CN110911558A - VOx gate tube with novel structure and material - Google Patents

VOx gate tube with novel structure and material Download PDF

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Publication number
CN110911558A
CN110911558A CN201911046660.2A CN201911046660A CN110911558A CN 110911558 A CN110911558 A CN 110911558A CN 201911046660 A CN201911046660 A CN 201911046660A CN 110911558 A CN110911558 A CN 110911558A
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layer
vox
gate tube
material layer
novel structure
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CN110911558B (en
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童浩
林琪
王伦
缪向水
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/801—Constructional details of multistable switching devices
    • H10N70/861—Thermal details
    • H10N70/8613—Heating or cooling means other than resistive heating electrodes, e.g. heater in parallel
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N70/00—Solid-state devices without a potential-jump barrier or surface barrier, and specially adapted for rectifying, amplifying, oscillating or switching
    • H10N70/20—Multistable switching devices, e.g. memristors

Abstract

The invention discloses a VOx gate tube with novel structure and material, which comprises a first metal electrode layer, a silver conductive medium layer, a chalcogenide material layer and a VOxThe material layer and a second metal electrode layer; through passing through VOxAnd a sulfur material layer and a silver conductive medium layer are added between the bottom electrode and the gate tube, and the sulfur material layer and the silver conductive medium layer form a switch layer of the gate tube device together, so that the switching performance of the gate tube can be improved. When voltage or current excitation is applied to the gate tube, silver diffuses into the chalcogenide material layer, a conductive wire can be formed in the chalcogenide material, so that current only flows through the conductive wire, and current in other areas is inhibited.

Description

VOx gate tube with novel structure and material
Technical Field
The invention belongs to the technical field of micro-nano electronics, and particularly relates to a VOx gate tube with a novel structure and material.
Background
The nonvolatile memory with two ends adopts gate tube devices with two ends to inhibit the leakage current problem widely existing in a large-scale array. The gating device is a switching device and has the working principle that: before the starting voltage/current is reached, the gate tube is in a closed state, the resistance is very high, and the leakage current can be effectively inhibited; after the starting voltage/current is reached, the gate tube is opened and is reduced to an extremely low resistance, so that enough operating current is provided for the corresponding storage unit. In a large-scale array, a gate tube is connected with a memory unit, when the memory unit is operated, voltage or current is applied to open the gate tube connected with a selected unit, and then read-write operation is carried out on the selected memory unit. The gate tube connected with the unselected memory unit is in a closed state at the same time, the resistance is very high, the leakage current can be inhibited, and the array power consumption is reduced. The two-end gating tube device can effectively solve the problem of leakage current, can be vertically stacked with the memory unit in the array integration process, does not need to occupy extra area, and improves the integration density; meanwhile, the structure integrating the memories at the two ends and the gate tube has the stacking capacity in the three-dimensional direction, and the storage density is further improved.
VOx is a material having a Metal-Insulator-Transition (MIT) property, which means that the conductivity of the material changes non-linearly due to various external stimuli such as electrical, thermal, magnetic and mechanical stimuli, and can be converted from a high-resistance insulating state to a low-resistance metallic state, and the low-resistance state can be maintained only when sufficient stimuli are continuously applied, or the material returns to the original high-resistance state. As the VOx material can generate resistance state change at about 70 ℃, for a common VOx gate tube, a device consists of a bottom electrode, a VOx functional layer and a top electrode from bottom to top, the working principle is that when excitation is applied to the device through the top electrode, the bottom electrode can be heated, and when the temperature rise of the bottom electrode reaches a certain value, the VOx material is converted into a low-resistance metal state from a high-resistance insulator, so that the gate tube is conducted.
