CN102255043A - Method for improving resistive storage performance of strontium titanate stannate thin film - Google Patents
Method for improving resistive storage performance of strontium titanate stannate thin film Download PDFInfo
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Abstract
The invention provides a method for improving the resistive storage performance of a strontium titanate stannate thin film. The method comprises the following step of: doping Mg and Mn into a strontium titanate stannate thin film material, wherein the Mg content of the strontium titanate stannate thin film material is 0.1 to 4 percent, and the Mn content of the strontium titanate stannate thin film material is 0.1 to 4 percent; and the chemical formula of the strontium titanate stannate thin film material is SrTi(1-x)SnxO3, and x is more than or equal to 0.01 and less than or equal to 0.25. In the method, the chemical element magnesium is doped in the preparation of the strontium titanate stannate thin film and supplemented by other acceptors or valence variable impurities such as manganese to improve the microstructure and physical properties of the strontium titanate stannate thin film, thereby increasing the high/low resistance state shear rate of the strontium titanate stannate thin film used as a resistive random access memory, making the resistive random access memory taking the strontium titanate stannate thin film as a dielectric layer easier to distinguish when read in a high resistance state and a low resistance state and further greatly improving the read/write operation reliability and information storage long-term performance of the resistive random access memory.
Description
Technical field
The present invention relates to a kind of method that improves strontium stannate titanate film resistance-change memory performance, especially relate to a kind of employing chemical element doping means, improve the method for the high/low Resistance states shear ratio of strontium stannate titanate film when being used for resistance-variable storing device.
Background technology
Along with the use more and more widely of portable consumer electronics quilt, also more and more urgent to the demand of big capacity non-volatility memorizer.Traditional erasable programmable read-only memory (EPROM) and electric erasable program read-only memory (E2PROM) can not satisfy the market demand now far away, and also denounced by industry owing to the circuit structure of higher operating voltage and complexity based on quickflashing (flash) memory of floating gate structure always, so various novel non-volatility memorizers of future generation arise at the historic moment, as ferroelectric memory (FeRAM), magnetic memory (MRAM), phase transition storage (PRAM), resistive formula memory (RRAM) etc.Compare other nonvolatile memories, resistive formula memory with its low operating voltage, low-power consumption, high writing speed, anti-erasable, non-destructive reads, the retention time is grown, simple in structure, with traditional cmos (complementary metal oxide semiconductors (CMOS)) technology advantage such as compatibility and extensively being ground mutually by industrial quarters and academia's extensive studies, very likely become the replacer of traditional flash nonvolatile memory.
In the middle of these novel non-volatility memorizers, the storage mechanism of FeRAM, MRAM and PRAM has been studied very thorough, but still there is very big difference in the understanding to resistive formula memory resistive mechanism, there is not unified theoretical explanation, during its memory property was further promoting, the performance that table 1 has been listed the various memories of having reported compared.
The performance of the various memories of table 1 relatively
| Memory | DRAM | SRAM | FLASH | PRAM | FeRAM | MRAM | RRAM |
| Non-volatile | Not | Not | Be | Be | Be | Be | Be |
| Programming power | Low | Low | High | Low | Low | High | Low |
| Program voltage | Low | Low | High | - | Low | In | Low |
| Read voltage range | 100-200mV | 100-200mV | The Delta electric current | - | - | 20-40％ | 10-106 |
| Write time | 50ns | 8ns | 1μs | 10ns | 30ns | 30ns | 10ns |
| Erasing time | 50ns | 8ns | 1-100ms | 50ns | 30ns | 30ns | 30ns |
| Time for reading | 50ns | 8ns | 50ns | 20ns | 30ns | 30ns | 20ns |
| The programming energy | In | High | High | Low | Low | In | Low |
| The integrated difficult point of high density | Capacitance | Transistor size | Gate oxide thickness/high pressure | Photoetching | Lure electric bulk area by force | Program current | Photoetching |
With respect to the parameter of open report in the table 1, the new calcium titanium ore strontium stannate titanate film of our research group's exploitation writes/clashes the time and shortened to and be not more than 4.1 nanoseconds (the test limits pulse duration minimum value of any noise generator of tester Agilent 81150A impulse function that we use was 4.1 nanoseconds).
