CN102931346A - Memristor device and manufacturing method thereof - Google Patents

Memristor device and manufacturing method thereof Download PDF

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Publication number
CN102931346A
CN102931346A CN2011102308812A CN201110230881A CN102931346A CN 102931346 A CN102931346 A CN 102931346A CN 2011102308812 A CN2011102308812 A CN 2011102308812A CN 201110230881 A CN201110230881 A CN 201110230881A CN 102931346 A CN102931346 A CN 102931346A
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oxide
oxygen
layer
memristor device
content
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刘明
李颖弢
龙世兵
吕杭炳
刘琦
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Institute of Microelectronics of CAS
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Institute of Microelectronics of CAS
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Abstract

The invention discloses a memristor device and a manufacturing method thereof. The memristor device comprises a substrate, a lower electrode formed above the substrate, a memory storage layer formed above the lower electrode and an upper electrode formed above the memory storage layer, wherein the memory storage layer comprises two layers of oxide materials with different oxygen contents. The method for manufacturing the memristor device comprises the following steps of: growing a conducting material on the substrate as the lower electrode; growing the memory storage layer on the lower electrode, wherein the memory storage layer comprises two layers of oxide materials, and the oxygen contents of the two layers of oxide materials are different; and growing a conducting material on the memory storage layer as the upper electrode. The manufacturing method provided by the invention is simple, and the manufacturing technology is compatible with the traditional CMOS (Complementary Metal Oxide Semiconductors) technology and has certain application prospect in the field of memories.

Description

Memristor device and preparation method thereof
Technical field
The present invention relates to microelectronics and memory technology field, relate in particular to a kind of memristor device and preparation method thereof.
Background technology
Memristor claims again memory resistor, is the 4th kind of basic passive electric circuit element after relay resistance, electric capacity and inductance enter the main flow electronic applications, because it as variable resistor, can " remember " to change the size of current of passing through by changing both end voltage.Therefore, in fact memristor is exactly a kind of nonlinear resistance that memory function is arranged, and can be used as memory element.
As far back as 1971, the scientist Cai Shaotang of Chinese origin of Univ California-Berkeley professor was during concerning between research electric charge, electric current, voltage and magnetic flux, the existence that has disclosed memristor from Circuit theory.Owing to be subject to the restriction of semiconductor process techniques, do not find at that time what material itself that the effect of obvious memristor is just arranged.Until 2008, the researcher of hewlette-packard has just produced the unit component with memristor function.This memristor device can be realized very little nano-scale assembly, and can not produce the problems of excessive heat that transistor size now dwindles.In addition, memristor is because its characteristic time memory to resistance makes it have broad application prospects in various fields such as sunykatuib analysis, electronic device, integrated circuit (IC) design, neural nets.Therefore, it is expected to become the new study hotspots in field such as electronics, material science, semiconductor device, neural net.
Memristor is as a kind of brand-new storage concept, and relevant research also is in the starting stage, in order to promote further developing of memristor, develops and develops the key point that effective and feasible technology is the art.
Summary of the invention
The technical problem that (one) will solve
In view of this, the object of the present invention is to provide a kind of memristor device and preparation method thereof.
(2) technical scheme
For achieving the above object, the invention provides a kind of memristor device, comprising: substrate 100; Be formed at the bottom electrode 101 on the substrate 100; Be formed at the memory storage layer 102 on the bottom electrode 101; And be formed at top electrode 103 on the memory storage layer 102.
In the such scheme, described anoxic oxide skin(coating) 102a is made of metal oxide materials aluminium oxide, titanium oxide, nickel oxide, zirconia or hafnium oxide, and the content of oxygen element lacks than the content of oxygen element in complete stoicheiometry aluminium oxide, titanium oxide, nickel oxide, zirconia or the hafnium oxide among the described anoxic oxide skin(coating) 102a.Described anoxic oxide skin(coating) 102a forms by reactive sputtering or atomic layer deposition technique, in reactive sputtering process, reduce the content that forms oxygen element in the oxide by the flow that reduces oxygen, in atomic layer deposition technique, provide the burst length of the reaction source of oxygen element to reduce the content of oxygen element in the oxide by minimizing.
