CN104037323A - Preparation method of RRAM (Resistive Random Access Memory) - Google Patents
Preparation method of RRAM (Resistive Random Access Memory) Download PDFInfo
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- CN104037323A CN104037323A CN201410268509.4A CN201410268509A CN104037323A CN 104037323 A CN104037323 A CN 104037323A CN 201410268509 A CN201410268509 A CN 201410268509A CN 104037323 A CN104037323 A CN 104037323A
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Abstract
The invention relates to the field of semiconductors, and aims to provide a preparation method of a RRAM (Resistive Random Access Memory). The preparation method comprises the steps of assembling a bottom electrode, a resistance changeable medium layer and a top electrode on a substrate in sequence; the preparation of the material of the resistance changeable medium comprises the following steps of: carrying a first precursor, an inert gas, a first reactant and the inert gas into a reactor in sequence, and preparing multiple circulating film substrates by using a plasma enhanced atomic layer deposition technology; then carrying a second precursor, the inert gas, a second reactant and the inert gas into the reactor in sequence, and preparing a single circulating doping layer by using the plasma enhanced atomic layer deposition technology; carrying out the steps mentioned above circularly, alternately and sequentially to obtain the resistance-changeable medium layer. The preparation method of the RRAM can control the thickness of the film of the resistance-changeable medium layer precisely, the prepared film is high in conformality and density, and large-area uniformity can be realized.
Description
Technical field
The invention relates to semiconductor applications, particularly a kind of preparation method of resistance-variable storing device.
Background technology
By the development along with information industry, many new nonvolatile semiconductor memory members arise at the historic moment, comprising ferroelectric memory, magnetic memory, phase transition storage and resistance-variable storing device (RRAM).In these novel memories, RRAM relies on that it is simple in structure, low in energy consumption, can fast reading and writing and can realize the advantages such as high density storage, have broad application prospects, be one of strong competitor of the following main flow memory technology of 32nm node of generally acknowledging in the world, be expected to become next generation's " general " type nonvolatile memory.
RRAM utilizes the resistance switch characteristic of insulator or semi-conducting material, realizes the storage of information.So-called resistance switch characteristic,, under the exciting of pulse voltage, device is realized the transformation between high-impedance state and low resistance state (0 and 1).The basic structural unit of RRAM is metal-insulator (or semiconductor)-metal (MIM); Its structure generally comprises substrate, hearth electrode, top electrode and the resistive dielectric layer between hearth electrode and top electrode.It is generally acknowledged that the micromechanism that RRAM realizes resistance switch characteristic is generation and the fracture of conductive nano silk in resistive dielectric layer.Conventionally, resistive dielectric layer must could be realized reversible resistance switch characteristic through an electric activation (electroforming process).Because RRAM is simple in structure, change resistance layer film very thin (conventionally only having tens nanometers), makes it be highly suitable for stacking integrated on three-dimensional; In addition, conductive nano silk only has several nanometers conventionally, can meet the requirement of memory device miniaturization, thereby greatly improves storage density.
The preparation technology of RRAM is simple, and with traditional semiconductor technology compatibility, wherein most critical is the preparation of resistive dielectric layer thin-film material.At present, the technology of preparing of resistive dielectric layer mainly contains the physical gas phase deposition technologies (PVD) such as sputter, electron beam evaporation and pulsed laser deposition, chemical vapour deposition technique (CVD), and technique for atomic layer deposition (ALD) etc.
Wherein, conventional film doping method mainly comprises: use the doping preparation of target materials film baking; Film is prepared in the common sputter of many targets; Pass into a certain proportion of mixing presoma and prepare film etc.But these doping means are difficult to realize the accurately controlled of doping component.Realize the ALD technology of thin film deposition based on ALT pulse endless form, compare with CVD method with traditional PVD, can more accurately control film thickness, obtain densification, evenly, there is the large area film of high conformality, three-dimensionally there is unique advantage aspect integrated extensive.Along with development and the requirement of semiconductor integrated circuit technique to device miniaturization of nanometer technology, as a kind of emerging ultrathin film technology of preparing, ALD is specially adapted to the manufacture of resistance-variable storing device.
