US-12624448-B2 - Systems, devices, and methods for forming layers comprising a group 14 element, a pnictogen, and a chalcogen

Abstract

Disclosed are methods for forming layers comprising a group 14 element, a pnictogen, and a chalcogen. In some embodiments, the group 14 element comprises germanium, the pnictogen comprises antimony, and the chalcogen comprises tellurium. The methods comprise executing a plurality of deposition cycles. A deposition cycle comprises exposing a substrate to two different group 14 precursors, to two different pnictogen precursors, or to two different chalcogen precursors. Further discloses are related systems and methods. Suitable systems include atomic layer deposition systems. Suitable devices include phase change memory devices.

Inventors

• Bart Vermeulen
• Varun Sharma
• Jerome Innocent
• Charles DEZELAH
• Michael Eugene Givens

Assignees

• ASM IP HOLDING B.V.

Dates

Publication Date

20260512

Application Date

20231122

Claims (19)

1. 1 . A method of forming a layer comprising a group 14 element, a pnictogen, and a chalcogen, the method comprising: providing a substrate to a reaction chamber; and executing a plurality of deposition cycles, a deposition cycle comprising a group 14 element pulse, a pnictogen pulse, and a chalcogen pulse, wherein the group 14 element pulse comprises providing a first group 14 element precursor to the reaction chamber; the pnictogen pulse comprises providing a first pnictogen precursor to the reaction chamber; and, the chalcogen pulse comprises providing a first chalcogen precursor to the reaction chamber, wherein the method further comprises providing one or more further precursors to the reaction chamber, the one or more further precursors is a precursor selected from a second group 14 element precursor different than the first group 14 element precursor, and/or a second pnictogen precursor different from the first pnictogen precursor, and a second chalcogen precursor different from the first chalcogen precursor and wherein the first group 14 element precursor comprises a first germanium precursor and the second group 14 element precursor comprises a second germanium precursor, wherein at least one of the first germanium precursor and the second germanium precursor comprises a germanium amidinate, or a germanium amide; and/or wherein the first pnictogen precursor comprises a first antimony precursor and wherein the second pnictogen precursor comprises a second antimony precursor, wherein at least one of the first antimony precursor and the second antimony precursor independently comprises a compound selected from the group consisting of a silyl antimonide, an antimony amide, and a heteroleptic antimony precursor comprising an alkylsilyl group and a halogen.
2. 2 . The method according to claim 1 , wherein the one or more further precursors comprises the second group 14 element precursor, and wherein the group 14 element pulse further comprises providing the second group 14 element precursor to the reaction chamber.
3. 3 . The method according to claim 1 , wherein the one or more further precursors comprises the second pnictogen precursor, and wherein the pnictogen pulse further comprises providing the second pnictogen precursor to the reaction chamber.
4. 4 . The method according to claim 1 , wherein the one or more further precursors further comprises a second chalcogen precursor different from the first chalcogen precursor, wherein the chalcogen pulse further comprises the second chalcogen precursor to the reaction chamber.
5. 5 . The method according to claim 1 , wherein one of the first germanium precursor and the second germanium precursor comprises a germanium halide.
6. 6 . The method according to claim 5 , the germanium halide precursor comprises GeHCl 3 .
7. 7 . The method according to claim 1 , wherein one of the first antimony precursor and the second antimony precursor comprises a compound selected from the group consisting of an antimony halide, and an antimony alkyl.
8. 8 . The method according to claim 7 , wherein one of the first antimony precursor and the second antimony precursor comprises a chemical bond between antimony and a group 14 element.
9. 9 . The method according to claim 1 , wherein the first chalcogen precursor comprises a first tellurium precursor or wherein the second chalcogen precursor comprises a second tellurium precursor.
10. 10 . The method according to claim 9 , wherein at least one of the first tellurium precursor and the second tellurium precursor comprises a compound selected from the group consisting of a tellurium halide, a tellurium alkoxide, and a tellurium alkylsilyl.
11. 11 . The method according to claim 10 , wherein one of the first tellurium precursor and the second tellurium precursor comprises a chemical bond between tellurium and a group 14 element.
12. 12 . A method of forming a layer comprising a group 14 element, a pnictogen, and a chalcogen, the method comprising: providing a substrate to a reaction chamber; and executing a plurality of deposition cycles, at least one deposition cycle of the plurality of deposition cycles comprises a first sub cycle and a second sub cycle, the first sub cycle comprising a first group 14 element pulse, a first pnictogen pulse, and a first chalcogen pulse, wherein the first group 14 element pulse comprises providing a first group 14 element precursor to the reaction chamber; the first pnictogen pulse comprises providing a first pnictogen precursor to the reaction chamber; and, the first chalcogen pulse comprises providing a first chalcogen precursor to the reaction chamber, the second sub cycle comprising a second group 14 element pulse, a second pnictogen pulse, and a second chalcogen pulse, wherein the second group 14 element pulse comprises providing a second group 14 element precursor to the reaction chamber; the second pnictogen pulse comprises providing a second pnictogen precursor to the reaction chamber; and, the second chalcogen pulse comprises providing a second chalcogen precursor to the reaction chamber, wherein the first group 14 element precursor is different from the second group 14 element precursor, wherein the first group 14 element precursor comprises a first germanium precursor and the second group 14 element precursor comprises a second germanium precursor, wherein at least one of the first germanium precursor and the second germanium precursor comprises a germanium amidinate or a germanium amide, and/or wherein the first pnictogen precursor is different from the second pnictogen precursor, wherein the first pnictogen precursor comprises a first antimony precursor and the second pnictogen precursor comprises a second antimony precursor, wherein at least one of the first antimony precursor and the second antimony precursor independently comprises a compound selected from the group consisting of a silyl antimonide, an antimony amide, and a heteroleptic antimony precursor comprising an alkylsilyl group and a halogen.
13. 13 . The method according to claim 12 , wherein one of the first germanium precursor and the second germanium percursor comprises a germanium halide.
14. 14 . The method according to claim 13 , wherein the germanium halide precursor comprises GeHCl 3 .
15. 15 . The method according to claim 1 , wherein the first chalcogen precursor is different from the second chalcogen precursor.
16. 16 . The method according to claim 15 , wherein the first chalcogen precursor comprises a first tellurium precursor and wherein the second chalcogen precursor comprises a second tellurium precursor.
17. 17 . The method according to claim 16 , wherein at least one of the first tellurium precursor and the second tellurium precursor comprises a compound selected from the group consisting of a tellurium halide, a tellurium alkoxide, a tellurium alkylsilyl, and tellurium alkylgermyl.
18. 18 . The method according to claim 13 , wherein at least one deposition cycle of the plurality of deposition cycles comprises more than one first sub cycle.
19. 19 . The method according to claim 13 , wherein at least one deposition cycle of the plurality of deposition cycles comprises more than one second sub cycle.

