# US 10,483,407 B2 · Methods of forming si3nX, methods of forming insulator material between a control gate and charge-storage material of a programmable charge-storage transistor, and methods of forming an array of elevationally-extending strings of memory cells and a programmable charge-storage transistor manufactured in accordance with methods > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,483,407 B2 - Document ID: US10483407B2 - Status: Granted - Kind: B2 - Application number: 15/957,594 - Filed: 2018-04-19 - Published: 2019-10-24 - Granted: 2019-11-19 - Earliest claimed: 2018-04-19 - Assignees: Micron Technology, Inc. - Applicants: Micron Technology, Inc. - Inventors: Fei Wang; Kunal Shrotri; Jeffery B. Hull; Anish A. Khandekar; Duo Mao; Zhixin Xu; Ee Ee Eng; Jie Li; Dong Liang - Web page: https://patentgrep.com/patent/US10483407B2 ## CPC - H10B 43/27: the channels comprising vertical portions, e.g. U-shaped channels - H10D 30/691: {having more than two programming levels} - G11C 16/0466: {comprising cells with charge storage in an insulating layer, e.g. metal-nitride-oxide-silicon [MNOS], silicon-oxide-nitride-oxide-silicon [SONOS] (G11C16/0483, G11C16/0491 take precedence)} - G11C 16/0483: {comprising cells having several storage transistors connected in series} - G11C 16/08: Address circuits; Decoders; Word-line control circuits - H10B 43/35: with cell select transistors, e.g. NAND - H10D 30/0413: {of FETs having charge-trapping gate insulators, e.g. MNOS transistors} - H10D 64/037: {comprising charge-trapping insulators} - H10B: ELECTRONIC MEMORY DEVICES - H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES - G11C: STATIC STORES (semiconductor memory devices H10B) ## Abstract A method of forming Si3Nx, where “x” is less than 4 and at least 3, comprises decomposing a Si-comprising precursor molecule into at least two decomposition species that are different from one another, at least one of the at least two different decomposition species comprising Si. An outer substrate surface is contacted with the at least two decomposition species. At least one of the decomposition species that comprises Si attaches to the outer substrate surface to comprise an attached species. The attached species is contacted with a N-comprising precursor that reacts with the attached species to form a reaction product comprising Si3Nx, where “x” is less than 4 and at least 3. Other embodiments are disclosed, including constructions made in accordance with method embodiments of the invention and constructions independent of method of manufacture. ## Claims ### Claim 1 A method of forming Si3Nx, where “x” is less than 4 and at least 3, comprising: decomposing a Si-comprising precursor molecule into at least two decomposition species that are different from one another within a chamber having a chamber pressure of from 100 to 500 mTorr, at least one of the at least two different decomposition species comprising Si; after the decomposing the Si-precursor molecule, contacting an outer substrate surface with the at least two decomposition species, at least one of the decomposition species that comprises Si attaching to the outer substrate surface to comprise an attached species; and after the contacting the outer substrate surface, contacting the attached species with a N-comprising precursor that reacts with the attached species to form a reaction product comprising Si3Nx, where “x” is less than 4 and at least 3. ### Claim 2 (depends on 1) The method of claim 1 wherein the decomposing comprises thermal decomposition of the Si-comprising precursor molecule and at a temperature of at least 500° C. ### Claim 3 (depends on 2) The method of claim 2 wherein the decomposing consists essentially of thermal decomposition. ### Claim 4 (depends on 1) The method of claim 1 comprising attaching the at least one of the decomposition species that comprises Si to the attached species. ### Claim 5 (depends on 1) The method of claim 1 wherein the decomposing occurs directly above the outer substrate surface. ### Claim 6 (depends on 1) The method of claim 1 comprising repeating said sequence. ### Claim 7 (depends on 1) The method of claim 1 wherein the Si-comprising precursor molecule comprises a silane. ### Claim 8 (depends on 7) The method of claim 7 wherein the silane comprises a chlorosilane. ### Claim 9 (depends on 1) The method of claim 1 wherein the N-comprising precursor comprises ammonia. ### Claim 10 (depends on 1) The method of claim 1 comprising during at least one of said contactings also contacting the outer substrate surface with N2. ### Claim 11 (depends on 10) The method of claim 10 comprising contacting the outer substrate surface with N2 during both of said contactings. ### Claim 12 (depends on 1) The method of claim 1 wherein “x” in the reaction product is at least 3.5. ### Claim 13 (depends on 1) The method of claim 1 wherein “x” in the reaction product is no more than 3.90. ### Claim 14 (depends on 1) The method of claim 1 wherein “x” in the reaction product is 3.75. ### Claim 15 (depends on 1) The method of claim 1 wherein only one of all said different decomposition species