In the such scheme, described oxygen-rich oxide thing layer 102b is made of metal oxide materials aluminium oxide, titanium oxide, nickel oxide, zirconia or hafnium oxide, and the content of oxygen element equals or close to the content of oxygen element in fully stoicheiometry aluminium oxide, titanium oxide, nickel oxide, zirconia or the hafnium oxide among the described oxygen-rich oxide thing layer 102b.Described oxygen-rich oxide thing layer 102b forms by reactive sputtering, atomic layer deposition or electron beam evaporation process, in reactive sputtering process, form oxygen-rich oxide thing layer 102b by the flow that increases oxygen, in atomic layer deposition technique, provide the burst length of the reaction source of oxygen element to form oxygen-rich oxide thing layer 102b by increase, in electron beam evaporation process, adopt the oxide material of complete stoicheiometry to form oxygen-rich oxide thing layer 102b as evaporation source.
For achieving the above object, the invention provides a kind of method for preparing the memristor device, comprising: the growth electric conducting material is as bottom electrode 101 on substrate 100; Growth memory storage layer 102 on bottom electrode 101; And the electric conducting material of growing on memory storage layer 102 is as top electrode 103.
(3) beneficial effect
Can find out that from technique scheme the present invention has following beneficial effect:
1, memristor device provided by the invention and preparation method thereof, the memory storage layer of memristor device is to be made of double-deck oxide material, and the content of oxygen element is different in this two-layer oxide material.Therefore, when applying a voltage at the device two ends, the oxygen room in the few oxide of oxygen content will float in the hyperoxic oxide insulating layer, makes device be in a low resistance state.On the contrary, by applying an opposite voltage, the oxygen room can turn back in the few oxide of oxygen content, thereby device is converted into high-impedance state.Utilize these two kinds different high and low resistance states just can realize the storage of data ' 1 ' and ' 0 '.
2, memristor device provided by the invention and preparation method thereof, the preparation method is simple, and preparation technology and traditional CMOS process compatible have certain application prospect in memory area.
Description of drawings
Fig. 1 is the structural representation according to the memristor device of first embodiment of the invention;
Fig. 2 is the structural representation according to the memristor device of second embodiment of the invention;
Fig. 3 is for preparing the method flow diagram of memristor according to first embodiment of the invention;
Fig. 4 is for preparing the method flow diagram of memristor according to second embodiment of the invention.
Embodiment
For making the purpose, technical solutions and advantages of the present invention clearer, below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described in more detail.
Only be used for the illustration embodiments of the invention at this accompanying drawing that provides and description thereof.Shape and size in each accompanying drawing only are used for schematic illustration, strictly do not reflect true form and dimension scale.In addition, embodiment shown in the present should not be considered to only limit to the given shape in zone shown in the figure, and the expression among the figure is schematically, rather than is used for limiting the scope of the invention.
As shown in Figure 1, Fig. 1 is the structural representation according to the memristor device of first embodiment of the invention, and this memristor device comprises: substrate 100; Be formed at the bottom electrode 101 on the substrate 100; Be formed at the memory storage layer 102 on the bottom electrode 101; And be formed at top electrode 103 on the memory storage layer 102.
The layer of memory storage described in Fig. 1 102 is made of the less anoxic oxide skin(coating) 102a of oxygen element content and the oxygen-rich oxide thing layer 102b of oxygen content abundance, and oxygen-rich oxide thing layer 102b is positioned on the anoxic oxide skin(coating) 102a.
In actual applications, consist of the anoxic oxide skin(coating) 102a of memory storage layer 102 and the position relationship of oxygen-rich oxide thing layer 102b and be not limited to mode shown in Figure 1, Fig. 2 has demonstrated its alternative way, and the oxide skin(coating) of anoxic described in Fig. 2 102a is positioned on the oxygen-rich oxide thing layer 102b.
The geometry of described substrate 100 is unrestricted, is generally made by silicon dioxide, silicon nitride, glass or other insulating material.
