This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2019-235257, filed on Dec. 25, 2019; the entire contents of which are incorporated herein by reference.
Embodiments disclosed herein relate to a resistance variable device.
A resistance variable device having a switch layer and a resistance variable layer as a nonvolatile memory layer, is used for a storage device. In such a resistance variable device, it is demanded to lower a threshold voltage (Vth) at which the switch layer transits from an off-state where a resistance value is high to an on-state where the resistance value is low, without impairing thermal stability of the switch layer.
A resistance variable device of an embodiment includes: a first electrode; a second electrode; and a stack arranged between the first electrode and the second electrode and including a resistance variable layer and a chalcogen-containing layer, in which the chalcogen-containing layer contains a material having a composition represented by a general formula: C1xC2yAz, where C1 is at least one element selected from the group consisting of Sc, Y, Zr, and Hf, C2 is at least one element selected from the group consisting of C, Si, Ge, B, Al, Ga, and In, A is at least one element selected from the group consisting of S, Se, and Te, and x, y, and z are numbers representing atomic ratios satisfying 0<x<1, 0<y<1, 0<z<1, and x+y+z=1, and when an oxidation number of the element C1 is set to a, and an oxidation number of the element C2 is set to b, the atomic ratio x of the element C1 satisfies x≤(3−(3+b)×y−z)/(3+a).
Hereinafter, a resistance variable device of an embodiment will be described while referring to the drawings. In respective embodiments, substantially the same constituent portions are denoted by the same reference numerals, and explanation thereof is sometimes partially omitted. The drawings are schematic, and the relation of thickness and planer dimension, a thickness ratio of the respective parts, and so on may be different from actual ones.
For the resistance variable layer 5, a memory layer in a conventionally well-known resistance variable type memory is used. As the resistance variable type memory, a resistive random access memory (ReRAM), a phase change memory (PCM), a magnetoresistive random access memory (MRAM), and so on are known. A memory layer in each of these various resistance variable type memories is used as the resistance variable layer 5. The resistance variable layer 5 is not limited to have a single-layer structure, and it may also be a multilayer film required for making functions of respective memories to be exhibited. For each of the first and second electrodes 2, 3, a metal electrode made of, for example, Cu, a Cu alloy, Al, an Al alloy, or the like, is used. Various additional layers may also be arranged between the first electrode 2 and the stack 4, between the second electrode 3 and the stack 4, and between the resistance variable layer 5 and the chalcogen-containing layer 6.
The chalcogen-containing layer 6 that functions as a switch layer (switch element) is electrically connected to the resistance variable layer 5, and has a function of switching on/off of a current with respect to the resistance variable layer 5 (switch function/switch operation). The chalcogen-containing layer 6 has an electric property such that when a threshold voltage (Vth) or more is applied thereto, it rapidly transits from an off-state with relatively high resistance to an on-state of relatively low resistance. Specifically, when the voltage which is applied to the chalcogen-containing layer 6 is lower than the threshold voltage (Vth), the chalcogen-containing layer 6 functions as an insulator, and it interrupts a current that flows through the resistance variable layer 5, to thereby make the resistance variable layer 5 turn into an off-state. When the voltage applied to the chalcogen-containing layer 6 becomes equal to or more than the threshold voltage (Vth), the resistance value of the chalcogen-containing layer 6 is rapidly lowered and the chalcogen-containing layer 6 functions as an electric conductor, resulting in that the current starts to flow through the resistance variable layer 5 via the chalcogen-containing layer 6, which makes the resistance variable layer 5 turn into an on-state. The variation in the resistance value based on the applied voltage with respect to the chalcogen-containing layer 6, occurs rapidly in a reversible manner.
The chalcogen-containing layer 6 that functions as the switch layer is a compound containing at least one element C1 selected from the group consisting of scandium (Sc), yttrium (Y), zirconium (Zr), and hafnium (Hf), at least one element C2 selected from the group consisting of carbon (C), silicon (Si), germanium (Ge), boron (B), aluminum (Al), gallium (Ga), and indium (In), and at least one element A selected from the group consisting of sulfur (S), selenium (Se), and tellurium (Te) (also referred to as a first layer composing material, hereinafter). The chalcogen-containing layer 6 may also further contains nitrogen (N), in addition to the element C1, the element C2, and the element A (also referred to as a second layer composing material, hereinafter).
