CN103441214A - Preparation method for resistive random access memory - Google Patents
Preparation method for resistive random access memory Download PDFInfo
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- CN103441214A CN103441214A CN2013103339319A CN201310333931A CN103441214A CN 103441214 A CN103441214 A CN 103441214A CN 2013103339319 A CN2013103339319 A CN 2013103339319A CN 201310333931 A CN201310333931 A CN 201310333931A CN 103441214 A CN103441214 A CN 103441214A
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Abstract
The invention discloses a preparation method for a resistive random access memory. The resistive random access memory comprises a bottom electrode, a resistance change dielectric layer material and a top electrode which are assembled in sequence. Preparation of the resistance change dielectric layer material includes the following steps that firstly, a first precursor, first inert gas, a second precursor and second inert gas are fed into a reactor in order, and a monolayer metallic oxide film is deposited on the bottom electrode through a cycle of hot atomic layer deposition; secondly, a plasma enhancement process is carried out on the film; finally, the steps are carried out circularly and alternately. In the preparation process of a resistance change dielectric layer, a brand new in-situ plasma enhancement hot atomic layer deposition technology is brought in, so the surface appearance and defects of the metallic oxide film can be adjusted on a large scale; the resistive random access memory obtained through the preparation method can achieve precision control over device resistance switching characteristics to enable the device switch ratio and erase/write voltage to be adjusted, and has excellent resistance change stability.
Description
Technical field
The present invention relates to semiconductor applications, relate in particular to a kind of preparation method of resistance-variable storing device.
Background technology
Along with the arriving of integrated circuit technology 32nm technology node, traditional Flash memory has run into a series of problem, wherein, topmost problem is, along with the tunnel oxide layer thickness is more and more less, the earial drainage of electric charge becomes more and more serious, directly affects the data retention of Flash memory.In recent years, various novel nonvolatile memories are developed rapidly, as ferroelectric memory, magnetic memory, phase transition storage and resistance-variable storing device (RRAM), but RRAM relies on its fast reading and writing simple in structure, low in energy consumption and can realize the advantage such as high density storage, becomes the most competitive " general " type nonvolatile memory of future generation.
RRAM utilizes the change resistance layer material under the voltage effect, has the resistance switch characteristic of resistance states reversible transition, realizes the storage of information.The structure of RRAM comprise substrate, hearth electrode, top electrode and be positioned at hearth electrode and top electrode between the resistive dielectric layer, wherein, the resistive dielectric layer is the core of RRAM, thickness only has tens nanometers usually.RRAM realizes that the micromechanism of electric resistance changing is generation and the fracture of conductive nano silk in the resistive dielectric layer.Because the conductive nano silk only has several nanometers usually, can meet the requirement of memory device miniaturization; In addition, the resistive dielectric layer is generally the simple metal oxide, and preparation technology and microelectronic technique are fully compatible.
The preparation technology of RRAM is simple, and wherein most critical is the preparation of resistive dielectric layer.At present, the technology of preparing of resistive dielectric layer mainly contains sputter, chemical vapour deposition (CVD), pulsed laser deposition, electron beam evaporation, ald (ALD) and Rong Jiao & Gel etc.Realize the ALD technology of thin film deposition based on the ALT pulse endless form, can accurately control film thickness, obtain densification, evenly, there is the large area film of high conformality.Along with the requirement to device miniaturization of the development of nanometer technology and semiconductor integrated circuit technique, as a kind of emerging ultrathin film technology of preparing, the ALD technology rely on its extensive three-dimensional integrated aspect the advantage of uniqueness, become a kind of important preparation means of resistance-variable storing device.
In the ALD technology, the growth of film is carried out in a kind of mode of circulation, and a circulation comprises four-stage: (1) the first presoma enters reaction chamber in the mode of gas pulses, and is chemisorbed on substrate surface; (2), after adsorption is saturated, with inert gas, unnecessary presoma is blown out to reaction chamber; (3) the second presoma enters reaction chamber in the mode of gas pulses, and is adsorbed on lip-deep the first presoma with the last time and reacts; (4) question response fully after, then with inert gas, unnecessary the second presoma and accessory substance thereof are blown out to reaction chamber.Cycling deposition one deck ultra-thin materials, deposition rate is that every circulation obtains film thickness and is about
repetitive cycling is until required film thickness.