It can also be seen that from table 1 photoetching is one of integrated difficult point of resistance-variable storing device high density of new generation, in practical devices was made, for photoetching is to realize the high density storage better, the film of smooth densification was vital.
In material science, doping vario-property is one of a kind of simple and effective conventional means, replaces by the doping of suitable impurity, can change and control the microstructure and the macro physical performance of material.From microcosmic angle, littler crystal grain means increasing of crystal boundary, and this helps the motion in oxonium ion (or oxygen room), and this is one of resistance shear physical mechanism of strontium stannate titanate film just also.When new generation of high density memory device stores unit narrows down to nanometer scale, littler crystal grain can make each memory cell have roughly the same crystal grain, crystal boundary and defective, this memory property that can make each memory cell of memory device is uniformity more, because resistance shear phenomenon is subjected to the influence and the control of crystal boundary and crystal defect more on microcosmic.
In a word, for make strontium stannate titanate film be used for better a new generation highly dense, at a high speed, the low-power consumption non-volatility memorizer, it is carried out suitable doping vario-property is very important to improve its resistance-change memory performance greatly.
Summary of the invention
The purpose of this invention is to provide a kind of method that improves strontium stannate titanate film resistance-change memory performance, the micro-structural and the physical property that are used for the strontium stannate titanate film of resistance-variable storing device by improvement, thus the high/low Resistance states shear ratio of strontium stannate titanate film when being used for resistance-variable storing device improved.It is that high/low two kinds of resistance states of resistance-variable storing device of dielectric layer are easier to distinguish when reading that this method can make with the strontium stannate titanate film, thereby improves the reliability of stored information greatly.
The present invention solves above-mentioned technical problem by the following technical solutions:
A kind of method that improves strontium stannate titanate film resistance-change memory performance, described method comprise that in strontium stannate titanate film material doping molar content is 0.1～4% Mg of described strontium stannate titanate film material and 0.1～4% Mn.
The chemical composition of described strontium stannate titanate film material is SrTi
(1-x)Sn
xO
3, 0.01≤x≤0.25 wherein.This structural formula SrTi
(1-x)Sn
xO
3In, the molar relationship between bottom right mark numeral and letter representation corresponding chemical element.
Improve the employed chemical element doping method of strontium stannate titanate film resistance-change memory performance among the present invention, both can also can realize with physical method such as rf magnetron sputtering with chemical method such as sol-gel process.
Adopting doping molar content in the sol-gel normal direction strontium stannate titanate film material is 0.1～4% Mg of described strontium stannate titanate film material and 0.1～4% Mn, may further comprise the steps:
A) presoma of strontium and the presoma of tin are pressed Sr (Ti
1-xSn
x) O
3In the metering ratio join in the glacial acetic acid, add acetate or the nitrate of Mg and Mn again by proportioning, be heated to the cooling of boiling back and obtain acetum;
B) presoma of titanium and the mixed solution of ethylene glycol ethyl ether and acetylacetone,2,4-pentanedione (AcAc) are joined in the acetum of step 1) gained;
C) add ethylene glycol ethyl ether the molar concentration of Sr element in the solution is adjusted to 0.05～0.3M;
D) step c) gained solution after aging 1-3 days, is coated on and forms gel mould on the substrate, in 650 ℃～700 ℃ following heat treatments 0.5～1 hour, obtain the strontium stannate titanate doping film again.
Preferable, the presoma of strontium is a strontium acetate, and the presoma of tin is tin acetate or Dibutyltin oxide, and the presoma of titanium is an isopropyl titanate.