Resistive dielectric layer material is the core of RRAM, selects different materials, and the resistive characteristic of RRAM exists larger difference, and the material category with resistive characteristic of having reported is at present various.Aluminium nitride, as a kind of important wide bandgap semiconductor, has excellent resistance switch characteristic.Conventionally use magnetically controlled sputter method to prepare AlN film as RRAM resistive dielectric layer material.For example, the people such as C.Chen (Bipolar resistive switching in Cu/AlN/Pt nonvolatile memory device, Appl.Phys.Lett.97,083502 (2010)) use magnetron sputtering technique to prepare AlN film, this film demonstrates good resistance switch characteristic, and devices switch ratio can reach 10
3magnitude.But because the resistance of AlN film is very large, device needs very high activation voltage, causes device resistive poor stability, high-impedance state change in resistance scope is large, and device is easy to breakdown.These have all limited the extensive use of ALD technology in resistance-variable storing device field.
Summary of the invention
Main purpose of the present invention is to overcome deficiency of the prior art, and a kind of resistance-variable storing device preparation method that can accurately control resistive dielectric layer film thickness, promote resistance-variable storing device stability is provided.For solving the problems of the technologies described above, solution of the present invention is:
A kind of preparation method of resistance-variable storing device is provided, is included on substrate and assembles successively hearth electrode, resistive dielectric layer and top electrode, the preparation of described resistive dielectric layer material comprises the following steps:
(1) successively the first presoma, inert gas, the first reactant, inert gas are passed in reactor, (in reactor, there is a pedestal at the air pressure of 0.2～2Torr and the underlayer temperature of 50～400 DEG C, substrate is placed on pedestal, the temperature of pedestal is generally all expressed as underlayer temperature) under, use plasma enhanced atomic layer deposition technology to prepare some circulation film matrix;
(2) successively the second presoma, inert gas, the second reactant, inert gas are passed in the reactor of step (1) again, under the underlayer temperature of the air pressure of 0.2～2Torr and 50～400 DEG C, use plasma enhanced atomic layer deposition technology to prepare single cycle doped layer;
(3) cycle alternation carries out, after above-mentioned steps (1) and step (2) 125～1000 times, obtaining the laminate film of doped monoatomic layer successively, for as resistive dielectric layer;
Wherein, described the first presoma is trimethyl aluminium; The metal alkoxide (titanium tetraisopropylate, amino titanium) that described the second presoma is titanium; Described the first reactant is N
2/ H
2gaseous mixture or NH
3plasma, and N
2/ H
2n in gaseous mixture
2and H
2volume ratio be 5:1～1:5; Described the second reactant is N
2/ H
2gaseous mixture, N
2/ O
2gaseous mixture, NH
3plasma or NO
xplasma, and N
2/ H
2n in gaseous mixture
2and H
2volume ratio be 5:1～1:5, N
2/ O
2n in gaseous mixture
2and O
2volume ratio be 5:1～1:5; The high-purity argon gas that described inert gas adopts purity to be greater than 99.99%.
As further improvement, in described step (1), the film matrix of preparation is the film matrix of aluminium nitride material, and some number of cycles are 1～20, and film matrix thickness is 0.08～1.6nm.
As further improvement, in described step (2), the single cycle doped layer of preparation is the single cycle doped layer of titanium nitride or titanium oxynitrides material, and single cycle doped layer thickness is 0.02nm.
As further improvement, in described step (3), the laminate film of the doped monoatomic layer of preparation is the laminate film of the aluminium nitride of monoatomic layer titanium nitride doping or the aluminium nitride material of monoatomic layer titanium oxynitrides doping, and the gross thickness of the laminate film of doped monoatomic layer is 10～80nm.
As further improvement, in described plasma enhanced atomic layer deposition technology, the radio frequency source power that plasma occurs is 30～1500W, and plasma-generating gas flow is 20～200 mark condition ml/min, and the plasma reaction time is 3～50s/ circulation.