comprises Si. ### Claim 16 (depends on 1) The method of claim 1 wherein the decomposing and the contacting of the outer substrate surface with the at least two decomposition species occur in the deposition chamber under identical the temperature and pressure conditions. ### Claim 17 A method of forming Si3Nx, where “x” is less than 4 and at least 3, comprising: decomposing silicon tetrachloride into at least two decomposition species that are different from one another, at least one of the at least two different decomposition species comprising Si; after the decomposing the Si-precursor molecule, contacting an outer substrate surface with the at least two decomposition species, at least one of the decomposition species that comprises Si attaching to the outer substrate surface to comprise an attached species; and after the contacting the outer substrate surface, contacting the attached species with a N-comprising precursor that reacts with the attached species to form a reaction product comprising Si3Nx, where “x” is less than 4 and at least 3. ### Claim 18 A method of forming Si3Nx, where “x” is less than 4 and at least 3, comprising: providing a single Si-comprising precursor into a chamber; decomposing the single Si-comprising precursor into at least two decomposition species that are different from one another, wherein each of at least two of said different decomposition species comprises Si; after the decomposing the Si-precursor molecule, contacting an outer substrate surface with the at least two decomposition species, at least one of the decomposition species that comprises Si attaching to the outer substrate surface to comprise an attached species; and after the contacting the outer substrate surface, contacting the attached species with a N-comprising precursor that reacts with the attached species to form a reaction product comprising Si3Nx, where “x” is less than 4 and at least 3. ### Claim 19 A method of forming Si3Nx, where “x” is less than 4 and at least 3, comprising: providing a single silicon- and chlorine-comprising precursor into a chamber, the single silicon- and chlorine-comprising precursor being selected from silicon tetrachloride, hexachlorodisilane and trichlorosilane; decomposing the silicon- and chlorine-comprising precursor molecule into at least two decomposition species that are different from one another, at least one of the at least two different decomposition species comprising Si, the decomposing comprising thermal decomposition of the silicon- and chlorine-comprising precursor molecule directly above an outer substrate surface at a temperature of at least 500° C.; contacting the outer substrate surface with the at least two decomposition species, at least one of the decomposition species that comprises Si attaching to the outer substrate surface to comprise an attached species and attaching the at least one of the decomposition species that comprises Si to the attached species; and after contacting the outer substrate surface with the at least two decomposition species, contacting the attached species with ammonia that reacts with the attached species to form a reaction product comprising Si3Nx, where “x” no more than 3.90 and at least 3. ### Claim 20 A method of forming insulator material that is ultimately between a control gate and charge-storage material of a programmable charge-storage transistor, comprising: decomposing a Si-comprising precursor molecule into at least two decomposition species that are different from one another, at least one of the at least two different decomposition species comprising Si; contacting an outer substrate surface with the at least two decomposition species, at least one of the decomposition species that comprises Si attaching to the outer substrate surface to comprise an attached species; contacting the attached species with a N-comprising precursor that reacts with the attached species to form a reaction product comprising Si3Nx, where “x” is less than 4 and at least 3; and providing the reaction product between a control gate and charge-storage material of a programmable charge-storage transistor. ### Claim 21 (depends on 20) The method of claim 20 comprising forming the programmable charge-storage transistor to be elevationally extending. ### Claim 22 (depends on 21) The method of claim 21 comprising forming the programmable charge-storage transistor to be vertical or within 10° of vertical. ### Claim 23 (depends on 20) The method of claim 20 comprising forming the programmable charge-storage transistor to be horizontal or within 10° of horizontal. ### Claim 24 (depends on 20) A programmable charge-storage transistor produced by the method of claim 20. ### Claim 25 A method of forming an array of elevationally-extending strings of memory cells, the method comprising: forming a stack comprising vertically-alternating insulative tiers and wordline tiers, the wordline tiers comprising control-gate material, channel openings extending into the alternating tiers; forming charge-blocking material comprising Si3Nx, where “x” is less than 4 and at least 3, in the channel openings elevationally along the