The technique for atomic layer deposition for preparing resistance-variable storing device in existing research is mainly hot atom layer deposition techniques and plasma enhanced atomic layer deposition (PEALD) technology, the preparation process of two kinds of technology all is deposited as basis with the periodic cycle of ALD: the hot atom layer deposition techniques is to using steam to react as the second presoma and the first presoma, for example, the people such as J.Zhang (Structural, optical, electrical and resistive switching properties of ZnO thin films deposited by thermal and plasma-enhanced atomic layer deposition, Appl.Surf.Sci.282, 395(2013)) use the hot atom layer deposition techniques to prepare zinc-oxide film, this film demonstrates good conductivity, resistivity can reach 10
-3Ω .cm magnitude, but zinc-oxide film prepared by the method does not possess the resistance switch characteristic, the plasma enhanced atomic layer deposition technology is to using plasma to react as the second presoma and the first presoma, for example, the people such as J.Zhang (Bipolar resistive switching characteristics of low temperature grown ZnO thin films by plasma-enhanced atomic layer deposition, Appl.Phys.Lett, 102, 012113 (2013)) use the plasma enhanced atomic layer deposition technology to prepare zinc-oxide film, Al/PEALD-ZnO/Pt resistance-variable storing device with this film preparation, resistance ratio between its high-impedance state and low resistance state is greater than 10
3, but also have the resistive poor stability, the problem that high-impedance state change in resistance scope is large.
The problems such as, also there is the resistive poor stability in other film (as aluminium oxide, titanium oxide etc.) that uses the ALD technology to prepare, and erasable voltage is larger, and high-impedance state change in resistance scope is large, these have all limited the extensive use of ALD technology in the resistance-variable storing device field.
Summary of the invention
The invention provides a kind of preparation method of resistance-variable storing device, introduced a kind of brand-new in-situ plasma and strengthen the hot atom layer deposition techniques in the preparation process of the resistive dielectric layer of resistance-variable storing device.The resistance-variable storing device prepared, can realize the accurate control to the device resistance switching characteristic, finally reaches adjustable to devices switch ratio, erasable voltage, and have splendid resistive stability.
In-situ plasma of the present invention strengthens to be processed, and is after each heat deposition circulation finishes, and all metal-oxide film is carried out to the gaseous plasma enhancing and processes, and the deposition cycle of metal-oxide film and plasma treatment circulation hocket successively.Described gas plasma process belongs to post-processing technology, and gaseous plasma does not participate in film deposition process, only affects surface topography and the defect of film.Can be by controlling plasma generation power, processing time and plasma-generating gas component, flow, quantitatively control the concentration of plasma intermediate ion, electronics and free radical, and then the defect kind in the control film, concentration, realize the resistance switch characteristic of regulating resistance-variable storing device on a large scale.
The invention discloses a kind of preparation method of resistance-variable storing device, described resistance-variable storing device comprises hearth electrode, resistive dielectric layer material and the top electrode of assembling successively, and the preparation of described resistive dielectric layer material comprises the following steps:
1) successively the first presoma, the first inert gas, the second presoma, the second inert gas are passed in reactor, through a circulation of pyrogen sublayer deposition, deposition one deck single metal oxide film on hearth electrode;
2) the single metal oxide film of step 1) deposition carried out to plasma enhanced process;
3) cycle alternation carries out above-mentioned step 1) and 2);
Ald has good volatility, thermal stability and reactivity while requiring the first presoma to enter reactor, described the first presoma is metal alkyl or metal alkoxide.As preferably, described the first presoma is diethyl zinc, trimethyl aluminium or titanium tetraisopropylate, and above three kinds of materials, as presoma, have sufficiently high vapour pressure, can guarantee to cover fully the surface of hearth electrode; Simultaneously, form the chemisorbed layer of monolayer on the hearth electrode surface, and the absorption that reaches capacity in scope in shorter circulation timei.