The material of described bottom electrode 101 and described top electrode 103 comprises the double-level-metal combination electrodes such as single-layer metal electrode, Pt/Ti, Cu/Au, Au/Cr, Ti/Ti, Cu/Al such as W, Al, Cu, Ni, Pt, Ti, also can be the metallic conduction compound electrodes such as TiN, TaN, ITO.The thickness of described bottom electrode 101 and described top electrode 103 is unrestricted.Described upper and lower electrode can adopt the techniques such as electron beam evaporation, sputter chemical vapor deposition, atomic layer deposition, thermal evaporation to form.
The anoxic oxide skin(coating) 102a of described formation memory storage layer 102 is made of metal oxide materials such as aluminium oxide, titanium oxide, nickel oxide, zirconia, hafnium oxide, and the content of oxygen element will lack than the content of the middle oxygen element of above-mentioned complete stoicheiometry oxide (for example aluminium oxide, titanium oxide, nickel oxide, zirconia, hafnium oxide) among the described anoxic oxide skin(coating) 102a.Main purpose is in order to introduce more oxygen room in 102a, to utilize the increase in oxygen room with the oxide-doped semiconductor that becomes.Described anoxic oxide skin(coating) 102a can pass through the techniques such as reactive sputtering, atomic layer deposition and form.In reactive sputtering process, reduce the content that forms oxygen element in the oxide by the flow that reduces oxygen.In the atomic layer deposition process, can provide the burst length of the reaction source of oxygen element to reduce the content of oxygen element in the oxide by minimizing.
The oxygen-rich oxide thing layer 102b of described formation memory storage layer 102 is made of metal oxide materials such as aluminium oxide, titanium oxide, nickel oxide, zirconia, hafnium oxide, and the content of oxygen element equals or close to the content of oxygen element in the complete stoicheiometry oxide (for example aluminium oxide, titanium oxide, nickel oxide, zirconia, hafnium oxide) among the described oxygen-rich oxide thing layer 102b.Purpose be for the oxide that forms the non-impurity-doped nature as insulating barrier.Described oxygen-rich oxide thing layer 102b can pass through the techniques such as reactive sputtering, atomic layer deposition, electron beam evaporation and form.In the process of reactive sputtering, form oxygen-rich oxide thing layer 102b by the flow that increases oxygen.In the atomic layer deposition process, provide the burst length of the reaction source of oxygen element to form oxygen-rich oxide thing layer 102b by increase.In the electron beam evaporation process, adopt the oxide material of complete stoicheiometry to form oxygen-rich oxide thing layer 102b as evaporation source.
The thickness of the anoxic oxide skin(coating) 102a that the oxygen element content of described formation memory storage layer 102 is less and oxygen-rich oxide thing layer 102b is unrestricted.The thickness that is appreciated that the less anoxic oxide skin(coating) 102a of described oxygen element content and oxygen-rich oxide thing layer 102b can be identical, also can be different.
Based on the structural representation of above-mentioned memristor device illustrated in figures 1 and 2, the present invention also provides a kind of method for preparing the memristor device, comprising: the growth electric conducting material is as bottom electrode 101 on substrate 100; Growth memory storage layer 102 on bottom electrode 101; And the electric conducting material of growing on memory storage layer 102 is as top electrode 103.
Wherein, Fig. 3 shows the method flow diagram for preparing memristor according to first embodiment of the invention, and the method may further comprise the steps: select substrate 100; At substrate 100 deposition bottom electrodes 101; At bottom electrode 101 deposition anoxic oxide skin(coating) 102a; At anoxic oxide skin(coating) 102a deposition oxygen-rich oxide thing layer 102b; At oxygen-rich oxide thing layer 102b deposition top electrode 103.
Fig. 4 shows the method flow diagram for preparing memristor according to second embodiment of the invention, and the method may further comprise the steps: select substrate 100; At substrate 100 deposition bottom electrodes 101; At bottom electrode 101 deposition oxygen-rich oxide thing layer 102b; At oxygen-rich oxide thing layer 102b deposition anoxic oxide skin(coating) 102a; At anoxic oxide skin(coating) 102a deposition top electrode 103.