In the above-mentioned sol-gel process provided by the present invention, described step a) and b) in the acetic acid and the ethylene glycol ethyl ether that are added be solvent, its addition can be with reference to the conventional amount used in the sol-gel technology in this area; Than about 1: 10, controlling the presoma of described titanium and the mol ratio of ethylene glycol ethyl ether is about 1: 10 as the mole of the integral molar quantity of may command Sr element and Sn element and glacial acetic acid.
In the described step b), the adding of acetylacetone,2,4-pentanedione (AcAc) be for the isopropyl titanate reacting forming complex; Stoichiometric proportion when its addition can be with reference to Ti element in the described isopropyl titanate and acetylacetone,2,4-pentanedione generation complex reaction, promptly with reference to the mol ratio of Ti element in the described isopropyl titanate and acetylacetone,2,4-pentanedione be 1: 2 definite, 5% error can be arranged between the two.
The mol ratio of Ti element and acetylacetone,2,4-pentanedione can be with reference to being controlled to be about 1: 2 in the described isopropyl titanate,
Preferable, described substrate is selected from LaNiO
3/ Pt/Ti/SiO
2/ Si (100) or Pt/Ti/SiO
2/ Si.
Described precursor solution is coated on forms gel mould on the substrate, can adopt the method that applies with the compatible mutually rotation of semiconductor technology.
The strontium stannate titanate film that described physical method such as radio frequency magnetron sputtering method prepare doping vario-property can adopt conventional ceramic process to prepare the strontium stannate titanate ceramic target of corresponding doping, and the target after utilize mixing carries out sputter and prepares film, and the gained film has just been realized corresponding doping vario-property.
The present invention also further discloses and has adopted strontium stannate titanate doping film that said method obtained and uses thereof.
The strontium stannate titanate doping film that adopts said method provided by the present invention to obtain can be used in the resistance-variable storing device, as the dielectric layer in the memory cell of resistance-variable storing device.
Preferable, the thickness of described strontium stannate titanate doping film is 40～80nm.
The structure of the memory cell of described resistance-variable storing device comprises: top electrode, described strontium stannate titanate doping film and hearth electrode; Wherein, described top electrode forms on described doping film; Described hearth electrode is to form on the substrate of described doping film.
Preferable, described hearth electrode is selected from LaNiO
3, LaSrCoO
3Or SrRuO
3Described hearth electrode can adopt known radio frequency magnetron sputtering method of those skilled in that art or sol-gel process preparation on substrate.
Preferable, described top electrode is selected from Al, TiN, W, Au or Pt.Described top electrode Al, W, Au or Pt prepare on described strontium stannate titanate film with magnetically controlled DC sputtering or rf magnetron sputtering sputter; Top electrode TiN prepares on described strontium stannate titanate film through magnetically controlled DC sputtering or rf magnetron sputtering sputter with the TiN target, perhaps uses the Ti target through magnetically controlled DC sputtering or rf magnetron sputtering and nitrogen (N
2) reactive sputtering prepares on described strontium stannate titanate film.
The present invention is aided with other impurity manganese of being led or appraise at the current rate again by doping chemical element magnesium in the strontium stannate titanate film preparation, has improved the micro-structural and the physical property of strontium stannate titanate film, thereby has improved the resistance-change memory performance of strontium stannate titanate film.
To adopt the strontium stannate titanate doping film that method of the present invention obtained to be used for resistance-variable storing device, compare with pure strontium stannate titanate film: prepared film of the present invention has fine and close more micro-structural and littler crystal grain on the one hand, this helps forming smooth smooth film surface so that photoetching better, thereby also helps forming the storage density that trickleer circuit improves device simultaneously; On the other hand, the purer strontium stannate titanate film of high-resistance resistors of the strontium stannate titanate doping film that the present invention is prepared enlarges markedly, and the low resistance state resistance variations is less, so just improved the ratio of strontium stannate titanate film high/low Resistance states when being used for resistance-variable storing device, making with the strontium stannate titanate film is that high/low two kinds of resistance states of resistance-variable storing device of dielectric layer are easier to distinguish when reading, thereby improves the reliability of resistance-variable storing device device read/write operation and the chronicity of the information of preservation greatly.
