# US 2022/0044974 A1 · Gas phase production of radicals for dielectrics > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2022/0044974 A1 - Document ID: US20220044974A1 - Status: Published application - Kind: A1 - Application number: 16/984,618 - Filed: 2020-08-04 - Published: 2022-02-10 - Earliest claimed: 2020-08-04 - Assignees: Tokyo Electron Limited - Applicants: Tokyo Electron Limited - Inventors: Anthony Dip - Web page: https://patentgrep.com/patent/US20220044974A1 ## CPC - H10P 74/23: {characterised by multiple measurements, corrections, marking or sorting processes} - C23C 16/308: {Oxynitrides} - C23C 16/45536: {Use of plasma, radiation or electromagnetic fields} - C23C 16/45551: {for relative movement of the substrate and the gas injectors or half-reaction reactor compartments} - C23C 16/45565: {Shower nozzles} - C23C 16/45574: {Nozzles for more than one gas} - C23C 16/4584: {the substrate being rotated} - C23C 16/50: using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)} - H10P 14/6336: {in the presence of a plasma [PECVD]} - H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD} - H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane} - H10P 14/6927: {the material being a silicon oxynitride, e.g. SiON or SiON:H} - H10P 14/69392: {the material containing hafnium, e.g. HfO2} - H10P 74/203: {Structural properties, e.g. testing or measuring thicknesses, line widths, warpage, bond strengths or physical defects} - H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10 - C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04) ## Abstract A method for depositing a dielectric material includes heating a substrate disposed in a dielectric deposition chamber; dispensing a dielectric precursor from a first showerhead towards a major outer surface of the substrate; dispensing a mixture containing oxygen and ammonia from a second showerhead towards the major outer surface of the substrate; and reacting the dielectric precursor with the mixture to deposit a layer of oxynitride dielectric material on the substrate. ## Claims ### Claim 1 A method for depositing a dielectric material, the method comprising: heating a substrate disposed in a dielectric deposition chamber; dispensing a dielectric precursor from a first showerhead towards a major outer surface of the substrate; dispensing a mixture containing oxygen and ammonia from a second showerhead towards the major outer surface of the substrate; and reacting the dielectric precursor with the mixture to deposit a layer of oxynitride dielectric material on the substrate. ### Claim 2 (depends on 1) The method of claim 1, further comprising: measuring a metric of the layer of oxynitride dielectric material; determining that the metric is not within a target process window for the metric; changing a ratio of oxygen to hydrogen in the mixture and adjusting a mole fraction of ammonia in the mixture; and repeating the heating and the reacting to deposit another layer of oxynitride on another substrate disposed in the dielectric deposition chamber. ### Claim 3 (depends on 2) The method of claim 2, wherein the metric is index of refraction, dielectric constant, dielectric leakage current, breakdown voltage, or pin hole density. ### Claim 4 (depends on 1, 2) The method of claim 2, wherein measuring the metric comprising determining a purity of the layer of oxynitride dielectric material using Fourier-transform infrared spectroscopy (FTIR), mass spectroscopy, x-ray diffraction, or energy dispersive x-ray spectroscopy (EDS).2. The method of claim 1, wherein the dielectric precursor is a chlorosilane and the dielectric material is silicon oxynitride. ### Claim 5 (depends on 1) The method of claim 1, wherein the dielectric precursor is a hafnium chloride and the oxynitride dielectric is hafnium oxynitride. ### Claim 6 (depends on 1) The method of claim 1, wherein dispensing the dielectric precursor comprises depositing dielectric atoms on the substrate, wherein the reacting comprises thermally reacting the mixture near the major outer surface producing NH2* radicals and O* radicals and reacting the NH2* radicals and O* radicals with the dielectric atoms to deposit the layer of oxynitride dielectric material. ### Claim 7 (depends on 1) The method of claim 1, wherein the mixture comprises hydrogen and wherein the reacting comprises thermally reacting the mixture near the major outer surface generating NH2* radicals by oxidizing ammonia with oxygen radicals formed during a thermal reaction of oxygen with hydrogen. ### Claim 8 (depends on 7) The method of claim 7, further comprising adjusting a ratio of oxygen to hydrogen in the mixture to between about 0.5 to 2.0 and adjusting a mole fraction of ammonia to between about 20% to 50% and thereby tuning a stoichiometry of nitrogen and oxygen in the layer of