CN114944452A - Threshold gating material, threshold gating device unit and preparation method thereof - Google Patents
Threshold gating material, threshold gating device unit and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 43
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- 238000007740 vapor deposition Methods 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 238000005229 chemical vapour deposition Methods 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000004544 sputter deposition Methods 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- 238000000231 atomic layer deposition Methods 0.000 claims description 7
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 7
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 7
- 229910004166 TaN Inorganic materials 0.000 claims description 6
- 229910008764 WNx Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 238000001451 molecular beam epitaxy Methods 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 2
- 230000015654 memory Effects 0.000 description 11
- 230000007704 transition Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 4
- 239000007769 metal material Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910005866 GeSe Inorganic materials 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000004770 chalcogenides Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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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 having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
- H10N70/8828—Tellurides, e.g. GeSbTe
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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 having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/011—Manufacture or treatment of multistable switching devices
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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 having no potential barriers, and specially adapted for rectifying, amplifying, oscillating or switching
- H10N70/801—Constructional details of multistable switching devices
- H10N70/881—Switching materials
- H10N70/882—Compounds of sulfur, selenium or tellurium, e.g. chalcogenides
- H10N70/8825—Selenides, e.g. GeSe
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Abstract
The invention relates to a threshold gating material, a threshold gating device unit and a preparation method thereof, wherein the chemical general formula of the threshold gating material is (In) x Te y ) a M 1‑a Wherein x/y is more than or equal to 0.1 and less than or equal to 1, x is more than 0 and less than or equal to 100, y is more than 0 and less than or equal to 100, x + y is 100, a is more than 0 and less than or equal to 0.2, and M is a threshold switching material comprising at least one sixth main group element. The threshold gating device unit has the advantages of low leakage current, low threshold voltage, large gating ratio, high starting speed and the like, and the service life and the reliability of the device are improved.
Description
Technical Field
The invention belongs to the technical field of microelectronics, and particularly relates to a threshold gating material, a threshold gating device unit and a preparation method thereof.
Background
With the popularization of smart phones and various information electronic devices, humans have entered a big data age with an explosion in information density. The storage of data is crucial to better handle this huge amount of data. The conventional memory has a low speed, which is not favorable for high-speed data transmission and processing. Therefore, a new storage technology with high speed, long service life and high density becomes a solution which is attracted by people. The new memories are represented by phase change memories, resistive random access memories and the like, and in order to realize a high-density memory architecture, the two memories often use three-dimensional stacking results, so that the basic constituent units of the two memories are memory cells and switch cells. Wherein the switch unit plays the role of suppressing leakage current and gating the memory unit in the chip. In recent years, threshold value switches (OTS) using chalcogenide thin film materials as a medium have been considered as the most practical gating devices. The basic principle of the OTS gate is as follows: the electrical signal is used for controlling the switch of the gating device, when the electrical signal is applied to the gating device unit and exceeds the threshold voltage, the material is converted from a high-resistance state to a low-resistance state, and the voltage device is maintained to be in an opening state continuously; when the electrical signal is removed, the material is changed from the low-resistance state to the high-resistance state, and the device is in a closed state. S.r.ovshinsky discovered for the first time a chalcogenide material with threshold transition characteristics in the end of the 60 th 20 th century, thus triggered the research of the threshold transition phenomenon by scientists, and based on this, discovered a series of chalcogenide compounds with threshold transition characteristics.
As for the gate device, in consideration of requirements such as limiting leakage current, driving the memory cell, compatibility with the memory cell and process scheme, and the like, performance requirements are low leakage current, high driving current, high on-off ratio, high speed, low threshold voltage, good thermal stability, long life, and high reliability. However, for the common gating Ge-Se material, the leakage current is large, the threshold voltage is high, the switching speed is slow, and the practical application is problematic. In view of this, how to develop new materials to reduce the threshold voltage and improve the starting speed, the switching ratio, the lifetime and the reliability so as to meet the practical requirements becomes a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a threshold gating material, a threshold gating device unit and a preparation method thereof, which are used for solving the problems that in the prior art, the leakage current, the gating speed, the gating ratio, the threshold voltage, the service life and the reliability of an OTS (optical transport system) gating device are all required to be further improved.