Description of drawings
Fig. 1 is with the performance comparison figure of electric pulse to 1000 high/low resistance shears of strontium stannate titanate doping film and pure strontium stannate titanate film.
Fig. 2 is that strontium stannate titanate doping film and pure strontium stannate titanate film are sheared towards retention performance comparison diagram after the high/low Resistance states by electric pulse among Fig. 1.
Fig. 3 is the performance comparison figure that doping strontium stannate titanate film and pure strontium stannate titanate film is carried out high/low resistance shear with the direct current scanning voltage.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment, should be understood that these embodiment only are used to the present invention is described and are not used in restriction protection scope of the present invention.
To component is Sr (Ti
1-xSn
x) O
3The strontium stannate titanate material carry out the Mg of y% and the Mn doping vario-property of z%, strengthen its resistance and become the shear performance, the component after the doping can be expressed as: Sr (Ti
1-xSn
x) O
3+ y%Mg+z%Mn, wherein 0.01≤x≤0.25,0.1≤y≤4,0.1≤z≤4; X, y, z all represent the molar ratio relation between respective element.
Below adopt known Prepared by Sol Gel Method strontium stannate titanate doping film in this area:
The chemical raw material that the preparation of precursor solution is adopted is strontium acetate [Sr (CH
3COO)
2], tin acetate [Sn (CH
3COO)
4] and isopropyl titanate [Ti (OC
3H
7)
4], magnesium acetate [Mg (CH
3COO)
2] and manganese acetate [Mn (CH
3COO)
2]; Solvent is glacial acetic acid and ethylene glycol ethyl ether.Earlier strontium acetate, tin acetate, magnesium acetate and manganese acetate are dissolved in well and are heated to boiling in the glacial acetic acid solution according to corresponding chemical metering (magnesium acetate both can also can be by the non-stoichiometric weighing by stoichiometric proportion) weighing, stop heating after 10 minutes, and be cooled to room temperature; Wherein, the mol ratio of the total amount of elements Sr and Sn and glacial acetic acid is 1: 10.Mixed solution with isopropyl titanate, ethylene glycol ethyl ether and acetylacetone,2,4-pentanedione (AcAc) joins in the glacial acetic acid solution that contains strontium and tin, wherein again: the mol ratio of Ti and AcAc is 1: 2, and the mol ratio of isopropyl titanate and ethylene glycol ethyl ether is 1: 10.Add ethylene glycol ethyl ether at last the concentration of Sr element in the final solution is adjusted to 0.05～0.3M, stirred 1-2 hour, place and be used for preparing film after 1-3 days.
Employed substrate is LaNiO
3/ Pt/Ti/SiO
2/ Si (100) or Pt/Ti/SiO
2/ Si, LaNiO
3, Pt, Ti, SiO
2With the thickness of Si sheet be respectively 150nm, 150nm, 50nm, 150nm and 3500nm.The method that adopts rotation to apply forms gel mould on substrate, rotary speed is 3000 rev/mins, 20 seconds time.Coated gel mould slowly pushed in 500 ℃ the tube furnace from room temperature, placed 30 minutes, be cooled to room temperature after the taking-up, apply one deck gel mould down, move in circles up to the film that obtains desired thickness (for the resistance-variable storing device film, its thickness is 40～80nm) generally speaking, the concentration of used precursor solution, the number of plies of coating and last to obtain the total thickness of film relevant, promptly molar concentration is big more, and its thickness is also just big more; The number of plies is many more, and its thickness is also big more.At last with this film 650 ℃～700 ℃ following heat treatments 0.5～1 hour.
Then at the upper surface of above-mentioned film with Ti target and nitrogen (N
2) preparing TiN as top electrode through dc magnetron reactive sputtering, its diameter is that 0.2mm, thickness are about 100nm.LaNiO on the substrate
3/ Pt has conductivity, can be directly as hearth electrode.
