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EP-4735662-A1 - IMPROVED DEPOSITION OF HIGH QUALITY METAL OXIDE AND METAL NITRIDE LAYERS

EP4735662A1EP 4735662 A1EP4735662 A1EP 4735662A1EP-4735662-A1

Abstract

An Intermittent Catalyzed Reaction Induced Surface Process (ICRISP) produces a metal oxide or metal nitride film or metal-oxy-nitride film. In this process, the metal-containing precursor is intermittently dosed with a nitrogen-containing or sulfur-containing compound. Apparatus suitable for the process is described.

Inventors

  • WEIMER, Matthew
  • Harris, Sara
  • LINDBLAD, Dane
  • DAMERON, ARRELAINE

Assignees

  • Forge Nano Inc.

Dates

Publication Date
20260506
Application Date
20240627

Claims (20)

  1. 1. An Intermittent Catalyzed Reaction Induced Surface Process (ICRISP) for producing an oxide or nitride fdm on a substrate, comprising: providing a substrate in a chamber; dosing the substrate with a metal-containing ALD precursor to make a first dosed substrate; purging or flushing the chamber; and either A or B A) dosing the first dosed substrate with an oxidant and a nitrogen-containing reactant to form a metal oxide; or B) dosing the first dosed substrate with a sulfur-containing reactant and a nitrogencontaining reactant to form a metal nitride; and purging or flushing the chamber.
  2. 2. The process of claim 1 for producing an oxide film comprising dosing the first dosed substrate with an oxidant and a nitrogen-containing reactant to form a metal oxide; wherein the dosing step comprises a sub-pulse with the oxidant without the nitrogencontaining reactant followed by a second sub-pulse with the oxidant and the nitrogen-containing reactant; followed by a third sub-pulse with the oxidant and without the nitrogen-containing reactant.
  3. 3. The process of claim 2 wherein the oxidant comprises ozone and the nitrogen-containing reactant comprises a hydrazine.
  4. 4. The process of claim 2 wherein the step of dosing the first dosed substrate with an oxidant further comprises the addition of H2S.
  5. 5. The process of claim 1 for producing a nitride film comprising dosing the first dosed substrate with a sulfur-containing reactant and a nitrogen-containing reactant to form a metal nitride; wherein the dosing step comprises a sub-pulse with the nitrogen-containing reactant followed by a second sub-pulse with the sulfur-containing reactant and the nitrogen-containing reactant; followed by a third sub-pulse with the nitrogen-containing reactant.
  6. 6. The process of claim 2 wherein the oxide film comprises: AI2O3, SiCh, TiCh, Nb20s, Ta20s, La20s, Y2O3, ZrCh, Ga2Ch, or In2O3.
  7. 7. The process of claim 5 wherein the nitride film comprises: ZrN, GaN, YN, InN, or Si 3 N 4 .
  8. 8. The process of claim 5 wherein the sulfur-containing reactant comprises: H2S (hydrogen sulfide), H2S2 (dihydrogen sulfide), mercaptan (HS(CHs) or methane thiol), ethanethiol (ethyl mercaptan), S(CH3)2 (dimethyl sulfide), thionyl chloride (SOCh), sulfuryl chloride (SO2CI2).
  9. 9. The process of any of the above claims wherein the substrate comprises Si, SiCh, AI2O3 (preferably in the form of corundum), SiC, GaN, AlGaN, GaAs, or InP.
  10. 10. The process of any of the above claims wherein the oxidant comprises O2, O3, H2O, H2O2, or N2O. As with any category described as comprising, there may be additional components and the oxidants can be mixed.
  11. 11. The process of any of the above claims wherein the nitrogen-containing reactant comprises: hydrazine, monomethylhydrazine (MMH), 1, 1 -dimethylhydrazine, 1,2- dimethylhydrazine, tert-butylhydrazine (tBuNNH), ammonia (NH3), pyridine, 2,3-Lutidine (2,3- dimethylpyridine), 2,4-Lutidine (2,4-dimethylpyridine), 2,5-Lutidine (2,5-dimethylpyridine), 2,6-Lutidine (2,6-dimethylpyridine), 3,4-Lutidine (3,4-dimethylpyridine), or 3,5-Lutidine (3,5- dimethylpyridine).
  12. 12. The process of any of the above claims conducted for 10 to 5000 cycles, or 10 to 1000 cycles or 20 to 200 cycles.
  13. 13. The process of any of the above claims wherein the ALD precursor comprises: o Ti - TiC14, TTIP (titanium(IV) isopropoxide), Ti(NEtMe)4 (titanium(IV)tetrakisetylmethylamine), Ti(NMe)4 (titanium(IV)tetrakisdimethylamine) o Hf - Hf(NEtMe)4 (hafnium(IV)tetrakisethylmethylamine), HyALD (hafnium(IV)cyclopentadienyl-trisdimethylamine) o Zr - Zr(NEtMe)4 (zirconium(IV)tetrakisethylmethylamine), ZyALD (zirconi um(I V)cy cl opentadi eny 1 -tri sdimethy 1 amine) o Si - BEMAS (bisethylmethlamino silane), BDEAS (bisdiethylaminosilane), 3DMAS (trisdimethylaminosilane) o Y - ArY a (yttrium(III)bisethylcy cl opentadi enyl-isopropylamidinate) o Al - TMA (trimethyl aluminum), AICI3, AlMeC12, and AlMe2Cl.
  14. 14. The process of claim 1 wherein the step of dosing the substrate with a metal -containing ALD precursor comprises a step of introducing the precursor into the chamber followed by a pulse step of introducing precursor and draw control simultaneously; wherein draw control comprises flow of an inert gas and applying vacuum; wherein the pulse step is conducted for between 5 to 50 ms; followed by a step of from 10 to 500 ms in which no precursor flows into the system.
  15. 15. The process of claim 14 wherein the step of dosing is conducted for 150 ms or less.
  16. 16. The process of claim 13 wherein an inert gas flows through the chamber for at least 200 ms; preferably wherein no precursor is introduced and no vacuum is applied to the chamber.
  17. 17. The process of claim 2 wherein the sub-pulses with the oxidant without the nitrogencontaining reactant are conducted for a longer period of time than the sub-pulse with the oxidant and the nitrogen-containing reactant, (the sub-pulses are summed together for this calculation)
  18. 18. The process of claim 17 wherein the sub-pulses with the oxidant without the nitrogencontaining reactant are conducted for a period of time at least two times longer than the subpulse with the oxidant and the nitrogen-containing reactant.
  19. 19. The process of claim 5 wherein the sub-pulses with the oxidant without the sulfur- containing reactant are conducted for a longer period of time than the sub-pulse with the oxidant and the sulfur-containing reactant, (the sub-pulses are summed together for this calculation)
  20. 20. The process of claim 17 wherein the sub-pulses with the oxidant without the sulfur- containing reactant are conducted for a period of time at least two times longer than the subpulse with the oxidant and the sulfur-containing reactant.