The gate tube has the advantages of providing larger driving current and relatively better electrical stability, but has the biggest defects that the leakage current of the device is generally larger and the on-off ratio is smaller, the ratio of V element and O element has great influence on the performance of the VOx gate tube, the VOx gate tube is required to be annealed after the VOx material layer is prepared in order to obtain materials with proper component ratio, the annealing temperature is generally about 500 ℃, the preparation temperature of the device is strictly required to be lower than 400 ℃ in the current three-dimensional memory, otherwise, the later preparation process can damage the previously prepared fine structure, and the preparation process of the VOx gate tube is incompatible with the VOx gate tube.
Disclosure of Invention
Aiming at least one of the defects or improvement requirements in the prior art, the invention provides the VOx gate tube with a novel structure and material, wherein a chalcogenide material layer and a silver conductive medium layer are arranged between the VOx and the bottom electrode, and the VOx material layer, the chalcogenide material layer and the silver conductive medium layer jointly form a switch layer of a gate tube device, so that the switching performance of the gate tube can be improved. The chalcogenide material and the silver conductive medium layer have the main functions that when voltage or current excitation is applied to the gate tube, silver is diffused into the chalcogenide material layer, and a conductive wire can be formed in the chalcogenide material, so that current only flows through the conductive wire, and the current of other areas is inhibited. And because the temperature of the conductive wire can reach very high under an electric field, the annealing process of the VOx material layer can be completed, so that the conductive wire is suitable for a three-dimensional memory, does not need a high-temperature process of 500 ℃, and can be compatible with a CMOS rear-end preparation process.
In order to achieve the above object, according to an aspect of the present invention, there is provided a VOx gate tube with a novel structure and material, including sequentially arranged:
a semiconductor substrate;
a first metal electrode layer;
the electric heating insulating layer is provided with small holes, and the bottom of each small hole is provided with the first metal electrode layer;
the silver conductive medium layer is formed in the small hole wrapped by the electric heating insulating layer, and the bottom of the silver conductive medium layer is formed on the top of the first metal electrode layer;
the chalcogenide material layer is formed in the small hole wrapped by the electric heating insulating layer, and the bottom of the chalcogenide material layer is formed on the top of the silver conductive medium layer; the chalcogenide material layer is a material which can form a conductive wire under the excitation of current or voltage;
the VOx material layer is formed in the small hole wrapped by the electric heating insulating layer, and the bottom of the VOx material layer is formed at the top of the chalcogenide material layer; the silver conductive medium layer, the chalcogenide material layer and the VOx material layer jointly form a gate tube switch layer;
and the second metal electrode layer is formed at the top of the gate tube switch layer.
Preferably, the VOxVO in the material layerxThe value range of x of the material is 1.9-2.1.
Preferably, the VOxThe area size of the material layer is 100nm2～30μm2。
Preferably, the VOxVO in the material layerxThe insulation state resistance of the material is greater than the metal state resistance.
Preferably, the ratio of the insulation state resistance to the metal state resistance is greater than 100.
Preferably, the gate tube is conducted by applying voltage or current excitation to the gate tube to diffuse silver into the chalcogenide material, thereby forming conductive filaments in the chalcogenide material layer, allowing current to flow only through the conductive filaments and suppressing current in other regions, and locally heating the VOx material layer to convert part of the VOx material from a metal state to an insulating state.
Preferably, the chalcogenide material in the chalcogenide material layer is selected from any one or any combination of GeTe, SbTe, BiTe, SnTe, AsTe, GeSe, SbSe, BiSe, SnSe, AsSe, InSe, GeSbTe and AgInSbTe.
Preferably, the chalcogenide material in the chalcogenide material layer is any one or any combination of GeTe, SbTe, BiTe, SnTe, AsTe, GeSe, SbSe, BiSe, SnSe, AsSe, InSe, GeSbTe and AgInSbTe, and is doped with a mixture of at least one element of S, N, O, Cu, Si and Au.
Preferably, the material of the first metal electrode layer is selected from any one or any combination of Pt, Ti, W, Au, Ru, Al, TiW, TiN, TaN, IrO2, ITO, and IZO.