The invention provides a threshold gating material, wherein the chemical general formula of the threshold gating material is (In) x Te y ) a M 1-a Wherein x/y is more than or equal to 0.1 and less than or equal to 1, x is more than 0 and less than or equal to 100, y is more than 0 and less than or equal to 100, x + y is 100, a is more than 0 and less than or equal to 0.2, and M is a threshold switching material comprising at least one sixth main group element.
The chemical general formula of the threshold switch material is Ge b As c Se 100-b-c ，0＜b≤20，10≤c≤45。
The threshold gating device unit comprises a lower electrode layer, a threshold gating material layer as claimed in claim 1, an upper electrode layer and an extraction electrode arranged on the upper electrode layer from bottom to top in sequence.
The material of the lower electrode layer comprises at least one of C, W, Cu, Al, Ti, Ta, TiN, WNx, TaN, Pt, Au, Ag, Co and Ni.
The material of the upper electrode layer comprises at least one of W, Cu, Al, C, Ti, Ta, TiN, WNx, TaN, Pt, Au, Ag, Co and Ni.
The material of the extraction electrode comprises at least one of W, Cu, Al, Co, Pt, Au and Ag.
The invention provides a preparation method of a threshold gating device unit, which comprises the following steps:
(1) preparing a lower electrode layer;
(2) depositing a threshold gating material layer on the lower electrode layer;
(3) preparing an upper electrode layer on the threshold gating material layer;
(4) and preparing an extraction electrode on the upper electrode layer.
The material is prepared by adopting a sputtering method, an evaporation method, a chemical vapor deposition method, a plasma enhanced chemical vapor deposition method, a low-pressure chemical vapor deposition method, a metal compound vapor deposition method, a molecular beam epitaxy method, an atomic vapor deposition method or an atomic layer deposition method.
Advantageous effects
The threshold gating device cell of the present invention,under the action of external energy, the transient transition from a high resistance state to a low resistance state can be realized; when the external energy is removed, the low resistance state can be immediately converted into the high resistance state. And, will (In) x Te y ) a M 1-a When the threshold gating material is used as a medium of the threshold gating device unit, the threshold gating device unit has the advantages of low leakage current, low threshold voltage, large gating ratio, high starting speed and the like, and the service life and the reliability of the device are improved.
Drawings
FIGS. 1-4 are cross-sectional views of steps of a method of fabricating a threshold gating device cell in accordance with the present invention.
FIG. 5 is a graph of voltage-current (V-I) curves measured by a threshold gating device cell under voltage excitation according to the present invention.
FIG. 6 is a fatigue life test of a threshold-gated device cell of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
Fig. 1 to 4 are cross-sectional views of steps showing a method for fabricating a threshold gating device cell according to the present invention.
Step 1) is performed first: and preparing a lower electrode layer. Referring to fig. 1, the lower electrode layer may be formed by any one of a sputtering method, an evaporation method, a Chemical Vapor Deposition (CVD), a Plasma Enhanced Chemical Vapor Deposition (PECVD), a Low Pressure Chemical Vapor Deposition (LPCVD), a metal compound vapor deposition (MOCVD), a Molecular Beam Epitaxy (MBE), an Atomic Vapor Deposition (AVD), or an Atomic Layer Deposition (ALD), and in this embodiment, the lower electrode layer is preferably formed by a CVD method, and the material of the lower electrode layer may be at least one of W, Cu, Al, C, Ti, Ta, TiN, WNx, TaN, Pt, Au, Ag, Co, and Ni. In this embodiment, the material of the lower electrode layer is preferably W, and the electrode of the W lower electrode layer prepared by the CVD method has a diameter of 120nm and a height of 200 nm.
