TRANSITION METAL DICHALCOGENIDE ALLOY AND METHOD OF MANUFACTURING THE SAME
20170267527 · 2017-09-21
Assignee
Inventors
Cpc classification
C23C16/45531
CHEMISTRY; METALLURGY
C01B19/002
CHEMISTRY; METALLURGY
H01L21/0262
ELECTRICITY
H01L21/02568
ELECTRICITY
International classification
C23C16/30
CHEMISTRY; METALLURGY
Abstract
Disclosed are a transition metal dichalcogenide alloy and a method of manufacturing the same. A method of manufacturing a transition metal dichalcogenide alloy according to an embodiment of the present disclosure includes a step of depositing transition metal dichalcogenide on a substrate using atomic layer deposition (ALD); and a step of forming a transition metal dichalcogenide alloy by thermally treating the transition metal dichalcogenide with a sulfur compound.
Claims
1. A method of manufacturing a transition metal dichalcogenide alloy, the method comprising: depositing transition metal dichalcogenide on a substrate using atomic layer deposition (ALD); and forming a transition metal dichalcogenide alloy by thermally treating the transition metal dichalcogenide with a sulfur compound, wherein the thermally treating of the transition metal dichalcogenide is performed at 900° C. to 1,000° C.
2. The method according to claim 1, wherein the transition metal dichalcogenide is composed of any one transition metal, which is selected from the group consisting of tungsten (W), molybdenum (Mo), and hafnium (Hf), and any one chalcogen, which is selected from selenium (Se) and tellurium (Te).
3. The method according to claim 1, wherein the sulfur compound is any one selected from the group consisting of hydrogen sulfide (H.sub.2S), dimethyl sulfide, diethyl sulfide, and dimethyl disulfide.
4. The method according to claim 1, wherein the atomic layer deposition is thermal atomic layer deposition (thermal ALD) or plasma enhanced atomic layer deposition (PEALD).
5. (canceled)
6. The method according to claim 1, wherein the thermally treating of the transition metal dichalcogenide is performed for 10 minutes to 120 minutes.
7. The method according to claim 3, wherein, in the forming of the transition metal dichalcogenide alloy, hydrogen (H.sub.2) gas is additionally supplied.
8. The method according to claim 7, wherein the sulfur compound is supplied at a rate of 10 sccm to 100 sccm, and the hydrogen (H.sub.2) gas is supplied at a rate of 10 sccm to 100 sccm.
9. A transition metal dichalcogenide alloy having a composition, represented by Formula 1 below manufactured according to the method of claim 1:
TS.sub.2xC.sub.2-2x, <Formula 1> wherein T is tungsten (W), molybdenum (Mo), or hafnium (Hf), S is sulfur (S), C is selenium (Se) or tellurium (Te), and x is 0.05 to 0.95.
10. A transition metal dichalcogenide alloy having a composition, represented by Formula 1 below manufactured according to the method of claim 2:
TS.sub.2xC.sub.2-2x, <Formula 1> wherein T is tungsten (W), molybdenum (Mo), or hafnium (Hf), S is sulfur (S), C is selenium (Se) or tellurium (Te), and x is 0.05 to 0.95.
11. A transition metal dichalcogenide alloy having a composition, represented by Formula 1 below manufactured according to the method of claim 3:
TS.sub.2xC.sub.2-2x, <Formula 1> wherein T is tungsten (W), molybdenum (Mo), or hafnium (Hf), S is sulfur (S), C is selenium (Se) or tellurium (Te), and x is 0.05 to 0.95.
12. A transition metal dichalcogenide alloy having a composition, represented by Formula 1 below manufactured according to the method of claim 4:
TS.sub.2xC.sub.2-2x, <Formula 1> wherein T is tungsten (W), molybdenum (Mo), or hafnium (Hf), S is sulfur (S), C is selenium (Se) or tellurium (Te), and
13. A transition metal dichalcogenide alloy having a composition, represented by Formula 1 below manufactured according to the method of claim 6:
TS.sub.2xC.sub.2-2x, <Formula 1> wherein T is tungsten (W), molybdenum (Mo), or hafnium (Hf), S is sulfur (S), C is selenium (Se) or tellurium (Te), and x is 0.05 to 0.95.