As further improvement, described substrate adopts SiO
2any one in the conventional substrate of/Si, SiC, glass, quartz plate or sapphire semiconductor technology.
As further improvement, described hearth electrode is the hearth electrode of inert metal material, and inert metal is Au or Pt.
As further improvement, described top electrode is the top electrode of any one material in Cu, Ag or Pt material.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention introduces a kind of brand-new doped monoatomic layer plasma enhanced atomic layer deposition technology, prepares resistance-variable storing device.; in film matrix, add the doped layer of individual layer; use highly active plasma as reactant; by regulating the thickness of matrix film to regulate and control the concentration of doped layer; significantly reduce the activation voltage of device; realize the accurate control of device resistance switching characteristic, finally reach the erasable voltage of device adjustable, the resistive stability of device is improved significantly.
The present invention, by the good aluminum nitride thin membrane matrix of insulation property, mixes the good titanium oxynitrides of electric conductivity or titanium nitride, changes the density of conductive nano silk in resistive dielectric layer, thereby improves the resistance switch characteristic of device.
The present invention uses ALD technology to realize monoatomic layer (pulse) doping, form by ALT pulse is by individual layer atom indentation in matrix film, and the vapour pressure that has solved traditional C VD method precursor source varies with temperature and the uncontrollable difficult problem of composition that causes adulterating.
The present invention can accurately control the thickness of resistive dielectric layer film, and the film of preparation has high conformality, high-compactness, and can realize large-area uniformity.
Brief description of the drawings
Fig. 1 is the structural representation of resistance-variable storing device of the present invention.
Fig. 2 is change resistance layer medium doping process schematic diagram.
Fig. 3 is the AlN base resistance-variable storing device electricity activation current-voltage characteristic curve of preparing respectively in embodiment 1 and comparative example 1.
Fig. 4 is the AlN base resistance-variable storing device resistance switch characteristic curve of preparing respectively in embodiment 1 and comparative example 1.
Fig. 5 is that voltage relative frequency distribution map is wiped, write to the AlN base resistance-variable storing device of preparation in comparative example 1.
Fig. 6 is that voltage relative frequency distribution map is wiped, write to the AlN base resistance-variable storing device of preparation in embodiment 1.
Fig. 7 is the high and low resistance state resistor cumulative frequency distributing graph of AlN base resistance-variable storing device of preparing respectively in embodiment 1 and comparative example 1.
Reference numeral in figure is: 1 top electrode; 2 resistive dielectric layers; 3 hearth electrodes; 4 substrates.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in further detail:
Embodiment 1
Adopt aluminium nitride as resistive dielectric layer film matrix, use titanium oxynitrides as doped layer.Use titanium tetraisopropylate as the second presoma, N
2/ H
2(1:1) gaseous mixture plasma, as reactant, comprises the following steps:
1) adopt magnetically controlled sputter method at SiO
2(300nm) inert metal Pt hearth electrode 3 is prepared on/Si (100) substrate 4 surfaces, and gained hearth electrode 3 thickness are 150nm, and the temperature of preparation is 150 DEG C, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
2) using plasma strengthens Atomic layer deposition method, taking trimethyl aluminium as the first presoma, titanium tetraisopropylate is the second presoma, N
2/ H
2(1:1) plasma of gaseous mixture is the first and second reactants, and argon gas, as cleaning inert gas, first deposits the aln layer matrix film of 2 circulations on Pt hearth electrode 3, and hypothallus thickness is 0.16nm; Then; At the titanium oxynitrides of the single circulation of aln layer matrix film surface deposition, titanium oxynitrides thickness is 0.02nm.Cycle alternation repeats said process successively, finally obtains the aluminium nitride film (AlN:Ti=2:1) of monoatomic layer titanium oxynitrides doping.Adjust circulation sum, the thickness that makes film is 20nm.The temperature of deposition is 332 DEG C; Deposition and processing air pressure are 1Torr; The radio frequency source power of plasma generator is 600W; N
2/ H
2(1:1) flow of gaseous mixture is 30:30sccm, and the reaction time is 5s/ circulation.
