Composition for layered transition metal chalcogenide compound layer and method of forming layered transition metal chalcogenide compound layer
Provided are a composition for forming a layered transition metal chalcogenide compound layer and a method of forming a layered transition metal chalcogenide compound layer by using the composition. The composition includes at least one of a transition metal precursor represented by Formula 1 and a chalcogenide precursor represented by Formula 2. M a (R 1 ) 6-b-c (H) b (R 2 ) c [Formula 1] wherein, in Formula 1, M, R 1 , R 2 , a, b, and c are the same as defined in the detailed description, and M′ k X 2 [Formula 2] wherein, in Formula 2, M′ and X are the same as defined in the detailed description.
1. A composition for forming a layered transition metal chalcogenide compound layer, the composition comprising:
i) at least one selected from a transition metal precursor represented by Formula 1 and a transition metal precursor represented by Formula 1d,
M a (R 1 ) 6-b-c (H) b (R 2 ) c , [Formula 1]
wherein, in the above Formula 1,
M is a transition metal,
R 1 is one of a hydrogen atom; a C1-C10 alkyl group; a C2-C10 alkenyl group; a halogen; a C6-C10 aryl group; a C5-C10 cycloalkyl group; a C5-C10 cycloalkenyl group; (C═O)R, where, R is one of a hydrogen atom and a C1-C10 alkyl group; a C1-C10 alkoxy group; a C1-C10 amidinate group; a C1-C10 amidino group; a C1-C10 alkylamide group; a C1-C10 alkylimide group; —N(R)(R′), where, R and R′ are each independently one of a C1-C10 alkyl group and a hydrogen atom; R(C═O)CN, where, R is one of a hydrogen atom and a C1-C10 alkyl group; and a C1-C10 β-diketonate group,
R 2 is one of a hydrogen atom; a C1-C10 alkyl group; a C2-C10 alkenyl group; a carbonyl group (C═O); a halogen; a C6-C10 aryl group; a C5-C10 cycloalkyl group; a C5-C10 cycloalkenyl group; (C═O)R, where, R is one of a hydrogen atom and a C1-C10 alkyl group; a C1-C10 alkoxy group; a C1-C10 amidinate group; a C1-C10 amidino group; a C1-C10 alkylamide group; a C1-C10 alkylimide group; —N(R)(R′), where, R and R′ are each independently one of a C1-C10 alkyl group and a hydrogen atom; R(C═O)CN, where, R is one of a hydrogen atom and a C1-C10 alkyl group; and a C1-C10 β-diketonate group,
a is 1 or 2,
b is an integer of 0 to 3,
c is an integer of 0 to 3, and
at least one of R 1 and R 2 is not a hydrogen atom;
M(R 1 ) d [Formula 1d]
wherein, in Formula 1d, M is a transition metal,
R 1 is a hydrogen atom; a C1-C10 alkyl group; a C2-C10 alkenyl group; a carbonyl group (C═O); a halide; a C6-C10 aryl group; a C5-C10 cycloalkyl group; a C6-C10 cycloalkenyl group; (C—O)R, where, R is a hydrogen atom or a C1-C10 alkyl group; a C1-C10 alkoxy group; a C1-C10 amidinate group; a C1-C10 alkylamide group; a C1-C10 alkylimide group; —N(R)(R′), where, R and R′ are each independently a C1-C10 alkyl group or a hydrogen atom; R(C═O)CN, where, R is a hydrogen atom or a C1-C10 alkyl group; or a C1-C10 β-diketonate group,
d is 3 or 4, and
ii) a chalcogenide precursor represented by Formula 2,
M′ k X 2 , [Formula 2]
wherein, in the above Formula 2,
M′ is a chalcogenide element,
each X is independently one of a hydrogen atom; a C1-C10 alkyl group; a C2-C10 alkenyl group; a carbonyl group (C═O); a halogen; a C6-C10 aryl group; a C5-C10 cycloalkyl group; a C5-C10 cycloalkenyl group; (C═O)R, where, R is one of a hydrogen atom and a C1-C10 alkyl group; a C1-C10 alkoxy group; a C1-C10 amidinate group; a C1-C10 alkylamide group; a C1-C10 alkylimide group; —N(R)(R′), where, R and R′ are each independently one of a C1-C10 alkyl group and a hydrogen atom; R(C═O)CN, where, R is one of a hydrogen atom and a C1-C10 alkyl group; and a C1-C10 β-diketonate group,
k is 1 or 2,
and at least one X among X 2 is not a hydrogen atom.
2. The composition of claim 1 , wherein the transition metal precursor represented by Formula 1 and the chalcogenide precursor represented by Formula 2 have a partial vapor pressure of 0.1 Torr or higher at a temperature of about 350° C. or lower.
