This application is based upon and claims the benefit of priority from Japanese Patent Application No. 2020-047243, filed on Mar. 18, 2020; the entire contents of which are incorporated herein by reference.
Embodiments disclosed herein generally relate to a switching device.
A resistance change device having a switching layer, a resistance change layer as a nonvolatile memory layer, and the like is used in a semiconductor memory device. In such a resistance change device, a switching device having a switching layer is used to switch current on/off to the resistance change layer or the like. There is a need for a switching layer and a switching device using the switching layer reducing cost and improving switching properties.
Hereinafter, switching devices according to embodiments are explained with reference to the drawings. In embodiments, substantially the same components are denoted by the same reference signs, and a description thereof may be sometimes omitted. The drawings are schematic, and the relation between thicknesses and plane dimensions, ratios of the thicknesses of respective parts, and the like may sometimes differ from actual ones.
When the voltage applied to the switching layer 4 is lower than the threshold value (Vth), the switching layer 4 functions as an insulator and interrupts current flowing through a functional layer, such as a resistance change layer added to the switching layer 4, bringing the functional layer into the off state. When the voltage applied to the switching layer 4 exceeds the threshold value (Vth), a resistance value of the switching layer 4 drops steeply, and the switching layer 4 functions as a conductor, allowing the current to flow through the switching layer 4 to the functional layer. The switching device 1 with the switching layer 4 is applied to on/off control of the current to the functional layer in various electronic devices, for example.
The switching device 1 illustrated in
A memory layer in a publicly-known resistance change memory can be used for the resistance change layer 5. A resistive random access memory (ReRAM), a phase change memory (PCM), a magnetoresistive random access memory (MRAM), and so on are known as the resistance change memories. The memory layers of these various resistance change memories are used as the resistance change layer 5. The resistance change layer 5 is not limited to a single-layer structure, but may also be a multilayer film necessary for each memory to function. The switching device 1 is used for switching of various electronic devices without being limited to the resistance change device 7.
In the resistance change device 7 illustrated in
In the switching device 1 of the first embodiment described above, the switching layer 4 contains at least hafnium nitride (HfN). The representation of HfN does not express a ratio of Hf and N, and expresses that Hf and N are contained. The representation of other compounds is similar, and AB or A-B expresses that A and B are contained, and ABC or A-B-C expresses that A, B and C are contained. For example, hafnium nitride with a composition represented by Hf3N4 has a band gap of approximately 1.84 eV. An example of a mechanism for switching properties is thought to be derived from an electrical conduction mechanism through localized states in the band gap due to an amorphous structure. HfN can have the amorphous structure based on conditions of film-formation and the like. The switching layer 4 containing hafnium nitride (HfN) thereby exhibits a property of transitioning between the high resistance state and the low resistance state (switching properties) based on the threshold value (Vth) of the voltage.
The switching layer 4 containing hafnium nitride (HfN) may further contain at least one selected from a group consisting of yttrium nitride (YN), zirconium nitride (ZrN), titanium nitride (TiN), and scandium nitride (ScN). The switching layer 4 may contain at least one element (hereinafter, referred to as element M) selected from the group consisting of yttrium (Y), zirconium (Zr), titanium (Ti), and scandium (Sc). By adding the nitride of the element M (MN) to hafnium nitride, various switching properties can be controlled. In other words, amorphization of the switching layer 4 containing HfN can be promoted by adding nitride of group 4 Zr or Ti, which is a same family of Hf, or nitride of group 3 Sc to HfN to multiply elements that form nitrides. The switching layer 4 made of such materials also exhibits the switching properties. The element composing the nitride may be the meat element.
Concrete constituent materials of the switching layer 4 made of a material containing HfN and at least one selected from the group consisting of YN, ZrN, TiN, and ScN (hereinafter, also referred to as Hf-containing composite nitride) include a mixture of HfN and MN such as HfYN, HfZrN, HfTiN, HfScN, HfZrTiN, HfZrScN, HfTiScN, HfZrTiScN, and are not particularly limited. The switching layer 4 may have a stack which a layer containing HfN and a layer containing MN are stacked, and examples include, for example, HfN/YN, HfN/ZrN, HfN/TiN, HfN/ScN, HfN/YN/TiN, HfN/ZrN/TiN, HfN/ZrN/ScN, HfN/TiN/ScN, HfN/ZrN/TiN/ScN, and the like, and are not particularly limited. The switching layer 4 may also be a stack of the Hf-containing composite nitrides, and examples include, for example, HfYN/YN, HfZrN/ZrN, HfZrNiTiN, HfZrN/ScN, HfN/ZrN/TiN, HfN/ZrN/ScN, HfZrN/TiZrN/ScN, HfN/ZrN/TiN/ScZrN, and so on, and are not particularly limited.
