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CN-122003519-A - Silicon-containing film having surface modified with halogenated silicon-containing compound

CN122003519ACN 122003519 ACN122003519 ACN 122003519ACN-122003519-A

Abstract

A process for depositing a high quality smooth and continuous silicon-containing film comprising a) providing at least one substrate in a reactor, b) heating the reactor to at least one temperature in the range of ambient temperature to about 750 ℃ and optionally maintaining the reactor at a pressure of about 100 Torr or less, C) introducing into the reactor at least one first silicon precursor comprising at least one organic amino group and at least one halo group and having the formula SiH m X n (NR 1 R 2 ) 4‑m‑n wherein m-0, 1. 2;n-1, 2, 3, and m+n <3;X is selected from the group consisting of Cl, Br and I, R 1 and R 2 are each independently selected from the group consisting of linear or branched C 1 to C 10 alkyl, Straight-chain or branched C 3 -C 10 alkenyl, straight-chain or branched C 3 -C 10 alkynyl, C 3 -C 10 cycloalkyl, c 2 to C 6 dialkylamino group, Electron withdrawing groups and C 6 to C 10 aryl groups to form a first silicon-containing layer, d) purging any unreacted precursor from the reactor with an inert gas, e) introducing a nitrogen source to react with the first silicon-containing layer to form a seed layer comprising at least one selected from the group consisting of silicon nitride and carbon doped silicon nitride, f) purging the reactor with an inert gas, g) introducing at least one second silicon precursor comprising a halogenated silicon-containing compound into the reactor to react with the seed layer and form a second silicon-containing layer comprising a compound selected from the group consisting of silicon nitride, carbon doped silicon nitride, and, At least one of the group consisting of carbon doped silicon nitride, silicon oxynitride, and carbon doped silicon oxynitride, h) purging the reactor with an inert gas, i) introducing a nitrogen source to react with the second silicon-containing layer to form silicon nitride or carbon doped silicon nitride, and j) purging the reactor with an inert gas.

Inventors

  • H. Chandra
  • ANTONIJEVIC BORIVOJE
  • M.R. MCDONALD
  • LEI XINJIAN

Assignees

  • 沃萨姆材料美国有限责任公司

Dates

Publication Date
20260508
Application Date
20241008
Priority Date
20231009

Claims (11)