The first layer composing material of the chalcogen-containing layer 6 can have a composition represented by the following composition formula (1), for example.
a general formula:
C1xC2yAz (1),
where x, y, and z are numbers representing atomic ratios satisfying 0<x<1, 0<y<1, 0<z<1, and x+y+z=1.
The second layer composing material of the chalcogen-containing layer 6 can have a composition represented by the following composition formula (2), for example.
a general formula:
C1xC2yAzNw (2),
where x, y, z, and w are numbers representing atomic ratios satisfying 0<x<1, 0<y<1, 0<z<1, 0<w<1, and x+y+z+w=1.
Each of the first layer composing material and the second layer composing material of the chalcogen-containing layer 6 may also be a compound containing at least one element C11 selected from the group consisting of Sc and Y, at least one element C2 selected from the group consisting of C, Si, Ge, B, Al, Ga, and In, and at least one element A selected from the group consisting of S, Se, and Te. The above-described material may further contain at least one element C12 selected from the group consisting of Zr and Hf, and may also contain N. In these cases, the first layer composing material can have a composition represented by the following composition formula (3), and the second layer composing material can have a composition represented by the following composition formula (4).
a general formula:
C11x1C12x2C2yAz (3),
where x1, x2, y, and z are numbers representing atomic ratios satisfying 0<x1<1, 0≤x2<1, 0<y<1, 0<z<1, and x1+x2+y+z=1.
a general formula:
C11x1C12x2C2yAzNw (4),
where x2, y, z, and w are numbers representing atomic ratios satisfying 0<x1<1, 0≤x2<1, 0<y<1, 0<z<1, 0<w<1, and x1+x2+y+z+w=1.
The function as the switch layer described above, can be obtained by a material containing at least one element A selected from the group consisting of S, Se, and Te (chalcogen element). The material containing the element A composing the chalcogen-containing layer 6 preferably has an amorphous structure. In order to obtain the above-described switch characteristic, the chalcogen-containing layer 6 is preferably an amorphous semiconductor having a large number of localized states in a band gap.
The element A is an element to be an anion, and an element that contributes to not only stabilization of the amorphous structure but also formation of trap level, and based on these, the switch operation can be exhibited. Specifically, with the use of the chalcogen-containing layer 6, it is possible to obtain a function of transiting between a high-resistance state and a low-resistance state (switch function) based on the threshold voltage (Vth). The switch function is derived from an electric conduction mechanism via the localized states in the band gap ascribable to the amorphous structure. The element A is preferably contained by 10 atom % or more in the first layer composing material or the second layer composing material, in order to obtain the switch function.
In order to obtain the amorphous structure, the chalcogen-containing layer 6 may contain N. N is an element to be an anion, similarly to the element A. The chalcogen-containing layer 6 containing N improves the thermal stability (glass transition temperature), and further contributes to the formation of the amorphous structure. Further, it is possible to reduce a leakage current. However, when N is excessively contained, there is a concern that deterioration of film properties is caused by desorption of N as N2, or the chalcogen-containing layer 6 is turned into an insulator due to increase of the band gap. For this reason, the content of N is preferably set within the range of appropriate values. A concrete composition ratio (atomic ratio) will be described later.
Each of the first and second layer composing materials of the chalcogen-containing layer 6 contains, in addition to the element A to be an anion and N which is contained according to need, the element C1 and the element C2 as elements to be cations. The element C2 is an element that increases a mean coordination number (MCN) of the first and second layer composing materials, to thereby stabilize the amorphous state. GeTe, SiTe, BTe, GeSe, and so on are known as materials exhibiting the switch function, and thus the material containing the element C2 and the element A can be considered to similarly exhibit the switch function. In order to obtain the switch function based on the stabilization of the amorphous state, the element C2 is preferably contained, by 10 atom % or more, in the first layer composing material or the second layer composing material. However, when the content of the element C2 is excessively large, there is a possibility that the first and second layer composing materials are crystallized, resulting in that the switch function cannot be obtained in some cases.
Each of the first and second layer composing materials contains, in addition to the element C2 as described above, at least one element C1 selected from the group consisting of Sc, Y, Zr, and Hf.