3) utilize electron beam evaporation method to prepare circular Cu top electrode 1 at film surface, the about 100nm of thickness of top electrode 1, diameter is 200um.The temperature of preparation is 25 DEG C.
Embodiment 1-2
Other conditions, with embodiment 1-1, change the first and second reactants into N
2/ H
2(5:1) plasma of gaseous mixture, changes the number of cycles of aln layer matrix film into 4, and hypothallus thickness is 0.32nm, finally obtains the aluminium nitride film (AlN:Ti=4:1) of monoatomic layer titanium oxynitrides doping.
Comparative example 1
1) adopt magnetically controlled sputter method at SiO
2(300nm)/Si (100) substrate surface is prepared inert metal Pt hearth electrode, and gained hearth electrode thickness is 150nm, and the temperature of preparation is 150 DEG C, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
2) using plasma strengthens Atomic layer deposition method, taking trimethyl aluminium as the first presoma, titanium tetraisopropylate is the second presoma, N
2/ H
2(1:1) plasma of gaseous mixture is the first and second reactants, and argon gas, as cleaning inert gas, deposits the aluminium nitride film of 250 circulations on Pt hearth electrode, and film thickness is 20nm.The temperature of deposition is 332 DEG C; Reaction pressure is about 1Torr; The radio frequency source power of plasma generator is 600W; N
2/ H
2(1:1) flow of gaseous mixture is 60sccm, and the reaction time is 5s/ circulation.
3) utilize electron beam evaporation method to prepare circular Cu top electrode at film surface, the about 100nm of thickness of top electrode, diameter is 200um.The temperature of preparation is 25 DEG C.
Comparing embodiment 1-1, embodiment 1-2 and comparative example 1 can find, three has ambipolar resistance switch characteristic, approximately 100 times of the on-off ratios of resistance-variable storing device.
Fig. 3 is the AlN base resistance-variable storing device electricity activation current-voltage characteristic curve of preparing respectively in embodiment 1 and comparative example 1.Wherein, curve 21,22 is respectively in comparative example 1 AlN:Ti=4:1 resistance-variable storing device electricity activation current-voltage characteristic curve in AlN resistance-variable storing device and embodiment 1.Can find, add after titanium oxynitrides doped layer, the electric activation voltage of device is reduced to 7V from 8.5V.In the time of AlN:Ti=2:1, device does not need the activation of forward voltage just to demonstrate reversible resistance switch characteristic.
Fig. 4 is the AlN base resistance-variable storing device resistance switch characteristic curve of preparing respectively in embodiment 1 and comparative example 1.Wherein, curve 31,32,33 is respectively in AlN resistance-variable storing device in comparative example 1, embodiment 1 AlN:Ti=2:1 resistance-variable storing device resistance switch characteristic curve in AlN:Ti=4:1 resistance-variable storing device, embodiment 1.Can find, by regulation and control doped layer concentration, resistance switch characteristic that can accuracy controlling device, along with the increase of doping ratio, device writes with the absolute value of erasing voltage and declines gradually.
For the stability of analysis device, device is done to 100 continuous circulation tests.Fig. 5 and Fig. 6 are respectively in comparative example 1 the AlN:Ti=2:1 resistance-variable storing device of preparation in the AlN base resistance-variable storing device of preparation and embodiment 1 and wipe, write voltage relative frequency distribution map.Wherein, 41,42 be respectively that AlN resistance-variable storing device in comparative example 1 writes, erasing voltage relative frequency distribution map; 51,52 be respectively AlN:Ti=2:1 resistance-variable storing device in embodiment 1 and write voltage, erasing voltage relative frequency distribution map.Fig. 7 be in comparative example 1 preparation AlN base resistance-variable storing device and embodiment 1 in preparation the high and low resistance state resistor cumulative frequency distributing graph of AlN:Ti=2:1 resistance-variable storing device.Wherein, curve 61,62 is respectively the high and low resistance state resistor cumulative frequency distributing graph of AlN resistance-variable storing device in comparative example 1; Curve 63,64 is respectively the high and low resistance state resistor cumulative frequency distributing graph of AlN:Ti=2:1 resistance-variable storing device in embodiment 1.Can find out from the large erasable voltage of device, high low resistance state statistics, after doping titanium oxynitrides, erasable voltage, the high low resistance state distribution of device significantly reduce, and device stability significantly promotes.