In atomic layer deposition process, inject interval in different presoma pulses and must pass into inert gas as carrier gas and cleaning reactor, isolate different presoma pulses simultaneously, described the first inert gas and the second inert gas are same gas.As preferably, adopt the inert gas of argon gas as the cleaning reactor in the present invention.
As preferably, argon gas is 20 mark condition ml/min (sccm) as the volume flow of carrier gas, under this flow, can be within the suitable time by reactor in unnecessary reactant or accessory substance clean out.
In the sedimentation of pyrogen sublayer, all using water as the second presoma.
Resistive dielectric layer material is the core of RRAM, selects different materials, and there is larger difference in the resistive characteristic of RRAM, and the material category with resistive characteristic of having reported at present is various.Described resistive dielectric layer material is metal-oxide film.Metal oxide have composition simple, be easy to preparation and with the advantage such as CMOS process compatible.As preferably, described metal oxide is ZnO, Al
2o
3or TiO
2.The film of these three kinds of metal oxides all has excellent resistance switch characteristic, and the ALD technology of preparing of film is simple, ripe, and deposition process can be carried out at low temperatures.
Metal oxide Direct precipitation in the present invention is on hearth electrode, so base reservoir temperature is the hearth electrode temperature, and described hearth electrode temperature is 50～400 ℃, and as preferably, described hearth electrode temperature is 150～250 ℃.Excess Temperature, the metal-oxide film of precursors and reaction preparation easily decomposes or, from surface desorption, affects deposition quality; Temperature is too low, and precursors is difficult to fully adsorb and react at matrix surface because of chemical absorption of surface and reaction barrier effect, the condensation of precursors even occurs, and reducing reaction rate also affects deposition quality.
Described deposition pressure is 0.1～2 holder (Torr), and as preferably, described deposition pressure is～1Torr.Deposition pressure affects the free path of the various active particles in plasma significantly.Air pressure is too low, and the free path of active particle is very long, is easy to destroy the membrane structure deposited, and even film is bombarded; Air pressure is too high, and free path is too short, and the particle activity is too low, is difficult to react with film.
Various active particles in plasma are comprised of ion, electronics and plasma free radical, have higher reactivity, can with film, react at low temperatures, and the defect in the regulation and control film.Plasma described in the present invention regulates and controls the defect in film by removing defect and introducing two kinds of modes of defect, and then regulate and control the resistance switch characteristic of resistance-variable storing device on a large scale: oxygen gas plasma can effectively be removed the defects such as hydrogen impurity, oxygen room, thus the on-off ratio of boost device.Hydrogen, nitrogen and hydrogen mixture plasma can be realized annotating hydrogen, annotating the effect of nitrogen to film, thereby generate such defect in film; Suitably, the quantitatively injection of defect, can maintain on the basis of certain on-off ratio, the stability of boost device, reduce erasable voltage.
When described the first presoma is diethyl zinc, described plasma is oxygen gas plasma, and the metal-oxide film prepared is ZnO film.Usually contain the defects such as hydrogen impurity, oxygen room in the ZnO film that uses the hot atom layer deposition techniques to prepare, these defects make film resistor very little, thus cause device do not have the resistance switch characteristic or on-off ratio very little.And oxygen gas plasma can be removed these defect and impurities effectively.By the processing of oxygen gas plasma, can reduce the content of hydrogen impurity in film, reduce the defects such as oxygen room, improve the resistance of film, thereby improve the on-off ratio of resistance-change memory device; Along with the increase in processing power, gas flow, processing time, in film, hydrogen impurity reduces thereupon, and initial resistance increases thereupon, and devices switch is than promote thereupon.
As preferably, the radio frequency source power of described plasma generation is 300～1000W; Further preferably, described power is 500W.When power is too small, what in film, hydrogen impurity reduced is few, and the on-off ratio of resistance-variable storing device promotes DeGrain; When power is excessive, plasma bombardment makes roughness of film significantly become large, has affected the stability of device.Therefore, by the radio frequency source power of plasma preferably in above-mentioned scope.