14. A transition metal dichalcogenide alloy having a composition, represented by Formula 1 below manufactured according to the method of claim 7:
TS.sub.2xC.sub.2-2x, <Formula 1> wherein T is tungsten (W), molybdenum (Mo), or hafnium (Hf), S is sulfur (S), C is selenium (Se) or tellurium (Te), and x is 0.05 to 0.95.
15. A transition metal dichalcogenide alloy having a composition, represented by Formula 1 below manufactured according to the method of claim 8:
TS.sub.2xC.sub.2-2x, <Formula 1> wherein T is tungsten (W), molybdenum (Mo), or hafnium (Hf), S is sulfur (S), C is selenium (Se) or tellurium (Te), and x is 0.05 to 0.95.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:
[0028]
[0029]
[0030]
[0031]
DETAILED DESCRIPTION OF THE INVENTION
[0032] Hereinafter, the embodiments of the present invention are described with reference to the accompanying drawings and the description thereof but are not limited thereto.
[0033] The terminology used in the present disclosure serves the purpose of describing particular embodiments only and is not intended to limit the disclosure. As used in the disclosure and the appended claims, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless context clearly indicates otherwise. It will be further understood that the terms “includes” and/or “including,” when used in this specification, specify the presence of stated features, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, elements, components, and/or groups thereof.
[0034] It should not be understood that arbitrary aspects or designs disclosed in “embodiments”, “examples”, “aspects”, etc. used in the specification are more satisfactory or advantageous than other aspects or designs.
[0035] In addition, the expression “or” means “inclusive or” rather than “exclusive or”. That is, unless otherwise mentioned or clearly inferred from context, the expression “x uses a or b” means any one of natural inclusive permutations.
[0036] Further, as used in the description of the invention and the appended claims, the singular forms “a”, “an” and “the” are intended to include the plural forms as well, unless context clearly indicates otherwise.
[0037] Furthermore, when an element such as a layer, a film, a region, and a constituent is referred to as being “on” another element, the element can be directly on another element or an intervening element can be present.
[0038] The present disclosure relates to a transition metal dichalcogenide alloy and a method of manufacturing the same. More particularly, a transition metal dichalcogenide alloy, which is formed by thermally treating transition metal dichalcogenide deposited on a substrate by atomic layer deposition (ALD), using a sulfur compound, and a method of manufacturing the same are disclosed.
[0039] According to an embodiment of the present disclosure, transition metal dichalcogenide may be deposited on a substrate uniformly over a large area by atomic layer deposition (ALD). In addition, due to the characteristics of atomic layer deposition, the thickness of the transition metal dichalcogenide may be easily controlled.
[0040] According to another embodiment of the present disclosure, a transition metal dichalcogenide alloy may be manufactured by thermally treating the transition metal dichalcogenide, which has been deposited uniformly over a large area, with a sulfur compound.
[0041] In addition, by controlling a condition of the thermal treatment with a sulfur compound, an ingredient ratio in the transition metal dichalcogenide alloy may be easily controlled. Accordingly, a band gap of the transition metal dichalcogenide alloy may be finely controlled.
[0042] Hereinafter, a transition metal dichalcogenide alloy according to an embodiment of the present disclosure and a method of manufacturing the same are described in detail with reference to the following examples and the accompanying drawings.
[0043]
[0044] As illustrated in
[0045] In S110 of the method of manufacturing the transition metal dichalcogenide alloy according to an embodiment of the present disclosure, the atomic layer deposition (ALD) may be thermal atomic layer deposition (thermal ALD) or plasma enhanced atomic layer deposition (Plasma Enhanced ALD, PEALD).
[0046] In particular, thermal ALD is characterized in that thermal energy is involved in reaction between a precursor and a reactant. PEALD is a method causing reaction between a precursor and a reactant, using plasma and PEALD may be performed at a relatively low temperature compared to thermal ALD.
[0047]
[0048] Referring to
[0049] The transition metal precursor gas supply step (S111) is performed by supplying transition metal precursor gas into an atomic layer deposition chamber. The transition metal precursor may be transported by inert gas.
[0050] For example, the transition metal precursor may be WCl.sub.6, MoCl.sub.5, Mo(CO).sub.6, or the like and the flow rate of the transition metal precursor gas may be 10 sccm to 100 sccm. In addition, an interior temperature of the atomic layer deposition chamber may be, without being limited to, 500° C. to 900° C.
[0051] In the inert gas purging step (S112), gas which has not been removed in the transition metal precursor gas supply step (S111) may be removed.