Embodiment 2-1
Adopt aluminium nitride as resistive dielectric layer film matrix, use titanium nitride as doped layer, use four (dimethylamino) titanium as the second presoma, N
2/ H
2(1:5) gaseous mixture plasma, as reactant, comprises the following steps:
1) adopt magnetically controlled sputter method to prepare inert metal Au hearth electrode 3 on quartz substrate 4 surfaces, gained hearth electrode 3 thickness are 150nm, and the temperature of preparation is 150 DEG C, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
2) using plasma strengthens Atomic layer deposition method, taking trimethyl aluminium as the first presoma, four (dimethylamino) titanium as the second presoma, N
2/ H
2(1:5) plasma of gaseous mixture is the first and second reactants, and argon gas, as cleaning inert gas, first deposits the aln layer matrix film of 9 circulations on Pt hearth electrode 3, and hypothallus thickness is 0.72nm; Then,, at the titanium nitride of the single circulation of aln layer matrix film surface deposition, titanium nitride thickness is 0.02nm.Alternately repeat said process, finally obtain the aluminium nitride film (AlN:Ti=9:1) of monoatomic layer titanium nitride doping.Adjust sum, the thickness that makes film is 10nm.The temperature of deposition is 100 DEG C; Air pressure is 0.2Torr; The radio frequency source power of plasma generator is 30W; N
2/ H
2(1:5) flow of gaseous mixture is 20sccm, and the reaction time is 50s/ circulation.
3) utilize electron beam evaporation method to prepare circular Cu top electrode 1 at film surface, the about 100nm of thickness of top electrode 1, diameter is 200um.The temperature of preparation is 25 DEG C.
Embodiment 2-2
Other conditions, with embodiment 2-1, change the second reactant into NH
3plasma or NO
xplasma, changes the number of cycles of aln layer matrix film into 20, and hypothallus thickness is 1.6nm, finally obtains the aluminium nitride film (AlN:Ti=20:1) of monoatomic layer titanium oxynitrides doping.
Comparative example 2
1) adopt magnetically controlled sputter method to prepare inert metal Au hearth electrode in quartz substrate surface, gained hearth electrode thickness is 150nm, and the temperature of preparation is 150 DEG C, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
2) using plasma strengthens Atomic layer deposition method, taking trimethyl aluminium as the first presoma, titanium tetraisopropylate is the second presoma, N
2/ H
2(1:5) plasma of gaseous mixture is the first and second reactants, and argon gas, as cleaning inert gas, deposits the aluminium nitride film of 125 circulations on Pt hearth electrode, and film thickness is 10nm.The temperature of deposition is 100 DEG C; Reaction pressure is about 0.2Torr; The radio frequency source power of plasma generator is 30W; N
2/ H
2(1:1) flow of gaseous mixture is 60sccm, and the reaction time is 50s/ circulation.
3) utilize electron beam evaporation method to prepare circular Cu top electrode at film surface, the about 100nm of thickness of top electrode, diameter is 200um.The temperature of preparation is 25 DEG C.
Experiment discovery, embodiment 2-1, embodiment 2-2 and comparative example 2 all have resistance switch characteristic, approximately 100 times of the on-off ratios of resistance-variable storing device.Add after titanium nitride doped layer, the electric activation voltage of device is reduced to 6V from 8.5V.In the time of AlN:Ti=9:1, device does not need the activation of forward voltage just to demonstrate reversible resistance switch characteristic.By regulation and control doped layer titanium nitride concentration, resistance switch characteristic that also can accuracy controlling device, along with the increase of doping ratio, device writes with the absolute value of erasing voltage and declines gradually.By 100 continuous circulation tests, erasable voltage, the high low resistance state distribution of device significantly reduce, and device stability significantly promotes.