Preferably, the material of the second metal electrode layer is the same as or different from the material of the first metal electrode layer.
The above-described preferred features may be combined with each other as long as they do not conflict with each other.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
1. according to the VOx gate tube with the novel structure and the novel material, silver can be diffused into the chalcogenide material when voltage or current excitation is applied to the gate tube, so that the conductive wire is generated in the chalcogenide material layer, current only flows through the conductive wire, the VOx material layer can be locally heated due to the heat effect of the current, and therefore part of VOx material is converted from an insulating state to a metal state, the gate tube can be conducted, and the threshold voltage or threshold current of a gate tube device can be remarkably reduced.
2. The VOx gate tube with the novel structure and the novel material can improve the off-state resistance of the device and the on-off ratio of the device, so when the VOx gate tube is applied to a phase change memory array, the integration density of the memory can be improved, the leakage current of an un-gated unit can be better inhibited, and the performance of the memory is greatly improved.
3. The VOx gate tube with the novel structure and the novel material can complete the annealing process of the VOx material layer due to the fact that the temperature of the conductive wire can be very high under an electric field, so that the VOx gate tube is suitable for a three-dimensional memory, does not need a high-temperature process of 500 ℃, and can be compatible with a CMOS rear-end preparation process.
Drawings
Fig. 1 is a schematic cross-sectional view of a simplified structure of a VOx gate tube with a novel structure and material according to an embodiment of the present invention;
fig. 2 is a schematic diagram of conductive filaments generated in the chalcogenide material layer by silver diffusion after excitation is applied to the device, and the VOx material layer is locally heated to make part of the VOx material undergo the transformation from an insulating state to a metal state, so that the gate tube is conducted.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other. The present invention will be described in further detail with reference to specific embodiments.
As a preferred embodiment of the present invention, as shown in fig. 1, the present invention provides a gate tube device with a novel material and structure, which comprises, from bottom to top:
a semiconductor substrate 100;
a first metal electrode layer 101, the first metal electrode layer 101 is prepared on the semiconductor substrate 100, the thickness of the first metal electrode layer 101 is 100-500nm, the material of the first metal electrode layer 101 is selected as follows: any one or any combination of Pt, Ti, W, Au, Ru, Al, TiW, TiN, TaN, IrO2, ITO and IZO;
an electrothermal insulation layer 102, the electrothermal insulation layer 102 is prepared on the bottom electrode, the material of the electrothermal insulation layer 102 is: a mixture of any one or more than two of nitride, oxide or other electric insulating materials, wherein the thickness of the electric heating insulating layer 102 is 100-200nm, one or more small holes are formed in the middle of the electric heating insulating layer 102, and the bottom of each small hole is a first metal electrode layer;
the silver conductive medium layer 103 is formed in the small hole wrapped by the electric heating insulating layer 102, the bottom of the silver conductive medium layer 103 is formed on the top of the first metal electrode layer, and the thickness of the silver conductive medium layer is 2-10 nm;
a chalcogenide material layer 104, the chalcogenide material layer 104 is located in the small hole surrounded by the electrothermal insulation layer 102, the chalcogenide material layer 104 is formed on the silver conductive medium layer 103, the thickness of the chalcogenide material layer 104 is 10-50nm, the chalcogenide material layer 104 is a material capable of forming a conductive wire under current or voltage excitation, and the material can be selected from: GeTe, SbTe, BiTe, SnTe, AsTe, GeSe, SbSe, BiSe, SnSe, AsSe, InSe, GeSbTe and AgInSbTe, or a mixture formed by doping at least one element of S, N, O, Cu, Si and Au;
a VOx material layer 105, the VOxA material layer 105 is located in the small hole surrounded by the electrothermal insulation layer 102, VOxA material layer 105 formed on the chalcogenide material layer 104, the VOxThe thickness of the material layer 105 is 50-200 nm; the silver conductive medium layer 103, the chalcogenide material layer 104 and the VOx material layer 105 jointly form a gate tube switch layer; the VOxVO in the material layer 105xThe value range of x of the material is 1.9-2.1, and VOxThe material layer 105 has an area size of 100nm2～30μm2The VOxVO in the material layer 105xThe insulation state resistance of the material is greater than the metal state resistance, and the ratio of the insulation state resistance to the metal state resistance is greater than 100;
a second metal electrode layer 106, the second metal electrode layer 106 is prepared on the electric heating insulation layer 102, the bottom of the second metal electrode layer 106 is formed on the top of the gate switch layer, the thickness of the second metal electrode layer 106 is 100nm and 500 nm; the material of the second metal electrode layer 106 is the same as the material of the first metal electrode layer 101, and is selected from: any one or any combination of Pt, Ti, W, Au, Ru, Al, TiW, TiN, TaN, IrO2, ITO and IZO; the material of the second metal electrode layer 106 and the material of the first metal electrode layer 101 may also be different.