control-gate material, the forming of the Si3Nx comprising: decomposing a Si-comprising precursor molecule into at least two decomposition species that are different from one another, at least one of the at least two different decomposition species comprising Si; contacting an outer substrate surface with the at least two decomposition species, at least one of the decomposition species that comprises Si attaching to the outer substrate surface to comprise an attached species; and after the contacting the outer substrate surface with the at least two decomposition species, contacting the attached species with a N-comprising precursor that reacts with the attached species to form a reaction product comprising Si3Nx, where “x” is less than 4 and at least 3; forming charge-storage material in the channel openings elevationally along the charge-blocking material comprising Si3Nx; and forming insulative charge-passage material then transistor channel material in the channel openings laterally over the charge-storage material; providing the control-gate material to have terminal ends corresponding to control-gate regions of individual memory cells, with the charge-blocking material being between the charge-storage material and individual of the control-gate regions. ### Claim 26 A method of forming an array of elevationally-extending strings of memory cells, the method comprising: forming a stack comprising vertically-alternating insulative tiers and wordline tiers, the wordline tiers comprising control-gate material having terminal ends corresponding to control-gate regions of individual memory cells, channel openings extending into the alternating tiers, the control-gate material being laterally-recessed from laterally-innermost surfaces of the channel openings; forming charge-blocking material comprising Si3Nx, where “x” is less than 4 and at least 3, in the channel openings elevationally along the laterally-recessed control-gate material, the forming of the Si3Nx comprising: decomposing a Si-comprising precursor molecule into at least two decomposition species that are different from one another, at least one of the at least two different decomposition species comprising Si; contacting an outer substrate surface with the at least two decomposition species, at least one of the decomposition species that comprises Si attaching to the outer substrate surface to comprise an attached species; and after the contacting an outer substrate surface with the at least two decomposition species, contacting the attached species with a N-comprising precursor that reacts with the attached species to form a reaction product comprising Si3Nx, where “x” is less than 4 and at least 3; forming charge-storage material in the channel openings elevationally along the charge-blocking material comprising Si3Nx; and forming insulative charge-passage material then transistor channel material in the channel openings laterally over the charge-storage material. ### Claim 27 A method of forming an array of elevationally-extending strings of memory cells, the method comprising: forming a stack comprising vertically-alternating tiers of different composition first and second materials, the first material being insulative; forming elevationally-extending channel openings into the alternating tiers; forming charge-blocking material comprising Si3Nx, where “x” is less than 4 and at least 3, in the channel openings elevationally along the alternating tiers, the forming of the Si3Nx comprising: decomposing a Si-comprising precursor molecule into at least two decomposition species that are different from one another, at least one of the at least two different decomposition species comprising Si; contacting an outer substrate surface with the at least two decomposition species, at least one of the decomposition species that comprises Si attaching to the outer substrate surface to comprise an attached species; and after the contacting an outer substrate surface with the at least two decomposition species, contacting the attached species with a N-comprising precursor that reacts with the attached species to form a reaction product comprising Si3Nx, where “x” is less than 4 and at least 3; forming charge-storage material in the channel openings elevationally along the alternating tiers and the charge-blocking material comprising Si3Nx; forming insulative charge-passage material in the channel openings elevationally along the charge-storage material; forming transistor channel material in the channel openings elevationally along the insulative charge-passage material; and after forming the transistor channel material, replacing at least some of the second material with control-gate material having terminal ends corresponding to control-gate regions of individual memory cells. ### Claim 28 A programmable charge-storage transistor comprising: channel material; insulative charge-passage material; charge-storage material; a control gate; and charge-blocking insulator material between the charge-storage material and the control gate, the charge-blocking insulator material comprising Si3Nx, where “x” is less than 4 and at least 3.