CN103500797A - Resistive random access memory unit and manufacturing method thereof - Google Patents
Resistive random access memory unit and manufacturing method thereof Download PDFInfo
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- CN103500797A CN103500797A CN201310487881.XA CN201310487881A CN103500797A CN 103500797 A CN103500797 A CN 103500797A CN 201310487881 A CN201310487881 A CN 201310487881A CN 103500797 A CN103500797 A CN 103500797A
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- access memory
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Abstract
The invention discloses a resistive random access memory unit and a manufacturing method thereof. The resistive random access memory unit comprises a bottom electrode, a top electrode and a resistance change material laminated layer positioned between the bottom electrode and the top electrode, wherein the resistance change material laminated layer comprises at least two layers which are made of different resistance change materials and are directly contacted with each other. The resistive random access memory unit can be used for nonvolatile memories with high switch resistance ratio and high stability.
Description
Technical field
The invention belongs to microelectronics technology, relate to particularly random access memory unit and manufacture method thereof.
Background technology
Nonvolatile memory has after power supply breaks still can preserve the characteristic of storage inside data for a long time, and it is widely used in various handheld terminal communications and multimedia equipment.The main flow nonvolatile memory is the Flash memory in the market, but Flash storage utensil has the single ﹑ storage density height of knot structure letter and electricity can wipe except the ﹑ overprogram, also have that this ﹑ of Di Cheng is high clashes the advantages such as speed and high reliability, but the Flash memory exists obvious defect and problem.On the one hand, due to the Flash memory to write voltage higher, read or write speed slow (read-write/erasing time: 1ms/0.1ms), erasable number of times is lower>10
5inferior.On the other hand, Flash memory basic principle is to utilize the floating gate charge memory technology to change the threshold property of metal-oxide-semiconductor to realize the data storage, further minification will cause the too small tunneling effect of electronics that causes of corresponding gate insulation layer thickness to manifest gradually, leakage current sharply increases, thereby affects the stable of device.
At present, most possibly the novel nonvolatile memory of alternative traditional flash memory mainly contains: ferroelectric memory (FRAM) ﹑ magnetic memory (MRAM) ﹑ phase transition storage (PRAM) and resistance-variable storing device (RRAM).Resistance-variable storing device (RRAM) is based on some oxide materials and induces the transition effect of lower generation resistance to grow up at direct voltage or pulse voltage.
RRAM generally includes hearth electrode, top electrode and is clipped in two resistive material layers between electrode.The resistive material is generally transition metal oxide, for example HfO
2, NiO, TiO
2, ZrO
2, ZnO, MgO, WO
3, Ta
2o
5, Al
2o
3, MoO
x, CeO
x, La
2o
3, Pr
0.7ca
0.3mnO
3, La
1-xca
xmnO
3etc., and can adopt elements such as Al, Gd, La, Sr, Ti to be adulterated.The resistive material can show two stable states, i.e. high-impedance state and low resistance state, corresponding digital " 0 " and " 1 " respectively.RRAM is used potential pulse to change the resistance state of resistive material and its resistance state afterwards of cutting off the power supply remains unchanged.RRAM Ju has the mono-﹑ storage density of Jie structure Jian Gao ﹑ read or write speed Kuai ﹑ Information preservation Wen to Ding ﹑ Gong Hao Di ﹑ and has fixedness, and is easy to realize the advantage of the integrated and multilevel storage of 3 D stereo.
Yet expectation further improves the electric resistance changing characteristic of RRAM to obtain good application prospect.
Summary of the invention
The object of the present invention is to provide random access memory unit and the manufacture method thereof of a kind of high switch resistance ratio and high stability.
According to an aspect of the present invention, provide a kind of random access memory unit, comprising: hearth electrode; Top electrode; And the resistive material laminate between hearth electrode and top electrode, wherein said resistive material laminate comprises by different resistive materials and forming and direct contact at least two-layer.
According to a further aspect in the invention, provide a kind of method of manufacturing random access memory unit, comprising: form hearth electrode; Form the resistive material laminate on hearth electrode, described resistive material laminate comprises by different resistive materials and forming and direct contact at least two-layer; And form top electrode on the resistive material laminate.
Preferably, described one deck at least two-layer is comprised of binary metal oxide.
Preferably, described another layer at least two-layer is comprised of perovskite oxide.
Preferably, described binary metal oxide comprise following any: HfO
2, NiO, TiO
2, ZrO
2, ZnO, MgO, WO
3, Ta
2o
5, Al
2o
3, MoO
x, CeO
x, La
2o
3and combination in any, wherein x=0-1.
