Method and apparatus for fabricating a high dielectric constant transistor gate using a low energy plasma system

• US 7,678,710 B2
• Filed: 12/20/2006
• Issued: 03/16/2010
• Est. Priority Date: 03/09/2006
• Status: Expired due to Fees

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Todorov, Valentin, Liu, Patricia M., Hung, Steven, Sato, Tatsuya, Chua, Thai Cheng, Paterson, Alex M., Holland, John P.
• Primary Examiner(s): EVERHART, CARIDAD
• Application Number:
  US11/614,019
• Publication Number:
  US 20070212895A1
• Time in Patent Office: 1,182 Days
• Field of Search: 438/681, 438/788, 438/792, 438/680, 438/784, 438/783, 438/763, 438/785, 427/255.28, 257/E21.489, 257/E21.494, 257/E21.586
• US Class Current: 438/784
• CPC Class Codes: H01J 37/32082 Radio frequency generated discharge H01J37/32357, H01J37/32366, H01J37/32394 and H01J37/32403 take precedence
• CPC Class Codes: H01J 37/32146 Amplitude modulation, includes pulsing
• CPC Class Codes: H01L 21/02148 the material containing hafnium, e.g. HfSiOx or HfSiON
• CPC Class Codes: H01L 21/02175 characterised by the metal H01L21/02197 takes precedence
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/02189 the material containing zirconium, e.g. ZrO2
• CPC Class Codes: H01L 21/02192 the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium
• CPC Class Codes: H01L 21/02266 deposition by physical ablation of a target, e.g. sputtering, reactive sputtering, physical vapour deposition or pulsed laser deposition
• CPC Class Codes: H01L 21/0234 treatment by exposure to a plasma
• 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 21/31155 by ion implantation
• CPC Class Codes: H01L 21/3144 on silicon
• CPC Class Codes: H01L 21/316 composed of oxides or glassy oxides or oxide based glass
• CPC Class Codes: H01L 29/495 the conductor material next to the insulator being a simple metal, e.g. W, Mo H01L29/4908, H01L29/4983 take precedence
• CPC Class Codes: H01L 29/4966 the conductor material next to the insulator being a composite material, e.g. organic material, TiN, MoSi2 H01L29/4908, H01L29/4983 take precedence
• CPC Class Codes: H01L 29/513 the variation being perpendicular to the channel plane

Abstract

The present invention generally provides methods and apparatuses that are adapted to form a high quality dielectric gate layer on a substrate. Embodiments contemplate a method wherein a metal plasma treatment process is used in lieu of a standard nitridization process to form a high dielectric constant layer on a substrate. Embodiments further contemplate an apparatus adapted to “implant” metal ions of relatively low energy in order to reduce ion bombardment damage to the gate dielectric layer, such as a silicon dioxide layer and to avoid incorporation of the metal atoms into the underlying silicon. In general, the process includes the steps of forming a high-k dielectric and then terminating the surface of the deposited high-k material to form a good interface between the gate electrode and the high-k dielectric material. Embodiments of the invention also provide a cluster tool that is adapted to form a high-k dielectric material, terminate the surface of the high-k dielectric material, perform any desirable post treatment steps, and form the polysilicon and/or metal gate layers.

Claims

1. A method of forming a semiconductor device, comprising:

forming a dielectric layer having a desired thickness on a surface of a substrate;

forming a concentration gradient of a first material within at least a portion of the thickness of the formed dielectric layer using a low energy sputtering process, wherein the low energy sputtering process comprises;

pulsing an RE energy delivered at a first RF frequency and a first RF power to a processing region of a low energy sputtering chamber using an RF generator;

pulsing a DC voltage delivered from a DC source assembly to a target disposed in the processing region; and

synchronizing the pulsed RF energy and the pulsed DC voltage so that an amount of the first material removed from the target can be disposed within the dielectric layer;

exposing the dielectric layer and the first material to an RF plasma comprising nitrogen; and

depositing a second material over the dielectric layer.

2. The method of claim 1, wherein the first RF frequency is between about 1 MHz and about 200 MHz.

3. The method of claim 1, wherein the thickness of the dielectric layer is less than about 40 Angstroms.

4. The method of claim 1, wherein the first material is hafnium and the concentration of the first material in the dielectric layer is less than about 30 atomic percent.

5. The method of claim 1, wherein the first material is selected from a group consisting of zirconium, hafnium, lanthanum, strontium, lead, yttrium, and barium.

6. The method of claim 1, wherein the dielectric layer contains a material selected from a group consisting of silicon dioxide, hafnium oxide, zirconium oxide, hafnium silicate oxides, lanthanum oxides, and aluminum oxide.

7. The method of claim 1, wherein the second material contains a material selected from a group consisting of polysilicon, tantalum, tantalum nitride, tantalum carbide, tungsten, tungsten nitride, tantalum silicon nitride, hafnium, aluminum, ruthenium, cobalt, titanium, nickel, and titanium nitride.

8. The method of claim 1, wherein the pulsed RF energy and the pulsed DC voltage do not overlap in time.

9. The method of claim 1, further comprising annealing the dielectric layer and the first material disposed on the substrates surface at a temperature between about 800°

C. and about 1100°

C.

10. The method of claim 1, further comprising exposing the surface of the substrate to an RF plasma comprising nitrogen prior to forming the dielectric layer.

11. The method of claim 1, further comprising disposing an amount of a third material within the dielectric layer before exposing the dielectric layer to an RF plasma comprising nitrogen, wherein the third material contains an element selected from a group consisting of hafnium, lanthanum, aluminum, titanium, zirconium, strontium, lead, yttrium, and barium.