Whether each of the above-described first and second layer composing materials has the property of transiting between the high-resistance state and the low-resistance state (switch characteristic) on the threshold voltage (Vth), can be judged from the band gaps (Eg) of tellurides, selenides, and sulfides of the elements C1 and the elements C2, for example. As illustrated in
As described above, with the use of the resistance variable device 1 that uses the chalcogen-containing layer 6 containing the element C1, as the switch layer, it is possible to improve the thermal stability. Besides, it is possible to reduce the threshold voltage (Vth) of the switch layer. The thermal stability and the threshold voltage (Vth) of the chalcogenide layer 6 will be further explained by
As illustrated in
Next, a composition ratio (atomic ratio) of the first and second layer composing materials will be described. As described above, the element C1 and the element C2 are elements to be cations, the oxidation number of Sc and Y is three (+3), the oxidation number of Hf and Zr is four (+4), the oxidation number of C, Si, and Ge is four (+4), and the oxidation number of B, Al, Ga, and In is three (+3). The element A and N are elements to be anions, the oxidation number of S, Se, and Te is two (−2), and the oxidation number of N is three (−3). In a material containing these elements, when a total oxidation number of cations exceeds a total oxidation number of anions, there is a concern that the cations remain as metallic states, which increases a leakage current of the chalcogen-containing layer 6 as the switch layer. Therefore, it is preferable to decide the composition ratio (atomic ratio) so that the total valence of the cations being the element C1 and the element C2, does not exceed the total valence of the anions being the element A and N.
When the oxidation number and the atomic ratio of the metal cation C1 are set to a and x, respectively, the oxidation number and the atomic ratio of the metal cation C2 are set to b and y, respectively, the atomic ratio of the anion A is set to z, and the atomic ratio of N is set to w, it is preferable that a condition represented by the following formula (5) is satisfied, in order to satisfy the atomic ratios of the cations and the anions described above.
a×x+b×y≤2×z+3×w (5)
When the aforementioned formula (5) is arranged, the following formula (6) is created. Therefore, the atomic ratio x of the element C1 in the first and second layer composing materials preferably satisfies the following formula (6).
x≤(3−(3+b)×y−z)/(3+a) (6)
As described above, the atomic ratio y of the element C2 is preferably set to 0.1 or more, and the atomic ratio z of the element A is preferably set to 0.1 or more. When these atomic ratios (y=0.1, z=0.1) are taken into consideration, a condition in which the leakage current of the chalcogen-containing layer 6 as the switch layer is likely to be increased, is represented by the following formula (7).
x>(2.6−0.1b)/(3+a)=xmax (7)
When Sc and Y of the oxidation number +3 are used as the elements C1, and the elements C2 are C, Si, and Ge of the oxidation number +4, the value of xmax in the aforementioned formula (7) becomes 0.367, and when the elements C2 are B, Al, Ga, and In of the oxidation number +3, xmax becomes 0.383. Therefore, when the element C1 includes at least one of Sc and Y, even if the element C2 is any element selected from C, Si, Ge, B, Al, Ga, and In, the atomic ratio x of the element C1 is preferably set to 0.01 or more and 0.38 or less, based on the larger value of xmax described above (0.383). The lower limit value of 0.01 is a value for effectively obtaining an improvement effect of the thermal stability and the like by doping the element C1 that includes at least one of Sc and Y.
When Hf and Zr of +4 are used as the elements C1, and the elements C2 are C, Si, and Ge of the oxidation number +4, the value of xmax in the aforementioned formula (7) becomes 0.314, and when the elements C2 are B, Al, Ga, and In of the oxidation number +3, xmax becomes 0.329. Therefore, when the element C1 includes at least one of Hf and Zr, even if the element C2 is any element selected from C, Si, Ge, B, Al, Ga, and In, the atomic ratio x of the element C1 is preferably set to 0.01 or more and 0.32 or less, based on the larger value of xmax described above (0.329). The lower limit value of 0.01 is a value for effectively obtaining the improvement effect of the thermal stability and the like by doping the element C1 that includes at least one of Hf and Zr.
In the case where the chalcogen-containing layer 6 as the switch layer contains N, when N is excessively contained, there is a concern that deterioration of film properties is caused by desorption of N as N), or the chalcogen-containing layer 6 is turned into an insulator since the band gap is increased, as described above. With respect to this point, there is a concern that when a total bonding number of nitrogen exceeds a value represented by [(bonding number of cation) (bonding number of chalcogen (element A))], bonding of N and N is formed by N atoms which cannot be bonded to cations, resulting in desorption of N2 molecules. Therefore, the atomic ratio w of N preferably satisfies a condition represented by the following formula (8).