Preferably, described perovskite oxide comprise following any: Pr
0.7ca
0.3mnO
3, La
1-xca
xmnO
3and combination in any, wherein x=0-1.
Two Resistance states of described memory cell performance.
The invention has the advantages that:
Random access memory unit according to the present invention utilizes compound resistive material laminate to replace the resistive material layer of individual layer, due to the interfacial effect of two-layer resistive material, has reduced the leakage current of device, has improved the stability of device change resistance performance.This random access memory unit shows the conversion characteristic between excellent high ﹑ low resistance state, shows two Resistance states, and the difference between its high low resistance state can be greater than 10
4doubly.This random access memory unit is stable through this difference after repeatedly changing, and with the resistance-variable storing device of single resistive material layer, compares and has improved write performance and erasable number of times, has extended storage life.This random access memory unit has also reduced electric resistance changing voltage, and then reduces the power consumption of device.In a preferred embodiment, laminated film has good light transmission to visible ray, can be applicable to non-volatile transparent memory.
The preparation of film can be used the preparation methods such as Ci control Jian She ﹑ pulsed laser deposition, has wide development space and market prospects.
The accompanying drawing explanation
Fig. 1 is the structural representation of random access memory unit according to an embodiment of the invention.
Fig. 2 is the I-V performance plot of random access memory unit according to an embodiment of the invention.
Fig. 3 is the variation of the resistance of the high-impedance state of random access memory unit according to an embodiment of the invention and low resistance state with the switch cycle-index.
Fig. 4 is the light transmittance to visible ray of random access memory unit according to an embodiment of the invention.
Embodiment
Hereinafter with reference to accompanying drawing, the present invention is described in more detail.For the sake of clarity, the various piece in accompanying drawing is not drawn in proportion.
Be to be understood that, when the structure of outlines device, when one deck, zone are called be positioned at another layer, another zone " above " or when " top ", can refer to be located immediately at another layer, another is above zone, or its and another layer, also comprise other layer or regional between another zone.And if, by the device upset, this one deck, a zone will be positioned at another layer, another zone " following " or " below ".If for describe be located immediately at another layer, another the zone above situation, this paper will adopt " directly existing ... top " or " ... top and with it the adjacency " form of presentation.
Described hereinafter many specific details of the present invention, for example structure of device, material, size, treatment process and technology, in order to more clearly understand the present invention.But such just as the skilled person will understand, can realize the present invention not according to these specific details.Unless particularly pointed out hereinafter, the various piece of memory cell can consist of the known material of those skilled in the art.The present invention can present by various forms, below will describe the some of them example.
Fig. 1 is the structural representation of random access memory unit 100 according to an embodiment of the invention.Random access memory unit 100 comprises substrate 101, be positioned at hearth electrode 102 on substrate 101, be positioned at the first resistive material layer 103 on hearth electrode 102, be positioned at the second resistive material layer 104 on the first resistive material layer 103 and be positioned at the top electrode 105 on the second resistive material layer 104.
The first resistive material layer 103 and the second resistive material layer 104 can be comprised of binary metal oxide and perovskite oxide respectively.Described binary metal oxide comprise following any: HfO
2, NiO, TiO
2, ZrO
2, ZnO, MgO, WO
3, Ta
2o
5, Al
2o
3, MoO
x, CeO
x, La
2o
3and combination in any, wherein x=0-1.Described perovskite oxide comprise following any: Pr
0.7ca
0.3mnO
3, La
1-xca
xmnO
3and combination in any, wherein x=0-1.
In an example, the first resistive material layer 103 can be comprised of ZnO or MgO, and thickness is the 50-100 nanometer.The second resistive material layer 104 can be by Pr
0.7ca
0.3mnO
3form, thickness is the 50-200 nanometer.
In a preferred embodiment, layer 101-105 is all transparent, thereby forms together transparent random access memory unit 100.Yet, should be appreciated that in layer 101-105 to appoint one or more layers can be nontransparent, still can be applied to resistance-variable storing device.In addition, the resistive material laminate comprises the first resistive material layer 103 and the second resistive material layer 104 of direct contact.Yet, should be appreciated that the resistive material laminate can also comprise more resistive material layer.
According to preferred embodiment, the method for random access memory unit 100 according to an embodiment of the invention of manufacturing comprises the following steps.
Adopt transparent flexible or non-flexible material to make substrate 101.By used substrate 101 use alcohol Ultrasonic Cleaning three times, each ten minutes, finally use washed with de-ionized water.