Preparation x=0.05, y=2, the SrTi that the resistance-variable storing device of z=1 mixes with Mg and Mn
0.95Sn
0.05O
3Film (SrTi
0.95Sn
0.05O
3+ 2%Mg+1%Mn): the precursor solution that the 24 hours aging molar concentrations of learning from else's experience are the strontium stannate titanate of 0.1M, at substrate LaNiO
3/ Pt/Ti/SiO
21 layer of the last coating of/Si, gel mould slowly push in 500 ℃ the tubular type gradient furnace, place and heat-treated in 15 minutes from room temperature, repeat this process and reach thickness 40～80 nanometers that need up to film.At last with this film 700 ℃ of following heat treatments 0.5 hour.The titanium nitride electrode is as top electrode in the method sputter of the dc magnetron reactive sputtering of surface employing thereon then, and its diameter is that 0.2mm, thickness are about 70nm, forms hearth electrode/(SrTi
0.95Sn
0.05O
3+ 2%Mg+1%Mn) film/top electrode plate condenser structure is with testing film resistance sex change energy.Adopt the same procedure preparation not contain the SrTi of Mg and Mn doping
0.95Sn
0.05O
3Film forms identical hearth electrode/(SrTi
0.95Sn
0.05O
3) film/top electrode structure, the same terms is its resistance sex change energy of test down.
Fig. 1 is the performance comparison figure of 1000 high/low resistance shears of the doping strontium stannate titanate film that above method made with electric pulse and pure strontium stannate titanate film, black triangle is represented the performance of doping strontium stannate titanate film among the figure, and open circles is represented the performance (down together) of pure strontium stannate titanate film.Shearing towards the impulse magnitude that high-resistance state applies from low resistance state is 3.5 volts (flow into top electrode with electric current and are defined as positive voltage), pulse duration was 4.1 nanoseconds, be-2 volts from high-resistance state to the impulse magnitude that the low resistance state shear is applied, pulse duration was 4.1 nanoseconds, and the read-out voltage of resistance states is-0.1 volt.As can be seen, the film after doping performance strengthens has obviously increased than the resistance window (being the shear ratio of high low resistance state) of pure strontium stannate titanate film.When stablizing shear, the ratio of the high low resistance state of pure strontium stannate titanate film is about 2～3 times, and the ratio of the high low resistance state of strontium stannate titanate doping film is about 10 times.This is very beneficial for the differentiation of resistance states (being stored information) in actual applications.
Fig. 2 a is that doping strontium stannate titanate film and pure strontium stannate titanate film are sheared towards retention performance comparison diagram after the high/low Resistance states by electric pulse among Fig. 1, and Fig. 2 b is the retention performance trend comparison diagram that Fig. 2 a was extrapolated to 10 years; Black triangle is represented the doping strontium stannate titanate film among the figure, and open circles is represented pure strontium stannate titanate film.As can be seen from the figure, As time goes on, the resistance of two kinds of Resistance states is slowly close, and the film after the doping performance boost is because the resistance window is bigger, the resistance of two states is easy to distinguish more, this can improve greatly resistance transition storage device preserve information reliability and chronicity
Fig. 3 a and Fig. 3 b be respectively with the mode of direct current scanning voltage to aforementioned two kinds of films carry out high/low resistance shear performance comparison figure (scanning voltage applies mode: 0V → 1.5V → 0V →-1.5V → 0V, step-length 0.1V circulates 110 times).Fig. 3 c is Fig. 3 a, electric current (inverse of the resistance) comparison diagram of high/low resistance states correspondence in the time of-0.1V voltage in the scanning voltage of direct current shown in the b.Black triangle is represented the doping strontium stannate titanate film among the figure, and open circles is represented pure strontium stannate titanate film.As can be seen, similar with the pulse shear, in the shear of direct current scanning voltage, doping rear film resistance window obtains increasing.