The memristor device that the method that adopts the present invention to propose is prepared, when apply a voltage at the device two ends, the oxygen room will float to from the few oxide-doped layer of oxygen content the oxide insulating layer of non-impurity-doped nature, makes device be in a low resistance state.On the contrary, by applying an opposite voltage, the oxygen room can turn back to doped layer, thereby device is converted into high-impedance state.These two kinds different high and low resistance states can realize the storage of data ' 1 ' and ' 0 '.In addition, the preparation method of memristor device provided by the invention is simple, and preparation technology and traditional CMOS process compatible have certain application prospect in memory area.
Above-described specific embodiment; purpose of the present invention, technical scheme and beneficial effect are further described; institute is understood that; the above only is specific embodiments of the invention; be not limited to the present invention; within the spirit and principles in the present invention all, any modification of making, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (20)

1. a memristor device is characterized in that, comprising:
Substrate (100);
Be formed at the bottom electrode (101) on the substrate (100);
Be formed at the memory storage layer (102) on the bottom electrode (101); And
Be formed at the top electrode (103) on the memory storage layer (102).
2. memristor device according to claim 1 is characterized in that, described substrate (100) is made by silicon dioxide, silicon nitride or glass.
3. memristor device according to claim 1 is characterized in that, described bottom electrode (101) or described top electrode (103) adopt single-layer metal electrode, double-level-metal combination electrode or metallic conduction compound electrode.
4. memristor device according to claim 3, it is characterized in that, described single-layer metal electrode adopts W, Al, Cu, Ni, Pt or Ti to be made, described double-level-metal combination electrode adopts Pt/Ti, Cu/Au, Au/Cr, Ti/Ti or Cu/Al to be made, and described metallic conduction compound electrode adopts TiN, TaN or ITO to be made.
5. memristor device according to claim 1 is characterized in that, described bottom electrode (101) or described top electrode (103) adopt electron beam evaporation, sputter chemical vapor deposition, atomic layer deposition or thermal evaporation technique to form.
6. memristor device according to claim 1, it is characterized in that, described memory storage layer (102) is made of the oxygen-rich oxide thing layer (102b) of the less anoxic oxide skin(coating) (102a) of oxygen element content and oxygen content abundance, and oxygen-rich oxide thing layer (102b) is formed on the anoxic oxide skin(coating) (102a), and perhaps anoxic oxide skin(coating) (102a) is formed on the oxygen-rich oxide thing layer (102b).
7. memristor device according to claim 6, it is characterized in that, described anoxic oxide skin(coating) (102a) is made of metal oxide materials aluminium oxide, titanium oxide, nickel oxide, zirconia or hafnium oxide, and the content of oxygen element lacks than the content of oxygen element in complete stoicheiometry aluminium oxide, titanium oxide, nickel oxide, zirconia or the hafnium oxide in the described anoxic oxide skin(coating) (102a).
8. memristor device according to claim 6, it is characterized in that, described anoxic oxide skin(coating) (102a) forms by reactive sputtering or atomic layer deposition technique, in reactive sputtering process, reduce the content that forms oxygen element in the oxide by the flow that reduces oxygen, in atomic layer deposition technique, provide the burst length of the reaction source of oxygen element to reduce the content of oxygen element in the oxide by minimizing.
9. memristor device according to claim 6, it is characterized in that, described oxygen-rich oxide thing layer (102b) is made of metal oxide materials aluminium oxide, titanium oxide, nickel oxide, zirconia or hafnium oxide, and the content of oxygen element equals or close to the content of oxygen element in fully stoicheiometry aluminium oxide, titanium oxide, nickel oxide, zirconia or the hafnium oxide in the described oxygen-rich oxide thing layer (102b).
10. memristor device according to claim 6, it is characterized in that, described oxygen-rich oxide thing layer (102b) passes through reactive sputtering, atomic layer deposition or electron beam evaporation process form, in reactive sputtering process, form oxygen-rich oxide thing layer (102b) by the flow that increases oxygen, in atomic layer deposition technique, provide the burst length of the reaction source of oxygen element to form oxygen-rich oxide thing layer (102b) by increase, in electron beam evaporation process, adopt the oxide material of complete stoicheiometry to form oxygen-rich oxide thing layer (102b) as evaporation source.