  1. 1. A method for depositing a high quality smooth and continuous silicon-containing film comprising: a) Providing at least one substrate in a reactor; b) Heating the reactor to at least one temperature in the range of ambient temperature to about 750 ℃ and optionally maintaining the reactor at a pressure of about 100 torr or less; c) Introducing into the reactor at least one first silicon precursor comprising at least one organoamino group and at least one halo group and having the formula: SiH m X n (NR 1 R 2 ) 4-m-n wherein m=0, 1, 2;n =1, 2, 3, and m+n+. 3;X is selected from the group consisting of Cl, br, and I, R 1 and R 2 are each independently selected from the group consisting of linear or branched C 1 to C 10 alkyl, linear or branched C 3 to C 10 alkenyl, linear or branched C 3 to C 10 alkynyl, C 3 to C 10 cycloalkyl, C 2 to C 6 dialkylamino, electron withdrawing groups, and C 6 to C 10 aryl, to form a first silicon-containing layer; d) Purging any unreacted precursor from the reactor using an inert gas; e) Introducing a nitrogen source to react with the first silicon-containing layer to form a seed layer comprising at least one selected from the group consisting of silicon nitride and carbon-doped silicon nitride; f) Purging the reactor with an inert gas; g) Introducing at least one second silicon precursor comprising a halogenated silicon-containing compound into the reactor to react with the seed layer and form a second silicon-containing layer comprising at least one selected from the group consisting of silicon nitride, carbon-doped silicon nitride, silicon oxynitride, and carbon-doped silicon oxynitride; h) Purging the reactor with an inert gas; i) Introducing a nitrogen source to react with the second silicon-containing layer to form silicon nitride or carbon-doped silicon nitride, and J) The reactor was purged with an inert gas.
  2. 2. The method of claim 1, wherein steps c through f are repeated to provide the seed layer with a thickness, and steps g through j are repeated to achieve a smooth and continuous second silicon-containing layer.
  3. 3. The method of claim 2, wherein steps c-f are repeated to achieve a thickness of the seed layer ranging from about 0.2 a to about 20 a, preferably 0.2 a to about 10 a, most preferably 0.2 a to about 5 a.
  4. 4. The method of claim 2, wherein steps g through j are repeated to achieve a thickness of the second silicon-containing layer ranging from about 5 a to about 2000 a.
  5. 5. The method of claim 1, wherein steps c through f are performed in one reactor chamber and steps g through j are performed in the same reactor chamber or another reactor chamber at the same or different substrate temperatures.
  6. 6. The method of claim 1, wherein the at least one first silicon precursor is one or more selected from the group consisting of (diisopropylamino) chlorosilane, (diisopropylamino) dichlorosilane, (diisopropylamino) trichlorosilane, (di-sec-butylamino) chlorosilane, (di-sec-butylamino) dichlorosilane, (di-sec-butylamino) trichlorosilane, (diisopropylamino) bromosilane and (diisopropylamino) dibromosilane, (diisopropylamino) iodosilane and (diisopropylamino) diiodosilane.
  7. 7. The method of claim 1 wherein the at least one second silicon precursor is at least one selected from the group consisting of i) a halosilane, ii) a halosiloxane, iii) a halosilazane, and iv) a halocarbosilane.
  8. 8. The method of claim 7, wherein the halogenated silane is selected from the group consisting of monochlorosilane, dichlorosilane, trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, dichlorosilane, monochlorosilane, monobromosilane, dibromosilane, tribromosilane, tetrabromosilane, monoiodosilane, diiodosilane, triiodosilane, and tetraiodosilane.
  9. 9. The method of claim 7, wherein the halogenated siloxane is selected from the group consisting of hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octachlorotrisiloxane.
  10. 10. The method of claim 7, wherein the silazane halide has a structure according to formula I: Wherein R 3 is selected from the group consisting of hydrogen, linear or branched C 1 to C 10 alkyl, linear or branched C 3 to C 10 alkenyl, Straight or branched chain C 3 to C 10 alkynyl, C 3 to C 10 cycloalkyl, C 2 to C 6 dialkylamino, An electron withdrawing group and a C 6 to C 10 aryl group, R 4 is selected from the group consisting of hydrogen, linear or branched C 1 to C 10 alkyl, Straight-chain or branched C 2 -C 6 alkenyl, straight-chain or branched C 3 -C 6 alkynyl, C 3 -C 10 cycloalkyl, C 2 to C 6 dialkylamino, C 6 to C 10 aryl, linear or branched C 1 to C 6 fluoroalkyl, An electron withdrawing group, a C 4 to C 10 aryl group, and a halo group selected from the group consisting of Cl, br, and I, and X is a halo group selected from the group consisting of Cl, br, and I.
  11. 11. The method of claim 7, wherein the halocarbosilane has a structure according to formula II or III: Wherein X 1 、X 2 、X 3 、X 4 、X 5 and X 6 are each independently selected from the group consisting of hydrogen, a halogen atom selected from F, cl, br and I, an isocyanate, an amino group having the formula NR 5 R 6 , wherein R 5 and R 6 are each independently selected from the group consisting of hydrogen, C 1-10 straight chain alkyl, C 3-10 branched chain alkyl, C 3-10 cycloalkyl, C 3-10 alkenyl, C 4-10 aryl and C 4-10 heterocyclyl, and are optionally joined together to form a ring, And wherein for formula II or formula III, one or more of the substituents X 1 、X 2 、X 3 、X 4 、X 5 and X 6 are optionally linked to form a substituted or unsubstituted, saturated or unsaturated cyclic group, or are optionally halo or amino as described above, provided that X 1 、X 2 、X 3 、X 4 、X 5 and X 6 cannot all be amino, and optionally in formula II or III, an amino group of formula NR 5 R 6 , R 5 and R 6 are linked together to form a ring.

