Method for forming thermally stable organosilicon polymer film

• US 10,483,099 B1
• Filed: 07/26/2018
• Issued: 11/19/2019
• Est. Priority Date: 07/26/2018
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holding B.V. (ASM International NV)
• Inventors: Blanquart, Timothee Julien Vincent
• Primary Examiner(s): Mandala, Victor A
• Application Number:
  US16/046,218
• Time in Patent Office: 481 Days
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/4554 Plasma being used non-continuously in between ALD reactions C23C16/56 takes precedence
• CPC Class Codes: C23C 16/45542 Plasma being used non-continuously during the ALD reactions
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 16/505 using radio frequency discharges
• CPC Class Codes: H01L 21/02118 carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC polymers per se C08G, photoresist per se G03F
• CPC Class Codes: H01L 21/02123 the material containing silicon
• CPC Class Codes: H01L 21/02167 the material being a silicon carbide not containing oxygen, e.g. SiC, SiC:H or silicon carbonitrides 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 21/02274 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 21/0234 treatment by exposure to a plasma
• CPC Class Codes: H01L 21/76224 using trench refilling with dielectric materials trench filling with polycristalline silicon H01L21/763; together with vertical isolation, e.g. trench refilling in a SOI substrate H01L21/76264

Abstract

A method of forming a thermally stable organosilicon polymer includes: (i) depositing an organosilicon polymer whose backbone is composed of silicon atoms on a substrate using a silicon-containing precursor in a reaction space; and (ii) exposing the organosilicon polymer deposited in step (i) to a hydrogen plasma in the absence of the precursor in the reaction space in a manner increasing Si—H bonds and decreasing C—H bonds in the organosilicon polymer without depositing an organosilicon polymer.

Claims

1. A method of forming a thermally stable organosilicon polymer, comprising:

(i) depositing an organosilicon polymer whose backbone is primarily or partly composed of silicon atoms on a substrate using a silicon-containing precursor in a reaction space; and

(ii) exposing the organosilicon polymer deposited in step (i) to a hydrogen plasma in the absence of the precursor in the reaction space in a manner increasing Si—

H bonds and decreasing C—

H bonds in the organosilicon polymer without depositing an organosilicon polymer.

2. The method according to claim 1, wherein step (i) comprises conducting one or more cycles of atomic layer deposition (ALD), and steps (i) and (ii) are repeated as step (iii) until a desired thickness of the organosilicon polymer is obtained.

3. The method according to claim 1, wherein step (i) comprises conducting chemical vapor deposition (CVD), and steps (i) and (ii) are repeated as step (iii) until a desired thickness of the organosilicon polymer is obtained.

4. The method according to claim 2, wherein the ALD is plasma-enhanced ALD (PEALD), and step (ii) is conducted 2 to 10 times after conducting each cycle of PEALD.

5. The method according to claim 3, wherein the CVD is thermal or plasma-enhanced CVD, and step (ii) is conducted after every deposition of the organosilicon polymer having a thickness of 1 to 50 nm in step (i).

6. The method according to claim 1, wherein step (ii) comprises applying RF power to the reaction space in a range of 0.07 W/cm² to 1.4 W/cm² to generate the hydrogen plasma.

7. The method according to claim 1, wherein step (ii) is conducted for 10 seconds to 60 seconds.

8. The method according to claim 1, wherein step (ii) comprises supplying hydrogen gas and noble gas to the reaction space at a ratio of hydrogen gas flow to total flow of gases including hydrogen gas and noble gas, which is 0.1 to 0.8.

9. The method according to claim 1, wherein step (ii) comprises supplying only hydrogen gas to the reaction space to generate the hydrogen plasma.

10. The method according to claim 2, further comprising, after step (iii), annealing the organosilicon polymer wherein the organosilicon polymer manifests substantially no shrinkage.

11. The method according to claim 1, wherein the organosilicon polymer is constituted by polysilane, polycarbosilane, polysilazane, or polysiloxane.

12. The method according to claim 1, wherein in step (ii), the hydrogen plasma is a pulsed plasma generated by applying RF power to the reaction space in pulses.

13. The method according to claim 1, wherein step (i) and step (ii) are conducted continuously in a same reaction chamber.