It is clear from the comparison between
The switching layer 4 made of HfN or the Hf-containing composite nitride described above may further contain at least one element (hereinafter, referred to as element SM) selected from the group consisting of boron (B), carbon (C), and phosphorus (P). These elements (B, C, and P) are all elements that promote amorphization. Stability or the like of the switching behavior by the switching layer 4 can be therefore increased. At least one element SM selected from B, C, and P may be added to either HfN or the Hf-containing composite nitride. Further, aluminum nitride (AlN), silicon nitride (SiN), and the like may be contained in some cases to adjust electrical conductivity and the like of HfN and the Hf-containing composite nitride.
In the above Hf-containing composite nitride, though a composition ratio of the metallic elements (Hf, Y, Zr, Ti, and Sc) is not particularly limited, a ratio of Hf to a total metallic element is preferably set to 1 atom % or more to stably obtain the switching properties based on HfN. A total ratio of the element M (Y, Zr, Ti, Sc) to the total metallic element is preferably 1 atom % or more and 50 atom % or less to promote amorphization and the like based on the metallic elements (M:Y, Zr, Ti, Sc) other than Hf. In the metallic elements in the Hf-containing composite nitride, the metallic element other than the element M is basically Hf. The metallic elements in the Hf-containing composite nitride preferably contain 1 atom % or more and 50 atom % or less of the element M and balancing Hf. Further, when HfN and the Hf-containing composite nitride contain the element SM (B, C, and P), a ratio of the element SM to the total constituent elements is preferably 50 atom % or less to maintain the properties and modes as nitride.
The switching layer 4 containing at least HfN as described above preferably has a microcrystal or amorphous structure to homogenize film properties and the like. Further, in obtaining the switching properties, the HfN layer and the HfMN layer making up the switching layer 4 preferably have the amorphous structure, as described above. In obtaining the amorphous structure, the HfN layer and the HfMN layer may contain at least one selected from the group consisting of B, C, and P to promote or stabilize the amorphization. A film thickness of the switching layer 4 is preferably 5 nm or more and 30 nm or less.
For forming the switching layer 4 made of HfN or HfMN, a sputtering method or a vapor-deposition method can be applied. The switching layer 4 made of HfN can be formed using, for example, an HfN target whose composition has been adjusted. Otherwise, an HfN film can be formed by exposing an Hf metal target to a nitrogen atmosphere or nitrogen plasma during or after film-formation. When the switching layer 4 made of HfMN is used, the film can be formed by sputtering or vapor-depositing a nitride (MN) target of at least one metallic element M selected from Y, Zr, Ti, and Sc with the HfN target. Otherwise, an HfMN film can be formed using a HfMN target whose composition has been adjusted. The HfMN film whose composition has been adjusted can also be obtained by alternately stacking the HfN film and the MN film.
Further, when the elements SM (B, C, and P) are added to HfN or HfMN, the HfN film or the HfMN film containing the elements SM can be obtained by using a target with a desired amount of the elements SM. The constituent materials of the switching layer 4 thus obtained include HfNB, HfYNB, HfZrNB, HfTiNB, HfScNB, HfYZrNB, HfZrTiNB, HfZrScNB, HfTiScNB, HfZrTiScNB, HfNC, HfZrNC, HfTiNC, HfScNC, HfZrTiNC, HfZrScNC, HfTiScNC, HfZrTiScNC, HfNP, HfZrNP, HfTiNP, HfScNP, HfZrTiNP, HfZrScNP, HfTiScNP, HfZrTiScNP, HfNBC, HfYNBC, HfZrNBC, HfTiNBC, HfScNBC, HfZrTiNBC, HfZrScNBC, HfTiScNBC, HfZrTiScNBC, HfNBP, HfYNBP, HfZrNBP, HfTiNBP, HfScNBP, HfZrTiNBP, HfZrScNBP, HfTiScNBP, HfZrTiScNBP, HfNCP, HfYNCP, HfZrNCP, HfTiNCP, HfScNCP, HfYTiNCP, HfZrTiNCP, HfZrScNCP, HfTiScNCP, HfYTiScNCP, HfZrTiScNCP, HfNBCP, HfZrNBCP, and HfTiNBCP, HfScNBCP, HfZrTiNBCP, HfZrScNBCP, HfTiScNBCP, or HfYZrTiScNBCP.