Then step 2) is performed: a layer of threshold gating material is prepared on the lower electrode. Referring to FIG. 2, a threshold gate material layer is formed on the lower electrode, the threshold gate material layer having a chemical formula of (In) x Te y ) a M 1-a Wherein x/y is more than or equal to 0.1 and less than or equal to 1, x is more than 0 and less than or equal to 100, y is more than 0 and less than or equal to 100, x + y is 100, a is more than 0 and less than or equal to 0.2, and M is a threshold switching material comprising at least one sixth main group element. Preferably, said (In) x Te y ) a M 1-a The threshold switching material has a chemical formula of (In) 40 Te 60 ) 0.1 (Ge 10 As 35 Se 55 ) 0.9 、(In 38 Te 62 ) 0.1 (Ge 15 As 35 Se 50 ) 0.9 、(In 37.5 Te 62.5 ) 0.1 (Ge 20 As 30 Se 50 ) 0.9 And the like, wherein the threshold value gating material layer may be prepared by any one of methods such as a sputtering method, an evaporation method, a chemical vapor deposition method, a plasma-enhanced chemical vapor deposition method, a low-pressure chemical vapor deposition method, a metal compound vapor deposition method, a molecular beam epitaxy method, an atomic vapor deposition method, or an atomic layer deposition method.
Then step 3) is performed: and forming a preparation upper electrode layer on the threshold gating material layer. Referring to fig. 3, as an example, the upper electrode layer may be formed on the threshold gate material layer by any one of a sputtering method, an evaporation method, a chemical vapor deposition method, a plasma enhanced chemical vapor deposition method, a low pressure chemical vapor deposition method, a metal compound vapor deposition method, a molecular beam epitaxy Atomic Vapor Deposition (AVD) method, or an atomic layer deposition method, and the material of the upper electrode layer may be at least one of W, Cu, Al, C, Ti, Ta, TiN, WNx, TaN, Pt, Au, Ag, Co, and Ni.
In the present embodiment, it is preferable that the threshold gate material isAn upper electrode layer is prepared on the material layer by adopting a magnetron sputtering method, the material of the upper electrode layer is preferably TiN, and the technological parameters are as follows: background air pressure of 1X 10 -5 Pa, the air pressure during sputtering is 0.2Pa, Ar/N 2 The gas flow ratio of (1): 1, the sputtering power is 100W, the substrate temperature is 25 ℃, and the sputtering time is 20-25 min. The electrode thickness of the resulting TiN upper electrode layer was about 20 nm.
Finally, step 4) is performed: referring to fig. 4, an extraction electrode is formed on the upper electrode layer, and the extraction electrode may be formed by any one of a sputtering method, an evaporation method, a chemical vapor deposition method, a plasma enhanced chemical vapor deposition method, a low pressure chemical vapor deposition method, a metal compound vapor deposition method, a molecular beam epitaxy method, an atomic vapor deposition method, or an atomic layer deposition method, as an example. Therefore, the upper electrode layer and the lower electrode layer can be integrated with other elements such as a storage unit, a driving circuit, a peripheral circuit and the like in the threshold gating device unit through the extraction electrode, so that the complete threshold gating device unit is prepared, and the adopted processing method is a conventional semiconductor process.
As an example, the material of the extraction electrode may include any one of the single metal materials W, Pt, Au, Ti, Al, Ag, Cu and Ni, or an alloy material composed of any two or more of the above single metal materials W, Pt, Au, Ti, Al, Ag, Cu and Ni, or a nitride including one of the above single metal materials W, Pt, Au, Ti, Al, Ag, Cu and Ni.
In this embodiment, preferably, the extraction electrode is prepared by a magnetron sputtering method, the material is Al, and the film thickness of the prepared extraction electrode is 200 nm.
Next, (In) is referred to In the present example 38 Te 62 ) 0.1 (Ge 15 As 35 Se 50 ) 0.9 The threshold switching device unit of the threshold switching material is tested for electrical performance, and a voltage-current (V-I) curve of the threshold switching device unit is shown in fig. 5 under the voltage excitation. As is well known to those skilled in the art, as the voltage increases, the current value continues to increase first,at a certain point, the current suddenly jumps and then continuously increases, and the point is the threshold point of the threshold switching device unit, and the voltage at the point is the threshold voltage.
