Chemical vapor deposition of high quality flow-like silicon dioxide using a silicon containing precursor and atomic oxygen

• US 7,825,038 B2
• Filed: 05/29/2007
• Issued: 11/02/2010
• Est. Priority Date: 05/30/2006
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Gee, Paul, Ingle, Nitin K., Sapre, Kedar, Yuan, Zheng
• Primary Examiner(s): Vu; David
• Assistant Examiner(s): CHI, SUBERR L
• Application Number:
  US11/754,440
• Publication Number:
  US 20070281496A1
• Time in Patent Office: 1,253 Days
• Field of Search: 438/778, 438/787, 438/788, 427/579
• US Class Current: 438/778
• CPC Class Codes: C23C 16/401 containing silicon
• 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 16/56 After-treatment
• CPC Class Codes: H01L 21/02164 the material being a silicon oxide, e.g. SiO2
• 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 21/02337 treatment by exposure to a gas or vapour
• CPC Class Codes: H01L 21/31612 on a silicon body

Abstract

Methods of depositing a silicon oxide layer on a substrate are described. The methods may include the steps of providing a substrate to a deposition chamber, generating an atomic oxygen precursor outside the deposition chamber, and introducing the atomic oxygen precursor into the chamber. The methods may also include introducing a silicon precursor to the deposition chamber, where the silicon precursor and the atomic oxygen precursor are first mixed in the chamber. The silicon precursor and the atomic oxygen precursor react to form the silicon oxide layer on the substrate, and the deposited silicon oxide layer may be annealed. Systems to deposit a silicon oxide layer on a substrate are also described.

Claims

1. A method of depositing a silicon oxide layer on a substrate, the method comprising:

providing a substrate to a deposition chamber;

generating atomic oxygen outside the deposition chamber, and introducing the atomic oxygen into the chamber;

introducing a silicon precursor to the deposition chamber, wherein the silicon precursor and the atomic oxygen are first mixed in the chamber;

reacting the silicon precursor and the atomic oxygen to form the silicon oxide layer on the substrate wherein the substrate is maintained at a temperature between about 0°

C. and about 150°

C. as the silicon oxide layer is formed, wherein the silicon oxide layer is initially-flowable following deposition; and

annealing the deposited silicon oxide layer.

2. The method of claim 1, wherein the substrate comprises a silicon wafer having a diameter of about 300 mm or less.

3. The method of claim 1, wherein a plurality of structures are formed on a surface of the substrate, wherein the structures include gaps and trenches having height to width aspect ratios of 7:

1 or more.

4. The method of claim 1, wherein the atomic oxygen is formed by:

forming a plasma from a gas mixture comprising argon; and

introducing an oxygen precursor to the plasma, wherein the oxygen precursor dissociates to form the atomic oxygen.

5. The method of claim 4, wherein the oxygen precursor is selected from the group consisting of molecular oxygen, ozone, water vapor (H₂O), and nitrogen dioxide.

6. The method of claim 1, wherein the atomic oxygen is formed by:

introducing an oxygen precursor into a photodissociation chamber; and

exposing the oxygen precursor to ultraviolet light, wherein the ultraviolet light dissociates the oxygen precursor to form the atomic oxygen.

7. The method of claim 6, wherein the oxygen precursor is selected from the group consisting of molecular oxygen, ozone, and nitrogen dioxide.

8. The method of claim 1, wherein the silicon precursor is selected from the group consisting of silane, dimethylsilane, trimethylsilane, tetramethylsilane, diethylsilane, tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), octamethyltrisiloxane (OMTS), octamethylcyclotetrasiloxane (OMCTS), tetramethyldimethyldimethoxydisilane, tetramethylcyclotetrasiloxane (TOMCATS), DMDMOS, DEMS, methyl triethoxysilane (MTES), phenyldimethylsilane, and phenylsilane.

9. The method of claim 1, wherein the silicon precursor is mixed with a carrier gas comprising helium.

10. The method of claim 1, wherein the deposition chamber comprises a wafer pedestal that supports the substrate, wherein the substrate temperature is adjusted by the wafer pedestal.

11. The method of claim 1, wherein the deposition chamber has a pressure of about 0.1 Torr to about 10 Torr as the silicon oxide layer is formed.

12. The method of claim 1, wherein the silicon oxide layer is formed at a rate of about 250 Å

/min to about 2 μ

m/min.

13. The method of claim 1, wherein the deposited silicon oxide annealing step comprises a thermal anneal, a steam anneal, a plasma anneal, an ultraviolet light anneal, an e-beam anneal, or a microwave anneal.

14. The method of claim 1, wherein the annealing of the deposited silicon oxide layer comprises:

heating the substrate at a first anneal temperature in the presence of steam; and

heating the substrate at a second anneal temperature in dry nitrogen.

15. The method of claim 14, wherein the first anneal temperature is up to about 950°

C. and the second anneal temperature is about 900°

C.

16. The method of claim 1, wherein the method comprises exposing the substrate to a pretreatment plasma before introducing the atomic oxygen precursor or silicon precursor to the deposition chamber.

17. The method of claim 16, wherein the pretreatment plasma is a high-density plasma comprising argon, helium, hydrogen (H₂), xenon, or ammonia.

18. The method of claim 1, wherein the deposition chamber is part of a high-density plasma chemical vapor deposition (HDPCVD) system.

19. A method of forming a silicon oxide layer on a substrate, the method comprising:

providing a silicon wafer substrate to a reaction chamber;

generating atomic oxygen from a dissociation of molecular oxygen in a high-density argon plasma, wherein the atomic oxygen is generated in a remote plasma generating chamber that is external to the reaction chamber;

mixing the atomic oxygen with a silicon precursor in the reaction chamber, wherein the atomic oxygen and the silicon precursor are not mixed before reaching the reaction chamber; and

depositing the silicon oxide layer on the substrate, wherein the silicon oxide layer comprises reaction products from the reaction of the atomic oxygen with the silicon precursor and the substrate is maintained at a temperature between about 0°

C. and about 150°

C. as the silicon oxide layer is deposited, wherein the silicon oxide layer is initially-flowable following deposition.

20. The method of claim 19, wherein the method further comprises annealing the deposited silicon oxide layer.

21. The method of claim 20, wherein the deposited silicon oxide annealing step comprises a thermal anneal, a steam anneal, a plasma anneal, an ultraviolet light anneal, an e-beam anneal, or a microwave anneal.

22. The method of claim 19, wherein the silicon precursor is selected from the group consisting of silane, dimethylsilane, trimethylsilane, tetramethylsilane, diethylsilane, tetramethylorthosilicate (TMOS), tetraethylorthosilicate (TEOS), phenyldimethylsilane, and phenylsilane.