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US-12628399-B2 - Methods and systems for forming a layer comprising a group 13 element on a substrate

US12628399B2US 12628399 B2US12628399 B2US 12628399B2US-12628399-B2

Abstract

Disclosed are methods and systems for depositing layers comprising a Group 13 element on a surface of a substrate via contacting the substrate with at least a vapor-phase first precursor and a vapor-phase second precursor comprising an alkyl halide. Exemplary structures in which the layers may be incorporated include field effect transistors, VNAND cells, and metal-insulator-metal (MIM).

Inventors

  • Charles DEZELAH
  • Petro Deminskyi
  • Qi Xie

Assignees

  • ASM IP HOLDING B.V.

Dates

Publication Date
20260512
Application Date
20230526

Claims (20)

  1. 1 . A method of forming a layer comprising a Group 13 element on a substrate, the method comprising: providing the substrate in a reaction chamber; executing at least one deposition cycle; wherein the at least one deposition cycle comprises: contacting the substrate with a vapor-phase first precursor to chemisorb the first precursor to the substrate, wherein the vapor-phase first precursor comprises a compound comprising a Group 13 element and three alkyl ligands bonded to the Group 13 element; and contacting the substrate with a vapor-phase second precursor comprising an alkyl halide to react the alkyl halide with the chemisorbed first precursor to form the layer on the substrate, wherein a halogen of the alkyl halide is bonded to a secondary or tertiary carbon atom.
  2. 2 . The method according to claim 1 , wherein each of the alkyl ligands bonded to the Group 13 element comprises a C1-C6 alkyl ligand.
  3. 3 . The method according to claim 1 , wherein the Group 13 element is selected from the group consisting of aluminum, gallium, indium, boron, and combinations thereof.
  4. 4 . The method according to claim 1 , wherein the vapor-phase first precursor comprises trimethylaluminum, trimethylindium, or trimethylgallium.
  5. 5 . The method according to claim 1 , wherein the vapor-phase first precursor comprises a monomer, dimer, or mixture of a monomer and a dimer of the compound comprising a Group 13 element and three alkyl ligands bonded to the Group 13 element.
  6. 6 . The method according to claim 1 , wherein the halogen of the alkyl halide comprises a member selected from the group consisting of I, Br, and Cl.
  7. 7 . The method according to claim 1 , wherein the alkyl halide comprises the formula C a H b X c , wherein a=3-8 and b+c=2a+2.
  8. 8 . The method according to claim 1 wherein the alkyl halide comprises tert-butyl iodide.
  9. 9 . The method according to claim 1 , wherein the alkyl halide comprises a branched C4 to C8 alkyl bonded to a halogen atom through a tertiary carbon atom.
  10. 10 . The method according to claim 1 , wherein the alkyl halide comprises two or more halogen atoms.
  11. 11 . The method according to claim 1 , wherein an alkyl of the alkyl halide comprises a β-carbon relative to an α-carbon bonded to a halogen, and wherein the β-carbon comprises at least one C—H bond.
  12. 12 . The method according to claim 1 , wherein the layer comprises at least two different Group 13 elements.
  13. 13 . The method according to claim 1 , wherein the at least one deposition cycle further comprises contacting the substrate with a vapor-phase third precursor to provide a second metal to the layer.
  14. 14 . The method according to claim 13 , wherein the vapor-phase third precursor comprises a compound comprising a Group 13 element different from that of the vapor-phase first precursor or comprises a transition metal.
  15. 15 . The method according to claim 1 , wherein the layer on the substrate comprises TiAlC.
  16. 16 . The method according to claim 1 , wherein the method comprises a cyclic deposition process, and wherein the method comprises repeating said at least one deposition cycle a plurality of times to form the layer on the substrate.
  17. 17 . A method of forming a layer comprising a Group 13 element on a substrate, the method comprising: providing the substrate in a reaction chamber; executing at least one deposition cycle; wherein the at least one deposition cycle comprises: contacting the substrate with a vapor-phase first precursor to chemisorb the first precursor to the substrate, wherein the vapor-phase first precursor comprises a compound comprising a Group 13 element and three alkyl ligands bonded to the Group 13 element; and contacting the substrate with a vapor-phase second precursor comprising an alkyl halide to react the alkyl halide with the chemisorbed first precursor to form the layer on the substrate, wherein the vapor-phase first precursor comprises a monomer, dimer, or mixture of a monomer and a dimer of the compound comprising a Group 13 element and three alkyl ligands bonded to the Group 13 element.
  18. 18 . The method according to claim 17 , wherein an alkyl of the alkyl halide comprises a β-carbon relative to an α-carbon bonded to a halogen, and wherein the β-carbon comprises at least one C—H bond.