Description

CROSS-REFERENCE TO RELATED APPLICATION(S) This application claims the benefit of U.S. Provisional Application 63/385,159 filed on Nov. 28, 2022, the entire contents of which are incorporated herein by reference. FIELD OF INVENTION The present disclosure generally relates to the field of semiconductor processing methods, devices, and systems, and to the field of integrated circuit manufacture. In particular, methods and systems suitable for forming layers comprising a group 14 element, a pnictogen, and a chalcogen. Further disclosed are related systems and devices. BACKGROUND OF THE DISCLOSURE Phase change materials have been proposed as memory elements for advanced semiconductor circuits. One class of candidate materials includes materials that comprise a group 14 element, a pnictogen precursor, and a chalcogen precursor. Exemplary materials in this class include germanium antimony telluride (GeSbTe). However, there remains to be a need for improved phase change materials. In particular, there remains a need for phase change materials improved durability. There additionally remains a need for phase change materials with improved phase stability. There additionally remains a need for phase change materials that can be deposited in a conformal way. There remains a need for homogeneous phase change materials. The remains a need for phase change memory cells having high endurance. Any discussion, including discussion of problems and solutions, set forth in this section has been included in this disclosure solely for the purpose of providing a context for the present disclosure. Such discussion should not be taken as an admission that any or all of the information was known at the time the invention was made or otherwise constitutes prior art. SUMMARY OF THE DISCLOSURE This summary may introduce a selection of concepts in a simplified form, which may be described in further detail below. This summary is not intended to necessarily identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter. Described herein is a method of forming a layer comprising a group 14 element, a pnictogen, and a chalcogen, the method comprising: providing a substrate to a reaction chamber; executing a plurality of deposition cycles, a deposition cycle comprising a group 14 element pulse, a pnictogen pulse, and a chalcogen pulse; wherein the group 14 element pulse comprises providing a first group 14 element to the reaction chamber; the pnictogen pulse comprises providing a first pnictogen precursor to the reaction chamber; and, the chalcogen pulse comprises providing a first chalcogen precursor to the reaction chamber; wherein the method further comprises providing one or more further precursors to the reaction chamber, the one or more further precursors comprising a precursor being selected from a second group 14 element precursor being different than the first group 14 element precursor, a second pnictogen precursor being different from the first pnictogen precursor, and a second chalcogen precursor being different from the first chalcogen precursor. In some embodiments, the one or more further precursors comprise the second group 14 element precursor, and the group 14 element pulse further comprises providing the second group 14 element precursor to the reaction chamber. In some embodiments, the second precursor comprises the second pnictogen precursor, and the pnictogen pulse further comprises providing the second pnictogen precursor to the reaction chamber. In some embodiments, the second precursor comprises the second chalcogen precursor, and the chalcogen pulse further comprises the second chalcogen precursor to the reaction chamber. Further described herein is a method of forming a layer comprising a group 14 element, a pictogen, and a chalcogen, the method comprising: providing a substrate to a reaction chamber; executing a plurality of deposition cycles, ones from the plurality of deposition cycles comprising a first sub cycle and a second sub cycle; the first sub cycle comprising a first group 14 element pulse, a first pnictogen pulse, and a first chalcogen pulse, wherein the first group 14 element pulse comprises providing a first group 14 element to the reaction chamber; the first pnictogen pulse comprises providing a first pnictogen precursor to the reaction chamber; and, the first chalcogen pulse comprises providing a first chalcogen precursor to the reaction chamber; the second sub cycle comprising a second group 14 element pulse, a second pnictogen pulse, and a second chalcogen pulse, wherein the second group 14 element pulse comprises providing a second group 14 element to the reaction chamber; the second pnictogen pulse comprises providing a second pnictogen precursor to the reaction chamber; and, the second chalcogen pulse comprises providing a second chalcogen precursor to the reaction chamber. In some embodiments, the first