11. a method for preparing the memristor device is characterized in that, comprising:
The growth electric conducting material is as bottom electrode (101) on substrate (100);
Growth memory storage layer (102) on bottom electrode (101); And
The growth electric conducting material is as top electrode (103) on memory storage layer (102).
12. the method for preparing the memristor device according to claim 11 is characterized in that, described substrate (100) is made by silicon dioxide, silicon nitride or glass.
13. the method for preparing the memristor device according to claim 11 is characterized in that, described bottom electrode (101) or described top electrode (103) adopt single-layer metal electrode, double-level-metal combination electrode or metallic conduction compound electrode.
14. the method for preparing the memristor device according to claim 13, it is characterized in that, described single-layer metal electrode adopts W, Al, Cu, Ni, Pt or Ti to be made, described double-level-metal combination electrode adopts Pt/Ti, Cu/Au, Au/Cr, Ti/Ti or Cu/Al to be made, and described metallic conduction compound electrode adopts TiN, TaN or ITO to be made.
15. the method for preparing the memristor device according to claim 1 is characterized in that, described bottom electrode (101) or described top electrode (103) adopt electron beam evaporation, sputter chemical vapor deposition, atomic layer deposition or thermal evaporation technique to form.
16. the method for preparing the memristor device according to claim 1, it is characterized in that, described memory storage layer (102) is made of the oxygen-rich oxide thing layer (102b) of the less anoxic oxide skin(coating) (102a) of oxygen element content and oxygen content abundance, and oxygen-rich oxide thing layer (102b) is formed on the anoxic oxide skin(coating) (102a), and perhaps anoxic oxide skin(coating) (102a) is formed on the oxygen-rich oxide thing layer (102b).
17. the method for preparing the memristor device according to claim 16, it is characterized in that, described anoxic oxide skin(coating) (102a) is made of metal oxide materials aluminium oxide, titanium oxide, nickel oxide, zirconia or hafnium oxide, and the content of oxygen element lacks than the content of oxygen element in complete stoicheiometry aluminium oxide, titanium oxide, nickel oxide, zirconia or the hafnium oxide in the described anoxic oxide skin(coating) (102a).
18. the method for preparing the memristor device according to claim 16, it is characterized in that, described anoxic oxide skin(coating) (102a) forms by reactive sputtering or atomic layer deposition technique, in reactive sputtering process, reduce the content that forms oxygen element in the oxide by the flow that reduces oxygen, in atomic layer deposition technique, provide the burst length of the reaction source of oxygen element to reduce the content of oxygen element in the oxide by minimizing.
19. the method for preparing the memristor device according to claim 16, it is characterized in that, described oxygen-rich oxide thing layer (102b) is made of metal oxide materials aluminium oxide, titanium oxide, nickel oxide, zirconia or hafnium oxide, and the content of oxygen element equals or close to the content of oxygen element in fully stoicheiometry aluminium oxide, titanium oxide, nickel oxide, zirconia or the hafnium oxide in the described oxygen-rich oxide thing layer (102b).
20. the method for preparing the memristor device according to claim 16, it is characterized in that, described oxygen-rich oxide thing layer (102b) passes through reactive sputtering, atomic layer deposition or electron beam evaporation process form, in reactive sputtering process, form oxygen-rich oxide thing layer (102b) by the flow that increases oxygen, in atomic layer deposition technique, provide the burst length of the reaction source of oxygen element to form oxygen-rich oxide thing layer (102b) by increase, in electron beam evaporation process, adopt the oxide material of complete stoicheiometry to form oxygen-rich oxide thing layer (102b) as evaporation source.