oxynitride dielectric material. ### Claim 9 (depends on 7) The method of claim 7, wherein a ratio of oxygen to hydrogen is about 1.5 and wherein a mole fraction of ammonia is about 30% in the mixture. ### Claim 10 (depends on 1) The method of claim 1, wherein the mixture comprises ozone and ammonia and wherein NH2* radicals are generated by reacting oxygen radicals generated by thermal decomposition of the ozone with the ammonia; or wherein the mixture comprises ammonia plus O* radicals generated in a remote plasma and wherein NH2* radicals are generated by a low pressure radical oxidation of ammonia by O* radicals. ### Claim 11 (depends on 1) The method of claim 1, wherein the first showerhead is a first chamber in a dual showerhead and wherein the second showerhead is a second chamber in the dual showerhead. ### Claim 12 (depends on 1) The method of claim 1, further comprising rotating the substrate under the first showerhead while dispensing the dielectric precursor and rotating the substrate under the second showerhead while dispensing the mixture. ### Claim 13 (depends on 1) The method of claim 1, wherein heating a substrate comprises heating the substrate to a temperature between about 600° C. and about 1100° C., wherein dispensing the mixture comprises maintaining a flow rate of the mixture to between about 5 and 15 slm, and wherein a pressure in the dielectric deposition chamber is between about 1 Torr and about 10 Torr. ### Claim 14 A method for depositing silicon oxynitride, the method comprising: heating a substrate disposed on a substrate holder in a dielectric deposition chamber; rotating the substrate holder under a first showerhead; dispensing a silicon precursor from the first showerhead towards a major outer surface of the substrate; rotating the substrate holder under a second showerhead; dispensing a mixture of hydrogen, oxygen, and ammonia from the second showerhead towards the major outer surface; and depositing the silicon oxynitride over the substrate by reacting the silicon precursor with the mixture. ### Claim 15 (depends on 14) The method of claim 14, further comprising adjusting a ratio of oxygen to hydrogen in the mixture to between about 0.5 to 2.0 and adjusting a mole fraction of ammonia in the mixture to between about 20% to 50% to tune a stoichiometry of nitrogen and oxygen in the silicon oxynitride. ### Claim 16 (depends on 14) The method of claim 14, wherein heating the substrate comprises heating the substrate to a temperature between about 600° C. and about 1100° C., wherein a flow rate of the mixture is between about 5 and 15 slm, and wherein a pressure in the dielectric deposition chamber is between about 1 Torr and about 10 Torr. ### Claim 17 (depends on 14) The method of claim 14, wherein the silicon precursor is a chlorosilane. ### Claim 18 (depends on 14) The method of claim 14, wherein dispensing the silicon precursor deposits a layer of silicon on the substrate, wherein dispensing the mixture generates NH2* and O* radicals proximal to the layer of silicon, and the NH2* and O* radicals react with the layer of silicon to deposit the silicon oxynitride. ### Claim 19 A method for depositing a dielectric material, the method comprising: loading a substrate on a substrate holder disposed within a processing chamber; heating the substrate within the processing chamber; dispensing a dielectric precursor from a first showerhead in a first zone over the substrate holder; dispensing a mixture of hydrogen, oxygen, and ammonia from a second showerhead in a second zone over the substrate holder; moving the substrate holder to repeatedly transfer the substrate between the first zone and the second zone; dispensing silicon precursor from the first showerhead towards a major surface of the substrate in the first zone; dispensing the mixture from the second showerhead towards the major surface of the substrate from the second showerhead; and depositing the dielectric material on the substrate by reacting the silicon precursor with the mixture. ### Claim 20 (depends on 19) The method of claim 19, wherein the dielectric precursor is a chlorosilane and the dielectric material is silicon oxynitride. ### Claim 21 (depends on 19) The method of claim 19, further comprising adjusting a ratio of oxygen to hydrogen in the mixture to between about 0.5 to 2.0 and adjusting a mole fraction of ammonia in the mixture to between about 20% to 50% to tune a stoichiometry of nitrogen and oxygen in the dielectric material. ### Claim 22 (depends on 19) The method of claim 19, wherein heating the substrate comprises heating the substrate to a temperature between about 600° C. and about 1100° C., wherein a flow rate of the mixture is between about 5 and 15 slm, and wherein a pressure in the processing chamber is between about 5 Torr and about 10 Torr.