Method to form ultra high quality silicon-containing compound layers

• US 7,651,953 B2
• Filed: 10/23/2007
• Issued: 01/26/2010
• Est. Priority Date: 07/19/2002
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM America Incorporated (ASM International NV)
• Inventors: Weeks, Keith D., Pomarede, Christophe F., Werkhoven, Christiaan J., Todd, Michael A.
• Primary Examiner(s): Lindsay, Jr.; Walter L
• Assistant Examiner(s): POMPEY, RON EVERETT
• Application Number:
  US11/877,480
• Publication Number:
  US 20080038936A1
• Time in Patent Office: 826 Days
• Field of Search: 438/763, 438/775, 438/785, 257/E21.192, 257/E21.267, 257/E21.268
• US Class Current: 438/763
• CPC Class Codes: C23C 16/24 Deposition of silicon only
• CPC Class Codes: C23C 16/345 Silicon nitride
• 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 16/56 After-treatment
• 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 21/02247 formation by nitridation, e.g. nitridation of the substrate
• CPC Class Codes: H01L 21/02252 formation by plasma treatment, e.g. plasma oxidation of the substrate after treatment of an insulating film by plasma H01L21/3105 and subgroups
• CPC Class Codes: H01L 21/3144 on silicon
• CPC Class Codes: H01L 21/31612 on a silicon body
• CPC Class Codes: H01L 21/31662 of silicon in uncombined form
• CPC Class Codes: H01L 21/3185 of siliconnitrides

Abstract

Multiple sequential processes are conducted in a reaction chamber to form ultra high quality silicon-containing compound layers, including silicon nitride layers. In a preferred embodiment, a silicon layer is deposited on a substrate using trisilane as the silicon precursor. A silicon nitride layer is then formed by nitriding the silicon layer. By repeating these steps, a silicon nitride layer of a desired thickness is formed.

Claims

1. A method for forming an integrated circuit, comprising:

forming a layer of an insulating silicon compound by performing a plurality of chemical vapor deposition cycles in a reaction chamber, each cycle comprising;

first, depositing a silicon layer on a substrate by exposing the substrate to a silicon source, wherein depositing the silicon layer is performed under mass transport limited deposition conditions; and

second, reacting the silicon layer to form part of the layer of the insulating silicon compound, wherein trisilane is the silicon source used to deposit a first silicon layer on the substrate in a first performance of a cycle of the plurality of cycles, wherein the silicon-containing compound layer has a thickness non-uniformity of about 5% or less and a step coverage of about 80% or greater.

2. The method of claim 1, wherein reacting comprises nitriding or oxidizing.

3. The method of claim 1, wherein the silicon source for depositing subsequent silicon layers after depositing the first silicon layer comprises a silicon compound selected from the group consisting of silanes having a silane chemical formula Si_nH_2n+2, where n=1 to 4, and halosilanes having a halosilane chemical formula R_4-XSiH_X, where R=Cl, Br or I and X=0 to 3.

4. The method of claim 3, wherein a first substrate temperature for depositing the first silicon layer is less than about 475°

C.

5. The method of claim 4, wherein a second substrate temperature for reacting the first silicon layer is greater than the first substrate temperature.

6. The method of claim 5, wherein depositing and reacting are performed isothermally after reacting the first silicon layer.

7. The method of claim 6, wherein a third substrate temperature for depositing and reacting, after reacting the first silicon layer, is between about 400°

C. and 650°

C.

8. The method of claim 1, wherein reacting the silicon layer comprises exposing the silicon layer to atomic nitrogen.

9. A method of forming an insulating film, comprising:

providing a substrate in a reaction chamber;

forming a silicon film by exposing the substrate to a silicon source, wherein the silicon source for forming a first silicon film on the substrate, after loading the substrate, is trisilane, wherein the first silicon film is deposited on the substrate under mass transport limited deposition conditions;

subsequently exposing the silicon film to a nitrogen source to form a silicon nitride film; and

sequentially repeating forming the silicon film and subsequently exposing the silicon film to grow the silicon nitride film to a desired thickness, the silicon nitride film of the desired thickness having a thickness non-uniformity of about 5% or less and a step coverage of about 80% or greater.

10. The method of claim 9, further comprising augmenting a silicon nitride film thickness by forming a silicon nitride layer directly over the silicon nitride film by a further CVD process in which silicon and nitrogen precursors are simultaneously introduced into the reaction chamber.

11. The method of claim 10, further comprising forming a silicon nitride sealing layer directly over the further silicon nitride layer, wherein the silicon nitride sealing layer is formed by a method comprising:

forming a silicon layer by exposing the substrate to a silicon source comprising trisilane; and

subsequently exposing the silicon layer to a nitrogen source.

12. The method of claim 9, wherein the silicon source for forming silicon films after forming the first silicon film comprises a compound having a chemical formula Si_nH_2n+2, wherein n is equal to a number from 1 to 4.

13. The method of claim 9, wherein a halosilane replaces trisilane as the silicon source after the first silicon film is formed.

14. The method of claim 9, wherein the first silicon film has a thickness of at least about a nitridation saturation depth.

15. The method of claim 14, wherein the nitridation saturation depth is between about 3 Å

and 30 Å

.

16. A process of forming a silicon nitride layer on a substrate, comprising:

loading a substrate having a crystalline silicon surface into a single substrate laminar flow process chamber;

forming a silicon layer on the crystalline silicon surface by decomposing a silicon source comprising trisilane, wherein forming the silicon layer is performed under mass transport limited deposition conditions; and

nitriding the silicon layer to form a silicon nitride layer by flowing a nitrogen source into the process chamber after forming the silicon layer,

wherein the silicon nitride layer has a thickness non-uniformity of about 5% or less and a step coverage of about 80% or greater.

17. The process of claim 16, further comprising repeating forming the silicon layer and nitriding the silicon layer until a silicon nitride layer of between about 3 Å

and 1000 Å

thick results.

18. The process of claim 16, wherein forming the silicon layer occurs substantially while the process chamber is substantially free of a precursor used for nitriding the silicon layer and wherein nitriding the silicon layer occurs substantially while the process chamber is substantially free of the polysilane.

19. The process of claim 16, wherein the substrate temperature is between about 450°

C. and 650°

C. during forming the silicon layer and nitriding the silicon layer.

20. The process of claim 19, wherein a process chamber pressure is between about 0.001 Torr and 100 Torr during forming the silicon layer and nitriding the silicon layer.

21. The process of claim 16, wherein a hydrogen concentration of the silicon nitride layer is less than about 0.2 atomic percent.

22. The process of claim 16, further comprising forming a gate electrode over the silicon nitride layer.

23. A method of forming a silicon nitride film, comprising:

providing a substrate in a reaction chamber;

depositing a silicon nitride film on the substrate by performing a plurality of chemical vapor deposition cycles, each cycle comprising;

chemical vapor depositing a silicon layer on the substrate under mass transport limited deposition conditions, the silicon layer having a thickness non-uniformity of about 5% or less and a step coverage of about 80% or greater, wherein a height of a top surface of the silicon layer over the substrate is greater than about a nitridation saturation depth, wherein the silicon precursor for the chemical vapor depositing is trisilane; and

nitriding the silicon layer.

24. The method of claim 23, wherein the reaction chamber is a single substrate laminar flow reaction chamber.