Atomic layer deposition of antimony oxide films

• US 9,514,934 B2
• Filed: 03/13/2015
• Issued: 12/06/2016
• Est. Priority Date: 10/12/2011
• Status: Active Grant

• Current Assignee: ASM International NV
• Original Assignee: ASM International NV
• Inventors: De Roest, David, Van Der Jeugd, Kees, Matero, Raija H., Lindroos, Linda, Sprey, Hessel, Maes, Jan Willem, Pierreux, Dieter, D'Urzo, Lucia, Blomberg, Tom E.
• Primary Examiner(s): Vinh, Lan
• Application Number:
  US14/658,000
• Publication Number:
  US 20150249005A1
• Time in Patent Office: 634 Days
• Field of Search: 438/694, 438/695, 438/720, 438/722, 438/741, 438/761, 438/754, 438/756, 438/745, 438/778, 216/72, 216/83, 216/106
• US Class Current: 1/1
• CPC Class Codes: C23F 1/26 for etching refractory metals
• CPC Class Codes: H01L 21/02175 characterised by the metal H01L21/02197 takes precedence
• 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 21/0332 characterised by their composition, e.g. multilayer masks, materials
• CPC Class Codes: H01L 21/2225 Diffusion sources
• CPC Class Codes: H01L 21/28194 by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence
• CPC Class Codes: H01L 21/31111 by chemical means
• CPC Class Codes: H01L 21/31122 of layers not containing Si, e.g. PZT, Al2O3
• 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

Abstract

Antimony oxide thin films are deposited by atomic layer deposition using an antimony reactant and an oxygen source. Antimony reactants may include antimony halides, such as SbCl₃, antimony alkylamines, and antimony alkoxides, such as Sb(OEt)₃. The oxygen source may be, for example, ozone. In some embodiments the antimony oxide thin films are deposited in a batch reactor. The antimony oxide thin films may serve, for example, as etch stop layers or sacrificial layers.

Claims

1. A method of depositing an antimony oxide thin film, comprising alternately and sequentially contacting a substrate in a reaction chamber with an antimony precursor and an oxygen source, wherein the antimony precursor has the formula Sb(NR₂)_xA_3-x, wherein x is from 1 to 3, wherein each R is independently selected to be a linear, branched or cyclic, saturated or unsaturated, C1-C12 alkyl or alkenyl group or hydrogen if the other R is not hydrogen, and wherein A is a ligand comprising alkylamine, halide, amine, silyl or alkyl.

2. The method of claim 1, wherein the alkyl or alkenyl is substituted with at least one substituent selected from the group consisting of halogens, amines, and silyls.

3. The method of claim 1, wherein the antimony precursor comprises Sb(NMe₂)₃.

4. The method of claim 1, wherein the antimony precursor is selected from the group consisting of Sb(NEt₂)₃, Sb(NPr₂)₃ and Sb(NⁱPr₂)₃.

5. The method of claim 1, wherein the oxygen source is selected from the group consisting of water, oxygen, hydrogen peroxide, aqueous solution of hydrogen peroxide, ozone, atomic oxygen, oxides of nitrogen, peracids (—

O—

O—

H), alcohols, oxygen-containing radicals and mixtures thereof.

6. The method of claim 1, wherein alternately and sequentially contacting the substrate comprises alternately and sequentially contacting the substrate at a process pressure of 0.01 mbar to 500 mbar.

7. The method of claim 1, wherein alternately and sequentially contacting the substrate comprises alternately and sequentially contacting the substrate at a deposition temperature of up to 500°

C.

8. The method of claim 1, wherein the substrate comprises a three-dimensional structure and the antimony oxide thin film is deposited over the three-dimensional structure with a step coverage of greater than 80%.

9. The method of claim 1, further comprising exposing the substrate to water.

10. The method of claim 9, wherein exposing the substrate to water comprises exposing the substrate subsequent to contacting the substrate with the antimony precursor and prior to contacting the substrate with the oxygen source.

11. A method of depositing an antimony oxide layer on a substrate by atomic layer deposition, comprising:

contacting a surface of the substrate with an antimony precursor having the formula Sb(NR₂)_xA_3-x, wherein x is from 1 to 3, and each R is independently selected to be linear, branched or cyclic, saturated or unsaturated, C1-C12 alkyl or alkenyl group or hydrogen if the other R is not hydrogen, and wherein A is a ligand comprising alkylamine, halide, amine, silyl or alkyl, such that the antimony precursor adsorbs on the substrate surface; and

exposing the substrate to an oxygen source, wherein the oxygen source reacts with the antimony precursor on the surface of the substrate to form the antimony oxide.

12. The method of claim 11, wherein contacting comprises contacting the substrate in a batch reactor.

13. The method of claim 11, wherein contacting comprises contacting the substrate in a single-wafer reactor.

14. The method of claim 11, wherein the oxygen source comprises ozone.

15. The method of claim 11, wherein the oxygen source is not water.

16. The method of claim 11, wherein exposing the substrate to the oxygen source comprises exposing the substrate to an oxygen-containing gas pulse, wherein the oxygen-containing gas pulse comprises the oxygen source and an inactive gas.

17. The method of claim 11, wherein the oxygen source comprises at least one of oxygen and ozone, and wherein the inactive gas comprises nitrogen or argon.

18. The method of claim 11, wherein the alkyl or alkenyl is substituted with at least one substituent selected from the group consisting of halogens, amines, and silyls.

19. The method of claim 18, wherein the antimony precursor comprises Sb(NR₂)₃.

20. The method of claim 19, wherein the R is a linear or branched, cyclic or linear, saturated or unsaturated, C1-C12 alkyl or alkenyl group.