CN101976675A - Phase change memory using wide band gap semiconductor diode as gating tube and method - Google Patents

Phase change memory using wide band gap semiconductor diode as gating tube and method Download PDF

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CN101976675A
CN101976675A CN 201010252343 CN201010252343A CN101976675A CN 101976675 A CN101976675 A CN 101976675A CN 201010252343 CN201010252343 CN 201010252343 CN 201010252343 A CN201010252343 A CN 201010252343A CN 101976675 A CN101976675 A CN 101976675A
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band gap
wide band
diode
phase
phase change
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CN101976675B (en
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吴良才
宋志棠
倪鹤南
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Shanghai Institute of Microsystem and Information Technology of CAS
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Shanghai Institute of Microsystem and Information Technology of CAS
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Abstract

The invention relates to a wide band gap semiconductor diode serving as a gating tube of a phase change memory and a method. The phase change memory unit is characterized by consisting of the wide band gap semiconductor diode and a reversible phase change storage medium. The wide band gap semiconductor material has the characteristics of large forbidden band width, high saturated electron drift velocity, high thermal conductivity, small dielectric constant, strong radiation resistance, high electric field breakdown strength, good chemical stability and the like, and is very suitable for manufacturing high-speed, high-density and radiation-resistant electronic devices; and the wide band gap semiconductor material is combined with the phase change material with properties of high speed, high demagnification capability, natural radiation resistance and the like to form a phase change storage unit with excellent properties of high speed, high density, low power consumption, voltage resistance, radiation resistance and the like, and the phase change storage unit is further prepared into the phase change memory with excellent properties of high speed, high density, low power consumption, radiation resistance and the like.

Description

The wide band gap semiconducter diode is as gate tube phase transition storage and method
Technical field
The present invention relates to a kind of phase transformation memory device unit and method of utilizing the wide band gap semiconducter diode as gate tube.Described phase transformation memory device unit is to be made of a wide band gap semiconducter diode and a reversible transition storage medium.The invention belongs to particular device and technology field in the microelectronics.
Background technology
Based on the microelectric technique of silicon in information technology still in occupation of consequence, but wide bandgap semiconductor materials has the characteristics such as chemical stability that energy gap is big, saturated electron drift velocity is high, thermal conductivity is big, dielectric constant is little, capability of resistance to radiation is strong, breakdown field strength is high and good, be very suitable for making high speed, high density, radiation-resistant electronic device, obtain application more and more widely at aspects such as high speed, high frequency, high-power, radiation.Wide band gap semiconducter is the third generation semiconductor that grows up after the first generation that is representative, second generation semiconductor with Si, GaAs, is a strategic new and high technology, has extremely important using value.Countries in the world government and commercial department attach great importance to the research of wide band gap semiconducter, and in recent years, the development of wide band gap semiconducter technology is very rapid.
Phase transition storage (chalcogenide based RAM based on sulphur based semiconductor material, PCRAM) it is low to have a cost, speed is fast, the storage density height, make simple and with the current good outstanding advantage of CMOS (complementary metal-oxide-semiconductor) ic process compatibility, be the most competitive memory technology of future generation in the present novel memory technology, receive the concern of world enterprise circle and researcher.In addition, PCRAM has performances such as anti-irradiation (ability of resistant to total dose is greater than 1Mrad (Si)), high-low temperature resistant (55-125 ℃), against violent vibration are moving, anti-electronic jamming, in national defence and aerospace field important application prospects is arranged.From 2003, international semiconductor TIA thought always that phase transition storage is most possible and replaces current main product such as present SRAM (static RAM), DRAM (dynamic random access memory) and FLASH memory (flash memory) and become the semiconductor storage unit of future generation of following memory main product.
Main in the world electronics and semiconductor company all is being devoted to the development of PCRAM at present.There are Ovonyx, Intel, Samsung, IBM, Bayer, ST Micron, AMD, Panasonic, Sony, Philips, British Areospace, Hitachi and Macronix etc. in main research unit.In May, 2005, American I BM, German Infineon science and technology, Taiwan Macronix International (Macronix International) are announced joint study exploitation phase transition storage, send 20~25 technical staff to participate in this research specially.3 companies provide the technology of being good at separately to study respectively, specifically, exactly with the relevant material that IBM is had and the basic research ability of physical characteristic, the research of the various internal memory products that Infineon has, exploitation and volume production technical capability, and the non-voltile memory technical capability of Macronix International is integrated in this research.2009, Samsung was announced to carry out the volume production of 512Mb.
