CN102227014A - Resistive random access memory possessing metal nanocrystalline electrode and preparation method thereof - Google Patents
Resistive random access memory possessing metal nanocrystalline electrode and preparation method thereof Download PDFInfo
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- CN102227014A CN102227014A CN2011100752936A CN201110075293A CN102227014A CN 102227014 A CN102227014 A CN 102227014A CN 2011100752936 A CN2011100752936 A CN 2011100752936A CN 201110075293 A CN201110075293 A CN 201110075293A CN 102227014 A CN102227014 A CN 102227014A
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Abstract
The invention belongs to the microelectronic technology field, and is a resistive random access memory (RRAM) possessing metal nanocrystalline electrode and a preparation method thereof specifically. The metal nanocrystalline bottom electrode is prepared with an ultrathin metallic film rapid heat annealing processing method, a drawing LB (Langmuir-Blodgett) film method or a metal nanometer particle chemical dispersion method. After the preparation of the bottom electrode, a resistive random access dielectric layer and a top electrode are deposited in order, finally an inorganic RRAM device possessing metal nanometer particle bottom electrode is formed. The typical characteristic of the memory is that: electric field of the metal nanometer particle is enhanced, after applying a certain voltage, dielectric layer contacting the metal nanometer particle electrode easily forms an electrically conductive path, and random distribution which the electrically conductive path forms in the resistive random access memory can be reduced to a great extent to achieve the purpose of resistive random access characteristic stabilization.
Description
Technical field
The invention belongs to microelectronics technology, be specifically related to a kind of inorganic resistance-variable storing device and preparation method thereof.
Background technology
Along with the continuous development of integrated circuit technique, traditional nonvolatile memory---the FLASH device is faced with stern challenge, this be embodied in the not enough of its erasable speed and further scaled down size etc. bring problem.In this case, resistance-variable storing device is fast because of its simple in structure, erasable speed, low-power consumption and be easy to extensive integrated characteristics and be subjected to paying close attention to widely, becomes the strong candidate of non-volatility memorizer of future generation.
Resistance-variable storing device has two kinds of recognizable states: high-resistance state (HRS) and low resistance state (LRS), the construction unit of sort memory is a kind of mim structure of similar plate condenser, generally be the insulating barrier in the middle of double layer of metal clips, this insulating barrier mostly is the binary metal oxide material in the research at present.When the RRAM two ends applied an electric pulse, according to height, width and the polarity of electric pulse, the reversible variation of several magnitude can take place in the resistance of device isolation layer, a kind of resistance switch characteristic that Here it is.
The RRAM(resistance-variable storing device) memory mechanism is based on the transformation of the high low resistance state of resistance, thereby realizes 0 and 1 storage, and its resistive mechanism is of a great variety, and that relatively generally acknowledges at present has filament (filament) conductivity theory and theoretical two big classes of stored charge resistive.Wherein, based on the resistive of filament conductivity theory, its stability is subjected to the influence of several factors, mainly contains: the formation and the stability of resistive material itself, the contact problems of electrode material and change resistance layer, and the mode of operation of SET and RESET.
The key difficult problem that present resistance-variable storing device faces is the unsteadiness that how to solve high-impedance state and low resistance state resistance.Experiment shows that the statistics of high low resistance state all shows certain discrete type.By the filament conductivity theory, in the transformation of resistance state and the change resistance layer formation of conductive path with disappear relevant, yet formation and the fracture of conductive path in change resistance layer has very big randomness.For example, twice identical potential pulse operation, the conductive path that forms in the change resistance layer of same device has a great difference, has randomness significantly.This comes from the capacity plate antenna structure of traditional RRAM, Electric Field Distribution in the change resistance layer is uniform, yet the formation of conductive path with disappear that electric field is relevant often, so the probability that conductive path occurs between electrode everywhere is basic identical, this has just caused the randomness that current path distributes in the change resistance layer, is unfavorable for the stable of electric resistance changing.Therefore,, utilize spike electrode place electric field strength to be higher than other local characteristics, can improve the probability that spike electrode place conductive path forms greatly, thereby the repeatability of device, stability are greatly improved if preparation has the electrode of spike figure.Simultaneously, the high electric field strength in spike place makes the operating voltage of device be reduced, and has reduced the power consumption of device to a certain extent.
Summary of the invention
The objective of the invention is to propose a kind of inorganic RRAM device and preparation method thereof with good reproducibility and stability.