3. The composition of claim 1 , wherein the transition metal is one of tungsten (W), molybdenum (Mo), zirconium (Zr), tantalum (Ta), hafnium (Hf), niobium (Nb), platinum (Pt), cobalt (Co), nickel (Ni), chrome (Cr), vanadium (V), palladium (Pd), gold (Au), rhenium (Re), yttrium (Y), technetium (Tc), and titanium (Ti).
4. The composition of claim 1 , wherein the transition metal precursor is represented by one of Formulae 1a to 1c:
M(R 3 ) 6 [Formula 1a]
M(R 4 ) 3 , and [Formula 1b]
M(R 4 ) 4 , [Formula 1c]
wherein, in the above Formulae 1a to 1c,
M is one of tungsten (W) and molybdenum (Mo),
each R 3 is independently one of a propylcyclopentadienyl group, a bicyclo[2.2.1]hepta-2,5-diene group, a cycloheptatriene group, and an acetonitrile group, and
each R 4 is independently one of a carbonyl group (CO), a propylcyclopentadienyl group, a bicyclo[2.2.1]hepta-2,5-diene group, a cycloheptatriene group, and an acetonitrile group.
5. The composition of claim 1 , wherein the chalcogenide precursor is represented by Formula 2a:
M′ k X 2 [Formula 2a]
wherein, in Formula 2a, M′ is one of sulfur (S) and tellurium (Te),
X is a C1-C10 alkyl group, and
k is 1 or 2.
6. The composition of claim 1 , wherein the transition metal precursor is at least one of (bicycle [2.2.1]hepta-2,5-diene)tetracarbonyl molybdenum(0), cyclopentadienylmolybdenum(II) tricarbonyl dimer, (propylcyclopentadienyl)molybdenum(I) tricarbonyl dimer, tricarbonyl(cycloheptatriene) molybdenum(0), tris(acetonitrile) tricarbonyl molybdenum(0), tungsten hexacarbonyl, bis(isopropylcyclopentadienyl)tungsten(IV) dihydride, cyclopentadienyltungsten(II) tricarbonyl hydride, bis(tert-butylimino)bis(dimethylamino)tungsten(VI), tetracarbonyl(1,3-cyclohexadiene)tungsten, and tetracarbonyl(1,5-cyclooctadiene)tungsten(0).
7. The composition of claim 1 , wherein the chalcogenide precursor is at least one of dimethyl sulfide, diethyl sulfide, di-tert-butyl sulfide, dimethyl disulfide, diethyl disulfide, di-tert-butyl disulfide, tert-butyl thiol, dimethyl selenide, diethyl diselenide, diisopropyl selenide, and di-tert-butyl selenide.
8. The composition of claim 1 , wherein
the transition metal precursor and the chalcogenide precursor are provided in a carrier gas, and
a mixing volume ratio of the transition metal precursor and the chalcogenide precursor is in a range of about 1:1 to about 1:1500.
9. A composition comprising:
one of a transition metal precursor represented by Formula 1 and a chalcogenide precursor represented by Formula 2 or Formula 3,
M a (R 1 ) 6-b-c (H) b (R 2 ) c [Formula 1]
M′ k X 2 [Formula 2]
M″ k X′ 2 [Formula 3]
wherein, in the above Formulas 1,2, and 3,
M is a transition metal,
M′is sulfur (S),
M″is a chalcogenide element that is different than sulfur (S),
R 1 is one of a hydrogen atom; a C1-C10 alkyl group; a C2-C10 alkenyl group; a halogen; a C6-C10 aryl group; a C5-C10 cycloalkyl group; a C5-C10 cycloalkenyl group; (C═O)R, where, R is one of a hydrogen atom and a C1-C10 alkyl group; a C1-C10 alkoxy group; a C1-C10 amidinate group; a C1-C10 amidino group; a C1-C10 alkylamide group; a C1-C10 alkylimide group; —N(R)(R′), where, R and R′ are each independently one of a C1-C10 alkyl group and a hydrogen atom; R(C═O)CN, where, R is one of a hydrogen atom and a C1-C10 alkyl group; and a C1-C10 β-diketonate group,
R 2 is one of a hydrogen atom; a C1-C10 alkyl group; a C2-C10 alkenyl group; a carbonyl group (C═O); a halogen; a C6-C10 aryl group; a C5-C10 cycloalkyl group; a C5-C10 cycloalkenyl group; (C═O)R, where, R is one of a hydrogen atom and a C1-C10 alkyl group; a C1-C10 alkoxy group; a C1-C10 amidinate group; a C1-C10 amidino group; a C1-C10 alkylamide group; a C1-C10 alkylimide group; —N(R)(R′), where, R and R′ are each independently one of a C1-C10 alkyl group and a hydrogen atom; R(C═O)CN, where, R is one of a hydrogen atom and a C1-C10 alkyl group; and a C1-C10 β-diketonate group,