CN2011102308812A 2011-08-12 2011-08-12 Memristor device and manufacturing method thereof Pending CN102931346A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018113142A1 (en) * 2016-12-20 2018-06-28 Nanjing University Of Posts And Telecommunications A porphyrin memristor and the fabrication method thereof
CN108365089A (en) * 2018-01-05 2018-08-03 中山大学 Prepared by a kind of solution combustion method has analog- and digital- multi-functional NiO bases memory resistor and preparation method
CN109065715A (en) * 2018-08-15 2018-12-21 电子科技大学 A kind of memristor switching device and preparation method thereof based on a-TSC:O ceramic membrane
CN109065716A (en) * 2018-08-15 2018-12-21 电子科技大学 A kind of nerve synapse device and preparation method thereof based on a-TSC:O ceramic membrane
CN110165056A (en) * 2019-04-12 2019-08-23 西交利物浦大学 A kind of CTM memory and preparation method thereof
CN110911559A (en) * 2019-11-08 2020-03-24 华中科技大学 Analog HfOx/HfOyHomogeneous junction memristor and regulation and control method thereof
CN110993788A (en) * 2019-12-26 2020-04-10 电子科技大学 Preparation method of titanium oxide film memristor
CN111564555A (en) * 2020-05-20 2020-08-21 浙江大学 Resistive random access memory with improved working stability and memory window and preparation method thereof
CN112563417A (en) * 2020-12-08 2021-03-26 华中科技大学 Simulated nerve synapse device and preparation method thereof
WO2021128994A1 (en) * 2019-12-24 2021-07-01 华中科技大学 Superlattice memristor functional layer material, and memristor unit and preparation method therefor
CN114824072A (en) * 2022-05-10 2022-07-29 山东科技大学 Memristor with oxygen-enriched vacancy doped zirconium dioxide and preparation method thereof
RU218020U1 (en) * 2022-12-01 2023-05-02 Акционерное общество "Научно-исследовательский институт молекулярной электроники" Memristor element based on CMOS technology
CN116507195A (en) * 2023-06-21 2023-07-28 武汉大学 Based on WO x /YO y Preparation method of double-heterojunction structure analog memristor

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018113142A1 (en) * 2016-12-20 2018-06-28 Nanjing University Of Posts And Telecommunications A porphyrin memristor and the fabrication method thereof
CN108365089A (en) * 2018-01-05 2018-08-03 中山大学 Prepared by a kind of solution combustion method has analog- and digital- multi-functional NiO bases memory resistor and preparation method
CN109065715A (en) * 2018-08-15 2018-12-21 电子科技大学 A kind of memristor switching device and preparation method thereof based on a-TSC:O ceramic membrane
CN109065716A (en) * 2018-08-15 2018-12-21 电子科技大学 A kind of nerve synapse device and preparation method thereof based on a-TSC:O ceramic membrane
CN110165056A (en) * 2019-04-12 2019-08-23 西交利物浦大学 A kind of CTM memory and preparation method thereof
CN110911559A (en) * 2019-11-08 2020-03-24 华中科技大学 Analog HfOx/HfOyHomogeneous junction memristor and regulation and control method thereof
CN110911559B (en) * 2019-11-08 2021-10-15 华中科技大学 Analog HfOx/HfOyHomogeneous junction memristor and regulation and control method thereof
WO2021128994A1 (en) * 2019-12-24 2021-07-01 华中科技大学 Superlattice memristor functional layer material, and memristor unit and preparation method therefor
CN110993788A (en) * 2019-12-26 2020-04-10 电子科技大学 Preparation method of titanium oxide film memristor
CN111564555A (en) * 2020-05-20 2020-08-21 浙江大学 Resistive random access memory with improved working stability and memory window and preparation method thereof
CN112563417A (en) * 2020-12-08 2021-03-26 华中科技大学 Simulated nerve synapse device and preparation method thereof
CN114824072A (en) * 2022-05-10 2022-07-29 山东科技大学 Memristor with oxygen-enriched vacancy doped zirconium dioxide and preparation method thereof
RU218020U1 (en) * 2022-12-01 2023-05-02 Акционерное общество "Научно-исследовательский институт молекулярной электроники" Memristor element based on CMOS technology
CN116507195A (en) * 2023-06-21 2023-07-28 武汉大学 Based on WO x /YO y Preparation method of double-heterojunction structure analog memristor
CN116507195B (en) * 2023-06-21 2023-10-17 武汉大学 Based on WO x /YO y Preparation method of double-heterojunction structure analog memristor

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Application publication date: 20130213