Then, form hearth electrode 102 on substrate 101.The preparation of hearth electrode 102 can be used pulsed laser deposition.Settling chamber's base vacuum degree must be higher than 10
-4pa, oxygen is pressed as 5Pa～10Pa, and depositing temperature is room temperature, and during deposition, energy is 100mJ～400mJ, and umber of pulse is 100～3000 pulses.Hearth electrode 102 is for example conductive oxide film, and thickness is 100nm～200nm.
Then, form the first resistive material layer 103 on hearth electrode 102.The preparation of the first resistive material layer 103 can adopt pulsed laser deposition.Settling chamber's base vacuum degree must be higher than 10
-4pa, oxygen is pressed as 1Pa～10Pa, and depositing temperature is room temperature, and during deposition, energy is 100mJ～400mJ, and umber of pulse is 100～3000 pulses.The first resistive material layer 103 is for example the binary metal oxide film, and thickness is 50nm～100nm.
Then, form the second resistive material layer 104 on the first resistive material layer 103.The preparation of the second resistive material layer 104 can adopt pulsed laser deposition.Settling chamber's base vacuum degree must be higher than 10
-4pa, during sputter, the oxygen pressure is 5～20Pa, and depositing temperature is room temperature, and during deposition, energy is 100mJ～400mJ, and umber of pulse is 100～3000 pulses.The second resistive material layer 104 is for example Pr
0.7ca
0.3mnO
3film, thickness is 50-200nm.
Then, form top electrode 105 on the second resistive material layer 104.The preparation method of top electrode 105 can be magnetron sputtering.Sputtering chamber base vacuum degree must be higher than 10
-5pa, sputter temperature is room temperature, sputtering pressure is 0.1～1Pa.Top electrode 105 is for example ito thin film, and thickness is 1000-200nm.
In an example, utilize pulsed laser deposition at substrate 101(ITO/ glass) upper deposition hearth electrode 102(zinc-oxide film).When settling chamber's base vacuum, taking out is 5 * 10
-4during Pa, pass into oxygen and make settling chamber reach the operating pressure of 10pa, depositing temperature is room temperature, and during deposition, energy is 300mJ, umber of pulse 3000 pulses, thereby form the first resistive material layer 103(zinc-oxide film), thickness is 80nm.Then, further utilize pulsed laser deposition the second resistive material layer 104(Pr
0.7ca
0.3mnO
3film), deposition pressure is 10pa, and depositing temperature is room temperature, and during deposition, energy is 300mJ, umber of pulse 4000 pulses.The thickness of the second resistive material layer 104 is 100nm.Then, utilize magnetron sputtering to form top electrode 105(ITO film by the mask method of blocking on the second resistive material layer 104).Top electrode 105 is for example that diameter is the round-shaped of 0.2mm, and thickness is 200nm.
Fig. 2 be adopt that the method for above-mentioned example manufactures the I-V performance plot of random access memory unit 100.When scanning voltage be-during 2.2V, memory cell changes low resistance into from high resistance; When scanning voltage is 2V, memory cell changes high resistance into from low resistance, and the shift voltage absolute value is in the 2V left and right, and this has reduced the power consumption of device greatly.
Fig. 3 be adopt that the method for above-mentioned example manufactures the high-impedance state of random access memory unit 100 and the resistance of low resistance state (be expressed as respectively R
hand R
l) with the variation of switch cycle-index.From then on figure can find out, this novel Memister is under direct voltage continuous sweep, and high switch resistance ratio can be greater than 10
4doubly.In the process of the high low resistance circulations of continuous 250 times, high low resistance still shows stability preferably.Thereby, with the resistance-variable storing device of single resistive material layer, compare, write performance and erasable number of times all be significantly improved.
Fig. 4 be adopt that the method for above-mentioned example manufactures the light transmittance to visible ray of random access memory unit 100.From then on figure can find out, memory cell light transmittance under wavelength 590nm visible ray reaches as high as 84.6%, at wavelength, is under the 450-750nm visible ray, and average transmittance is 80.6%, has good light transmission.Thereby the present invention has potential using value on non-volatile transparent memory.
Above-described embodiment is of the present invention giving an example, although disclose for the purpose of illustration embodiments of the invention and accompanying drawing, but it will be appreciated by those skilled in the art that: without departing from the spirit and scope of the invention and the appended claims, various replacements, variation and modification are all possible.Therefore, the present invention should not be limited to embodiment and the disclosed content of accompanying drawing.
Claims (8)
1. a random access memory unit comprises:
Hearth electrode;
Top electrode; And
Resistive material laminate between hearth electrode and top electrode,
Wherein said resistive material laminate comprises by different resistive materials and forming and direct contact at least two-layer.