  19. 19 . A method of forming a layer comprising a Group 13 element on a substrate, the method comprising: providing the substrate in a reaction chamber; executing at least one deposition cycle; wherein the at least one deposition cycle comprises: contacting the substrate with a vapor-phase first precursor to chemisorb the first precursor to the substrate, wherein the vapor-phase first precursor comprises a compound comprising a Group 13 element and three alkyl ligands bonded to the Group 13 element; and contacting the substrate with a vapor-phase second precursor comprising an alkyl halide to react the alkyl halide with the chemisorbed first precursor to form the layer on the substrate, wherein the alkyl halide comprises a member selected from the group consisting of tert-butyl iodide, diiodoethane, iodoethane, triiodoethane, tetraiodoethane, and 1,3-diiodopropane.
  20. 20 . The method according to claim 19 , wherein each of the alkyl ligands bonded to the Group 13 element comprises a C1-C6 alkyl ligand.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Application No. 63/346,924, filed May 30, 2022, which is incorporated by reference herein in its entirety. FIELD The present disclosure generally relates to the field of semiconductor processing methods and systems, and to the field of integrated circuit manufacture. In particular, the present disclosure relates to methods and systems suitable for forming a layer comprising a Group 13 element, such as a layer comprising a Group 13 element and carbon or a layer comprising a Group 13 element, carbon, and a second metal, e.g., TiAlC, on a substrate. The layer may comprise the Group 13 element in elemental form, such as elemental aluminum, thereby further providing the layer with desired resistivity and work function properties for use in semiconductor devices. BACKGROUND The scaling of semiconductor devices, such as, for example, complementary metaloxide-semiconductor (CMOS) devices, has led to significant improvements in speed and density of integrated circuits. However, conventional device scaling techniques face significant challenges for future technology nodes. For example, one challenge has been finding suitable conducting materials for use as a gate electrode in aggressively scaled CMOS devices. Various gate materials may be used, such as, for example, a metal, such as a titanium nitride layer. However, in some cases, where greater work function (WF) values are desired than those obtained with titanium nitride layers, e.g., in PMOS regions of a CMOS device, improved materials for gate electrodes are desired. In particular, such materials can include p-dipole shifting layers, and can be used, e.g., for threshold voltage tuning. In addition, there remains a need for new materials in other semiconductor devices, such as MIM (metal-insulator-metal) structures, DRAM capacitors, and VNAND cells. 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 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. Various embodiments of the present disclosure relate to methods of forming one or more layers (hereinafter “a layer,” “the layer,” “layers,” or “the layers”) comprising a Group 13 element, carbon, and optionally a second metal on a substrate, to structures and devices formed using such methods, and to apparatus for performing the methods and/or for forming the structures and/or devices. The layers may be used in a variety of applications, including work function adjustment layers and threshold voltage adjustment layers. For example, the layers may be used in a gate electrode in n- or p-channel metal oxide semiconductor field effect transistors (MOSFETS). In one aspect, the present disclosure relates to methods and systems for forming a layer comprising a Group 13 element on a substrate utilizing readily available and inexpensive starting materials to provide layers having low resistivity and desired work function properties that are in high demand globally. In some embodiments, the formed layer may comprise the Group 13 element along with carbon. In some embodiments, the formed layer may comprise the Group 13 element, carbon, and a second metal compound, such as a highly sought after TiAlC layer. In particular embodiments, the Group 13 element is provided in elemental form. In another aspect, the present disclosure relates to a method of forming a layer comprising a Group 13 element on a substrate. The method comprises providing the substrate in a reaction chamber; executing the at least one deposition cycle, the at least one deposition cycle comprising: contacting the substrate with a vapor-phase first precursor (hereinafter “first precursor”) to chemisorb the first precursor to the substrate, wherein the first precursor comprises a compound comprising a Group 13 element and three alkyl ligands bonded to the Group 13 element; and contacting the substrate with a vapor-phase second precursor (hereinafter “second precursor”) comprising an alkyl halide to react the alkyl halide with the chemisorbed first precursor to form the layer on the substrate. In some embodiments, the method further comprises contacting the substrate with a vapor-phase third precursor (hereinafter “third precursor”) comprising a metal compound to provide a second metal to the layer, wherein the third precursor is different from the first precursor. In an embodiment, the