As preferably, the flow of described plasma-generating gas is 30～200sccm; Further preferably, described flow is 60sccm.With gas flow, increase, in film, defect increases thereupon, if flow is excessive, is unfavorable for that plasma occurs, and also can make on-off ratio significantly descend simultaneously.
As preferably, the described plasma enhanced process time is 5～30s/ circulation; Further preferably, the described processing time is the 20s/ circulation.When the processing time is too short, the resistance-variable storing device on-off ratio of preparation is too small or there is no a resistance switch characteristic; Processing time is long, and it is large that roughness of film significantly becomes.Therefore, by the plasma enhanced process time preferably in above-mentioned scope.
As preferably, described cycle alternation number of times is 100～1500, and the thickness of gained ZnO film is 10～300nm.The thickness of the ZnO single thin film obtained by atomic heat deposition is about
resistive thickness of dielectric layers in the resistance-change memory device generally is no more than 300nm, therefore the cycle alternation number of times is limited in above-mentioned scope.
Take diethyl zinc as the first presoma, while adopting oxygen gas plasma to process, as preferably, the radio frequency source power of described plasma generation is 500W, the flow of plasma-generating gas is 60sccm, the plasma enhanced process time is the 20s/ circulation time, in the metal-oxide film obtained defect content in optimum value, the optimal stability of the resistance-variable storing device prepared.
When described the first presoma is trimethyl aluminium or titanium tetraisopropylate, described plasma is hydrogen gas plasma or nitrogen and hydrogen mixture plasma, and the metal-oxide film prepared is Al
2o
3film or TiO
2film.Due to Al
2o
3and TiO
2initial resistance very big, the erasable voltage of the resistance-variable storing device prepared is also very big, causes the stability decreases of device.By the processing of hydrogen gas plasma, can in film, inject more hydrogen impurity, reduce the film initial resistance, thereby reduce the erasable voltage of resistance-change memory device, improve the stability of device; Along with the increase in processing power, gas flow, processing time, in film, hydrogen impurity increases thereupon, and initial resistance reduces thereupon, is maintaining under the prerequisite of certain on-off ratio, and the erasable voltage of memory device reduces thereupon, and the stability of device promotes thereupon.By the processing of nitrogen and hydrogen mixture plasma, can in film, inject the nitrogen element, form metal oxynitride, thereby improve the stability of device; Along with the increase in processing power, gas flow, processing time, in film, nitrogen content increases thereupon, when nitrogen content during in a particular value, and the optimal stability of device.
As preferably, the radio frequency source power of described plasma generation is 100～800W; Further preferably, described power is 300W.Power is too small, and treatment effect is not obvious; Power is excessive, and on-off ratio significantly descends.
As preferably, the flow of described plasma-generating gas is 10～100sccm; Further preferably, described flow is 30sccm.With gas flow, increase, in film, defect increases thereupon, if flow is excessive, is unfavorable for that plasma occurs, and also can make on-off ratio significantly descend simultaneously.
As preferably, the described plasma enhanced process time is 3～15s/ circulation, and further preferably, the described processing time is the 5s/ circulation.The trace that is introduced as of defect is introduced, and the processing time is long, and defect is introduced too much, and on-off ratio significantly descends.
Described cycle alternation number of times is 100～3000, and the thickness of gained metal-oxide film is 10～300nm.With cycle-index, increase, the thickness of metal-oxide film increases, and the monolayer film thickness of deposition is different with the kind of film.Resistive thickness of dielectric layers in the resistance-change memory device generally is no more than 300nm.General film is thicker, and initial resistance is larger, and on-off ratio is larger, but erasable voltage is higher.According to actual needs, by the thickness of metal-oxide film preferably in above-mentioned scope.
Take trimethyl aluminium or titanium tetraisopropylate as the first presoma, while adopting hydrogen gas plasma or nitrogen and hydrogen mixture plasma treatment, as preferably, the radio frequency source power of described plasma generation is 300W, the flow of plasma-generating gas is 30sccm, the plasma enhanced process time is the 5s/ circulation time, in the metal-oxide film obtained defect content in optimum value, the optimal stability of the resistance-variable storing device prepared.