Embodiment 3-1
Adopt aluminium nitride as resistive dielectric layer film matrix, use titanium oxynitrides as doped layer, use four (dimethylamino) titanium as the second presoma, NH
3plasma is as the first reactant, N
2/ O
2(5:1) gaseous mixture plasma, as the second reactant, comprises the following steps:
1) adopt magnetically controlled sputter method to prepare inert metal Pt hearth electrode 3 on glass substrate 4 surfaces, gained hearth electrode 3 thickness are 150nm, and the temperature of preparation is 150 DEG C, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
2) using plasma strengthens Atomic layer deposition method, taking trimethyl aluminium as the first presoma, four (dimethylamino) titanium as the second presoma, NH
3plasma is as the first reactant, N
2/ O
2(5:1) gaseous mixture plasma is as the second reactant, and argon gas, as cleaning inert gas, first deposits the aln layer matrix film of 1 circulation on Pt hearth electrode 3, and hypothallus thickness is 0.08nm; Then,, at the titanium nitride of the single circulation of aln layer matrix film surface deposition, titanium nitride thickness is 0.02nm.Alternately repeat said process, finally obtain the aluminium nitride film (AlN:Ti=1:1) of monoatomic layer titanium nitride doping.Adjust sum, the thickness that makes film is 80nm.The temperature of deposition is 400 DEG C; Air pressure is 2Torr; The radio frequency source power of plasma generator is 1500W; NH
3and N
2/ O
2(5:1) flow of gaseous mixture is respectively 200sccm, and the reaction time is 3s/ circulation.
3) utilize electron beam evaporation method to prepare circular Ag top electrode 1 at film surface, the about 100nm of thickness of top electrode 1, diameter is 200um.The temperature of preparation is 25 DEG C.
Embodiment 3-2
Other conditions, with embodiment 2-1, change the second reactant into N
2/ O
2(1:1) gaseous mixture plasma or N
2/ O
2(1:5) gaseous mixture, changes the number of cycles of aln layer matrix film into 2, and hypothallus thickness is 0.16nm, finally obtains the aluminium nitride film (AlN:Ti=2:1) of monoatomic layer titanium oxynitrides doping.
Comparative example 3
1) adopt magnetically controlled sputter method to prepare inert metal Pt hearth electrode at glass substrate surface, gained hearth electrode thickness is 150nm, and the temperature of preparation is 150 DEG C, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
2) using plasma strengthens Atomic layer deposition method, taking trimethyl aluminium as the first presoma, titanium tetraisopropylate is the second presoma, NH
3plasma is as reactant, and argon gas, as cleaning inert gas, deposits the aluminium nitride film of 1000 circulations on Pt hearth electrode, and film thickness is 80nm.The temperature of deposition is 400 DEG C; Reaction pressure is about 2Torr; The radio frequency source power of plasma generator is 1500W; NH
3flow be 200sccm, the reaction time is 3s/ circulation.
3) utilize electron beam evaporation method to prepare circular Ag top electrode at film surface, the about 100nm of thickness of top electrode, diameter is 200um.The temperature of preparation is 25 DEG C.
Experiment discovery, embodiment 3-1, embodiment 3-2 and comparative example 3 all have resistance switch characteristic, approximately 100 times of the on-off ratios of resistance-variable storing device.Add after titanium oxynitrides doped layer, the electric activation voltage of device is reduced to 10V from 30V.In the time of AlN:Ti=1:1, device does not need the activation of forward voltage just to demonstrate reversible resistance switch characteristic.By regulation and control doped layer titanium nitride concentration, resistance switch characteristic that also can accuracy controlling device, along with the increase of doping ratio, device writes with the absolute value of erasing voltage and declines gradually.By 100 continuous circulation tests, erasable voltage, the high low resistance state distribution of device significantly reduce, and device stability significantly promotes.
