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US-20260130139-A1 - LOW TEMPERATURE SI-CONTAINING FILMS DEPOSITED FROM CHLOROSILANE AND AMINOSILANE REACTIONS

US20260130139A1US 20260130139 A1US20260130139 A1US 20260130139A1US-20260130139-A1

Abstract

A method for deposition of silicon and nitrogen containing dielectric film via an atomic layer deposition (ALD) or in an ALD-like process. The method includes the steps of a) providing at least one substrate into a reactor and heating the reactor to at least one temperature ranging from about 25° C. to about 600° C. and optionally maintaining the reactor at a pressure of about 100 torr or less; b) introducing into the reactor at least a first precursor comprising a halogenated silicon-containing compound that forms a silicon-containing layer; c) purging any unreacted precursor from the reactor using inert gas; d) introducing at least a second precursor, comprising at least two or more primary amino-containing silicon atoms, which reacts with the silicon-containing layer to form a film comprising silicon and nitrogen; e) purging the reactor using inert gas; f) introducing a plasma source into the reactor to react with the film comprising silicon and nitrogen; g) purging any reaction by-products from the reactor using inert gas, and repeating steps b to g to bring the film comprising silicon and nitrogen to a desired thickness.

Inventors

  • Matthew R. MacDonald
  • Haripin Chandra
  • Randall Higuchi
  • Xinjian Lei
  • Son Hoang

Assignees

  • VERSUM MATERIALS US, LLC

Dates

Publication Date
20260507
Application Date
20231012

Claims (18)