Embodiment 2
Preparation x=0.01, y=1, the SrTi that the resistance-variable storing device of z=0.1 mixes with Mg and Mn
0.99Sn
0.01O
3Film (SrTi
0.99Sn
0.01O
3+ 1%Mg+0.1%Mn): the precursor solution that the 24 hours aging molar concentrations of learning from else's experience are the strontium stannate titanate of 0.05M, at substrate LaNiO
3/ Pt/Ti/SiO
21 layer of the last coating of/Si, gel mould slowly push in 500 ℃ the tubular type gradient furnace, place and heat-treated in 15 minutes from room temperature, repeat this process and reach thickness 40～80 nanometers that need up to film.At last with this film 650 ℃ of following heat treatments 1 hour.The titanium nitride electrode is as top electrode in the method sputter of the dc magnetron reactive sputtering of surface employing thereon then, and its diameter is that 0.2mm, thickness are about 70nm, forms hearth electrode/(SrTi
0.99Sn
0.01O
3+ 1%Mg+0.1%Mn) film/top electrode plate condenser structure is with testing film resistance sex change energy.Adopt the same procedure preparation not contain the SrTi of Mg and Mn doping
0.95Sn
0.05O
3Film forms identical hearth electrode/(SrTi
0.95Sn
0.05O
3) film/top electrode structure, the same terms is its resistance sex change energy of test down.
With electric pulse doping strontium stannate titanate film and the pure strontium stannate titanate film that above method makes carried out 1000 high/low resistance shears.When stablizing shear, the ratio of the high low resistance state of pure strontium stannate titanate film is about 2～3 times, and the ratio of the high low resistance state of strontium stannate titanate doping film is about 7～10 times.
Embodiment 3
Preparation x=0.25, y=1, the SrTi that the resistance-variable storing device of z=4 mixes with Mg and Mn
0.75Sn
0.25O
3Film (SrTi
0.75Sn
0.25O
3+ 1%Mg+4%Mn): the precursor solution that the 24 hours aging molar concentrations of learning from else's experience are the strontium stannate titanate of 0.3M, at substrate LaNiO
3/ Pt/Ti/SiO
21 layer of the last coating of/Si, gel mould slowly push in 500 ℃ the tubular type gradient furnace, place and heat-treated in 15 minutes from room temperature, repeat this process and reach thickness 40～70 nanometers that need up to film.At last with this film 750 ℃ of following heat treatments 1 hour.The titanium nitride electrode is as top electrode in the method sputter of the dc magnetron reactive sputtering of surface employing thereon then, and its diameter is that 0.2mm, thickness are about 70nm, forms hearth electrode/(SrTi
0.99Sn
0.01O
3+ 1%Mg+0.1%Mn) film/top electrode plate condenser structure is with testing film resistance sex change energy.Adopt the same procedure preparation not contain the SrTi of Mg and Mn doping
0.95Sn
0.05O
3Film forms identical hearth electrode/(SrTi
0.95Sn
0.05O
3) film/top electrode structure, the same terms is its resistance sex change energy of test down.
With electric pulse doping strontium stannate titanate film and the pure strontium stannate titanate film that above method makes carried out 1000 high/low resistance shears.When stablizing shear, the ratio of the high low resistance state of pure strontium stannate titanate film is about 2～3 times, and the ratio of the high low resistance state of strontium stannate titanate doping film is about 7～10 times.
Embodiment 4
Preparation x=0.05, y=0.1, the SrTi that the resistance-variable storing device of z=2 mixes with Mg and Mn
0.75Sn
0.25O
3Film (SrTi
0.75Sn
0.25O
3+ 1%Mg+4%Mn): the precursor solution that the 24 hours aging molar concentrations of learning from else's experience are the strontium stannate titanate of 0.1M, at substrate LaNiO
3/ Pt/Ti/SiO
21 layer of the last coating of/Si, gel mould slowly push in 500 ℃ the tubular type gradient furnace, place and heat-treated in 15 minutes from room temperature, repeat this process and reach thickness 40～70 nanometers that need up to film.At last with this film 750 ℃ of following heat treatments 1 hour.The titanium nitride electrode is as top electrode in the method sputter of the dc magnetron reactive sputtering of surface employing thereon then, and its diameter is that 0.2mm, thickness are about 70nm, forms hearth electrode/(SrTi
0.99Sn
0.01O
3+ 1%Mg+0.1%Mn) film/top electrode plate condenser structure is with testing film resistance sex change energy.Adopt the same procedure preparation not contain the SrTi of Mg and Mn doping
0.95Sn
0.05O
3Film forms identical hearth electrode/(SrTi
0.95Sn
0.05O
3) film/top electrode structure, the same terms is its resistance sex change energy of test down.