The construction unit of resistance-variable storing device is followed successively by substrate, hearth electrode, resistive dielectric layer and top electrode from bottom to up.
Described substrate is dielectric substrate, is preferably SiO
2/ Si, glass, quartz or sapphire, the SiO that more preferably technique is simple, structure is ripe
2/ Si substrate.
Described hearth electrode material, require it not react with plasma, has excellent conductivity simultaneously, and as preferably, described hearth electrode material is inert metal, and further preferably, described inert metal is Au or Pt.
As preferably, adopt the method for electron beam evaporation or magnetron sputtering to prepare hearth electrode in the substrate surface deposition.
The selection of top electrode will be considered the factors such as contact interface of stability of material, conductivity, work function, electrode and dielectric layer, described top electrode material is metal, as preferably, described metal is a kind of in metal Ti commonly used in precious metals pt, Au, Ag or CMOS technique, Al.
As preferably, adopt photoetching, metal mask control electrode shape, adopt the method for electron beam evaporation, thermal evaporation or magnetron sputtering to prepare top electrode at resistive dielectric layer surface deposition.
In conventional PEALD technology, gaseous plasma reacts as reactant and presoma, its concentration, kind and reaction time all can the appreciable impact film growth rate, can't be effectively and regulate film defects on a large scale, be difficult to realize the regulation and control to resistance-variable storing device resistance switch characteristic.
With conventional PEALD technology, compare, in the present invention, gaseous plasma reacts as the film of reactant and generation, and surface chemical reaction and defect Regulation Mechanism are different from the PEALD technology fully.The preparation method that the present invention adopts can realize regulating more broadly the resistance switch characteristic of device.
The invention provides a kind of preparation method of resistance-variable storing device, introduce a kind of brand-new in-situ plasma and strengthened the hot atom layer deposition techniques in the preparation process of the resistive dielectric layer of resistance-variable storing device, fully combined the advantage of hot atom layer deposition techniques and plasma enhanced atomic layer deposition technology.
Present technique can accurately be controlled the thickness of metal-oxide film, and the film of preparation has high conformality, high-compactness, and can realize large-area uniformity; Simultaneously, by in-situ plasma, strengthen processing, can regulate the defect in metal-oxide film on a large scale.
Resistance-variable storing device prepared by this method can be realized the accurate control to the device resistance switching characteristic, finally reaches adjustable to devices switch ratio, erasable voltage, and has splendid resistive stability.
The accompanying drawing explanation
Fig. 1 is existing resistance variation memory structure schematic diagram;
The preparation process schematic diagram that Fig. 2 is ZnO resistive dielectric layer in embodiment 1 and Comparative Examples 1;
Fig. 3 is the resistance cumulative frequency distributing graph of the high and low resistance state of zno-based resistance-variable storing device of preparation respectively in embodiment 1 and Comparative Examples 1;
Fig. 4 is the resistance-time variation diagram of the high and low resistance state of zno-based resistance-variable storing device of preparation respectively in embodiment 1 and Comparative Examples 1.
In Fig. 1: 11-top electrode, 12-resistive dielectric layer, 13-hearth electrode, 14-substrate;
In Fig. 2:
(a) preparation process of ZnO resistive dielectric layer in embodiment 1;
(b) preparation process of ZnO resistive dielectric layer in Comparative Examples 1;
In Fig. 3:
The high-resistance resistors cumulative frequency of the zno-based resistance-variable storing device of 31-embodiment 1 preparation distributes;
The low resistance state resistance cumulative frequency of the zno-based resistance-variable storing device of 32-embodiment 1 preparation distributes;
The high-resistance resistors cumulative frequency of the zno-based resistance-variable storing device of 33-Comparative Examples 1 preparation distributes;
The low resistance state resistance cumulative frequency of the zno-based resistance-variable storing device of 34-Comparative Examples 1 preparation distributes;
In Fig. 4:
Resistance-the time changing curve of the zno-based resistance-variable storing device high-impedance state of 41-embodiment 1 preparation;
Resistance-the time changing curve of the zno-based resistance-variable storing device low resistance state of 42-embodiment 1 preparation;
Resistance-the time changing curve of the zno-based resistance-variable storing device high-impedance state of 43-Comparative Examples 1 preparation;
Resistance-the time changing curve of the zno-based resistance-variable storing device low resistance state of 44-Comparative Examples 1 preparation.
