US2017073812A1PendingUtilityA1

Laser-assisted atomic layer deposition of 2D metal chalcogenide films

48
Assignee: ULTRATECH INCPriority: Sep 15, 2015Filed: Sep 6, 2016Published: Mar 16, 2017
Est. expirySep 15, 2035(~9.2 yrs left)· nominal 20-yr term from priority
Inventors:Ganesh Sundaram
H10P 14/24H10P 14/3436H10P 14/2905H10P 14/2921C23C 16/56C23C 16/483C23C 16/50C23C 16/45525C23C 16/52C23C 16/305C23C 16/4401C23C 16/45527C23C 16/45553C23C 16/45536H10P 72/72H10P 95/90H10D 64/01342H10P 14/6336H01J 37/32357H01J 37/32724H01J 37/32458C23C 16/45542C23C 16/405C23C 16/45544
48
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Claims

Abstract

Methods of forming 2D metal chalcogenide films using laser-assisted atomic layer deposition are disclosed. A direct-growth method includes: adhering a layer of metal-bearing molecules to the surface of a heated substrate; then reacting the layer of metal-bearing molecules with a chalcogenide-bearing radicalized precursor gas delivered using a plasma to form an amorphous 2D film of the metal chalcogenide; then laser annealing the amorphous 2D film to form a crystalline 2D film of the metal chalcogenide, which can have the form MX or MX 2 , where M is a metal and X is the chalcogenide. An indirect growth method that includes forming an MO 3 film is also disclosed.

Claims

exact text as granted — not AI-modified
What is claimed is: 
     
         1 . A method of forming a substantially two-dimensional (2D) film of a metal chalcogenide on a surface of a substrate, the method comprising:
 a) adhering a layer of metal-bearing molecules to the surface of a heated substrate using an atomic layer deposition (ALD) process;   b) reacting the layer of metal-bearing molecules with a chalcogenide-bearing radicalized precursor gas delivered using a plasma to form an amorphous and substantially 2D film of the metal chalcogenide; and   c) laser annealing the amorphous and substantially 2D film to form therefrom a substantially crystalline and substantially 2D film of the metal chalcogenide, wherein the metal chalcogenide can have the form MX or MX 2 , where M is a metal and X is a chalcogenide.   
     
     
         2 . The method according to  claim 1 , wherein the metal M is one of Mo and W and wherein the chalcogenide X is one of S, Se and Te. 
     
     
         3 . The method according to  claim 1 , wherein the plasma includes X-bearing radicals. 
     
     
         4 . The method according to  claim 3 , wherein the X-bearing radicals include H 2 S*. 
     
     
         5 . The method according to  claim 1 , further comprising processing the substrate to remove the substantially crystalline and substantially 2D film from the surface of the substrate. 
     
     
         6 . The method according to  claim 1 , wherein the substantially crystalline and substantially 2D film of the metal chalcogenide has dimensions of 25 mm×25 mm or greater. 
     
     
         7 . The method according to  claim 1 , wherein acts a) and b) are repeated multiple times before performing act c). 
     
     
         8 . A method of forming a substantially two-dimensional (2D) film of a metal chalcogenide on a surface of a substrate, the method comprising:
 a) adhering a layer of metal-bearing molecules to the surface of a heated substrate using an atomic layer deposition (ALD) process;   b) causing an oxidant precursor gas to react with the layer of metal-bearing molecules to form a layer of MO 3 ;   c) repeating acts a) and b) to form an MO 3  film having multiple layers of MO 3 ;   d) causing a chalcogenide-bearing radicalized precursor gas to react with the MO 3  film to form an amorphous and substantially 2D film of the metal chalcogenide; and   e) laser annealing the amorphous and substantially 2D film to form therefrom a substantially crystalline and substantially 2D film of the metal chalcogenide, wherein the metal chalcogenide can have the form MX or MX 2 , where M is a metal and X is a chalcogenide.   
     
     
         9 . The method according to  claim 8 , wherein the metal M is one of Mo and W and wherein the chalcogenide X is one of S, Se and Te. 
     
     
         10 . The method according to  claim 8 , wherein act d) includes providing the chalcogenide-bearing radicalized precursor gas using a plasma. 
     
     
         11 . The method according to  claim 10 , wherein the chalcogenide-bearing radicalized precursor gas comprises H 2 S*. 
     
     
         12 . The method according to  claim 8 , further comprising processing the substrate to remove the substantially crystalline and substantially 2D film from the surface of the substrate. 
     
     
         13 . The method according to  claim 8 , wherein the substantially crystalline and substantially 2D film of the metal chalcogenide has dimensions of 25 mm×25 mm or greater. 
     