The inorganic RRAM device that the present invention proposes comprises the substrate, hearth electrode, inorganic medium layer and the top electrode that coincide successively; Wherein, be distributed with nano metal crystal grain on the hearth electrode, this nano metal crystallite dimension forms the spike shape of hearth electrode between 2 ~ 30nm, and this spike is shaped as sphere, elliposoidal, taper or cylindrical; Top electrode is a flat form.
The inorganic RRAM device that the present invention proposes with needle pattern hearth electrode, smooth top electrode, make the electric field in the dielectric layer have certain distribution, and the electric field at spike place is a maximum, make the spike place help forming conductive filament most, thereby strengthen repeatability, stability and switch current ratio based on the RRAM device of filament conduction.
The inorganic RRAM preparation of devices method that the present invention proposes, concrete steps are as follows:
1, use through cleaning, the monocrystalline silicon of oven dry is as substrate, adopts hot growth method one deck SiO that grows on substrate
2
2, adopt PVD technology or vacuum evaporation coating membrane technology large tracts of land deposit hearth electrode;
3, adopt another layer of PVD method deposit metallic film, thickness 1 ~ 5nm;
4, utilize the metallic film rapid thermal anneal process that metallic film is carried out the rapid thermal annealing of nitrogen environment, make metallic film disperse to form to have the nano metal crystal grain of a certain size and shape, thereby obtain having the hearth electrode of needle pattern; Perhaps utilize method of drawing the LB film or the chemical dispersion method that adopts metal nanoparticle, make to be distributed with nano metal crystal grain on the hearth electrode, thereby obtain having the hearth electrode of needle pattern;
5, adopt ALD technology growth one deck change resistance layer material;
6, adopt the CMP technology, with the leveling of change resistance layer upper surface;
7, utilize the vacuum evaporation coating membrane technology,, form the round point shape top electrode by evaporated metal and by the round point shape mask, thus the final inorganic resistance-variable storing device that forms with needle pattern hearth electrode, smooth top electrode.
Among the present invention, the hearth electrode material is a polysilicon, perhaps is metal Ru, Pd, Ti, Au, Ag, Pt, Ni, Cu or TiN, perhaps is the alloy material of above-mentioned metal material, and deposition technology adopts vacuum coating technology or PVD technology.
Among the present invention, the size of each spike figure of hearth electrode (being the size of nano metal crystal grain) between 2 ~ 30nm, spike be shaped as sphere, elliposoidal, taper, cylindrical, the thickness of described change resistance layer material is 10 ~ 100nm.
Among the present invention, the described metallic film material of step (3) is Pd, Ru, Ti, Au, Ag, Pt, Ni or Cu.
Among the present invention, the hearth electrode preparation technology of described resistance-variable storing device adopts the metallic film rapid thermal anneal process, perhaps adopts LB(Langmuir-Blodgett) legal system is equipped with the chemical dispersion method of individual layer nano-metal particle technology and metal nanoparticle.
Among the present invention, RRAM device top electrode adopts metal Pt, Ti, Pd, Ni, Cu, W or TiN material, and deposition technology adopts the PVD technology by the vacuum coating technology of mask or cooperation photoetching.
Because hearth electrode is a needle pattern, after applying certain voltage, the electric field at spike place is the highest, so the easiest formation conductive path of dielectric layer herein, can reduce the randomness that conductive path forms to a great extent in resistance-variable storing device, thereby reach the purpose of resistive stability of characteristics.
Concrete steps are:
1, adopts custom integrated circuit technology to obtain planless monocrystalline substrate structure sample, adopt the SiO of hot growth method growth one deck 20 ~ 100nm
2
2, adopt PVD technology or vacuum vapor plating large tracts of land deposit hearth electrode, as W, thickness 20 ~ 100nm;
3, adopt magnetron sputtering PVD method deposit layer of metal film, as Pd, Pt etc., thickness 1 ~ 5nm;
4, utilize the metallic film rapid thermal anneal process metals deposited film to be carried out the rapid thermal annealing of nitrogen environment, the metallic nano crystal that has a certain size and shape with formation, annealing temperature 600 ~ 900 degree, annealing time 30 ~ 90s finishes the preparation of hearth electrode peak structure this moment;
5, adopt ALD technology growth one deck change resistance layer material, as HfO
2, thickness 20 ~ 100nm,
6, adopt chemical Mechanical Polishing Technique, make the leveling of change resistance layer upper surface;
7, utilize the vacuum evaporation coating membrane technology,, form round point shape metal roof electrode (material such as Ni), thickness of electrode 50 ~ 100nm, round dot diameter 50nm ~ 1mm by evaporated metal and by the round point shape mask.Thereby the final inorganic resistance-variable storing device that forms with needle pattern hearth electrode, smooth top electrode.