As shown in fig. 2, the chalcogenide material and the silver conductive medium layer mainly function to diffuse silver into the chalcogenide material when voltage or current is applied to the gate tube for excitation, so that the conductive filament 107 can be formed in the chalcogenide material layer 104, and thus current can only flow through the conductive filament 107 and suppress current in other regions, and since the conductive filament is very thin, the VOx material layer 105 can be locally heated, so that part of the VOx material undergoes a transition from a metal state to an insulating state (see a part of the region 108 in the VOx material layer in fig. 2 where the insulating state is changed into the metal state), and thus the gate tube is turned on, so that the threshold voltage or threshold current of the gate tube can be significantly reduced, and the off-state resistance of the gate tube can be increased, thereby significantly increasing the on-off ratio of the device and better suppressing the leakage current of the device.
The preparation method of the gate tube with the novel material and the structure is described by specific examples, and comprises the following steps:
step 1: preparing a layer of bottom electrode on a silicon substrate with a crystalline phase of <100> and a layer of silicon dioxide on the surface by magnetron sputtering, wherein the thickness of the bottom electrode is 100nm, and the bottom electrode is made of platinum;
step 2: preparing an electrothermal insulating layer on the bottom electrode, wherein the thickness of the electrothermal insulating layer is 100nm, and the material is SiO2；
And step 3: preparing small holes on the electric heating insulating layer by using a micro-nano processing technology, wherein the hole diameter is 50nm, and the depth is 100 nm;
and 4, step 4: filling a silver conductive medium layer with the thickness of 2nm into the small hole;
and 5: filling GeSbTe material into the small hole, wherein the thickness of the GeSbTe material is 10 nm;
step 6: filling VO into the small holexThe thickness of the material is 50nm, and the value of x is stabilized between 1.9 and 2.1 through annealing treatment.
And 7: and photoetching the surface of the electric heating insulating layer, preparing a layer of top electrode on the surface of the electric heating insulating layer, and stripping to obtain the top electrode corresponding to each small hole, wherein the top electrode is made of platinum and has the thickness of 100 nm.