     
         14 . A method of forming a substantially two-dimensional (2D) film of a metal chalcogenide on a surface of a substrate, the method comprising:
 a) adhering a layer of metal-bearing molecules to the surface of a heated substrate using an atomic layer deposition (ALD) process;   b) causing an oxidant precursor gas to react with the layer of metal-bearing molecules to form a layer of MO 3 ;   c) repeating acts a) and b) to form an MO 3  film having multiple layers of MO 3 ;   d) laser annealing the MO 3  film to form therefrom an MO 2  film;   e) causing a chalcogenide-bearing radicalized precursor gas to react with the MO 2  film to form an amorphous and substantially 2D film of the metal chalcogenide; and   f) laser annealing the amorphous and substantially 2D film to form therefrom a substantially crystalline and substantially 2D film of the metal chalcogenide, wherein the metal chalcogenide can have the form MX or MX 2 , where M is a metal and X is a chalcogenide.   
     
     
         15 . The method according to  claim 14 , wherein the metal M is one of Mo and W and wherein the chalcogenide X is one of S, Se and Te. 
     
     
         16 . The method according to  claim 14 , wherein act e) includes providing the chalcogenide-bearing radicalized precursor gas using a plasma. 
     
     
         17 . The method according to  claim 16 , wherein the chalcogenide-bearing radicalized precursor gas comprises H 2 S*. 
     
     
         18 . The method according to  claim 14 , further comprising processing the substrate to remove the substantially crystalline and substantially 2D film from the surface of the substrate. 
     
     
         19 . The method according to  claim 14 , wherein the substantially crystalline and substantially 2D film of the metal chalcogenide has dimensions of 25 mm×25 mm or greater. 
     
     
         20 . A method of forming a substantially two-dimensional (2D) film of a metal monochalcogenide (MX) or a metal dichalcogenide (MX 2 ) on a surface of a substrate using an atomic layer deposition process, the method comprising:
 a) providing the substrate in a chamber interior having a pressure in the range from 0.1 Torr to 0.5 Torr and heating the substrate to a temperature of between 150° C. and 500° C.;   b) introducing a metal-bearing precursor gas having a metal M to the chamber interior, wherein the metal-bearing precursor gas reacts with and remains on the substrate;   c) purging the chamber interior of excess metal-bearing precursor gas;   d) introducing a chalcogenide precursor gas into the chamber interior using a plasma, wherein the chalcogenide precursor gas reacts with the metal-bearing precursor gas that remains on the substrate, to produce an amorphous film of MX or MX 2 ;   e) purging the chamber interior; and   f) scanning a laser beam over the amorphous film to heat the amorphous film to a temperature of between 650° C. and 1200° C. to produce the substantially 2D film of either MX or MX 2  on the surface of the substrate, wherein the substantially 2D film is substantially crystalline.   
     
     
         21 . The method according to  claim 20 , wherein the metal M is one of Mo and W. 
     
     
         22 . The method according to  claim 20 , wherein the chalcogenide X is one of S, Se and Te. 
     
     
         23 . The method according to  claim 20 , wherein the plasma includes X-bearing radicals. 
     
     
         24 . The method according to  claim 23 , wherein the X-bearing radicals include H 2 S*. 
     
     
         25 . The method according to  claim 20 , further comprising processing the substrate to remove the substantially crystalline and substantially 2D film from the surface of the substrate. 
     
     
         26 . The method according to  claim 20 , wherein the laser beam has a nominal wavelength of 532 nm. 
     
     
         27 . The method according to  claim 20 , wherein in act d), the providing of the chalcogenide precursor gas is performed in a continuous manner or a pulsed manner. 
     
     
         28 . The method according to  claim 20 , wherein the 2D film has dimensions of 25 mm×25 mm or greater. 
     
     
         29 . The method according to  claim 20 , wherein in act f), the laser scanning is performed in a raster scan. 
     
     
         30 . The method according to  claim 20 , wherein the substrate is made of silicon or sapphire. 
     
     
         31 . The method according to  claim 20 , wherein acts b) through e) are repeated multiple times before performing act f). 
     
     
         32 . A method of forming a two-dimensional (2D) film of either a metal monochalcogenide (MX) or a metal dichalcogenide (MX 2 ) on a surface of a substrate using an atomic layer deposition process, the method comprising:
 a) providing the substrate in a chamber interior having a pressure in the range from 0.1 Torr to 0.5 Torr and heating the substrate to an initial temperature of between 150° C. and 500° C.;   b) providing a metal-bearing precursor gas having a metal M to the chamber interior, including purging any excess metal-bearing precursor gas, wherein the metal M is one of Mo and W;   c) providing an oxidant precursor gas into the chamber interior to form a layer of MO 3 , and purging any excess oxidant gas;   d) repeating acts b) and c) to form an MO 3  film having multiple layers of MO 3 ;   e) introducing a chalcogenide precursor gas into the chamber interior using a plasma, wherein the chalcogenide precursor gas reacts with the MO 3  film to produce a film of amorphous MX or MX 2 , and purging the chamber interior; and   f) scanning a laser beam over the amorphous film of MX or MX 2  to heat the amorphous film of MX or MX 2  to a temperature of between 650° C. and 1200° C. to produce a substantially crystalline film of either MX or MX 2 .   
     