Finally, it should be noted that above what enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, can also have a lot of distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (8)
1. a preparation method for resistance-variable storing device, is included on substrate and assembles successively hearth electrode, resistive dielectric layer and top electrode, it is characterized in that, the preparation of described resistive dielectric layer material comprises the following steps:
(1) successively the first presoma, inert gas, the first reactant, inert gas are passed in reactor, under the underlayer temperature of the air pressure of 0.2～2Torr and 50～400 DEG C, use plasma enhanced atomic layer deposition technology to prepare some circulation film matrix;
(2) successively the second presoma, inert gas, the second reactant, inert gas are passed in the reactor of step (1) again, under the underlayer temperature of the air pressure of 0.2～2Torr and 50～400 DEG C, use plasma enhanced atomic layer deposition technology to prepare single cycle doped layer;
(3) cycle alternation carries out, after above-mentioned steps (1) and step (2) 125～1000 times, obtaining the laminate film of doped monoatomic layer successively, for as resistive dielectric layer;
Wherein, described the first presoma is trimethyl aluminium; The metal alkoxide (titanium tetraisopropylate, amino titanium, four (dimethylamino) titanium) that described the second presoma is titanium; Described the first reactant is N
2/ H
2gaseous mixture or NH
3plasma, and N
2/ H
2n in gaseous mixture
2and H
2volume ratio be 5:1～1:5; Described the second reactant is N
2/ H
2gaseous mixture, N
2/ O
2gaseous mixture, NH
3plasma or NO
xplasma, and N
2/ H
2n in gaseous mixture
2and H
2volume ratio be 5:1～1:5, N
2/ O
2n in gaseous mixture
2and O
2volume ratio be 5:1～1:5; The high-purity argon gas that described inert gas adopts purity to be greater than 99.99%.
2. the preparation method of a kind of resistance-variable storing device according to claim 1, it is characterized in that, in described step (1), the film matrix of preparation is the film matrix of aluminium nitride material, and some number of cycles are 1～20, and film matrix thickness is 0.08～1.6nm.
3. the preparation method of a kind of resistance-variable storing device according to claim 1, it is characterized in that, in described step (2), the single cycle doped layer of preparation is the single cycle doped layer of titanium nitride or titanium oxynitrides material, and single cycle doped layer thickness is 0.02nm.
4. the preparation method of a kind of resistance-variable storing device according to claim 1, it is characterized in that, in described step (3), the laminate film of the doped monoatomic layer of preparation is the laminate film of the aluminium nitride of monoatomic layer titanium nitride doping or the aluminium nitride material of monoatomic layer titanium oxynitrides doping, and the gross thickness of the laminate film of doped monoatomic layer is 10～80nm.
5. the preparation method of a kind of resistance-variable storing device according to claim 1, it is characterized in that, in described plasma enhanced atomic layer deposition technology, the radio frequency source power that plasma occurs is 30～1500W, plasma-generating gas flow is 20～200 mark condition ml/min, and the plasma reaction time is 3～50s/ circulation.
6. the preparation method of a kind of resistance-variable storing device according to claim 1, is characterized in that, described substrate adopts SiO
2any one in the conventional substrate of/Si, SiC, glass, quartz plate or sapphire semiconductor technology.
7. the preparation method of a kind of resistance-variable storing device according to claim 1, is characterized in that, described hearth electrode is the hearth electrode of inert metal material, and inert metal is Au or Pt.
8. the preparation method of a kind of resistance-variable storing device according to claim 1, is characterized in that, described top electrode is the top electrode of any one material in Cu, Ag or Pt material.
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| KR20170024552A (en) * | 2015-08-25 | 2017-03-07 | 에이에스엠 아이피 홀딩 비.브이. | Deposition of titanium nanolaminates for use in integrated circuit fabrication |
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| KR20110074052A (en) * | 2009-12-24 | 2011-06-30 | 경희대학교 산학협력단 | Method for preparing barrier film for plastic substrate by using low frequency plasma enhanced atomic layer deposition |
| CN102315387A (en) * | 2010-07-02 | 2012-01-11 | 南亚科技股份有限公司 | RRAM structure and method of making the same |
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| KR102385821B1 (en) | 2015-08-25 | 2022-04-12 | 에이에스엠 아이피 홀딩 비.브이. | Deposition of titanium nanolaminates for use in integrated circuit fabrication |
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