Description of drawings
Fig. 1-Fig. 5 is the schematic diagram (end view) of technological process.Wherein, Fig. 5 is the device-side view of last process step formation.
Number in the figure: 1 is the Si substrate, and 2 is SiO
2, 3 is hearth electrode Pt, and 4 is spike electrode Pd, and 5 is HfO
2, 6 is top electrode Ni, wherein 3 and 4 common formation RRAM hearth electrodes.
Embodiment
Further describe the present invention below by concrete processing step:
1, choose the P type silicon chip in (100) crystal orientation, adopt standard RCA technology that silicon chip is cleaned, 2% hydrofluoric acid is removed natural oxidizing layer.Adopt the thick SiO of hot growth method growth one deck 100nm
2, as Fig. 1;
2, adopt the thick Pt hearth electrode of vacuum evaporation coating embrane method large tracts of land deposit one deck 100nm, vacuum degree 10
-5Pa is as Fig. 2;
3, adopt magnetron sputtering method deposit one deck Pd metallic film, argon flow amount 35sccm, direct current power 10W, operating air pressure 0.8Pa, substrate rotating speed 8rpm, sputtering time 5min, the about 3nm of Pd film thickness;
4, the film for preparing is annealed under nitrogen environment 60s, annealing temperature 750 degree, it is nanocrystalline to form Pd, about diameter 7nm, as Fig. 3;
5, adopt the ALD(atomic layer deposition) method growth one deck HfO
2Dielectric layer, thickness 30nm;
6, adopt the CMP(chemico-mechanical polishing), the change resistance layer upper surface is polished, the about 20nm of dielectric film thickness this moment is as Fig. 4;
7, adopt the vacuum evaporation coating membrane technology, use metal mask net mask, large tracts of land deposit layer of Ni top electrode, film thickness 100nm, top electrode size 50x50 μ m, vacuum degree 10
-5Pa is as Fig. 5.
Claims (7)
1. the resistance-variable storing device with metallic nano crystal electrode is characterized in that comprising the substrate, hearth electrode, inorganic medium layer and the top electrode that coincide successively; Wherein, be distributed with nano metal crystal grain on the hearth electrode, this nano metal crystallite dimension forms the spike shape of hearth electrode between 2 ~ 30nm, and this spike is shaped as sphere, elliposoidal, taper or cylindrical; Top electrode is a flat form.
2. the preparation method of an inorganic resistance-variable storing device as claimed in claim 1 is characterized in that concrete steps are:
(1), use through cleaning, the monocrystal silicon sample of oven dry, adopt hot growth method growth one deck SiO
2
(2), adopt PVD technology or vacuum evaporation coating membrane technology, large tracts of land deposit hearth electrode;
(3), adopt magnetron sputtering technique or another layer of PVD deposition techniques metallic film, thickness is 1 ~ 5nm;
(4), utilize metallic film rapid thermal annealing method, metallic film is carried out the rapid thermal annealing of nitrogen environment, make metallic film disperse to form to have the nano metal crystal grain of a certain size and shape, thereby obtain having the hearth electrode of needle pattern;
Perhaps utilize method of drawing the LB film or the chemical dispersion method that adopts metal nanoparticle, make to be distributed with nano metal crystal grain on the hearth electrode, thereby obtain having the hearth electrode of needle pattern;
(5), adopt ALD technology growth one deck change resistance layer material;
(6), adopt the CMP technology, with the leveling of change resistance layer upper surface;
(7), utilize the vacuum evaporation coating membrane technology, formation point-like top electrode, thereby the final inorganic resistance-variable storing device that forms with spike shape hearth electrode, smooth top electrode.
3. preparation method as claimed in claim 2, it is characterized in that the described hearth electrode material of step (2) is semi-conducting material Si, perhaps being metal Ru, Pd, Ti, Au, Ag, Pt, Ni, Cu or TiN, perhaps is alloy materials several in the above-mentioned metal material.
4. preparation method according to claim 2 is characterized in that the described metallic film material of step (3) is Pd, Ru, Ti, Au, Ag, Pt, Ni or Cu.
5. preparation method according to claim 2 is characterized in that the described nano metal crystallite dimension of step (4) between 2 ~ 30nm, spike be shaped as sphere, elliposoidal, taper or cylindrical.
6. preparation method according to claim 2 is characterized in that the described change resistance layer material of step (5) is HfO
2, ZnO, Al
2O
3, SiO
2Or ZrO
2, thickness is 10 ~ 100nm.