  1. 1 . A method for deposition of silicon and nitrogen containing dielectric film via an atomic layer deposition (ALD) process, comprising: a) providing at least one substrate into a reactor at a temperature ranging from about 25° C. to about 600° C. and optionally maintaining the reactor at a pressure of about 100 torr or less; b) introducing into the reactor at least a first silicon precursor comprising at least two halogen atoms to form a silicon-containing layer; c) purging any unreacted precursor from the reactor using inert gas; d) introducing into the reactor at least a second silicon precursor, comprising at least two primary amino moieties, which reacts with the silicon-containing layer to form a film comprising silicon and nitrogen; e) purging the reactor using inert gas; f) introducing a plasma source into the reactor to react with the film comprising silicon and nitrogen; g) purging any reaction by-products from the reactor using inert gas, and h) repeating steps b to g to bring the film comprising silicon and nitrogen to a desired thickness.
  2. 2 . The method according to claim 1 wherein the first silicon precursor comprising at least two halogen atoms is at least one selected from the group consisting of: i) halogenated silanes, ii) halogenated siloxanes, iii) halogenated silazanes, and iv) halogenated carbosilanes.
  3. 3 . The method according to claim 1 wherein the first silicon precursor comprising at least two halogen atoms is selected from the group consisting of trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, and dichlorosilane.
  4. 4 . The method according to claim 1 wherein the first silicon precursor comprising at least two halogen atoms is a halogenated siloxane selected from the group consisting of hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octaclorotrisiloxane.
  5. 5 . The method according to claim 1 wherein the first silicon precursor comprising at least two halogen atoms is a halogenated silazane selected from the groups represented by the following Formula I: wherein R 1 is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 10 alkenyl group, a linear or branched C 2 to C 10 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, an electron withdrawing group, and a C 6 to C 10 aryl group; R 2 is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 6 alkenyl group, a linear or branched C 3 to C 6 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, a C 6 to C 10 aryl group, a linear or branched C 1 to C 6 fluorinated alkyl group, an electron withdrawing group, and a halide selected from the group consisting of Cl, Br, and I; and X is a halide selected from the group consisting of Cl, Br, and I.
  6. 6 . The method according to claim 1 , wherein the second silicon precursor primary amino-containing silicon compound is selected from the group consisting of compounds represented by the following Formula II below: wherein R is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 10 alkenyl group, a linear or branched C 2 to C 10 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, an electron withdrawing group, and a C 6 to C 10 aryl group; R 1 is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 6 alkenyl group, a linear or branched C 3 to C 6 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, a C 6 to C 10 aryl group, a linear or branched C 1 to C 6 fluorinated alkyl group, an electron withdrawing group, and a halide selected from the group consisting of Cl, Br, and I; and n=0, 1, and 2.
  7. 7 . The method according to claim 6 , wherein the second silicon precursor primary amino-containing silicon compound is one or both of Si(HNEt) 4 , and Si(HNPr-n) 4
  8. 8 . The method according to claim 1 , wherein the second silicon precursor, comprising at least two primary amino moieties, is selected from the group consisting of compounds according to Formula III below: wherein R is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 10 alkenyl group, a linear or branched C 2 to C 10 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, an electron withdrawing group, and a C 6 to C 10 aryl group; R 1 is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 6 alkenyl group, a linear or branched C 2 to C 6 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, a C 6 to C 10 aryl group, a linear or branched C 1 to C 6 fluorinated alkyl group, an electron withdrawing group, and a halide selected from the group consisting of Cl, Br, and I; and n=0, 1, and 2.
  9. 9 . The method according to claim 8 wherein the silicon precursor, comprising at least two primary amino moieties is selected from the group consisting of Si 2 (HNEt) 6 , Me(EtNH) 2 SiSi(HNEt) 2 Me, Me 2 (EtNH)SiSi(HNEt)Me 2 , Si 2 (HNMe) 6 , Me(MeNH) 2 SiSi(HNMe) 2 Me, and Me 2 (MeNHe)SiSi(HNMe)Me 2 .
  10. 10 . A method for deposition of silicon and nitrogen containing dielectric film via an atomic layer deposition (ALD) process, comprising: a) providing at least one substrate into a reactor at a temperature ranging from about 25° C. to about 600° C. and optionally maintaining the reactor at a pressure of about 100 torr or less; b) introducing at least a first silicon precursor comprising at least two primary amino moieties to form a film comprising a silicon containing layer; c) purging any unreacted precursor from the reactor using inert gas; d) introducing into the reactor at least a second silicon precursor comprising at least two halogen atoms to react with the silicon containing layer to form a film comprising silicon and nitrogen; e) purging the reactor using inert gas; f) introducing a plasma source into the reactor to react with the film comprising silicon and nitrogen; g) purging any reaction by-products from the reactor using inert gas, and h) repeating steps b to g to bring the film comprising silicon and nitrogen to a desired thickness.
  11. 11 . The method according to claim 10 wherein the second silicon precursor comprising at least two halogen atoms is at least one selected from the group consisting of: i) halogenated silanes, ii) halogenated siloxanes, iii) halogenated silazanes, and iv) halogenated carbosilanes.
  12. 12 . The method according to claim 10 wherein the second silicon precursor comprising at least two halogen atoms is selected from the group consisting of trichlorosilane, tetrachlorosilane, hexachlorodisilane, pentachlorodisilane, tetrachlorodisilane, octachlorotrisilane, and dichlorosilane.
  13. 13 . The method according to claim 10 wherein the second silicon precursor comprising at least two halogen atoms is a halogenated siloxane selected from the group consisting of hexachlorodisiloxane, pentachlorodisiloxane, tetrachlorodisiloxane, and octaclorotrisiloxane.
  14. 14 . The method according to claim 10 wherein the second silicon precursor comprising at least two halogen atoms is a halogenated silazane selected from the groups represented by the following Formula I: wherein R 1 is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 10 alkenyl group, a linear or branched C 2 to C 10 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, an electron withdrawing group, and a C 6 to C 10 aryl group; R 2 is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 6 alkenyl group, a linear or branched C 3 to C 6 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, a C 6 to C 10 aryl group, a linear or branched C 1 to C 6 fluorinated alkyl group, an electron withdrawing group, and a halide selected from the group consisting of Cl, Br, and I; and X is a halide selected from the group consisting of Cl, Br, and I.
  15. 15 . The method according to claim 10 , wherein the primary amino-containing silicon compound is selected from the group consisting of compounds represented by the following Formula II below: wherein R is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 10 alkenyl group, a linear or branched C 2 to C 10 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, an electron withdrawing group, and a C 6 to C 10 aryl group; R 1 is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 6 alkenyl group, a linear or branched C 3 to C 6 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, a C 6 to C 10 aryl group, a linear or branched C 1 to C 6 fluorinated alkyl group, an electron withdrawing group, and a halide selected from the group consisting of Cl, Br, and I; and n=0, 1, and 2.
  16. 16 . The method according to claim 15 , wherein the primary amino-containing silicon compound is one or both of Si(HNEt) 4 , and Si(HNPr-n) 4
  17. 17 . The method according to claim 10 , wherein the first silicon precursor, comprising at least two primary amino moieties, is selected from the group consisting of compounds according to Formula III below: wherein R is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 10 alkenyl group, a linear or branched C 2 to C 10 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, an electron withdrawing group, and a C 6 to C 10 aryl group; R 1 is selected from the group consisting of hydrogen, a linear or branched C 1 to C 10 alkyl group, a linear or branched C 2 to C 6 alkenyl group, a linear or branched C 2 to C 6 alkynyl group, a C 3 to C 10 cyclic alkyl group, a C 2 to C 6 dialkylamino group, a C 6 to C 10 aryl group, a linear or branched C 1 to C 6 fluorinated alkyl group, an electron withdrawing group, and a halide selected from the group consisting of Cl, Br, and I; and n=0, 1, and 2.
  18. 18 . The method according to claim 17 wherein the first silicon precursor, comprising at least two primary amino moieties, is selected from the group consisting of Si 2 (HNEt) 6 , Me(EtNH) 2 SiSi(HNEt) 2 Me, Me 2 (EtNH)SiSi(HNEt)Me 2 , Si 2 (HNMe) 6 , Me(MeNH) 2 SiSi(HNMe) 2 Me, and Me 2 (MeNHe)SiSi(HNMe)Me 2 .

