CN103400937A - Preparation method of resistance switch adopting TiO2/SnO2 composite nano-rods - Google Patents
Preparation method of resistance switch adopting TiO2/SnO2 composite nano-rods Download PDFInfo
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- CN103400937A CN103400937A CN2013103516135A CN201310351613A CN103400937A CN 103400937 A CN103400937 A CN 103400937A CN 2013103516135 A CN2013103516135 A CN 2013103516135A CN 201310351613 A CN201310351613 A CN 201310351613A CN 103400937 A CN103400937 A CN 103400937A
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Abstract
The invention discloses a preparation method of a resistance switch adopting TiO2/SnO2 composite nano-rods. The preparation method comprises the following steps: 1), directly growing TiO2/SnO2 composite nano-rod arrays on a conductive substrate according to a hydrothermal method; 2) annealing the conductive substrate, which is obtained in step 1) and provided with the TiO2/SnO2 composite nano-rod arrays grown thereon under 200 to 800 DEG C for 1 to 5 hours, so as to obtain the resistance switch adopting the TiO2/SnO2 composite nano-rods. The preparation method has the advantages that the indoor temperature resistance switch characteristic of the resistance switch adopting the TiO2/SnO2 composite nano-rod array structure can be better; the resistance switch effect under a low temperature can be higher; the circulating stability is favorable; the master mould of a resistance switch-type non-volatile memorizer can be prepared.
Description
Technical field
The present invention relates to a kind of preparation method of resistance switch, particularly a kind of TiO
2/ SnO
2The preparation method of composite nanorod resistance switch.
Background technology
Memory occupies very consequence always in whole IC market.According to statistics in 2007, the sales volume of global storage market was up to 60,000,000,000 dollars, and the market share is also in continuous expansion.The memory that uses at present can be divided into two classes, i.e. volatile random asccess memory and non-volatility memorizer.The former major product has dynamic random access memory and static random access memory, and data rate memory is fast, but after finishing power supply, stored data can disappear very soon, so canned data need to constantly refresh.The latter mainly contains ROM (read-only memory), PROM (programmable storage), EEPROM (electricity erasable memorizer), Flash (flash memory) etc., their storage speed is relatively slow, but still can continue to keep the characteristic of data after having outage, be widely used in various handheld terminals and multimedia equipment, wherein Flash has become the non-volatility memorizer of the most ripe main flow.The Databeans of market survey mechanism points out, global Flash sales volume reached 194.72 hundred million dollars in 2009, accounted for 8.7% of semiconductor industry, estimated that global Flash sales volume in 2010 will reach 254.28 hundred million dollars.
Resistance switch formula non-volatility memorizer is based on a kind of memory of resistance switch effect, and structure is similar to magnetic memory, be the sandwich structure of conductor/insulation body/conductor formation, but the dielectric layer both sides is not magnetic material, but conductor material.Generally, conductor is metal, so the structure of resistance-type memory is conductor/insulation body/conductor type structure.By applying the potential pulse of certain polarity, in conductor/insulation body/conductor structure, the resistance of insulating barrier can be changed between high-impedance state and low resistance state, realizes thus the storage of information.
The advantages such as it is high that resistance-type memory has storage density, and read or write speed is fast, and structure is relatively simple.In addition, the manufacture craft of resistance-type memory and traditional CMOS technique compatible fine, easily realize in enormous quantities, low-cost production manufacturing.
Summary of the invention
In view of this, the invention provides a kind of TiO
2/ SnO
2The preparation method of composite nanorod resistance switch, the TiO of preparation
2/ SnO
2The resistance switch of composite nanorod array structure can be realized the switch performance of higher rate, and has at low temperatures better performance, and has extended cycle life.
TiO of the present invention
2/ SnO
2The preparation method of composite nanorod resistance switch comprises the following steps:
1) by hydro thermal method direct growth TiO on conductive substrate
2/ SnO
2The composite nanorod array;
2) growth that step 1) is obtained has TiO
2/ SnO
2The conductive substrate of composite nanorod array was annealed 1～5 hour under 200～800 ℃, obtain TiO
2/ SnO
2The composite nanorod resistance switch.