[0052] In the chalcogen precursor gas supply step (S113), the chalcogen precursor may be, for example, dimethyl selenide, diethyl selenide, diethyl diselenide, or the like.
[0053] By the inert gas purging step (S114), the chalcogen precursor and by-products which have not been removed in the chalcogen precursor gas supply step (S113) and remain in the atomic layer deposition chamber, may be removed.
[0054] According to an embodiment of the present disclosure, the transition metal dichalcogenide may be deposited on a substrate to a large area and uniform by atomic layer deposition such as thermal ALD or PEALD. In addition, the thickness of the transition metal dichalcogenide may be easily controlled due to the characteristics of atomic layer deposition.
[0055] The transition metal dichalcogenide deposited on a substrate by atomic layer deposition according to an embodiment of the present disclosure may be a transition metal dichalcogenide consisting of any one transition metal, selected from the group consisting of tungsten (W), molybdenum (Mo), and hafnium (Hf), and any one chalcogen, which is selected from selenium (Se) and tellurium (Te).
[0056] In particular, the transition metal dichalcogenide according to an embodiment of the present disclosure may be WSe.sub.2, WTe.sub.2, MoSe.sub.2, MoTe.sub.2, HfSe.sub.2, or HfTe.sub.2.
[0057] In S120 of the method of manufacturing the transition metal dichalcogenide alloy according to an embodiment of the present disclosure, a transition metal dichalcogenide alloy is formed by thermally treating the transition metal dichalcogenide with a sulfur compound.
[0058] In particular, in S120 according to an embodiment of the present disclosure, a transition metal dichalcogenide alloy, in which the transition metal dichalcogenide is sulfurated, is formed by thermally treating the transition metal dichalcogenide, which has been formed by S110, with a compound containing sulfur.
[0059] In S120 of the method of manufacturing the transition metal dichalcogenide alloy according to an embodiment of the present disclosure, the sulfur compound refers to gas including sulfur. For example, the sulfur compound may be hydrogen sulfide (H.sub.2S), dimethyl sulfide, diethyl sulfide, or dimethyl disulfide, particularly hydrogen sulfide (H.sub.2S).
[0060] The sulfur compound may be supplied at a rate of 10 sccm to 100 sccm, particularly 10 sccm to 50 sccm. For example, hydrogen sulfide (H.sub.2S) may be supplied at a rate of 10 sccm to 100 sccm.
[0061] In S120 of the method of manufacturing the transition metal dichalcogenide alloy according to an embodiment of the present disclosure, hydrogen (H.sub.2) gas, other than the sulfur compound, may be additionally supplied. In addition, inert gas may additionally supplied thereto. The inert gas may be, for example, argon (Ar) gas.
[0062] The hydrogen (H2) gas may be supplied at a rate of 10 sccm to 100 sccm, particularly 20 sccm to 50 sccm. The inert gas may be supplied to 5 sccm to 100 sccm, particularly 20 sccm to 50 sccm.
[0063] In S120 of the method of manufacturing the transition metal dichalcogenide alloy according to an embodiment of the present disclosure, the thermal treatment may be performed at 600° C. to 1,200° C., particularly 900° C. to 1,100° C.
[0064] In addition, the thermal treatment may be performed for 10 minutes to 120 minutes, particularly 30 minutes to 60 minutes.
[0065] For example, in S120 of the present disclosure, the transition metal dichalcogenide formed by S110 may be thermally treated at 1,100° C. for 30 minutes in a sulfur compound atmosphere at 20 sccm, at a hydrogen gas supply rate of 25 sccm, and in an inert gas atmosphere at 50 sccm.
[0066] A transition metal dichalcogenide alloy, an ingredient ratio of which has been easily controlled, may be manufactured by thermally treating the transition metal dichalcogenide, which has been formed on a substrate by atomic layer deposition, with a sulfur compound according to an embodiment of the present disclosure.
[0067] In particular, an ingredient ratio of the transition metal dichalcogenide alloy may be easily controlled by, when the transition metal dichalcogenide is thermally treated with a sulfur compound, controlling a process condition such as a temperature condition of the thermal treatment, a partial pressure condition of the sulfur compound, or a partial pressure condition of the hydrogen gas.
[0068] In addition, since an ingredient ratio of the transition metal dichalcogenide alloy may be easily controlled, a band gap of the transition metal dichalcogenide alloy may be controlled. The band gap may be finely controlled in a range of 1.62 eV to 1.97 eV.