In order to realize highdensity phase change memory, further improve performances such as the speed of phase transition storage, anti-irradiation, the present invention intends proposing a kind of phase transformation memory device unit that utilizes the wide band gap semiconducter diode as gate tube.Because wide bandgap semiconductor materials has the characteristics such as chemical stability that energy gap is big, saturated electron drift velocity is high, thermal conductivity is big, dielectric constant is little, capability of resistance to radiation is strong, breakdown field strength is high and good, be fit to make high speed, high density, radiation-resistant electronic device.The phase change memory device unit that the present invention proposes is made of a diode and a reversible transition storage medium that is formed by wide band gap semiconducter, the wide band gap semiconducter diode not only has speed-sensitive switch, lower thermal conductivity, characteristic such as high pressure resistant, and has a very strong anti-irradiation ability, the wide band gap semiconducter diode with have at a high speed, high miniature ability, phase change memory medium combination with performances such as natural radioresistances, can be integrated go out at a high speed, high density, low-power consumption, withstand voltage, the phase-change memory cell of anti-irradiation, and then prepare at a high speed, high density, radiation-resistant phase change memory chip.
Summary of the invention
The object of the present invention is to provide a kind of phase change memory device unit and method of utilizing the wide band gap semiconducter diode as gate tube.Described phase-change memory cell is to be made of a diode based on wide band gap semiconducter (diode can be the p-n junction diode, also can be Schottky diode) and a phase change memory medium, and wherein diode is as switch.Wide band gap semiconducter diode as switch can be the p-n junction diode that is formed by wide bandgap semiconductor materials, also can be the Schottky barrier diode that is formed by wide bandgap semiconductor materials and metal material.Wide band gap semiconducter diode in the phase change memory device unit is following, and the phase change memory medium is vertical arrangement architecture last, thereby can form highdensity phase change memory device unit.Because wide bandgap semiconductor materials has energy gap big (prohibiting broadband degree Eg between 2.0-6.0eV), saturated electron drift velocity height, thermal conductivity is big, dielectric constant is little, capability of resistance to radiation is strong, breakdown field strength is high and good characteristics such as chemical stability, is fit to make high speed, high density, radiation-resistant electronic device.The wide band gap semiconducter diode combines with the phase change memory medium that has high speed, high miniature ability, have performances such as natural radioresistance, the phase-change memory cell that can be integrated goes out high speed, low-power consumption, withstand voltage, anti-irradiation, and then prepare high speed, high density, radiation-resistant phase change memory chip, have using value in fields such as high speed, high density, irradiation.
Main technique step of the present invention following (dividing p-n junction diode and Schottky diode two kinds of situation explanations):
(1) key step of preparation wide band gap semiconducter p-n junction diode:
(1) preparation p molded breadth gap semiconductor film on substrate, thickness 20-200nm;
(2) preparation n N-type semiconductor N film on p molded breadth gap semiconductor film, thickness 20-200nm;
(3) etching forms p-n junction, and size is at 50-2000nm.
(4) prepare heating electrode on p-n junction, thickness is at 10-100nm, and size is at 20-1000nm.;
(5) prepare phase-change material on heating electrode, thickness is at 30-300nm, and size is at 10-500nm.;
(6) photoetching and wet etching form the top electrode of memory cell on phase-change material;
(7) above-mentioned phase change memory device unit is connected in the electrical measurement system, carries out the writing of phase transformation memory device unit, wiping, read operation, study characteristics such as its storage and fatigue.