X is one of a hydrogen atom; C2-C10 alkenyl group; a carbonyl group (C═O); a C6-C10 aryl group; a C5-C10 cycloalkenyl group; (C═O)R, where, R is one of a hydrogen atom and a C1-C10 alkyl group; a C1-C10 alkoxy group; a C1-C10 amidinate group; a C1-C10 amidino group; a C1-C10 alkylamide group; a C1-C10 alkylimide group; —N(R)(R′), where, R and R′are each independently one of a C1-C10 alkyl group and a hydrogen atom; R(C═O)CN, where, R is one of a hydrogen atom and a C1-C10 alkyl group; and a C1-C10 β-diketonate group, and
X′is one of a hydrogen atom; a C1-C10 alkyl group; a C2-C10 alkenyl group; a carbonyl group (C═O); a halogen; a C6-C10 aryl group; a C5-C10 cycloalkyl group; a C5-C10 cycloalkenyl group; (C═O)R, where, R is one of a hydrogen atom and a C1-C10 alkyl group; a C1-C10 alkoxy group; a C1-C10 alkylimide group; —N(R)(R′), where, R and R′are each independently one of a C1-C10 alkyl group and a hydrogen atom; R(C═O)CN, where, R is one of a hydrogen atom and a C1-C10 alkyl group; and a C1-C10 β-diketonate group,
a is 1 or 2,
b is an integer of 0 to 3,
c is an integer of 0 to 3,
k is 1 or 2,
at least one of R 1 and R 2 is not a hydrogen atom, and
at least one X among X 2 is not a hydrogen atom.
10. The composition of claim 9 , wherein
the one of the transition metal precursor and the chalcogenide precursor is the transition metal precursor.
11. The composition of claim 10 , wherein the transition metal is one of tungsten (W), molybdenum (Mo), zirconium (Zr), tantalum (Ta), hafnium (Hf), niobium (Nb), platinum (FL), cobalt (Co), nickel (Ni), chrome (Cr), vanadium (V), palladium (Pd), gold (Au), rhenium (Re), yttrium (Y), technetium (Tc), and titanium (Ti).
12. The composition of claim 10 , wherein the transition metal precursor is represented by one of Formulae 1a to 1c:
M(R 3 ) 6 [Formula 1a]
M(R 4 ) 3 ,and [Formula 1b]
M(R 4 ) 4 , wherein, in the above Formulae 1a to 1c, [Formula 1c]
M is one of tungsten (W) and molybdenum (Mo),
R 3 is one of a propylcyclopentadienyl group, a bicyclo[2.2.1]hepta-2,5-diene group, a cycloheptatriene group, and an acetonitrile group, and
R 4 is one of a carbonyl group (CO), a propylcyclopentadienyl group, a bicyclo[2.2.1]hepta-2,5-diene group, a cycloheptatriene group, and an acetonitrile group.
13. The composition of claim 9 , wherein
the one of the transition metal precursor and the chalcogenide precursor is the chalcogenide precursor.
14. The composition of claim 13 , wherein the chalcogenide precursor is represented by Formula 3a:
M″ k X′ 2 [Formula 3a]
wherein, in Formula 3a, M″ is tellurium (Te),
X′ is a C1-C10 alkyl group, and
k is 1 or 2.
15. The composition of claim 13 , wherein the chalcogenide precursor is at least one of tert-butyl thiol, dimethyl selenide, diethyl diselenide, diisopropyl selenide, and di-tert-butyl selenide.
16. A method of preparing a layered transition metal chalcogenide compound layer, the method comprising:
loading a substrate into a reactor;
independently providing the composition of claim 9 and an other of the transition metal precursor and the chalcogenide precursor in a gaseous state on the substrate loaded into the reactor; and
performing chemical vapor deposition (CVD) by contacting the transition metal precursor and the chalcogenide precursor with the substrate.
17. The method of claim 16 , wherein the performing chemical vapor deposition is performed at a reactor temperature in a range of about 550° C. to about 950° C.
18. The method of claim 16 , further comprising:
performing a heat-treatment on the substrate after performing the CVD.
19. The method of claim 16 , wherein the independently providing the composition and an other of the transition metal precursor and the chalcogenide precursor includes:
storing the transition metal precursor and the chalcogenide precursor in containers that are independent from each other; and
supplying the transition metal precursor and the chalcogenide precursor from the containers to the reactor through independent injection lines.
20. A layered transition metal chalcogenide compound layer obtained by the method of claim 16 .
21. The composition of claim 3 , wherein
the transition metal is molybdenum (Mo), and
the chalcogenide element is sulfur (S).