Further, in described step 1), by hydro thermal method direct growth TiO on conductive substrate
2/ SnO
2The concrete grammar of composite nanorod array is: the mol ratio according to 1:1 takes tetraisopropyl titanate and SnCl
45H
2O is dissolved in deionized water, and adds hydrochloric acid, stirs and is made into mixed solution; Then conductive substrate is inserted in mixed solution, 100～300 ℃ of lower hydro-thermal reactions 1～5 hour, obtaining growth had TiO
2/ SnO
2The conductive substrate of composite nanorod array.
Further, in described step 1), hydrothermal temperature is 180 ℃, and the reaction time is 3 hours.
Further, described step 2) in, annealing temperature is 450 ℃, annealing time is 2 hours.
Further, described conductive substrate is the FTO electro-conductive glass.
Beneficial effect of the present invention is: the present invention utilizes the hydro thermal method TiO that grows on conductive substrate
2/ SnO
2The composite nanorod array, further utilized the method for high annealing, effectively improved TiO
2And SnO
2Crystallization degree, make simultaneously TiO
2And SnO
2Can form a large amount of oxygen cavities, form hole and have the unique physical character of good transmission electronics, due to TiO
2And SnO
2Band gap staggered and be more or less the same, this staggered band gap, not only can effectively reduce the compound of hole and electronics, and can increase widely the transition probability of electronics between band gap; Therefore, the TiO of the present invention's preparation
2/ SnO
2The resistance switch of composite nanorod array structure can be realized room temperature resistance switching characteristic preferably, and larger resistance switch effect is arranged at low temperatures, and cyclical stability is good, can be used in the archetype for preparing resistance switch formula non-volatility memorizer.
Description of drawings
In order to make the purpose, technical solutions and advantages of the present invention clearer, the present invention is described in further detail below in conjunction with accompanying drawing, wherein:
Fig. 1 is that embodiment is by hydro thermal method direct growth TiO on conductive substrate
2/ SnO
2The schematic diagram of composite nanorod array;
Fig. 2 is the TiO that embodiment prepares
2/ SnO
2XRD figure and the EDX elementary analysis figure of composite nanorod resistance switch;
Fig. 3 is the TiO that embodiment prepares
2/ SnO
2The SEM figure of composite nanorod resistance switch and TEM figure;
Fig. 4 is the test circuit connection layout;
Fig. 5 is Current Voltage Diagram and the resistance switch design sketch of test circuit in different voltage scan range;
Fig. 6 is Current Voltage Diagram and the resistance switch design sketch of test circuit under different temperatures;
Fig. 7 is Current Voltage Diagram and the resistance switch design sketch of test circuit different voltage scan range when 50K;
Fig. 8 is the impedance figure of test circuit under different temperatures;
Fig. 9 is test circuit open circuit voltage-time diagram when 50K.
Embodiment
Hereinafter with reference to accompanying drawing, the preferred embodiments of the present invention are described in detail.
Fig. 1 is that embodiment is by hydro thermal method direct growth TiO on conductive substrate
2/ SnO
2The schematic diagram of composite nanorod array, as shown in Figure 1, the TiO of the present embodiment
2/ SnO
2The preparation method of composite nanorod resistance switch comprises the following steps:
1) take 200 μ L tetraisopropyl titanates and 7mL concentrated hydrochloric acid (12mol/L) is dissolved in the 6.5mL deionized water, then the mol ratio by 1:1 adds appropriate SnCl
45H
2O, stir and be made into mixed solution, and mixed solution is transferred to having in the teflon-lined reactor of 50mL; Then (area is about 3cm with cleaned FTO electro-conductive glass
2, use successively acetone, ethanol, deionized water ultrasonic cleaning) be inserted in mixed solution, reactor is put in air dry oven and is heated, and 180 ℃ of lower hydro-thermal reactions 3 hours, obtaining growth had TiO
2/ SnO
2The FTO electro-conductive glass of composite nanorod array;
2) be cooled to room temperature when reactor, taking out growth has TiO
2/ SnO
2The FTO electro-conductive glass of composite nanorod array, use deionized water rinsing, and annealing is 2 hours under 450 ℃, obtains TiO
2/ SnO
2The composite nanorod resistance switch.