(2) key step of preparation wide band gap semiconducter Schottky diode:
(1) on substrate, prepare negative electrode, but cathode material aluminium, gold, molybdenum, nickel and titanium etc., thickness 50-500nm;
(2) on negative electrode, prepare wide-band gap semiconductor thin film, thickness 20-200nm;
(3) prepare anode on wide-band gap semiconductor thin film, anode material can be selected tungsten, titanium, TiN, gold, molybdenum, nickel etc., thickness 50-500nm for use;
(4) prepare dielectric layer on anode, original position forms the hole of heating electrode material, the degree of depth 50nm-150nm of hole, hole diameter 20-200nm on dielectric layer;
(5) utilize method deposit heating electrode materials in hole such as magnetron sputtering, CVD or ALD;
(6) in above-mentioned hole, behind the filling heating electrode material, carry out etching or CMP, remove hole heating electrode material in addition, form column heating electrode array;
(7) prepare phase-change material on heating electrode, thickness is at 30-300nm, and photoetching forms phase-variant material array then, and size is at 10-500nm;
(8) utilize CVD, ALD or method deposit one deck electrode materials on phase-variant material array such as high vacuum magnetically controlled sputter method, electron beam evaporation;
(9) photoetching forms the top electrode of memory cell;
Described backing material is unrestricted, for substrate any and this wide bandgap semiconductor materials coupling, and as Sapphire Substrate, the SiC substrate, Si substrate, or GaN substrate, or the like.
The described wide bandgap semiconductor materials that is used to make Schottky diode is unrestricted, can be diamond, III group-III nitride, carbide, boron nitride and oxide semiconductor (ZnO etc.) and solid solution etc.
The cathode material of described making Schottky diode is unrestricted, is not limited to aluminium, gold, molybdenum, nickel and titanium etc., can be the metal material of other any and used wide bandgap semiconductor materials coupling, and its thickness is 50-500nm.
Described dielectric material is unrestricted, can be SiO commonly used 2, SiN xMaterial also can be other dielectric material.
Hole on the described dielectric layer can use any micro-nano processing method such as focused-ion-beam lithography method, electron beam exposure and reactive ion etching method to obtain.
Described III group-III nitride comprises GaN, InN, AlN etc. and ternary and quaternary alloy (comprising InGaN, AlGaN and AlInGaN etc.).
Described carbide semiconductor comprises carborundum (SiC), 4H carborundum (4H-SiC), 6H carborundum (6H-SiC) etc.
Described oxide semiconductor comprises zinc oxide (ZnO), titanium oxide (TiO 2), tungsten oxide (W 2O 3) etc., but be not limited to these oxides.
Described reversible transition material is unrestricted, it can be the phase-change material of series such as Ge-Sb-Te, Sb-Te, Ge-Te, also can be the phase-change material that other any series has the reversible transition ability, as Si-Sb-Te, GeSbTe and the SiSbTe of Si-Sb series or doping Sn, Ag or N.
Description of drawings
Fig. 1 wide band gap semiconducter p-n junction structural representation;
The memory device schematic diagram that Fig. 2 wide band gap semiconducter p-n junction and phase-change material are formed;
The memory device schematic diagram that Fig. 3 forms based on the Schottky diode and the phase-change material of wide band gap semiconducter (is example with GaN).
Among the figure, 1.P section bar material; 2.n section bar material; 3. heating electrode; 4. phase-change material; 5. top electrode; 6. negative electrode; 7.i-GaN; 8.i-AlGaN; 9.i-AlGaN; 10. anode; 11. dielectric material; 12. column heating electrode.
Embodiment
Below by specific embodiment, further illustrate substantive distinguishing features of the present invention and obvious improvement, but the present invention only is confined to described embodiment by no means.
Embodiment 1:
(1) as depicted in figs. 1 and 2, utilize MOCVD in-situ preparing on Sapphire Substrate to go out P type GaN, n type GaN earlier, every layer thickness is at 20-200nm, and etching forms GaN semiconductor p-n junction;
(2) utilize magnetron sputtering deposit heating electrode material W, phase-change material Ge-Sb-Te, top electrode material TiN and Ti successively on GaN semiconductor p-n junction, phase-change material thickness is at 50-200nm, and TiN thickness is 10-50nm, and Ti thickness is 50-200nm;
(3) the ordinary optical photoetching forms discrete device architecture, and diameter is more than 1000nm.
Embodiment 2:
(1) utilize MOCVD in-situ preparing on Sapphire Substrate to go out P type GaN, n type GaN, every layer thickness forms GaN semiconductor p-n junction at 20-200nm;
(2) utilize magnetron sputtering deposit heating electrode material W, phase-change material Ge-Sb-Te, electrode material TiN and Ti successively on GaN semiconductor p-n junction, phase-change material thickness is at 50-200nm, and TiN thickness is 10-50nm, and Ti thickness is 50-200nm;
(3) electron beam lithography forms discrete device architecture, and diameter is below 1000nm.