3×w≤a×x+b×y−2×z (8)
When the aforementioned formula (8) is arranged, the following formula (9) is created. Therefore, the atomic ratio w of N in the second layer composing material preferably satisfies the following formula (9).
w≤(a−(a−b)×y(a+2)×z)/(3+a) (9)
When the atomic ratio of the element C2 and the atomic ratio of the element A described above (y=0.1, z=0.1) are taken into consideration, a condition in which the N2 molecules are likely to escape from the chalcogen-containing layer 6 as the switch layer, is represented by the following formula (10).
w>(0.8×a+0.1×b−0.2)/(3+a)=wmax (10)
When Sc and Y of the oxidation number +3 are used as the elements C1, and the elements C2 are C, Si, and Ge of the oxidation number +4, the value of wmax in the aforementioned formula (10) becomes 0.433, and when the elements C2 are B, Al, Ga, and In of of the oxidation number +3, wmax becomes 0.417. Therefore, when the element C1 includes at least one of Sc and Y, even if the element C2 is any element selected from C, Si, Ge, B, Al, Ga, and In, the atomic ratio w of N is preferably set to 0.01 or more and 0.43 or less, based on the larger value of wmax described above (0.433). The lower limit value of 0.01 is a value for effectively obtaining the improvement effect of the thermal stability and the like by doping N.
When Hf and Zr of the oxidation number +4 are used as the elements C1, and the elements C2 are C, Si, and Ge of the oxidation number +4, the value of wmax in the aforementioned formula (10) becomes 0.486, and when the elements C2 are B, Al, Ga, and In of the oxidation number +3, wmax becomes 0.471. Therefore, when the element C1 includes at least one of Hf and Zr, even if the element C2 is any element selected from C, Si, Ge, B, Al, Ga, and In, the atomic ratio w of N is preferably set to 0.01 or more and 0.48 or less, based on the larger value of wmax described above (0.486). The lower limit value of 0.01 is a value for effectively obtaining the improvement effect of the thermal stability and the like by doping N.
As described above, when the chalcogen-containing layer 6 as the switch layer is composed of the material having a composition represented by the composition formula (1), the atomic ratio x of the element C1 preferably satisfies x≤(3−(3+b)×y−z)/(3+a). Further, the atomic ratio x of the element C1 is preferably set to 0.01 or more and 0.38 or less, the atomic ratio y of the element C2 is preferably set to 0.1 or more, and the atomic ratio z of the element A is preferably set to 0.1 or more. Further, when the element C1 includes at least one of Sc and Y, the atomic ratio x of the element C1 is preferably set to 0.01 or more and 0.38 or less. When the element C1 includes at least one of Hf and Zr, the atomic ratio x of the element C1 is preferably set to 0.01 or more and 0.32 or less.
When the chalcogen-containing layer 6 as the switch layer is composed of the material represented by the composition formula (2), the atomic ratio x of the element C1 preferably satisfies x≤(3−(3+b)×y−z)/(3+a), and the atomic ratio w of N preferably satisfies w≤(a−(a−b)×y−(a+2)×z)/(3+a). Further, the atomic ratio x of the element C1 is preferably set to 0.01 or more and 0.38 or less, the atomic ratio y of the element C2 is preferably set to 0.1 or more, the atomic ratio z of the element A is preferably set to 0.1 or more, and the atomic ratio w of N is preferably set to 0.01 or more and 0.48 or less. Further, when the element C1 includes at least one of Sc and Y, the atomic ratio x of the element C1 is preferably set to 0.01 or more and 0.38 or less, and the atomic ratio w of nitrogen is preferably set to 0.01 or more and 0.43 or less. When the element C1 includes at least one of Hf and Zr, the atomic ratio x of the element C1 is preferably set to 0.01 or more and 0.32 or less, and the atomic ratio w of nitrogen is preferably set to 0.01 or more and 0.48 or less.
Note that while certain embodiments of the present invention have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. The novel embodiments described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions, changes, and so on may be made therein without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the inventions.
Number | Date | Country | Kind |
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2019-235257 | Dec 2019 | JP | national |