[0069] In addition, since a band gap of the transition metal dichalcogenide alloy manufactured according to an embodiment of the present disclosure may be easily controlled, the transition metal dichalcogenide alloy may be applied to a channel layer of a transistor, an active layer of a solar cell, and the like. In particular, the transition metal dichalcogenide alloy according to an embodiment of the present disclosure may be usefully applied also to flexible devices.
[0070] Hereinafter, compositional characteristics of the transition metal dichalcogenide alloy according to an embodiment of the present disclosure are described with reference to
[0071]
[0072] In particular, Raman spectrum of the transition metal dichalcogenide alloy (WSe.sub.2xS.sub.2-2x) manufactured by thermally treating transition metal dichalcogenide (WSe.sub.2), which has been formed by atomic layer deposition according to an embodiment of the present disclosure, with a sulfur compound (H.sub.2S) varying temperature from 600° C. to 1,100° C. is illustrated in
[0073] Here, the thermal treatment using a sulfur compound (H.sub.2S) was performed for 30 minutes in a hydrogen sulfide (H.sub.2S) atmosphere at 10 sccm, in a hydrogen gas atmosphere at 5 sccm, and in at an argon gas supply rate of 50 sccm, other than the aforementioned temperature conditions. However, when a temperature was 600° C., the thermal treatment was performed for 120 minutes.
[0074] First, referring to
[0075] In particular, it can be confirmed that, by thermally treating WSe.sub.2 with H.sub.2S, a portion of WSe.sub.2 is changed into WS.sub.2 and thus a transition metal dichalcogenide alloy, such as WSe.sub.2xS.sub.2-2x, is formed. In addition, it can be confirmed that, with increasing temperature of thermal treatment of WSe.sub.2 with H.sub.2S, peaks of WSe.sub.2 are reduced and peaks of WS.sub.2 increase. Accordingly, it can be confirmed that a composition ratio of WS.sub.2 increases with increasing thermal treatment temperature.
[0076] In addition, referring to
[0077]
[0078] In particular, Raman spectrum of a transition metal dichalcogenide alloy (WSe.sub.2xS.sub.2-2x) manufactured by thermally treating the transition metal dichalcogenide (WSe.sub.2), which has been formed by atomic layer deposition according to an embodiment of the present disclosure, with a sulfur compound (H.sub.2S) varying temperature from 1,000° C. to 1,150° C. and a hydrogen gas partial pressure condition from 5 sccm to 25 sccm is illustrated in
[0079] In
[0080] In addition, thermal treatment with a sulfur compound (H.sub.2S) was performed at an H.sub.2S supply rate of 10 sccm and at an argon supply rate of 50 sccm, other than the aforementioned temperature conditions and hydrogen gas partial pressure conditions.
[0081] Referring to
[0082] On the other hand, when WSe.sub.2 was thermally treated at 1,100° C. or more in an H.sub.2S atmosphere, a change in Raman spectrum was observed with increasing partial pressure of hydrogen gas.
[0083] In particular, it can be conformed that, when WSe.sub.2 is thermally treated with H.sub.2S at 1,100° C. or more, peaks of WSe.sub.2 are reduced and peaks of WS.sub.2 increase, with increasing partial pressure of hydrogen gas.
[0084] That is, it can be confirmed that, when WSe.sub.2 is thermally treated with H.sub.2S at 1,100° C. or more, a conversion efficiency of WSe.sub.2 into WS.sub.2 increases with increasing partial pressure of hydrogen gas, and thus, a composition ratio of WS.sub.2 increases.
[0085]
[0086] In particular, the Raman spectrum of a transition metal dichalcogenide alloy (WSe.sub.2xS.sub.2-2x) manufactured by thermally treating the transition metal dichalcogenide (WSe.sub.2), which has been formed by atomic layer deposition according to an embodiment of the present disclosure, with a sulfur compound (H.sub.2S) varying a partial pressure condition of a sulfur compound from 10 sccm to 20 sccm is illustrated in
[0087] In
[0088] In addition, thermal treatment with a sulfur compound (H.sub.2S) was performed at 1,100° C. for 30 minutes at a hydrogen gas supply rate of 25 sccm and at an argon gas supply rate of 50 sccm, other than the aforementioned sulfur compound partial pressure conditions.