Constituent materials of the electrodes 2 and 3 in direct or indirect contact with the switching layer 4 containing at least HfN are not particularly limited, but include, for example, a TiN film, a TiN/Ti stacked film, a C/TiN/Ti stacked film, a W film, a C/W/TiN stacked film, and the like. In addition to the above, metal electrodes made of a W alloy, Cu, a Cu alloy, Al, an Al alloy, and the like used as electrodes in various semiconductor elements may also be applied to the electrodes 2 and 3.
In the switching device 1 of the first embodiment, the switching layer 4 is made of HfN, HfMN, or a material with the elements SM added to HfN or HfMN, and the switching layer 4 as stated above exhibits the switching properties which make a transition between the high resistance state and the low resistance state based on the threshold value (Vth) of the voltage, as mentioned above. Accordingly, it is possible to provide the switching device 1 having good properties and cost reduction without using selenium (Se) or tellurium (Te), which is the chalcogen element, as the main component.
A switching device in a second embodiment includes the first electrode 2, the second electrode 3, and the switching layer 4 disposed between the first electrode 2 and the second electrode 3 as same as the switching device 1 in the first embodiment illustrated in
The switching device 1 in the second embodiment is applied to on/off control of the current to functional layers in various electronic devices as same as the switching device 1 in the first embodiment. Concretely, the switching device 1 in the second embodiment is applied to the resistance change device 7 in which the stacked film 6 of the switching layer 4 and the resistance change layer 5 functioning as the nonvolatile memory layer is disposed between the first electrode 2 and the second electrode 3, as illustrated in
In the switching device 1 of the second embodiment, the switching layer 4 is made of a material containing bismuth (Bi) and at least one selected from the group consisting of silicon oxide (SiO), aluminum oxide (AlO), zirconium oxide (ZrO), and gallium oxide (GaO) (hereinafter, also referred to as Bi-based composite material). The oxide of at least one element selected from the group consisting of Si, Al, Zr, and Ga (hereinafter, also referred to as element A) (oxide is AO) is an insulator. According to the material in which semi-metallic Bi is added to the oxide (AO) (hereinafter, also referred to as Bi-AO material), it is possible to obtain semiconducting conductivity and a band gap as large as that of a compound containing the chalcogen element. A state density of Si29O58Bi13 calculated by a first-principles calculation is illustrated in
In the switching device 1 of the second embodiment, a Bi—Al—O layer, a Bi—Zr—O layer, and a Bi—Ga—O layer can be used instead of the Bi—Si—O layer. The Bi—Al—O layer, the Bi—Zr—O layer, and the Bi—Ga—O layer also exhibit the same properties as the Bi—Si—O layer and thus can function as the switching layer 4.
Further, the metal oxide to which Bi is added is not limited to the aforementioned single oxide of the element A, but may also be a composite oxide of at least two or more metallic elements selected from Si, Al, Zr, and Ga. Examples of concrete materials include binary metal oxides such as SiAlO, SiZrO, SiGaO, AlZrO, AlGaO, and ZrGaO, ternary metal oxides such as SiAlZrO, SiAlGaO, SiZrGaO, and AlZrGaO, and quaternary metal oxides such as SiAlZrGaO. Even when Bi is added to multi-component metal oxides as stated above, the switching device 1 exhibiting the switching properties can be achieved.
In the switching layer 4 made of the Bi-AO material described above, a composition ratio of Bi to AO is not particularly limited.
