive gate conductor
• CPC Class Codes: H01L 21/28194 by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence
• CPC Class Codes: H01L 21/28202 in a nitrogen-containing ambient, e.g. nitride deposition, growth, oxynitridation, NH3 nitridation, N2O oxidation, thermal nitridation, RTN, plasma nitridation, RPN
• CPC Class Codes: H01L 21/31616 Deposition of Al2O3
• CPC Class Codes: H01L 29/40114 the electrodes comprising a conductor-insulator-conductor-insulator-semiconductor structure
• CPC Class Codes: H01L 29/517 the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate H01L29/518 takes precedence
• CPC Class Codes: H01L 29/518 the insulating material containing nitrogen, e.g. nitride, oxynitride, nitrogen-doped material

Abstract

A process is provided for the formation of a thin film of gate dielectric or similar material on a silicon semiconductor substrate from an organic precursor by atomic layer epitaxy, wherein the organic precursor is introduced to react with the treated surface to form a bonded monolayer of reactive species. A second reactant is introduced to react with the surface to form the desired dielectric. After each step in the cycle, the reaction chamber is purged with an inert gas to prevent reactions except on the surface. The cycle is repeated tens to hundreds of times to achieve a desired final film thickness. No less frequently than every third cycle, the film undergoes a discrete treatment step wherein ozone is introduced into the chamber to oxidize carbon contaminants therein to form volatile products which are removed from the reaction chamber by purging with the inert gas. In a preferred embodiment where the substrate is silicon or polysilicon, a sub-monolayer of a protection material is formed by boding to silicon sites on the surface before the deposition of dielectric is begun. A preferred dielectric is gate aluminum oxide that is deposited using trimethyl aluminum as a precursor.

Claims

1. A process for forming a thin film of dielectric on a semiconductor substrate, said film having reduced carbon contamination, comprising heating the substrate under an inert atmosphere in a suitable reaction chamber to a temperature such that a selected gaseous organic precursor for said dielectric will react to form a bonded reactant on the surface, and carrying out multiple deposition cycles at said temperature to form said thin dielectric film, each deposition cycle comprising:

a) introducing the gaseous organic precursor into the reaction chamber so that it reacts to form said bonded reactant on the surface;

b) purging the reaction chamber with an inert gas;

c) introducing a second gaseous reactant into the chamber which reacts with said bonded reactant to form said dielectric film; and

d) purging the reaction chamber with the inert gas,

wherein no less frequently than every third cycle, introducing ozone into the reaction chamber following step d) to react with carbon contaminants in the film thereby forming gaseous products and purging the reaction chamber with said inert gas to remove such products prior to initiating the next cycle.

2. A process in accordance with claim 1, wherein the substrate is silicon and the film is a gate dielectric of aluminum oxide.

3. A process in accordance with claim 2, wherein the gaseous organic precursor is trimethyl aluminum and the second gaseous reactant is water vapor.

4. A process in accordance with claim 3, wherein the substrate is initially heated to a temperature from about 190°

to 300°

C.

5. A process in accordance with claim 4, wherein the substrate is initially heated to a temperature of about 190°

C.

6. A process in accordance with claim 1, wherein ozone is introduced into the reaction chamber after every one to three cycles.

7. A process in accordance with claim 6, wherein ozone is introduced into the reaction chamber after every cycle.

8. A process in accordance with claim 1, wherein the inert gas is nitrogen.

9. A process in accordance with claim 1, wherein prior to step a) of said first cycle, the surface of the substrate is pretreated by introducing ozone into the reaction chamber to form gaseous products from contaminants on the substrate surface and the chamber is purged with said inert gas.

10. A process in accordance with claim 1, wherein the substrate surface does not contain hydroxyl groups and, prior to step a) of said first cycle, the surface is treated to form hydroxyl groups thereon.

11. A process in accordance with claim 10, wherein the surface is treated with water vapor at the reaction temperature.

12. A process in accordance with claim 10, wherein the surface of the substrate is treated prior to being admitted to the reaction chamber.

13. A process in accordance with claim 12, wherein the substrate is silicon and the surface is treated with hydrogen peroxide to form hydroxyl groups thereon.

14. A process in accordance with claim 1, wherein after each of said ozone treatment and purge with inert gas, the surface of the substrate is treated with water vapor at the reaction temperature to form hydroxyl groups thereon and the reaction chamber thereafter purged with said inert gas prior to initiating the next cycle.

15. A process in accordance with claim 1, wherein the substrate is silicon or polysilicon and, prior to step a), the reactive silicon sites on the surface are bonded to a protection material such that a sub-monolayer of protective material is formed thereon.

16. A process in accordance with claim 15 where said protection material is selected from the group consisting of silicon dioxide, silicon oxynitride and silicon nitride.

17. A process in accordance with claim 15, wherein said sub-monolayer is formed by atomic layer epitaxy from an inorganic precursor.

18. A process in accordance with claim 15, said protection material is silicon dioxide and said sub-monolayer is formed by thermo-oxidation of the substrate.

23. A semiconductor substrate having formed thereon a film of dielectric by the process of claim 1.

19. A process for forming a thin film of aluminum oxide gate dielectric on a semiconductor substrate, said film having reduced carbon contamination, comprising heating the substrate under an inert atmosphere in a suitable reaction chamber to a temperature such that a trimethyl aluminum will react to form a bonded reactant on the surface thereof, treating the surface of the substrate with water vapor to form hydroxyl groups thereon and carrying out multiple deposition cycles at said temperature to form said thin gate dielectric film, each deposition cycle comprising:

a) introducing trimethyl aluminum into the reaction chamber so that it reacts to form said bonded reactant on the surface;

b) purging the reaction chamber with an inert gas;

c) introducing water vapor into the chamber which reacts with said bonded reactant to form said aluminum oxide gate dielectric film; and

d) purging the reaction chamber with the inert gas,

wherein no less frequently than every third cycle, introducing ozone into the reaction chamber following step d) to react with carbon contaminants in the film thereby forming gaseous products and purging the reaction chamber with said inert gas to remove such products prior to initiating the next cycle.

20. A process in accordance with claim 19 further wherein, prior treating the surface of the substrate to form hydroxyl groups thereon, the surface is pretreated by introducing ozone into the reaction chamber to form gaseous products from contaminants on the substrate surface and the chamber is purged with said inert gas.

21. A process in accordance with claim 20, wherein the substrate is silicon or polysilicon and, prior to treating the surface to form hydroxyl groups thereon, the reactive silicon sites on the surface are bonded to a protection material such that a sub-monolayer of protective material is formed thereon.

22. A process in accordance with claim 19, wherein after each of said ozone treatment and purge with inert gas, the surface of the substrate is treated with water vapor at the reaction temperature to form hydroxyl groups thereon and the reaction chamber thereafter purged with said inert gas prior to initiating the next cycle.

24. A silicon semiconductor substrate having formed thereon a film of aluminum oxide gate dielectric by the process of claim 19.

25. A silicon semiconductor substrate having formed thereon a film of aluminum oxide gate dielectric by the process of claim 21.