Embodiment 3:
(1) utilize MOCVD in-situ preparing on the Si substrate to go out P type GaN, n type GaN, every layer thickness forms GaN semiconductor p-n junction at 20-200nm;
(2) utilize magnetron sputtering deposit heating electrode material W, phase-change material Ge-Sb-Te, electrode material TiN and Ti successively on GaN semiconductor p-n junction, phase-change material thickness is at 50-200nm, and TiN thickness is 10-50nm, and Ti thickness is 50-200nm;
(3) utilize FIB to form discrete device architecture, diameter is at 10-200nm.
Embodiment 4:
(1) as shown in Figure 3, utilize MOCVD in-situ preparing on Sapphire Substrate to go out negative electrode 6, wide-band gap semiconductor thin film (7,8 and 9) GaN and anode 10 earlier, prepare Schottky diode, diameter 100-1000nm based on GaN;
(2) utilize PECVD technology thick SiO of deposit one deck 20-100nm on the GaN Schottky diode 2Dielectric film 11;
(3) at the thick SiO of above-mentioned 20-100nm 2Utilize the FIB technology to prepare the nano aperture array on the dielectric layer, the hole bottom links to each other with the Schottky diode anode, and hole diameter is in the 20-200nm scope;
(4) utilize CVD technology deposit W film in hole, reaction source is WE 6, SiH 4And H 2Three's mixture fills up until hole;
(5) utilize chemical Mechanical Polishing Technique (CMP) to throw and remove the W electrode material of hole with exterior domain;
(6) magnetron sputtering phase-change material Ge-Sb-Te, the about 80nm of thickness, base vacuum are 3 * 10 -6Torr, the sputter vacuum is 0.08Pa, power 100W;
(7) utilize electron beam lithography to form GeSbTe film pattern array, then prepare the Al top electrode, obtain memory device unit;
Embodiment 5:
Change the phase-change material Ge-Sb-Te among above-mentioned all embodiment into Si-Sb-Te, perhaps change the GeSbTe of doping such as Sn, Ag, N and the SiSbTe that Sn, Ag, N etc. mix into, other step is constant.So also can obtain the corresponding devices performance, even some performance gets a promotion, as the operating current that reduces device or improve device speed etc.
Embodiment 6:
The upper end of W heating electrode among above-mentioned all embodiment is prepared one deck TiN or TiO 2Deng the film of high resistivity more, can obtain the better heating result.

Claims (9)

1. a phase transformation memory device unit that utilizes the wide band gap semiconducter diode as gate tube is characterized in that
(a) described phase transformation memory device unit is to constitute based on wide band gap semiconducter diode and a phase change memory medium by one, and wherein the wide band gap semiconducter diode is as switch;
(b) be p-n junction diode that forms by wide bandgap semiconductor materials or the Schottky barrier diode that forms by wide bandgap semiconductor materials and metal material as the wide band gap semiconducter diode of switch;
(c) the energy gap Eg of wide bandgap semiconductor materials is between 2.0-6.0eV;
(d) the wide band gap semiconducter diode in the memory cell is following, and the phase change memory medium is vertical arrangement architecture last, thereby forms highdensity phase change memory device unit.
2. by the described phase transformation memory device unit of claim 1, it is characterized in that wide bandgap semiconductor materials comprises diamond, the III group-III nitride, carbide, boron nitride, ZnO are at interior oxide semiconductor and solid solution.
3. by the described phase transformation memory device unit of claim 2, it is characterized in that:
1. described III group-III nitride is GaN, InN, AlN, InGaN, AlGaN or AlInGaN;
2. described carbide is SiC, 4H-SiC or 6H-SiC;
3. described oxide is ZnO, TiO 2Or W 2O 3
4. by the described gate tube that utilizes the wide band gap semiconducter diode as phase transition storage of claim 1, it is characterized in that the upper and lower electrode of the Schottky barrier diode that wide bandgap semiconductor materials and metal material form is to comprise aluminium, copper, tungsten or titanium at interior metal material.