12. The method of claim 11, wherein the third material is lanthanum that has a concentration less than about 10 atomic percent or the third material is aluminum that has a concentration less than about 10 atomic percent.

13. The method of claim 11, further comprising exposing the dielectric layer, the first material and the third material to an oxidizing environment, wherein the oxidizing environment using a thermal oxidation process or a plasma oxidation process.

14. A method of forming a semiconductor device, comprising:

forming a dielectric layer having a desired thickness on a surface of a substrate;

forming a concentration gradient of a first material within at least a portion of the thickness of the formed dielectric layer using a low energy sputtering process, wherein the low energy sputtering process comprises;

pulsing an RF energy delivered at a first RF frequency and a first RF power to a processing region of a low energy sputtering chamber using an RF generator;

pulsing a DC voltage delivered from a DC source assembly to a target disposed in the processing region; and

synchronizing the pulsed RF energy and the pulsed DC voltage so that an amount of the first material removed from the target can be disposed within the dielectric layer;

annealing the substrate at a temperature between about 800°

C. and about 1100 °

C.; and

depositing a second material over the dielectric layer.

15. The method of claim 14, further comprising exposing the surface of the substrate or the formed dielectric layer to an RF plasma comprising nitrogen.

16. The method of claim 14, wherein the first RF frequency is between about 1 MHz and about 200 MHz.

17. The method of claim 14, wherein the thickness of the dielectric layer is less than about 40 Angstroms.

18. The method of claim 14, wherein the first material is hafnium and the concentration of the first material in the dielectric layer is less than about 30 atomic percent.

19. The method of claim 14, wherein the first material is selected from a group consisting of zirconium, hafnium, lanthanum, strontium, lead, yttrium, and barium.

20. The method of claim 14, wherein the dielectric layer contains a material selected from a group consisting of silicon dioxide, hafnium oxide, zirconium oxide, hafnium silicate oxides, lanthanum oxides, and aluminum oxide.

21. The method of claim 14, further comprising exposing the dielectric layer, the first material and the third material to an oxidizing environment, wherein the oxidizing environment using a thermal oxidation process or a plasma oxidation process.

22. The method of claim 14, wherein the second material contains a material selected from a group consisting of polysilicon, tantalum, tantalum nitride, tantalum carbide, tungsten, tungsten nitride, tantalum silicon nitride, hafnium, aluminum, ruthenium, cobalt, titanium, nickel, and titanium nitride.

23. The method of claim 14, wherein the pulsed RF energy and the pulsed DC voltage do not overlap in time.

24. The method of claim 14, further comprising disposing an amount of a third material within the dielectric layer before exposing the dielectric layer to an RF plasma comprising nitrogen, wherein the third material contains an element selected from a group consisting of hafnium, lanthanum, aluminum, titanium, zirconium, strontium, lead, yttrium, and barium.

25. The method of claim 24, wherein the third material is lanthanum that has a concentration less than about 10 atomic percent or the third material is aluminum that has a concentration less than about 10 atomic percent.

26. The method of claim 14, further comprising depositing a high-k dielectric layer over the dielectric layer.

27. The method of claim 26, wherein the high-k dielectric layer contains a material selected from a group consisting silicon dioxide, zirconium oxide, hafnium silicate oxides, lanthanum oxides, and aluminum oxide.

28. A method of forming a semiconductor device, comprising:

positioning a substrate having a dielectric layer disposed on a surface of a substrate in a processing region of a low energy sputtering chamber;

forming a concentration gradient of a first material within at least a portion of the thickness of the formed dielectric layer using a low energy sputtering process, wherein the low energy sputtering process comprises;

pulsing an RF energy delivered at a first RF frequency and a first power to a first target which comprises the first material, wherein the first frequency is between about 1 MHz and about 200 MHz;

pulsing a DC voltage delivered to the target from a DC source assembly; and

synchronizing the pulsed RF energy and the pulsed DC voltage.

29. The method of claim 28, further comprising depositing a second material over the dielectric layer, wherein the second material contains at least one material selected from a group consisting of polysilicon, tantalum, tantalum nitride, tantalum carbide, tungsten, tungsten nitride, tantalum silicon nitride, hafnium, aluminum, ruthenium, cobalt, titanium, nickel, titanium aluminum nitride, ruthenium nitride, hafnium nitride, nickel silicide, and titanium nitride.

30. The method of claim 28, wherein the thickness of the dielectric layer is less than about 40 Angstroms.

31. The method of claim 28, wherein the dielectric layer contains a material selected from a group consisting silicon dioxide, zirconium oxide, hafnium silicate oxides, lanthanum oxides, and aluminum oxide.

32. The method of claim 28, further comprising annealing the dielectric layer and the first material at a temperature between about 800°

C. and about 1100°

C.

33. The method of claim 28, wherein pulsing further comprises providing pulses at a duty cycle between about 1 and about 50%.

34. The method of claim 28, further comprising disposing an amount of a second material within the dielectric layer to form a concentration gradient within at least a portion of the thickness of the formed dielectric layer using a low energy sputtering process, wherein the low energy sputtering process comprises providing an RF energy at a second RF frequency and a second power to a second target comprising a second material, wherein the second frequency is between about 1 MHz and about 200 MHz.

35. The method of claim 34, wherein the first material is hafnium and the second material is lanthanum or aluminum.

36. The method of claim 28, wherein the first material is hafnium and the concentration of the first material in the dielectric layer is less than about 30 atomic percent.

37. The method of claim 36, wherein the second material is lanthanum that has a concentration that is less than about 10 atomic percent or the second material is aluminum that has a concentration that is less than about 10 atomic percent.