7. preparation method according to claim 2 is characterized in that the described top electrode material of step (7) adopts metal Pt, Ti, Pd, Ni, Cu, W or TiN.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013152536A1 (en) * | 2012-04-12 | 2013-10-17 | 北京大学 | Resistive random access memory of small electrode structure and preparation method therefor |
| CN103456883A (en) * | 2012-06-01 | 2013-12-18 | 飞思卡尔半导体公司 | Field focusing features in a reram cell |
| CN103633243A (en) * | 2012-08-28 | 2014-03-12 | 中国科学院微电子研究所 | Preparation method of resistive memory |
| CN104835909A (en) * | 2014-02-11 | 2015-08-12 | 力晶科技股份有限公司 | Resistive random access memory |
| CN108682739A (en) * | 2018-05-03 | 2018-10-19 | 五邑大学 | A kind of metal quantum point enhancing ZnO resistive memories and preparation method thereof |
| CN109360887A (en) * | 2018-09-18 | 2019-02-19 | 南京工业大学 | Variable-voltage controllable resistive random access memory and preparation method thereof |
| CN111564556A (en) * | 2020-05-22 | 2020-08-21 | 北京大学 | Pyramid-shaped resistive random access memory and preparation method thereof |
| CN111628077A (en) * | 2020-06-05 | 2020-09-04 | 福州大学 | Electronic synapse device modified by silver nanoparticles |
| CN113130742A (en) * | 2021-03-19 | 2021-07-16 | 厦门半导体工业技术研发有限公司 | Semiconductor integrated circuit device and method for manufacturing the same |
| CN113206195A (en) * | 2021-04-30 | 2021-08-03 | 华中科技大学 | Memristor for regulating and controlling positioning of conductive filament based on quantum dots and preparation method of memristor |
| CN113675334A (en) * | 2020-05-14 | 2021-11-19 | 北京大学 | Memristor network based on movable conductive nanoparticles and self-organized evolution operation application |
| WO2023039847A1 (en) * | 2021-09-17 | 2023-03-23 | 华为技术有限公司 | Resistance random access memory unit, resistance random access memory, and electronic device |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013152536A1 (en) * | 2012-04-12 | 2013-10-17 | 北京大学 | Resistive random access memory of small electrode structure and preparation method therefor |
| US9142768B2 (en) | 2012-04-12 | 2015-09-22 | Peking University | Resistive memory with small electrode and method for fabricating the same |
| CN103456883A (en) * | 2012-06-01 | 2013-12-18 | 飞思卡尔半导体公司 | Field focusing features in a reram cell |
| CN103456883B (en) * | 2012-06-01 | 2018-10-23 | 恩智浦美国有限公司 | Field aggregation characteristic portion in ReRAM units |
| CN103633243A (en) * | 2012-08-28 | 2014-03-12 | 中国科学院微电子研究所 | Preparation method of resistive memory |
| CN104835909A (en) * | 2014-02-11 | 2015-08-12 | 力晶科技股份有限公司 | Resistive random access memory |
| CN104835909B (en) * | 2014-02-11 | 2017-05-17 | 力晶科技股份有限公司 | Resistive random access memory |
| CN108682739A (en) * | 2018-05-03 | 2018-10-19 | 五邑大学 | A kind of metal quantum point enhancing ZnO resistive memories and preparation method thereof |
| CN109360887A (en) * | 2018-09-18 | 2019-02-19 | 南京工业大学 | Variable-voltage controllable resistive random access memory and preparation method thereof |
| CN113675334A (en) * | 2020-05-14 | 2021-11-19 | 北京大学 | Memristor network based on movable conductive nanoparticles and self-organized evolution operation application |
| CN113675334B (en) * | 2020-05-14 | 2024-05-24 | 北京大学 | Memristor network based on movable conductive nano particles and self-organizing evolution operation application |
| CN111564556A (en) * | 2020-05-22 | 2020-08-21 | 北京大学 | Pyramid-shaped resistive random access memory and preparation method thereof |
| CN111628077A (en) * | 2020-06-05 | 2020-09-04 | 福州大学 | Electronic synapse device modified by silver nanoparticles |
| CN113130742A (en) * | 2021-03-19 | 2021-07-16 | 厦门半导体工业技术研发有限公司 | Semiconductor integrated circuit device and method for manufacturing the same |
| CN113206195A (en) * | 2021-04-30 | 2021-08-03 | 华中科技大学 | Memristor for regulating and controlling positioning of conductive filament based on quantum dots and preparation method of memristor |
| WO2023039847A1 (en) * | 2021-09-17 | 2023-03-23 | 华为技术有限公司 | Resistance random access memory unit, resistance random access memory, and electronic device |
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Application publication date: 20111026 |