Fig. 2 (a) is the TiO of embodiment preparation
2/ SnO
2The XRD figure of composite nanorod resistance switch, as seen from the figure, TiO
2With SnO
2Crystallization degree is good, and TiO
2Anatase type and rutile-type all exist.Fig. 2 (b) is the TiO of embodiment preparation
2/ SnO
2The EDX elementary analysis figure of composite nanorod resistance switch, as seen from the figure, it comprises Ti, Sn and O element, and the ratio of Sn element is approximately 8%, then without other impurity elements.
Fig. 3 (a) and the TiO that (b) for embodiment, prepares
2/ SnO
2The SEM figure of composite nanorod resistance switch, illustration is single nanometer rods, as seen from the figure, TiO
2/ SnO
2The diameter of composite nanorod is approximately 300nm.Fig. 3 (c) and the TiO that (d) for embodiment, prepares
2/ SnO
2The TEM figure of composite nanorod resistance switch, as seen from the figure, TiO
2And SnO
2Compound even, and crystallization is good.
Fig. 4 is the test circuit connection layout, with the TiO of embodiment preparation
2/ SnO
2The composite nanorod resistance switch is as bottom electrode, with the about 8mm of area of section
2Columned silver is as top electrode, and as the test two-used table of current/voltage, the test circuit that forms as shown in Figure 4 carries out performance test with electrochemical workstation, and its result is as follows:
Fig. 5 is the Current Voltage Diagram of test circuit in different voltage scan range, and its illustration is its corresponding resistance switch design sketch, demonstrates good resistance switch effect.
Fig. 6 (a) is the Current Voltage Diagram of test circuit under different temperatures, and Fig. 6 (b) is corresponding resistance switch design sketch, and as seen from the figure, it has larger resistance switch effect at low temperatures.
Fig. 7 is the Current Voltage Diagram of test circuit different voltage scan range when 50K, and its illustration is its corresponding resistance switch design sketch, and as seen from the figure, its cyclical stability is good, not too large decay after 200 circulations.
Fig. 8 is the impedance figure of test circuit under different temperatures, and as seen from the figure, along with the rising of temperature, its impedance also diminishes gradually, and this may be that carrier transition is easier because temperature is higher.
Fig. 9 is test circuit open circuit voltage-time diagram when 50K, and as seen from the figure, its open circuit voltage is about-140mV after arriving and stablizing.
Can prove the TiO that embodiment prepares by above-mentioned experiment
2/ SnO
2The composite nanorod resistance switch has good crystallization degree, simultaneously at TiO
2/ SnO
2The nanometer rods the inside has formed a large amount of oxygen rooms, thereby has improved the resistance switch effect, and this resistance switch can be realized room temperature resistance switching characteristic preferably, and larger resistance switch effect is arranged at low temperatures, and cyclical stability is good.
In the present invention, nanometer rods length and thickness (draw ratio) can be controlled by hydrothermal reaction condition, and hydrothermal temperature can be 100～300 ℃, and preferred 180 ℃, the hydro-thermal reaction time can be 1～5 hour, preferred 3 hours; The temperature of annealing need to be controlled between 200～800 ℃, annealing time 1～5 hour, and most preferred annealing temperature is 450 ℃, annealing time is 2 o'clock; Conductive substrate is not limited to the FTO electro-conductive glass, and other sheet metal or conductive film also can be used for the present invention, but annealing conditions can be adjusted according to substrate for use character.
Explanation is finally, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although by invention has been described with reference to the preferred embodiments of the present invention, but those of ordinary skill in the art is to be understood that, can make various changes to it in the form and details, and not depart from the spirit and scope of the present invention that appended claims limits.
Claims (5)
1. TiO
2/ SnO
2The preparation method of composite nanorod resistance switch is characterized in that: comprise the following steps:
1) by hydro thermal method direct growth TiO on conductive substrate
2/ SnO
2The composite nanorod array;
2) growth that step 1) is obtained has TiO
2/ SnO
2The conductive substrate of composite nanorod array was annealed 1～5 hour under 200～800 ℃, obtain TiO
2/ SnO
2The composite nanorod resistance switch.