Embodiment
Embodiment 1
1) adopt magnetically controlled sputter method at SiO
2(300nm)/Si (100) substrate surface prepares inert metal Pt hearth electrode, and gained hearth electrode thickness is 150nm, and the temperature of preparation is 150 ℃, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
2) adopt in-situ plasma to strengthen pyrogen sublayer sedimentation, the diethyl zinc of take is the second presoma as the first presoma, steam, argon gas is purge gas, first on the Pt hearth electrode, form the zinc-oxide film of one deck individual layer after the deposition of pyrogen sublayer, then utilize oxygen gas plasma to carry out in-situ plasma treatment to this film, repeat 250 circulations, finally obtain zinc-oxide film, the thickness of this film is about 42nm.The temperature of Pt hearth electrode is 150 ℃; The argon carrier flow is 20sccm; Deposition and processing air pressure are 1Torr; The radio frequency source power of plasma generator is 500W; The oxygen gas plasma flow is 60sccm, and the processing time is the 20s/ circulation.
3) utilize magnetically controlled sputter method at the circular Al top electrode of ZnO film surface preparation, the about 100nm of the thickness of top electrode, diameter is 200um.The temperature of preparation is 25 ℃, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
Comparative Examples 1
1) adopt magnetically controlled sputter method at SiO
2(300nm)/Si (100) substrate surface prepares inert metal hearth electrode Pt, and gained hearth electrode thickness is 150nm, and the temperature of preparation is 150 ℃, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
2) adopt the hot atom layer deposition techniques, using diethyl zinc as the first presoma, steam as the second presoma, argon gas is purge gas, after 250 circulations, obtains the zinc-oxide film that thickness is about 42nm.The temperature of Pt hearth electrode is 150 ℃; The argon carrier flow is 20sccm; Deposition and processing air pressure are 1Torr.
3) using oxygen plasma to step 2) zinc-oxide film that obtains carries out the ex situ processing; Deposition and processing air pressure are 1Torr; The temperature of Pt hearth electrode is 150 ℃; Radio frequency source power is 500W; The oxygen gas plasma flow is 60sccm, and the processing time is 250 * 20s.
4) utilize magnetically controlled sputter method to prepare circular top electrode A l at film surface, the about 100nm of thickness of electrode, electrode diameter is 200um.The temperature of preparation is 25 ℃, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
Comparing embodiment 1 and Comparative Examples 1 can find, the two all has ambipolar resistance switch characteristic, and the on-off ratio of resistance-variable storing device all is greater than 100 times.Fig. 3 is the test of resistance-change memory device cyclical stability, and wherein, curve 31,32 is respectively the high and low resistance state resistor value of embodiment 1 described device, the high and low resistance state resistor value that curve 33,34 is Comparative Examples 1 described device; The device information holding time surpasses 10
4s, in Fig. 4, curve 41,42 is respectively the high and low resistance state temporal evolution curve of embodiment 1 described device, and curve 43,44 is the high and low resistance state temporal evolution of the described device of Comparative Examples 1 curve.Device meets the instructions for use of resistance-variable storing device.Through 100 loop tests, the resulting film resistance switches of original position oxygen plasma treatment that embodiment 1 adopts is 3 times of non-in-situ treatment film than mean value, and large on-off ratio has proved that in-situ treatment method is better than ex situ and processes.
Embodiment 2
1) adopt magnetically controlled sputter method at SiO
2(300nm)/Si (100) substrate surface prepares inert metal Pt hearth electrode, and gained hearth electrode thickness is 150nm, and the temperature of preparation is 150 ℃, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
2) adopt in-situ plasma to strengthen pyrogen sublayer sedimentation, the diethyl zinc of take is the second presoma as the first presoma, steam, argon gas is purge gas, first on the Pt hearth electrode, form the zinc-oxide film of one deck individual layer after the deposition of pyrogen sublayer, then utilize oxygen gas plasma to carry out in-situ plasma treatment to this film, repeat 250 circulations, finally obtain zinc-oxide film, the thickness of this film is about 42nm.The temperature of Pt hearth electrode is 150 ℃; The argon carrier flow is 20sccm, and the deposition of reaction chamber and processing air pressure are 1Torr, and the oxygen gas plasma flow is 60sccm.