In summary, the invention provides a VOx gate tube with a novel structure and material, wherein when voltage or current excitation is applied to the gate tube, silver is diffused into a chalcogenide material, so that a conductive filament is generated in a chalcogenide material layer, and current only flows through the conductive filament, so that the VOx material layer can be locally heated due to the thermal effect of the current, and partial VOx material is converted from an insulating state to a metal state, so that the gate tube is conducted, and the threshold voltage or threshold current of a gate tube device can be remarkably reduced. The VOx gate tube with the novel structure and the novel material can improve the off-state resistance of the device and the on-off ratio of the device, so when the VOx gate tube is applied to a phase change memory array, the integration density of the memory can be improved, the leakage current of an un-gated unit can be better inhibited, and the performance of the memory is greatly improved. The VOx gate tube with the novel structure and the novel material can complete the annealing process of the VOx material layer due to the fact that the temperature of the conductive wire can be very high under an electric field, so that the VOx gate tube is suitable for a three-dimensional memory, does not need a high-temperature process of 500 ℃, and can be compatible with a CMOS rear-end preparation process.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. The utility model provides a VOx gate tube with novel structure and material which characterized in that, including setting gradually:
a semiconductor substrate (100);
a first metal electrode layer (101);
an electric heating insulating layer (102) with small holes, wherein the bottom of the small hole is provided with the first metal electrode layer (101);
the silver conductive medium layer (103) is formed in the small hole wrapped by the electric heating insulating layer (102), and the bottom of the silver conductive medium layer (103) is formed on the top of the first metal electrode layer;
a chalcogenide material layer (104) formed in the small hole wrapped by the electrothermal insulation layer (102), wherein the bottom of the chalcogenide material layer (104) is formed on the top of the silver conductive medium layer (103); the chalcogenide material layer (104) is a material that can form a conductive filament (107) under current or voltage excitation;
a VOx material layer (105), wherein the VOx material layer (105) is formed in the small hole wrapped by the electrothermal insulation layer (102), and the bottom of the VOx material layer (105) is formed on the top of the chalcogenide material layer (104); the silver conductive medium layer (103), the sulfur material layer (104) and the VOx material layer (105) jointly form a gate tube switch layer;
a second metal electrode layer (106), wherein the second metal electrode layer (106) is formed on the top of the gate switch layer.
2. A VOx gate tube with novel structure and material as claimed in claim 1, characterized in that:
the VOxVO in the material layer (105)xThe value range of x of the material is 1.9-2.1.
3. A VOx gate tube with novel structure and material as claimed in claim 1, characterized in that:
the VOxThe material layer (105) has an area size of 100nm2～30μm2。
4. A VOx gate tube with novel structure and material as claimed in claim 1, characterized in that:
the VOxVO in the material layer (105)xThe insulation state resistance of the material is greater than the metal state resistance.
5. A VOx gate tube with novel structure and material as claimed in claim 4, characterized in that:
the ratio of the insulation state resistance to the metal state resistance is greater than 100.
6. A VOx gate tube with novel structure and material as claimed in claim 1, characterized in that:
and applying voltage or current excitation to the gate tube to diffuse silver into the chalcogenide material, thereby forming a conductive wire (107) in the chalcogenide material layer (104), enabling current to only flow through the conductive wire (107) and inhibiting the current in other areas, locally heating the VOx material layer (105), and enabling part of VOx material to generate the conversion from a metal state to an insulating state, thereby enabling the gate tube to be conducted.
7. A VOx gate tube with novel structure and material as claimed in claim 1, characterized in that:
the sulfur material in the sulfur material layer (104) is selected from any one or any combination of GeTe, SbTe, BiTe, SnTe, AsTe, GeSe, SbSe, BiSe, SnSe, AsSe, InSe, GeSbTe and AgInSbTe.
8. A VOx gate tube with novel structure and material as claimed in claim 1, characterized in that:
the sulfur material in the sulfur material layer (104) is any one or any combination of GeTe, SbTe, BiTe, SnTe, AsTe, GeSe, SbSe, BiSe, SnSe, AsSe, InSe, GeSbTe and AgInSbTe, and is doped with a mixture formed by at least one element of S, N, O, Cu, Si and Au.
9. A VOx gate tube with novel structure and material as claimed in claim 1, characterized in that:
the material of the first metal electrode layer (101) is selected from any one or any combination of Pt, Ti, W, Au, Ru, Al, TiW, TiN, TaN, IrO2, ITO and IZO.
10. A VOx gate tube with novel structure and material as claimed in claim 1, characterized in that:
the material of the second metal electrode layer (106) is the same as or different from the material of the first metal electrode layer (101).
CN201911046660.2A 2019-10-30 2019-10-30 VOx gate tube with novel structure and material Active CN110911558B (en)

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