Description

Silicon-containing film having surface modified with halogenated silicon-containing compound Cross Reference to Related Applications The present application claims priority from U.S. provisional patent application No. 63/588,994, filed on 10/9 at 2023, which is incorporated herein by reference in its entirety. Technical Field The present invention relates to compositions and methods for manufacturing electronic devices. More particularly, the present invention relates to compounds, compositions, and methods for depositing high quality silicon-containing films such as, but not limited to, silicon nitride, carbon-doped silicon nitride films, silicon oxynitride, and carbon-doped silicon oxynitride films. Background Silicon nitride films are used in semiconductors for a variety of applications. For example, silicon nitride films are commonly used as a final passivation and mechanical protection layer for integrated circuits, a masking layer for selective oxidation of silicon, as one of the dielectric materials in a stacked oxide-nitride-oxide (O-N-O) layer in a DRAM capacitor or 3D NAND flash memory chip, or as a CMP stop layer in shallow trench isolation applications. A conformal and continuous thin layer (< 200 a or less, < 150 a or less, < 100 a or less, < 50 a or less, < 30 a or less, < 20a or less, < 15 a or less, < 10 a or less) of a high quality silicon-containing film (such as silicon nitride, carbon doped silicon oxide, silicon oxynitride or carbon doped silicon oxynitride) is required to be formed on an oxide surface (such as silicon oxide or other metal oxide). High quality silicon nitride is typically deposited using chlorosilanes or chlorodisilanes (e.g., dichlorosilane and hexachlorodisilane) and ammonia-based processes. However, the chlorine ligands have a relatively high activation energy for reacting with the oxide surface, which results in so-called island growth. For chlorosilane-based films, the silicon-containing film needs to be at a certain critical thickness to achieve a smooth and continuous film. Furthermore, the pitch width is reduced with each generation of semiconductor devices, which in turn results in the film being reduced. In some applications, a thin silicon nitride layer is deposited on top of silicon oxide or other type of metal oxide using an Atomic Layer Deposition (ALD) process that includes chlorosilane/chlorodisilane and ammonia. At the beginning of the deposition process, the film has heterogeneous and discontinuous island-like growth. After a certain critical thickness is reached, the island growth becomes a smooth and continuous layer of nitrided Si. Accordingly, there is a need to develop processes that use Chemical Vapor Deposition (CVD) or Atomic Layer Deposition (ALD) processes or ALD-like processes (such as, but not limited to, cyclic CVD processes) to form smooth and continuous high quality silicon-containing films such as silicon nitride or carbon-doped silicon nitride. Olsen, "Analysis of LPCVD Process Conditions for the Deposition of Low Stress Silicon Nitride",5 Materials Science in Semiconductor Process 51 (2002) Various process conditions for optimizing deposition of low stress silicon nitride films by low pressure chemical vapor deposition are described. The results show that increasing the refractive index to over 2.3 by increasing the gas flow does not significantly reduce the residual stress, but has a significant adverse effect on thickness uniformity and deposition rate. M, tanaka et al , "Film Properties of Low-k Silicon Nitride Films Formed by Hexachlorodisilane and Ammonia",147 J. Electrochem. Soc. 2284 (2000) describe a low temperature process for forming silicon nitride (SiN) with good step coverage by Low Pressure Chemical Vapor Deposition (LPCVD) using Hexachlorodisilane (HCDS). JP2000100812 describes a method of depositing a film using SiCl 4 and NH 3 as source gases. Prior to deposition, the substrate surface may be nitrided using NH 3. An extremely thin film having improved insulator properties is formed. The silicon nitride film can be used as a capacitor insulator film of a semiconductor integrated circuit. US patent No. 6,355,582 describes a method of forming a silicon nitride film in which a substrate to be subjected to film formation is heated, and silicon tetrachloride and ammonia gas are supplied to the substrate heated to a predetermined temperature. US patent number 10,049,882 describes an Atomic Layer Deposition (ALD) method for manufacturing a semiconductor device, which includes the step of forming a dielectric layer on a structure having a height difference. The method includes forming a structure having a height difference on a substrate and forming a dielectric layer structure on the structure. Forming the dielectric layer structure includes forming a first dielectric layer comprising silicon nitride over the structure having a height differential. Forming the first dielectric layer includes supplying a first gas including Pe