3) the radio frequency source power of regulating plasma generator is 300,500,800W; The oxygen gas plasma processing time is fixed as the 20s/ circulation.Utilize magnetically controlled sputter method at the circular Al top electrode of ZnO film surface preparation, the about 100nm of the thickness of top electrode, diameter is 200um.The temperature of preparation is 25 ℃, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
4) the radio frequency source power of plasma generator is fixed as to 500W; Regulate the oxygen gas plasma processing time and be 0,5,10,15, the 20s/ circulation.Utilize magnetically controlled sputter method at the circular Al top electrode of ZnO film surface preparation, the about 100nm of the thickness of top electrode, diameter is 200um.The temperature of preparation is 25 ℃, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
Process through step 3) the thin-film device obtained and all have ambipolar resistance switch characteristic, the thin-film device on-off ratio of processing through 300W only is greater than 50 times; Its on-off ratio of device through 500W and 800W processing all is greater than 100 times.
Process the thin-film device obtained through step 4), the device that 0s and 5s process does not have the resistance switch characteristic; The device that 10s, 15s, 20s process demonstrates ambipolar resistance switch characteristic, and its on-off ratio of device that 10s and 15s process only has tens times, and the device of 10s after processing erasable through 20 times after, the device resistance switch performance disappears; The device of processing through 20s, in film, the defect such as hydrogen impurity, oxygen room significantly reduces, and the devices switch ratio is greater than 100 times.
Embodiment 3
Adopt the hot atom layer deposition techniques to prepare the aluminum oxide film resistance-variable storing device, and use hydrogen gas plasma to carry out in-situ treatment, comprise the following steps:
1) adopt magnetically controlled sputter method at SiO
2(300nm)/Si (100) substrate surface prepares inert metal hearth electrode Pt, and gained hearth electrode thickness is 150nm, and the temperature of preparation is 150 ℃, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
2) adopt technique for atomic layer deposition, the trimethyl aluminium of take is the second presoma as the first presoma, steam, argon gas is purge gas, first on the Pt hearth electrode, form the aluminum oxide film of one deck individual layer after the deposition of pyrogen sublayer, then utilize hydrogen gas plasma to carry out in-situ plasma treatment to this film, repeat 200 circulations, finally obtain aluminum oxide film, the thickness of this film is about 20nm.The temperature of Pt hearth electrode is 300 ℃; The argon carrier flow is 20sccm; Deposition and processing air pressure are 1Torr; The radio frequency source power of plasma generator is 300W; Hydrogen flowing quantity is 30sccm, and the processing time is the 5s/ circulation.
3) adopt magnetically controlled sputter method to prepare circular top electrode Ti at film surface, the about 100nm of thickness of electrode, electrode diameter is 200um.The temperature of preparation is 25 ℃, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
Undressed aluminum oxide film film resistance is very large, and～10
9Ω.After carrying out the hydrogen plasma processing, the film initial resistance reduces 2～3 orders of magnitude.After an electric activation, device demonstrates ambipolar resistance switch characteristic.Now, film thickness is compared substantially constantly with untreated, but activation voltage is reduced to 4～6V by 6～8V.Device after electricity is activated is tested through 100 cyclical stabilities, the resistance switch ratio of device is greater than 100 times, after processing, device stability is improved, write voltage range and be reduced to 0.5～1.7V by 0.6 original～3V, the erasing voltage scope by-1V～-become-0.8V of 3V～-2.2V.
