Graded thin films

• US 20030032281A1
• Filed: 09/23/2002
• Published: 02/13/2003
• Est. Priority Date: 03/07/2000
• Status: Active Grant

• Current Assignee: ASM International NV
• Original Assignee: ASM International NV
• Inventors: Raaijmakers, Ivo, Werkhoven, Christiaan J., Haukka, Suvi P.
• Granted Patent: US 6,933,225 B2
• Time in Patent Office: Days
• US Class Current: 438/640
• CPC Class Codes: C23C 16/029 Graded interfaces
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/403 of aluminium, magnesium or beryllium
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/452 by activating reactive gas streams before their introduction into the reaction chamber, e.g. by ionisation or addition of reactive species
• CPC Class Codes: C23C 16/45529 specially adapted for making a layer stack of alternating different compositions or gradient compositions
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: C23C 16/45534 Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
• CPC Class Codes: C30B 25/14 Feed and outlet means for the gases; Modifying the flow of the reactive gases
• CPC Class Codes: H01L 21/0214 the material being a silicon oxynitride, e.g. SiON or SiON:H
• CPC Class Codes: H01L 21/02178 the material containing aluminium, e.g. Al2O3
• 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 21/02194 the material containing more than one metal element
• CPC Class Codes: H01L 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• CPC Class Codes: H01L 21/02274 in the presence of a plasma [PECVD]
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• 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 21/28562 : Selective deposition
• CPC Class Codes: H01L 21/3141 : Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/3145 : formed by deposition from a gas or vapour
• CPC Class Codes: H01L 21/31612 : on a silicon body
• CPC Class Codes: H01L 21/3162 : on a silicon body
• CPC Class Codes: H01L 21/31641 : Deposition of Zirconium oxides, e.g. ZrO2
• CPC Class Codes: H01L 21/3185 : of siliconnitrides
• CPC Class Codes: H01L 21/76846 : Layer combinations
• CPC Class Codes: H01L 21/76873 : for electroplating
• CPC Class Codes: H01L 21/76879 : by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating plating on semiconductors in general H01L21/288
• CPC Class Codes: H01L 2221/1089 : Stacks of seed layers
• CPC Class Codes: H01L 29/4908 : for thin film semiconductor, e.g. gate of TFT
• CPC Class Codes: H01L 29/513 : the variation being perpendicular to the channel plane
• 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
• CPC Class Codes: H01L 2924/00 : Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 : Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• CPC Class Codes: Y10T 428/24942 : including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/2495 : Thickness [relative or absolute]

Abstract

Thin films are formed by atomic layer deposition, whereby the composition of the film can be varied from monolayer to monolayer during cycles including alternating pulses of self-limiting chemistries. In the illustrated embodiments, varying amounts of impurity sources are introduced during the cyclical process. A graded gate dielectric is thereby provided, even for extremely thin layers. The gate dielectric as thin as 2 nm can be varied from pure silicon oxide to oxynitride to silicon nitride. Similarly, the gate dielectric can be varied from aluminum oxide to mixtures of aluminum oxide and a higher dielectric material (e.g., ZrO₂) to pure high k material and back to aluminum oxide. In another embodiment, metal nitride (e.g., WN) is first formed as a barrier for lining dual damascene trenches and vias. During the alternating deposition process, copper can be introduced, e.g., in separate pulses, and the copper source pulses can gradually increase in frequency, forming a graded transition region, until pure copper is formed at the upper surface. Advantageously, graded compositions in these and a variety of other contexts help to avoid such problems as etch rate control, electromigration and non-ohmic electrical contact that can occur at sharp material interfaces.

Claims

1. A method of forming a liner layer with a varying composition in a damascene trench, comprising:

placing a substrate in a reaction chamber;

introducing first metal and nitrogen vapor phase reactants in alternate and temporally separated pulses to the substrate in a plurality of atomic layer deposition (ALD) cycles; and

introducing varying amounts of a second metal vapor phase reactant to the substrate during said plurality of deposition cycles.

2. The method of claim 1, wherein introducing varying amounts of the second metal vapor phase reactant comprises linearly grading the copper concentration from a lower surface of the liner layer to an upper surface of the liner layer.

3. The method of claim 2, wherein introducing varying amounts of the second metal phase reactant comprises providing 0% copper at the lower surface and about 50% copper at the upper surface.