5. preparation is characterized in that as each described phase transformation memory device unit among the claim 1-3
(A) key step of preparation wide band gap semiconducter p-n junction diode:
(a) preparation p molded breadth gap semiconductor film on substrate, thickness 20-200nm;
(b) preparation n N-type semiconductor N film on p molded breadth gap semiconductor film, thickness 20-200nm;
(c) etching forms p-n junction;
(d) prepare heating electrode on p-n junction, thickness is at 10-100nm;
(e) prepare phase-change material on heating electrode, thickness is at 30-300nm;
(f) photoetching and wet etching form the top electrode of memory cell on phase-change material;
(B) key step of preparation wide band gap semiconducter Schottky diode:
(a) prepare negative electrode on substrate, cathode material is aluminium, gold, molybdenum, nickel or titanium; Thickness 50-500nm;
(b) on negative electrode, prepare wide-band gap semiconductor thin film, thickness 20-200nm;
(c) prepare anode on wide-band gap semiconductor thin film, anode material is tungsten, titanium, TiN, gold, molybdenum or nickel, thickness 50-500nm;
(d) prepare layer of dielectric material on anode, original position forms the hole of heating electrode material on dielectric layer, and the hole bottom links to each other the degree of depth 50nm-150nm of hole, hole diameter 20-200nm with the Schottky diode anode;
(e) utilize magnetron sputtering, CVD or the reversible heating electrode material of ALD method deposit in hole;
(f) in above-mentioned hole, behind the filling phase-change material, carry out etching or CMP, remove hole heating electrode material in addition, form column heating electrode array;
(g) prepare phase-change material on heating electrode, thickness is at 30-300nm, and photoetching forms the shape-changing material array then;
(h) utilize CVD, ALD or high vacuum magnetically controlled sputter method, electron beam evaporation method deposit one deck electrode material on phase-variant material array;
(i) photoetching forms the top electrode of memory cell.
6. by the described preparation method of claim 5, it is characterized in that backing material is sapphire, SiC, Si or GaN among method A and the B.
7. by the described preparation method of claim 5, it is characterized in that:
1. described dielectric layer material is for comprising SiO 2Or SiN xAt interior dielectric material; Described heating electrode material is W;
2. the method for original position formation hole is focused-ion-beam lithography, electron beam exposure or reactive ion etching on the dielectric layer.
8. by the described preparation method of claim 5, it is characterized in that described reversible transition material is GeSbTe and the SiSbTe of Ge-Sb-Te, SbTe, Ge-Te, Si-Sb, Si-Sb-Te or doping Sn, Ag or N.
9. by the described preparation method of claim 7, it is characterized in that preparation one deck TiN or TiO on the W heating electrode 2The film of high resistivity improves heats.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109560104A (en) * 2018-12-20 2019-04-02 上海集成电路研发中心有限公司 A kind of phase transition storage and preparation method thereof
CN109686755A (en) * 2018-12-26 2019-04-26 上海集成电路研发中心有限公司 High-density phase-change memory and preparation method thereof
CN112652714A (en) * 2020-12-23 2021-04-13 华中科技大学 Preparation method of phase change memory array
CN113838886A (en) * 2021-09-01 2021-12-24 深圳大学 Phase change memory and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101114666A (en) * 2007-08-03 2008-01-30 中国科学院上海微***与信息技术研究所 Anti-irradiation high-reliability phase transition memory device unit and manufacturing method thereof
CN101477987A (en) * 2009-01-08 2009-07-08 中国科学院上海微***与信息技术研究所 Tri-dimension stacked resistance conversion memory and manufacturing process thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101114666A (en) * 2007-08-03 2008-01-30 中国科学院上海微***与信息技术研究所 Anti-irradiation high-reliability phase transition memory device unit and manufacturing method thereof
CN101477987A (en) * 2009-01-08 2009-07-08 中国科学院上海微***与信息技术研究所 Tri-dimension stacked resistance conversion memory and manufacturing process thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109560104A (en) * 2018-12-20 2019-04-02 上海集成电路研发中心有限公司 A kind of phase transition storage and preparation method thereof
WO2020124929A1 (en) * 2018-12-20 2020-06-25 上海集成电路研发中心有限公司 Phase change memory and preparation method therefor
CN109686755A (en) * 2018-12-26 2019-04-26 上海集成电路研发中心有限公司 High-density phase-change memory and preparation method thereof
CN109686755B (en) * 2018-12-26 2022-07-05 上海集成电路研发中心有限公司 High-density phase change memory and preparation method thereof
CN112652714A (en) * 2020-12-23 2021-04-13 华中科技大学 Preparation method of phase change memory array
CN113838886A (en) * 2021-09-01 2021-12-24 深圳大学 Phase change memory and preparation method thereof

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