Deposition of boron and carbon containing materials

• US 9,576,790 B2
• Filed: 04/14/2015
• Issued: 02/21/2017
• Est. Priority Date: 10/16/2013
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holding B.V. (ASM International NV)
• Inventors: Pore, Viljami J., Kimura, Yosuke, Namba, Kunitoshi, Adachi, Wataru, Fukuda, Hideaki, Knaepen, Werner, Pierreux, Dieter, Jongbloed, Bert
• Primary Examiner(s): Sarkar, Asok K
• Application Number:
  US14/686,595
• Publication Number:
  US 20150287591A1
• Time in Patent Office: 679 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 16/30 Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
• CPC Class Codes: C23C 16/32 Carbides
• CPC Class Codes: C23C 16/45523 Pulsed gas flow or change of composition over time
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: H01L 21/02112 characterised by the material of the layer
• CPC Class Codes: H01L 21/0217 the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz H01L21/02126 and H01L21/0214 take precedence
• CPC Class Codes: H01L 21/02211 the compound being a silane, e.g. disilane, methylsilane or chlorosilane
• CPC Class Codes: H01L 21/02271 deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/0234 treatment by exposure to a plasma
• CPC Class Codes: H01L 21/2254 from or through or into an applied layer, e.g. photoresist, nitrides
• CPC Class Codes: H01L 21/31111 by chemical means

Abstract

Methods of depositing boron and carbon containing films are provided. In some embodiments, methods of depositing B, C films with desirable properties, such as conformality and etch rate, are provided. One or more boron and/or carbon containing precursors can be decomposed on a substrate at a temperature of less than about 400° C. One or more of the boron and carbon containing films can have a thickness of less than about 30 angstroms. Methods of doping a semiconductor substrate are provided. Doping a semiconductor substrate can include depositing a boron and carbon film over the semiconductor substrate by exposing the substrate to a vapor phase boron precursor at a process temperature of about 300° C. to about 450° C., where the boron precursor includes boron, carbon and hydrogen, and annealing the boron and carbon film at a temperature of about 800° C. to about 1200° C.

Claims

1. A method of doping a semiconductor substrate, comprising:

depositing a boron and carbon film over the semiconductor substrate in a reaction space by exposing the substrate to a vapor phase boron precursor at a process temperature of 300°

C. to 450°

C., wherein the boron precursor comprises boron, carbon and hydrogen; and

annealing the boron and carbon film at a temperature of 800°

C. to 1200°

C.

2. The method of claim 1, wherein the vapor phase boron precursor decomposes on the substrate.

3. The method of claim 1, wherein the vapor phase boron precursor comprises triethylboron or trimethylboron.

4. The method of claim 1, wherein the vapor phase boron precursor is supplied to the reaction space with a carrier gas comprising argon.

5. The method of claim 1, further comprising depositing a silicon oxide film on the substrate prior to depositing the boron and carbon film.

6. The method of claim 1, wherein the boron and carbon film is deposited directly on the semiconductor substrate.

7. The method of claim 1, further comprising depositing a boron dopant film on the substrate prior to depositing the boron and carbon film, wherein the boron dopant film is different from the boron and carbon film, and wherein the boron dopant film and the boron and carbon film are deposited sequentially and without exposing the substrate to ambient air between depositing the boron and carbon film and depositing the boron dopant film.

8. The method of claim 1, further comprising maintaining a pressure of 0.5 Torr to 10 Torr within the reaction space during exposing the substrate to the vapor phase boron precursor.

9. The method of claim 1, wherein the boron and carbon film has a thickness of up to 5 nm.

10. A method of doping a substrate, comprising:

depositing a boron and carbon film over a substrate in a reaction space using a chemical vapor deposition process, wherein depositing the boron and carbon film comprises;

exposing the substrate to a vapor phase boron precursor in an inert gas atmosphere at a process temperature greater than 300°

C.; and

purging the reaction space subsequent to exposing the three-dimensional structure on the substrate to the vapor phase boron precursor; and

annealing the boron and carbon film in a nitrogen atmosphere, wherein no cap layer is formed over the boron and carbon film prior to annealing.

11. The method of claim 10, wherein depositing comprises depositing the boron and carbon film on a three-dimensional structure on the substrate.

12. The method of claim 11, wherein the three-dimensional structure has an aspect ratio of greater than 8:

1 and wherein the boron and carbon film has a step coverage of greater than 80%.

13. The method of claim 10, wherein the boron and carbon film has a thickness of up to 5 nm.

14. The method of claim 10, further comprising depositing a silicon oxide film on the substrate prior to depositing the boron and carbon film.

15. The method of claim 10, wherein the vapor phase boron precursor is supplied to the reaction space with a carrier gas comprising argon.

16. The method of claim 10, further comprising annealing at a temperature of 800°

C. to 1200°

C.

17. A method of depositing a boron and carbon containing film on a substrate in a reaction space, comprising:

a cyclic process comprising contacting the substrate with a vapor phase boron precursor at a process temperature of 250°

C. up to 400°

C. in at least two deposition cycles separated by a purge step to form the boron and carbon containing film on the substrate,

wherein the vapor phase boron precursor decomposes on the substrate, and

wherein the film has a thickness of less than 30 angstroms.

18. The method of claim 17, wherein the boron and carbon containing film has a thickness of less than 15 angstroms.

19. The method of claim 18, wherein the boron and carbon containing film has a thickness of less than 5 angstroms.

20. The method of claim 17, wherein the boron and carbon film is substantially resistant to dilute hydrofluoric acid solution.

21. The method of claim 17, further comprising depositing the boron and carbon containing film in a batch reactor.

22. The method of claim 17, further comprising forming at least one of a silicon oxide, an aluminum nitride, an aluminum oxide and a silicon nitride over the boron and carbon containing film in the reaction space.

23. The method of claim 17, further comprising depositing the boron and carbon containing film over at least one of a silicon oxide, an aluminum nitride, an aluminum oxide and a silicon nitride.

24. The method of claim 23, further comprising forming the at least one of the silicon oxide, aluminum nitride, an aluminum oxide and silicon nitride in the reaction space.

25. The method of claim 17, wherein the cyclic process comprises less than 100 deposition cycles.

26. The method of claim 17, wherein the boron and carbon containing film has a 1-sigma non-uniformity of less than 5%.