With electric pulse doping strontium stannate titanate film and the pure strontium stannate titanate film that above method makes carried out 1000 high/low resistance shears.When stablizing shear, the ratio of the high low resistance state of pure strontium stannate titanate film is about 2～3 times, and the ratio of the high low resistance state of strontium stannate titanate doping film is about 7～10 times.
Embodiment 5
Preparation x=0.05, y=4, the SrTi that the resistance-variable storing device of z=1 mixes with Mg and Mn
0.75Sn
0.25O
3Film (SrTi
0.75Sn
0.25O
3+ 1%Mg+4%Mn): the precursor solution that the 24 hours aging molar concentrations of learning from else's experience are the strontium stannate titanate of 0.1M, at substrate LaNiO
3/ Pt/Ti/SiO
21 layer of the last coating of/Si, gel mould slowly push in 500 ℃ the tubular type gradient furnace, place and heat-treated in 15 minutes from room temperature, repeat this process and reach thickness 40～70 nanometers that need up to film.At last with this film 750 ℃ of following heat treatments 1 hour.The titanium nitride electrode is as top electrode in the method sputter of the dc magnetron reactive sputtering of surface employing thereon then, and its diameter is that 0.2mm, thickness are about 70nm, forms hearth electrode/(SrTi
0.99Sn
0.01O
3+ 1%Mg+0.1%Mn) film/top electrode plate condenser structure is with testing film resistance sex change energy.Adopt the same procedure preparation not contain the SrTi of Mg and Mn doping
0.95Sn
0.05O
3Film forms identical hearth electrode/(SrTi
0.95Sn
0.05O
3) film/top electrode structure, the same terms is its resistance sex change energy of test down.
With electric pulse doping strontium stannate titanate film and the pure strontium stannate titanate film that above method makes carried out 1000 high/low resistance shears.When stablizing shear, the ratio of the high low resistance state of pure strontium stannate titanate film is about 2～3 times, and the ratio of the high low resistance state of strontium stannate titanate doping film is about 7～10 times.
Embodiment 6
Preparation x=0.1, y=0.1, the SrTi that the resistance-variable storing device of z=2 mixes with Mg and Mn
0.75Sn
0.25O
3Film (SrTi
0.75Sn
0.25O
3+ 1%Mg+4%Mn): the precursor solution that the 24 hours aging molar concentrations of learning from else's experience are the strontium stannate titanate of 0.1M, at substrate LaNiO
3/ Pt/Ti/SiO
21 layer of the last coating of/Si, gel mould slowly push in 500 ℃ the tubular type gradient furnace, place and heat-treated in 15 minutes from room temperature, repeat this process and reach thickness 40～70 nanometers that need up to film.At last with this film 750 ℃ of following heat treatments 1 hour.The titanium nitride electrode is as top electrode in the method sputter of the dc magnetron reactive sputtering of surface employing thereon then, and its diameter is that 0.2mm, thickness are about 70nm, forms hearth electrode/(SrTi
0.99Sn
0.01O
3+ 1%Mg+0.1%Mn) film/top electrode plate condenser structure is with testing film resistance sex change energy.Adopt the same procedure preparation not contain the SrTi of Mg and Mn doping
0.95Sn
0.05O
3Film forms identical hearth electrode/(SrTi
0.95Sn
0.05O
3) film/top electrode structure, the same terms is its resistance sex change energy of test down.