Embodiment 4
Adopt the hot atom layer deposition techniques to prepare the thin film of titanium oxide resistance-variable storing device, and use ammonia plasmas to carry out in-situ treatment, comprise the following steps:
1) adopt magnetically controlled sputter method at SiO
2(300nm)/Si (100) substrate surface prepares inert metal hearth electrode Pt, and gained hearth electrode thickness is 150nm, and the temperature of preparation is 150 ℃, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
2) adopt technique for atomic layer deposition, the titanium tetraisopropylate of take is the second presoma as the first presoma, steam, argon gas is purge gas, first on the Pt hearth electrode, form the thin film of titanium oxide of one deck individual layer after the deposition of pyrogen sublayer, then utilize ammonia plasmas to carry out in-situ plasma treatment to this film, repeat 2000 circulations, finally obtain thin film of titanium oxide, the thickness of this film is about 40nm.The temperature of Pt hearth electrode is 250 ℃; The argon carrier flow is 20sccm; Deposition and processing air pressure are 1Torr; The radio frequency source power of plasma generator is 300W; Nitrogen and hydrogen mixture (1:1) flow is 30sccm, and the processing time is the 5s/ circulation.
3) adopt magnetically controlled sputter method to prepare circular top electrode Pt at film surface, the about 100nm of thickness of electrode, electrode diameter is 200um.The temperature of preparation is 25 ℃, and depositing main gas is that argon gas, pressure are 0.5Pa, and sputtering power is 300W.
After thin film of titanium oxide is carried out to the nitrogen and hydrogen mixture plasma treatment, film becomes the titanium oxynitrides film containing trace nitrogen.The conductivity of titanium oxynitrides is better than thin film of titanium oxide, makes the thin-film device through in-situ treatment no longer need electric activation, can realize reversible monopole type resistance switch characteristic.Device stability is improved, and writes voltage and becomes 1.1～1.6V by 1.6～3.1V, and erasing voltage becomes 0.4～0.8V by 0.4～1V.
It should be noted that, above-described embodiment only is not used in and limits the scope of the invention for the present invention is described.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (6)
1. the preparation method of a resistance-variable storing device, described resistance-variable storing device comprises hearth electrode, resistive dielectric layer material and the top electrode of assembling successively, it is characterized in that, the preparation of described resistive dielectric layer material comprises the following steps:
1) successively the first presoma, the first inert gas, the second presoma, the second inert gas are passed in reactor, through a circulation of pyrogen sublayer deposition, deposition one deck single metal oxide film on hearth electrode;
2) the single metal oxide film of step 1) deposition carried out to plasma enhanced process;
3) cycle alternation carries out above-mentioned step 1) and 2);
Described the first presoma is metal alkyl or metal alkoxide;
The radio frequency source power of described plasma generation is 30～1500W;
The flow of described plasma-generating gas is 5～200 mark condition ml/min;
The described plasma enhanced process time is 3～50s/ circulation.
2. the preparation method of resistance-variable storing device according to claim 1, it is characterized in that, described the first presoma is diethyl zinc, trimethyl aluminium or titanium tetraisopropylate, and described plasma is oxygen gas plasma, hydrogen gas plasma or nitrogen and hydrogen mixture plasma.
3. the preparation method of resistance-variable storing device according to claim 1, is characterized in that, described cycle alternation number of times is 100～3000, and the thickness of gained metal-oxide film is 10～300nm.
4. the preparation method of resistance-variable storing device according to claim 1 and 2, is characterized in that, when the first presoma is diethyl zinc, described plasma is oxygen gas plasma, and the radio frequency source power of plasma generation is 100～800W; The flow of described plasma-generating gas is 10～100 mark condition ml/min; The described plasma enhanced process time is 3～15s/ circulation.
5. the preparation method of resistance-variable storing device according to claim 1 and 2, it is characterized in that, when the first presoma is trimethyl aluminium or titanium tetraisopropylate, described plasma is hydrogen gas plasma or nitrogen and hydrogen mixture plasma, and the radio frequency source power of plasma generation is 300～1000W; The flow of described plasma-generating gas is 30～200 mark condition ml/min; The described plasma enhanced process time is 5～30s/ circulation.
6. the preparation method of resistance-variable storing device according to claim 1, is characterized in that, described hearth electrode material is inert metal, and described inert metal is Au or Pt.
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