     
         33 . The method according to  claim 32 , wherein the oxidant precursor gas is one of H 2 O, O 3 , O* and O 2 . 
     
     
         34 . The method according to  claim 32 , wherein the chalcogenide precursor gas includes sulfur. 
     
     
         35 . The method according to  claim 32 , wherein the metal-bearing precursor gas is selected from the group of precursor gases consisting of:
 Bis(tert-butylimido)bis(dimethylamido)Molybdenum, MoCl 5 , Molybdenum hexacarbonyl, bis(tert-butylimido)bis(dimethylamido)Tungsten, WH 2 (iPrCp) 2  and WF 6 .   
     
     
         36 . The method according to  claim 32 , wherein the laser beam has a nominal wavelength of 532 nm. 
     
     
         37 . The method according to  claim 32 , wherein in act e), the providing of the chalcogenide precursor gas is performed in either a continuous manner or a pulsed manner. 
     
     
         38 . The method according to  claim 32 , further comprising removing the substantially crystalline film of either MX or MX 2  from the surface of the substrate. 
     
     
         39 . The method according to  claim 32 , wherein the laser scanning is performed in a raster scan. 
     
     
         40 . The method according to  claim 32 , wherein the substrate is made of silicon or sapphire. 
     
     
         41 . The method according to  claim 32 , wherein the substrate is supported by a heated chuck, and in act a), the substrate is heated to the initial temperature by the heated chuck. 
     
     
         42 . The method according to  claim 32 , wherein the MO 3  film has between 3 and 8 layers of MO 3 . 
     
     
         43 . A method of forming a two-dimensional (2D) film of either a metal monochalcogenide (MX) or a metal dichalcogenide (MX 2 ) on a surface of a substrate using an atomic layer deposition process, the method comprising:
 a) providing the substrate in a chamber interior having a pressure in the range from 0.1 Torr to 0.5 Torr and heating the substrate to an initial temperature of between 150° C. and 500° C.;   b) providing a metal-bearing precursor gas having a metal M to the chamber interior, including purging any excess metal-bearing precursor gas, wherein the metal M is one of Mo and W;   c) providing an oxidant precursor gas into the chamber interior to form a layer of MO 3 , and purging any excess oxidant gas;   d) repeating acts b) and c) to form an MO 3  film having multiple layers of MO 3 ;   e) laser annealing the MO 3  film to form an MO 2  film;   f) introducing a chalcogenide precursor gas into the chamber interior using a plasma, wherein the chalcogenide precursor gas reacts with the MO 2  film to produce a film of amorphous MX or MX 2 , and purging the chamber interior; and   g) scanning a laser beam over the amorphous film of MX or MX 2  to heat the amorphous film of MX or MX 2  to a temperature of between 650° C. and 1200° C. to produce a substantially crystalline film of either MX or MX 2 .   
     
     
         44 . The method according to  claim 43 , wherein the oxidant precursor gas is one of H 2 O, O 3 , O* and O 2 . 
     
     
         45 . The method according to  claim 43 , wherein the chalcogenide precursor gas includes sulfur. 
     
     
         46 . The method according to  claim 43 , wherein the metal-bearing precursor gas is selected from the group of precursor gases consisting of:
 Bis(tert-butylimido)bis(dimethylamido)Molybdenum, MoCl 5 , Molybdenum hexacarbonyl, bis(tert-butylimido)bis(dimethylamido)Tungsten, WH 2 (iPrCp) 2  and WF 6 .   
     
     
         47 . The method according to  claim 43 , wherein the laser beam has a nominal wavelength of 532 nm. 
     
     
         48 . The method according to  claim 43 , wherein in act e), the providing of the chalcogenide precursor gas is performed in either a continuous manner or a pulsed manner. 
     
     
         49 . The method according to  claim 43 , further comprising removing the substantially crystalline film of either MX or MX 2  from the surface of the substrate. 
     
     
         50 . The method according to  claim 43 , wherein the laser scanning is performed in a raster scan. 
     
     
         51 . The method according to  claim 43 , wherein the substrate is made of silicon or sapphire. 
     
     
         52 . The method according to  claim 43 , wherein the substrate is supported by a heated chuck, and in act a), the substrate is heated to the initial temperature by the heated chuck. 
     
     
         53 . The method according to  claim 43 , wherein the MO 3  film has between 3 and 8 layers of MO 3 .

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