Please refer to fig. 5 for base (In) 38 Te 62 ) 0.1 (Ge 15 As 35 Se 50 ) 0.9 Two dc operations of the threshold switching device cell of (a), it can be seen that for the (In) -based 38 Te 62 ) 0.1 (Ge 15 As 35 Se 50 ) 0.9 The threshold voltage of the threshold switch device unit is about 2.9V, compared with the threshold voltage of GeSe of 4.5V, the threshold voltage is greatly reduced, and meanwhile, the device has extremely low leakage current of 1.32 nA. The starting current and the switching ratio are increased, and after the threshold voltage is reduced, the damage to the threshold switch device unit caused by each operation is small, so that the service life of the device is prolonged, and the reliability is further improved.
Please refer to fig. 6 for the base (In) 38 Te 62 ) 0.1 (Ge 15 As 35 Se 50 ) 0.9 Fatigue life test of the threshold switching device unit. It can be seen that for (In) -based 38 Te 62 ) 0.1 (Ge 15 As 35 Se 50 ) 0.9 The fatigue life of the threshold switch device unit can reach 4 x 10 7 Far greater than 10 of general GeSe material 5 Therefore, the threshold switch device unit improved by applying the technology of the invention is more suitable for practical application.
In addition, other process conditions involved in the present invention are conventional process conditions, which belong to the scope familiar to those skilled in the art, and are not described herein again.
In summary, (In) of the present invention x Te y ) a M 1-a The advantages of the threshold switch material, the threshold switch device unit and the preparation method thereof are shown in the following aspects:
1. under the action of external energy, (In) x Te y ) a M 1-a The threshold switch material can smoothly realize transient transition between a high-resistance state and a low-resistance state, wherein the high-resistance state represents a closed state, the low-resistance state represents an open state, and the transition between the high-resistance state and the low-resistance state controls the switch of the device.
2. In is mixing (In) x Te y ) a M 1-a When the threshold switch material is used as a gating medium of the threshold switch device unit, extremely low leakage current is realized under the condition of relatively low threshold voltage, the starting current and the on-off ratio of the threshold switch device unit can be improved, and meanwhile, the low threshold voltage is helpful for effectively improving the reliability and the service life of the threshold switch device unit.
Claims (8)
1. A threshold gating material, characterized by: the chemical formula of the threshold gating material is (In) x Te y ) a M 1-a Wherein x/y is more than or equal to 0.1 and less than or equal to 1, x is more than 0 and less than or equal to 100, y is more than 0 and less than or equal to 100, x + y is 100, a is more than 0 and less than or equal to 0.2, and M is a threshold switching material comprising at least one sixth main group element.
2. The threshold gating material of claim 1, wherein: the chemical general formula of the threshold switch material is Ge b As c Se 100-b-c ，0＜b≤20，10≤c≤45。
3. A threshold gating device cell, characterized by: the threshold gating device unit comprises a lower electrode layer, a threshold gating material layer as claimed in claim 1, an upper electrode layer and an extraction electrode arranged on the upper electrode layer from bottom to top in sequence.
4. The threshold gating device cell of claim 3, wherein: the lower electrode layer is made of at least one of C, W, Cu, Al, Ti, Ta, TiN, WNx, TaN, Pt, Au, Ag, Co and Ni.
5. The threshold gating device cell of claim 3, wherein: the material of the upper electrode layer comprises at least one of W, Cu, Al, C, Ti, Ta, TiN, WNx, TaN, Pt, Au, Ag, Co and Ni.
6. The threshold gating device cell of claim 3, wherein: the material of the extraction electrode comprises at least one of W, Cu, Al, Co, Pt, Au and Ag.
7. A preparation method of a threshold gating device unit comprises the following steps:
(1) preparing a lower electrode layer;
(2) depositing a layer of threshold gating material as claimed in claim 1 on the lower electrode layer;
(3) preparing an upper electrode layer on the threshold gating material layer;
(4) and preparing an extraction electrode on the upper electrode layer.
8. The method of claim 7, wherein: the material is prepared by adopting a sputtering method, an evaporation method, a chemical vapor deposition method, a plasma enhanced chemical vapor deposition method, a low-pressure chemical vapor deposition method, a metal compound vapor deposition method, a molecular beam epitaxy method, an atomic vapor deposition method or an atomic layer deposition method.
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