4. The method of claim 1, wherein the nitrogen vapor phase reactant comprises ammonia.

5. The method of claim 4, wherein the second metal vapor phase reactant comprises copper.

6. The method of claim 5, wherein the first metal vapor phase reactant comprises an element selected from the group consisting of tungsten, tantalum, and titanium.

7. The method of claim 5, wherein introducing varying amounts of the second metal phase reactant comprises forming a pure metal nitride at a lower surface of the liner layer and a pure copper layer at an upper surface of the liner layer.

8. The method of claim 7, wherein the copper layer comprises a seed layer.

9. The method of claim 7, further comprising copper electroplating to fill the damascene trench.

10. The method of claim 9, wherein the damascene trench is a dual damascene trench.

11. The method of claim 10, wherein the dual damascene trench comprises a copper interconnect.

12. The method of claim 1, wherein introducing varying amounts of the second metal vapor phase reactant comprises providing second metal vapor phase reactant pulses to the deposition cycles with varying frequency as the deposition proceeds, the second metal vapor phase reactant pulses having the second metal vapor phase reactant as the sole reactant for such pulses.

13. The method of claim 12, wherein introducing varying amounts of the second metal vapor phase reactant comprises providing pulses of the second metal vapor phase reactant to the deposition cycles with lesser frequency as the deposition proceeds.

14. The method of claim 12, wherein introducing varying amounts of the second metal vapor phase reactant comprises providing pulses of the second metal vapor phase reactant to the deposition cycles with greater frequency as the deposition proceeds.

15. The method of claim 1, wherein introducing varying amounts of the second metal vapor phase reactant comprises providing varying levels of the second metal vapor phase reactant in each of the deposition cycles as the deposition proceeds.

16. The method of claim 15, wherein the varying levels of the second metal vapor phase reactant are provided by varying exposure of adsorbed species to a thermodynamically favored substitution reaction.

17. The method of claim 15, wherein the varying levels of the second metal vapor phase reactant are provided in separate pulses of varying duration.

18. The method of claim 15, wherein the varying levels of the second vapor phase reactant replace atoms at the surface of the thin film from a previous pulse.

19. A method of forming a metal nitride and copper containing thin film in a dual damascene trench, comprising:

placing a substrate in a reaction chamber; and

introducing varying amounts of a metal precursor, a nitrogen precursor, and a copper precursor in alternate and temporally separated pulses to the substrate in a plurality of atomic layer deposition (ALD) cycles,

wherein a lower surface of the thin film and an upper surface of the thin film have different copper concentrations.

20. The method of claim 19, wherein the metal precursor comprises a metal selected from the group consisting of tungsten, tantalum, and titanium.

21. The method of claim 20, wherein the nitrogen precursor comprises ammonia.

22. The method of claim 19, wherein introducing varying amounts of the metal, nitrogen, and copper precursors comprises adding the copper precursor as the deposition proceeds.

23. The method of claim 22, wherein introducing comprises providing copper precursor pulses to the deposition cycles with varying frequency as the deposition proceeds.

24. The method of claim 22, wherein introducing comprises providing varying quantities of the copper precursor in each of the deposition cycles as the deposition proceeds.

25. The method of claim 22, wherein introducing comprises transitioning from adding constant levels of the metal and nitrogen precursors in each of the deposition cycles as the deposition begins to adding less metal and nitrogen vapor phase reactants in sequential deposition cycles as the deposition proceeds.

26. The method of claim 25, wherein adding less comprises providing the metal and nitrogen precursors with progressively lesser frequency as the deposition proceeds.

27. The method of claim 25, wherein adding less comprises providing no metal and nitrogen precursors.

28. The method of claim 27, wherein the copper concentration is lowest at the lower surface and highest at the upper surface.

29. The method of claim 28, wherein the thin film comprises a pure metal nitride layer at the lower surface.

30. The method of claim 29, wherein the metal nitride layer comprises a barrier layer.

31. The method of claim 30, wherein the barrier layer is between about 20 Å

and 200 Å

thick.

32. The method of claim 19, further comprising filling the dual damascene trench with copper by electroplating.

33. The method of claim 32, further comprising a polishing step to remove excess metal outside of the dual damascene trench.