In the switching device 1 of the second embodiment, at least one selected from the group consisting of bismuth oxide (BiO), bismuth nitride (BiN), bismuth boride (BiB), and bismuth sulfide (BiS) (hereinafter, also referred to as Bi compound) may be applied to the switching layer 4, instead of the above-mentioned Bi-AO material. For example, BiO with the composition represented by Bi2O3 has a band gap of approximately 2.6 eV. BiN has a band gap of approximately 1.2 eV. Further, an example of the mechanism for the switching properties may be derived from the electrical conduction mechanism through localized states in the band gap due to the amorphous structure. The above-mentioned Bi compounds can have the amorphous structure based on film formation conditions and the like. The switching layer 4 containing the Bi compound such as BiO, BiN, BiB, and BiS thereby exhibits the switching properties.
Further, at least one oxide (AO) selected from the group consisting of silicon oxide (SiO), aluminum oxide (AO), zirconium oxide (ZrO), and gallium oxide (GaO) may be added to the above-described Bi compound and applied to the constituent material of the switching layer 4.
The switching layer 4 made of the Bi-AO materials, the Bi compounds, or the Bi compound-AO materials described above may further contain at least one element (element SM) selected from the group consisting of boron (B), carbon (C), and phosphorus (P). These element SM (B, C, and P) are all elements promoting amorphization, as mentioned above. The stability or the like of the switching behavior by the switching layer 4 can be therefore increased. The elements SM (B, C, P) may be added to any of the Bi-AO materials, the Bi compounds, and the Bi compound-AO materials. Further, aluminum nitride (AlN), silicon nitride (SiN), and the like may be contained in some cases to adjust the electrical conductivity and the like of the Bi-AO material, the Bi compound, or the Bi compound-AO material.
The switching layer 4 made of the Bi-AO material, the Bi compound, or the Bi compound-AO material as described above preferably has the microcrystal structure or the amorphous structure to homogenize the film properties. Further, in obtaining the switching properties, the Bi-AO material layer, the Bi compound layer, or the Bi compound-AO material layer making up the switching layer 4, as described above, preferably has the amorphous structure. In obtaining the amorphous structure, the Bi-AO material layer, the Bi compound layer, or the Bi compound-AO material layer may contain at least one element SM selected from the group consisting of B, C, and P to promote or stabilize the amorphization. The film thickness of the switching layer 4 is preferably 5 nm or more and 30 nm or less.
For example, the sputtering method or the vapor-deposition method can be applied to form the switching layer 4 made of the Bi-AO material layer, the Bi-compound layer, or the Bi compound-AO material layer. The switching layer 4 made of the Bi compound layer can be formed using, for example, a BiO target, a BiN target, a BiB target, a BiS target, or a composite target of these, whose composition has been adjusted. The switching layer 4 made of BiO or BiN can be obtained by exposing to an oxygen or nitrogen atmosphere during or after film-formation of the Bi film. The switching layer 4 made of the Bi-AO material layer and the Bi compound-AO material layer can be formed using composite targets whose compositions have been adjusted, respectively. Besides, a Bi-AO material film or a Bi compound-AO material film whose composition has been adjusted can be also obtained by alternately stacking the Bi film or the Bi-compound and the AO film. Further, a BiO-AO film can also be obtained by exposing to the oxygen atmosphere during or after film-formation of the Bi-A film.
Constituent materials of the electrodes 2 and 3 in direct or indirect contact with the switching layer 4 made of the Bi-AO material layer, the Bi compound layer, or the Bi compound-AO material layer are not particularly limited, but include a TiN film, a TiN/Ti stacked film, a C/TiN/Ti stacked film, a W film, a C/W/TiN stacked film, and the like. In addition to these, metal electrodes made of Cu, a Cu alloy, Al, an Al alloy, or the like, which are used as electrodes in various semiconductor elements, may also be applied to the electrodes 2 and 3.
In the switching device 1 of the second embodiment, the switching layer 4 is constituted by the Bi-AO material layer, the Bi-compound layer, or the Bi compound-AO material layer, or the material where the element SM (B, C, P) are added to the above materials as described above, and the switching layer 4 exhibits the switching properties that make a transition between the high resistance state and the low resistance state based on the threshold value (Vth) of the voltage as mentioned above. Accordingly, it is possible to provide the switching device 1 improving switching properties and having good switching properties and cost reduction.
While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the novel embodiments described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the embodiments described herein may be made 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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2020-047243 | Mar 2020 | JP | national |