2. random access memory unit according to claim 1, wherein said one deck at least two-layer is comprised of binary metal oxide.
3. random access memory unit according to claim 2, wherein said another layer at least two-layer is comprised of perovskite oxide.
4. random access memory unit according to claim 1, two Resistance states of wherein said memory cell performance.
5. a method of manufacturing random access memory unit comprises:
Form hearth electrode;
Form the resistive material laminate on hearth electrode, described resistive material laminate comprises by different resistive materials and forming and direct contact at least two-layer; And
Form top electrode on the resistive material laminate.
6. method according to claim 5, wherein said one deck at least two-layer is comprised of binary metal oxide.
7. method according to claim 6, wherein said another layer at least two-layer is comprised of perovskite oxide.
8. method according to claim 5, two Resistance states of wherein said memory cell performance.
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Cited By (8)
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|---|---|---|---|---|
| CN105322091A (en) * | 2015-12-09 | 2016-02-10 | 中国科学院物理研究所 | Optical-write-in resistive random storage unit, as well as preparation and operation methods and application thereof |
| CN105720195A (en) * | 2016-04-21 | 2016-06-29 | 南京理工大学 | Inorganic halogen perovskite resistive random access memory and preparation method |
| CN105957962A (en) * | 2016-06-20 | 2016-09-21 | 西安交通大学 | TiO<x>/Al<2>O<3>/TiO<x> sandwich laminated layer resistive random access memory thin film and preparation method therefor |
| CN106159083A (en) * | 2014-08-14 | 2016-11-23 | 台湾积体电路制造股份有限公司 | Oxidation film scheme for RRAM structure |
| CN106992249A (en) * | 2017-02-22 | 2017-07-28 | 北京航空航天大学 | A kind of ionic memristor with quantum conductance effect |
| CN108922965A (en) * | 2018-07-24 | 2018-11-30 | 湖北大学 | A kind of resistance-variable storing device and preparation method thereof based on perovskite material |
| CN110707212A (en) * | 2019-08-31 | 2020-01-17 | 郑州大学 | Application of PVAm modified OHP film, polymer perovskite RRAM device and preparation method thereof |
| CN110739395A (en) * | 2019-10-30 | 2020-01-31 | 上海华力微电子有限公司 | Resistive random access memory and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159083B (en) * | 2014-08-14 | 2019-08-30 | 台湾积体电路制造股份有限公司 | Oxidation film scheme for RRAM structure |
| CN106159083A (en) * | 2014-08-14 | 2016-11-23 | 台湾积体电路制造股份有限公司 | Oxidation film scheme for RRAM structure |
| CN105322091B (en) * | 2015-12-09 | 2018-09-25 | 中国科学院物理研究所 | A kind of light write-in variable-resistance memory unit and its preparation, operating method and application |
| CN105322091A (en) * | 2015-12-09 | 2016-02-10 | 中国科学院物理研究所 | Optical-write-in resistive random storage unit, as well as preparation and operation methods and application thereof |
| CN105720195A (en) * | 2016-04-21 | 2016-06-29 | 南京理工大学 | Inorganic halogen perovskite resistive random access memory and preparation method |
| CN105720195B (en) * | 2016-04-21 | 2018-07-31 | 南京理工大学 | A kind of inorganic halogen perovskite resistance-variable storing device and preparation method thereof |
| CN105957962A (en) * | 2016-06-20 | 2016-09-21 | 西安交通大学 | TiO<x>/Al<2>O<3>/TiO<x> sandwich laminated layer resistive random access memory thin film and preparation method therefor |
| CN106992249A (en) * | 2017-02-22 | 2017-07-28 | 北京航空航天大学 | A kind of ionic memristor with quantum conductance effect |
| CN106992249B (en) * | 2017-02-22 | 2019-05-03 | 北京航空航天大学 | A kind of ionic memristor with quantum conductance effect |
| CN108922965A (en) * | 2018-07-24 | 2018-11-30 | 湖北大学 | A kind of resistance-variable storing device and preparation method thereof based on perovskite material |
| CN110707212A (en) * | 2019-08-31 | 2020-01-17 | 郑州大学 | Application of PVAm modified OHP film, polymer perovskite RRAM device and preparation method thereof |
| CN110707212B (en) * | 2019-08-31 | 2022-07-26 | 郑州大学 | Application of PVAm modified OHP film, polymer perovskite RRAM device and preparation method thereof |
| CN110739395A (en) * | 2019-10-30 | 2020-01-31 | 上海华力微电子有限公司 | Resistive random access memory and preparation method thereof |
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