With electric pulse doping strontium stannate titanate film and the pure strontium stannate titanate film that above method makes carried out 1000 high/low resistance shears.When stablizing shear, the ratio of the high low resistance state of pure strontium stannate titanate film is about 2～3 times, and the ratio of the high low resistance state of strontium stannate titanate doping film is about 7～10 times.
Claims (6)
1. method that improves strontium stannate titanate film resistance-change memory performance, described method comprise that in strontium stannate titanate film material doping molar content is 0.1～4% Mg of described strontium stannate titanate film material and 0.1～4% Mn; The chemical composition of described strontium stannate titanate film material is SrTi
(1-x)Sn
xO
3, 0.01≤x≤0.25 wherein.
2. the method for claim 1 is characterized in that, adopting doping molar content in the sol-gel normal direction strontium stannate titanate film material is 0.1～4% Mg of described strontium stannate titanate film material and 0.1～4% Mn, may further comprise the steps:
A) presoma of strontium and the presoma of tin are pressed Sr (Ti
1-xSn
x) O
3In the metering ratio join in the glacial acetic acid, add acetate or the nitrate of Mg and Mn again by proportioning, be heated to the cooling of boiling back and obtain acetum;
B) presoma of titanium and the mixed solution of ethylene glycol ethyl ether and acetylacetone,2,4-pentanedione are joined in the acetum of step 1) gained;
C) add ethylene glycol ethyl ether the molar concentration of Sr element in the solution is adjusted to 0.05～0.3M;
D) step c) gained solution after aging 1～3 day, is coated on and forms gel mould on the substrate, in 650 ℃～750 ℃ following heat treatments 0.5～1 hour, obtain the strontium stannate titanate doping film again.
3. method as claimed in claim 2 is characterized in that, the presoma of strontium is a strontium acetate, and the presoma of tin is tin acetate or Dibutyltin oxide, and the presoma of titanium is an isopropyl titanate.
4. method as claimed in claim 2 is characterized in that described substrate is selected from LaNiO
3/ Pt/Ti/SiO
2/ Si (100) or Pt/Ti/SiO
2/ Si.
5. method as claimed in claim 2 is characterized in that, the thickness of described strontium stannate titanate doping film is 40～80nm.
6. the strontium stannate titanate doping film that obtains according to the described method of arbitrary claim among the claim 1-5, the application in resistance-variable storing device.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709472A (en) * | 2012-05-18 | 2012-10-03 | 河南大学 | Full-transparent resistive random access memory and application of barium stannate on aspect of using barium stannate as transparent material with stable resistance changing characteristic |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01289206A (en) * | 1988-05-17 | 1989-11-21 | Matsushita Electric Ind Co Ltd | Voltage-dependent nonlinear resistance element and manufacture thereof |
| CN1947863A (en) * | 2005-10-13 | 2007-04-18 | 同济大学 | Method for preparing barium stan-titanate ferroelectric film |
-
2010
- 2010-05-20 CN CN 201010179696 patent/CN102255043B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01289206A (en) * | 1988-05-17 | 1989-11-21 | Matsushita Electric Ind Co Ltd | Voltage-dependent nonlinear resistance element and manufacture thereof |
| CN1947863A (en) * | 2005-10-13 | 2007-04-18 | 同济大学 | Method for preparing barium stan-titanate ferroelectric film |
Non-Patent Citations (2)
| Title |
|---|
| 周歧刚等: "Mn-Mg共掺杂对钛酸锶钡薄膜介电性能的影响", 《无机材料学报》 * |
| 朱连杰等: "SrTi1-xSnxO3的水热合成与结构研究", 《高等学校化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709472A (en) * | 2012-05-18 | 2012-10-03 | 河南大学 | Full-transparent resistive random access memory and application of barium stannate on aspect of using barium stannate as transparent material with stable resistance changing characteristic |
| CN102709472B (en) * | 2012-05-18 | 2014-09-03 | 河南大学 | Full-transparent resistive random access memory and application of barium stannate on aspect of using barium stannate as transparent material with stable resistance changing characteristic |
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