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. provisional patent application Ser. No. 63/379,433, filed Oct. 13, 2022. FIELD OF THE INVENTION The present invention is directed to compositions and methods for the fabrication of an electronic device. More specifically, the invention is directed to compounds, compositions and methods for the deposition of a high quality dense silicon-containing film such as, without limitation, a stoichiometric silicon nitride, a carbon-doped silicon nitride film, and a carbon-doped silicon oxynitride film. BACKGROUND OF THE INVENTION Silicon nitride films are used in semiconductors for a variety of applications. For example, a silicon nitride film is commonly used as a final passivation and mechanical protective layer for integrated circuits, a mask 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 in 3D NAND flash memory chips, or as a CMP stop layer in a shallow trench isolation application. In one particular application, the O—N—O stack in a 3D NAND flash requires silicon nitride with low stress and a high wet etch rate in phosphoric acid. Olsen, “Analysis of LPCVD Process Conditions for the Deposition of Low Stress Silicon Nitride”, 5 Materials Science in Semiconductor Process 51 (2002) describes a wide range of process conditions that are used to optimize the deposition of low stress silicon nitride films by low-pressure chemical vapor deposition. The results show that an increase in the index of refraction beyond 2.3 by means of increasing the gas flow did not reduce the residual stress appreciably but had a significant detrimental effect on the 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) describes a low-temperature process with good step coverage of silicon nitride (SiN) formed by low-pressure chemical vapor deposition (LPCVD) using hexachlorodisilane (HCD). JP2000100812 describes a method for depositing a film using SiCl4 and NH3 as source gases. The substrate surface may be nitrided using NH3 prior to deposition. An extremely thin film having an improved insulator property is formed. The silicon nitride film is useful as a capacitor insulator film of a semiconductor integrated circuit. U.S. Pat. No. 6,355,582 describes a method for forming a silicon nitride film wherein the substrate to be subjected to the film formation is heated, and silicon tetrachloride and ammonia gases are supplied to the substrate heated to a predetermined temperature. U.S. Pat. No. 10,049,882 describes an atomic layer deposition (ALD) method for fabricating a semiconductor device including the step of forming a dielectric layer on a structure having a height difference. The method includes forming a structure with 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 including silicon nitride on the structure with the height difference. Forming the first dielectric layer includes feeding a first gas including pentachlorodisilane (PCDS) or diisopropylamine pentachlorodisilane (DPDC) as a silicon precursor, and a second gas including nitrogen components into a chamber including the substrate such that the first dielectric layer is formed in situ on the structure having the height difference. PCT Pub. No. WO2018063907 discloses a class of chlorodisilazanes, silicon-heteroatom compounds synthesized therefrom, devices containing the silicon-heteroatom compounds, methods of making the chlorodisilazanes, the silicon-heteroatom compounds, and the devices; and uses of the chlorodisilazanes, silicon-heteroatom compounds, and devices. PCT Pub. No. WO2018057677 discloses a composition that includes trichlorodisilane as a silicon precursor for use in film forming. The composition includes the silicon precursor compound and at least one of an inert gas, molecular hydrogen, a carbon precursor, a nitrogen precursor, and an oxygen precursor. The publication also discloses a method of forming a silicon-containing. film on a substrate using the silicon precursor compound and the silicon-containing film formed thereby. U.S. Pat. No. 9,984,868 discloses cyclical methods of depositing a silicon nitride film on a substrate. In one embodiment such a method includes supplying a halogen silane as a silicon precursor into a reactor; supplying a purge gas to the reactor; and providing an ionized nitrogen precursor into the reactor to react with the substrate and form the silicon nitride film. US Pub. No. 2009/0155606 discloses cyclical methods of depositing a silicon nitride film on a substrate. In one embodiment a method includes supplying a chlorosilane to a reactor in which a substrate is processed; supplying a purge gas to