Description

Improved Deposition of High Quality Metal Oxide and Metal Nitride Layers Related Applications This application claims the priority benefit of United States Provisional Patent Application Ser. No. 63/523,579 filed June 27, 2023. Introduction Dielectric layers of oxides and some nitrides and metal electrodes are important for the performance and functionality of microelectronic devices such as transistors and memory capacitors. For example, the gate dielectric layers and gate electrode layers are critical components that are necessary for the operation of a metal-oxide-semiconductor field-effect transistor (MOSFET) devices. Likewise, a dielectric layer and an inner electrode are needed in a dynamic random-access memory (DRAM) capacitor, where they are used for storage of charge and access to the charge stored within the capacitor. To accommodate shrinking devices, the improvement of deposition processes for high-permittivity (high-k) materials has experienced increased demand, especially for high-k materials used as gate insulators and capacitor dielectrics as an alternative to SiC>2. Zirconium dioxide (ZrCL) has already been proven as a suitable high-k material and is used industrially owing to its wide band gap (~5.8 eV), high dielectric constant (17-47), and high thermal stability. Hafnium dioxide, (HfCL) is an emerging attractive material for use as a dielectric barrier in high-power SiC and GaN electronics, both MOSFET and HEMT, due to its even higher band gap, dielectric constant and thermal stability. Silicon nitride (SisNr, SixNy, or SiN for short), zirconium nitride (ZrsN4, ZrxNy, or ZrN for short), other metal nitrides and a wider array of metal oxynitrides are also provide sufficient dielectric properties to be applicable for certain types of microelectronic devices. Shrinking device size is accompanied by increasing aspect ratios, which means higher efficiency thermal ALD systems and processes will become increasingly favorable over plasma-based processes that comprise reactive species that may extinguish prior to exposure to high aspect ratio, hidden, or otherwise challenging to reach surfaces. As with many ALD processes, the success or failure of the coatings that can be produced for a particular device or feature is oftentimes linked to the specific apparatus used for the deposition. Existing thermal ALD apparatuses have struggled with the trade-off between the need to shorten reaction times and improve chemical utilization efficiency, and on the other hand, the need to minimize purge-gas residence and chemical removal times. Certain ALD systems of the prior art contain chemical delivery manifolds using synchronized actuation of multiple valves. In such systems, satisfactory elimination of flow excursions is impossible because valve actuation with perfect synchronization is itself practically impossible. As a result, the inevitable flow excursions are notorious for generating backflow of gas that leads to adverse chemical mixing. As a conventional ALD apparatus is utilized, “memory” effects tend to reduce the efficiency of the ALD reactor. Such memory effects are caused by the tendency of chemicals to adsorb on the walls of the ALD reactor and consequentially release from the walls of the ALD reactor on a time scale that is dictated by the adsorption energy and the temperature of the walls. This phenomenon tends to increase the residence time of trace amounts of chemicals in the ALD reactor. As a result, memory effects tend to increase the purge-time required for removal of chemicals. Thus, a need exists for an ALD apparatus that minimizes memory effects. Thus, a need exists for an ALD apparatus that can promote faster reaction times without sacrificing precursor utilization efficiency, one that minimizes purge-gas residence and chemical removal times, and one that can improve the deposition of high-k dielectric materials (oxides, nitrides and oxynitrides) using lower cost of ownership thermal ALD processes. Current techniques for depositing many high-k materials by thermal atomic layer deposition (ALD) tend to produce low density and performing films, and many microelectronics manufacturers have adopted plasma enhanced ALD (PEALD) processes instead. PEALD is employed to improve the performance of the films, yet the high field and fast switching requirements of the device can make the resulting dielectric barriers derived from PEALD insufficient. In addition, not all applications can accommodate plasma, resulting in damage to the incoming substrate, degrading performance. Most critically, plasma processes will have an inherent limit to the aspect ratio that can be conformally coated. At some distance from the opening, usually no greater than 10:1, 10 times deeper than the opening diameter or distance, a sufficient concentration of plasma species will fail to interact with the surface. Since PEALD relies on the amount of radical species for a saturated amount of film per cycle, as well as for