[0089] Referring to
[0090] In particular, it can be confirmed that, when WSe.sub.2 is thermally treated with H.sub.2S at 1,100° C., peaks of WSe.sub.2 are reduced and peaks of WS.sub.2 increase, with increasing H.sub.2S partial pressure from 10 sccm (A) to 20 sccm (B).
[0091] That is, it can be confirmed that, when WSe.sub.2 is thermally treated with H.sub.2S, conversion efficiency of WSe.sub.2 into WS.sub.2 increases with increasing partial pressure, and thus, a composition ratio of WS.sub.2 increases.
[0092] According to an embodiment of the present disclosure, when transition metal dichalcogenide, which has been formed on a substrate by atomic layer deposition, is thermally treated with a sulfur compound, an ingredient ratio of the transition metal dichalcogenide alloy may be easily controlled by controlling a process condition such as a temperature condition, a partial pressure condition of a sulfur compound, or a partial pressure condition of hydrogen gas.
[0093] In particular, a band gap of the transition metal dichalcogenide alloy may be controlled by controlling an ingredient ratio of the transition metal dichalcogenide alloy, and thus, a band gap of the transition metal dichalcogenide alloy may be finely controlled in a range of 1.62 eV to 1.97 eV.
[0094] Hereinafter, a composition of the transition metal dichalcogenide alloy manufactured by the method according to an embodiment of the present disclosure is described in detail.
[0095] The transition metal dichalcogenide alloy manufactured by the method according to an embodiment of the present disclosure has a composition represented by Formula 1 below:
TS.sub.2xC.sub.2-2x, <Formula 1>
wherein T is tungsten (W), molybdenum (Mo), or hafnium (Hf), S is sulfur (S), C is selenium (Se) or tellurium (Te), and x is 0.05 to 0.95.
[0096] In particular, Formula 1 of the transition metal dichalcogenide alloy according to an embodiment of the present disclosure may be WS.sub.2xSe.sub.2-2x, WS.sub.2xTe.sub.2-2x, MoS.sub.2xSe.sub.2-2x, MoS.sub.2xTe.sub.2-2x, HfS.sub.2xSe.sub.2-2x, or HfS .sub.2xTe.sub.2-2x.
[0097] In addition, in Formula 1, x may be greater than 0 and less than 1, for example, 0.05 to 0.95.
[0098] According to an embodiment of the present disclosure, a transition metal dichalcogenide alloy having a composition represented by Formula 1 may be formed to have various ingredient ratios depending upon change in the x value.
[0099] In particular, when the x value increases, an ingredient ratio of sulfur increases and, at the same time, an ingredient ratio of chalcogen decreases. On the other hand, as the x value decreases, an ingredient ratio of sulfur decreases and, at the same time, an ingredient ratio of chalcogen increases.
[0100] For example, when, in Formula 1, T is tungsten (W), S is sulfur (S), C is selenium (Se), and x is 0.48, a transition metal dichalcogenide alloy according to an aspect of the present disclosure may have a composition of WS.sub.0.96Se.sub.0.04.
[0101] According to an embodiment of the present disclosure, an ingredient ratio of a transition metal dichalcogenide alloy may be easily controlled by controlling a process condition, such as a temperature condition, a partial pressure condition of a sulfur compound, or a partial pressure condition of a hydrogen gas, when the transition metal dichalcogenide, which has been formed on a substrate by atomic layer deposition, is thermally treated with a sulfur compound. Accordingly, a band gap of the transition metal dichalcogenide alloy may be finely controlled in a range of 1.62 eV to 1.97 eV.
[0102] According to an embodiment of the present disclosure, transition metal dichalcogenide may be deposited on a substrate uniformly over a large area, using atomic layer deposition (ALD).
[0103] According to another embodiment of the present disclosure, when transition metal dichalcogenide, which has been formed on a substrate by atomic layer deposition, is thermally treated with a sulfur compound, a transition metal dichalcogenide alloy, an ingredient ratio of which is easily controlled, may be manufactured. Further, since an ingredient ratio of the transition metal dichalcogenide alloy may be controlled, a band gap of the transition metal dichalcogenide alloy may be finely controlled in a range of 1.62 eV to 1.97 eV.
[0104] Although the present invention has been described through limited examples and figures, the present invention is not intended to be limited to the examples. Those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention.
[0105] It should be understood, however, that there is no intent to limit the invention to the embodiments disclosed, rather, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention as defined by the claims.