2. TiO according to claim 1
2/ SnO
2The preparation method of composite nanorod resistance switch is characterized in that: in described step 1), by hydro thermal method direct growth TiO on conductive substrate
2/ SnO
2The concrete grammar of composite nanorod array is: the mol ratio according to 1:1 takes tetraisopropyl titanate and SnCl
45H
2O is dissolved in deionized water, and adds hydrochloric acid, stirs and is made into mixed solution; Then conductive substrate is inserted in mixed solution, 100～300 ℃ of lower hydro-thermal reactions 1～5 hour, obtaining growth had TiO
2/ SnO
2The conductive substrate of composite nanorod array.
3. TiO according to claim 2
2/ SnO
2The preparation method of composite nanorod resistance switch is characterized in that: in described step 1), hydrothermal temperature is 180 ℃, and the reaction time is 3 hours.
4. TiO according to claim 1
2/ SnO
2The preparation method of composite nanorod resistance switch is characterized in that: described step 2), annealing temperature is 450 ℃, and annealing time is 2 hours.
5. TiO according to claim 1
2/ SnO
2The preparation method of composite nanorod resistance switch is characterized in that: described conductive substrate is the FTO electro-conductive glass.
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Cited By (6)
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| CN105261700A (en) * | 2015-09-07 | 2016-01-20 | 武汉理工大学 | Fiber-based non-volatile memory device and preparation method thereof |
| CN106159285A (en) * | 2015-04-23 | 2016-11-23 | 中国科学院大连化学物理研究所 | The preparation method of a kind of ordered ultrathin Catalytic Layer and Catalytic Layer and application |
| CN108281548A (en) * | 2018-02-07 | 2018-07-13 | 中南大学 | A kind of bipolarity bistable state memristor and preparation method thereof |
| CN108682716A (en) * | 2018-05-09 | 2018-10-19 | 大连理工大学 | A kind of preparation method of high-performance semiconductor oxide composite structure ultraviolet light detector |
| CN110165052A (en) * | 2019-05-31 | 2019-08-23 | 湘潭大学 | A kind of inorganic flexible resistance-variable storing device and preparation method thereof |
| CN112429768A (en) * | 2020-11-11 | 2021-03-02 | 厦门大学 | Flower-like titanium dioxide nanowire and preparation method and application thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159285A (en) * | 2015-04-23 | 2016-11-23 | 中国科学院大连化学物理研究所 | The preparation method of a kind of ordered ultrathin Catalytic Layer and Catalytic Layer and application |
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| CN105261700A (en) * | 2015-09-07 | 2016-01-20 | 武汉理工大学 | Fiber-based non-volatile memory device and preparation method thereof |
| CN105261700B (en) * | 2015-09-07 | 2018-05-01 | 武汉理工大学 | Nonvolatile semiconductor memory member based on fiber and preparation method thereof |
| CN108281548A (en) * | 2018-02-07 | 2018-07-13 | 中南大学 | A kind of bipolarity bistable state memristor and preparation method thereof |
| CN108281548B (en) * | 2018-02-07 | 2019-09-03 | 中南大学 | A kind of bipolarity bistable state memristor and preparation method thereof |
| CN108682716A (en) * | 2018-05-09 | 2018-10-19 | 大连理工大学 | A kind of preparation method of high-performance semiconductor oxide composite structure ultraviolet light detector |
| CN108682716B (en) * | 2018-05-09 | 2020-06-16 | 大连理工大学 | Preparation method of high-performance semiconductor oxide composite structure ultraviolet light detector |
| CN110165052A (en) * | 2019-05-31 | 2019-08-23 | 湘潭大学 | A kind of inorganic flexible resistance-variable storing device and preparation method thereof |
| CN110165052B (en) * | 2019-05-31 | 2023-04-25 | 湘潭大学 | Inorganic flexible resistive random access memory and preparation method thereof |
| CN112429768A (en) * | 2020-11-11 | 2021-03-02 | 厦门大学 | Flower-like titanium dioxide nanowire and preparation method and application thereof |
| CN112429768B (en) * | 2020-11-11 | 2022-02-18 | 厦门大学 | Flower-like titanium dioxide nanowire and preparation method and application thereof |
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