CN101826597B - Organic resistive random access memory and preparation method thereof - Google Patents
Organic resistive random access memory and preparation method thereof Download PDFInfo
- Publication number
- CN101826597B CN101826597B CN2010101614229A CN201010161422A CN101826597B CN 101826597 B CN101826597 B CN 101826597B CN 2010101614229 A CN2010101614229 A CN 2010101614229A CN 201010161422 A CN201010161422 A CN 201010161422A CN 101826597 B CN101826597 B CN 101826597B
- Authority
- CN
- China
- Prior art keywords
- organic
- metal
- random access
- access memory
- resistive random
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention provides an organic resistive random access memory and a preparation method thereof, which belong to the technical field of very large scale integrated circuit. The organic resistive random access memory comprises a substrate, a bottom electrode on the substrate, a middle organic functional layer and a top electrode, wherein the middle organic functional layer is a metal-doped TiOPc film. During the growth process of the TiOPc film, the even metal doping is introduced to realize the redox reaction of the metal impurity and the organic thin film and to further realize the resistive bistable state. Meanwhile, the even metal doping is artificially introduced to realize the even trap distribution, thereby effectively reducing the instability of the characteristics of a single device and the inhomogeneity of resistive characteristics among different devices, caused by the trap random distribution. The organic resistive random access memory has good chemical stability and temperature stability, and can be realized on the soft substrate, and has high application value in the field of the organic memory with low cost and high performance.
Description
Technical field
The invention belongs to the very large scale integration technology field, specifically is a kind of organic resistive random access memory and preparation method.
Background technology
In the digital times of current information explosion, people's production and life be unable to do without high density, high-speed memory.Use at present the most extensively, develop the most ripe non-volatility memorizer be flash memory (flash memory) device.Along with the microelectric technique node is constantly pushed ahead, near its physics limit, had a strong impact on the memory function of unit based on the flash memory of traditional FGS floating gate structure, the step that can't follow the integrated circuit Moore's Law develops down.Have more high storage density, faster response speed, low operating voltage more, simpler preparation technology's resistance-variable storing device of new generation (RRAM) arises at the historic moment, and because of it has the potentiality that replace flash memory, becomes the research focus of international renowned company and numerous scientific research institutions.
Resistance-variable storing device has brand-new storage concept, is different from traditional flash threshold voltage and changes the realization storage.Utilize the controlled resistance change effect that exists in some inorganic oxides or the organic substance/polymer; Promptly under the different voltages with different excitation, resistance-variable storing device can demonstrate two kinds of diverse impedance states (low-resistance and high resistant, corresponding " ON state " and " OFF state "); Difference representative data " 1 " and " 0 "; And after voltage removed, state still kept, and had therefore realized the storage of data.That the advantage of RRAM is is simple in structure, low in energy consumption, speed is fast, storage density is high, manufacturing process is simple, very likely replaces traditional non-volatility memorizer and captures semiconductor memory market.
Organic resistive random access memory can be applicable to low-cost electronic device and flexible electronic (Flexible Electronics) devices field; Except advantage with above-mentioned RRAM; But also has Rao Quxing than inorganic resistance-variable storing device; Preparation technology is simple, and is with low cost, and material can design molecular structure with superior parts such as raising performances.But organic resistive random access memory research has just marched toward the starting stage.The organic material that the organic RRAM that reports at present chooses shows the problem of chemical stability and poor heat stability mostly.The stability of device resistance attitude conversion also has problems in addition; For example: cause hindering the condition that becomes the material transitions state amplitude and the time of the potential pulse on the organic memory (as be applied to) and all can change because of the fluctuation of different components; Even for same device, the difference that the numerical value of the opening and closing voltage of resistance changes needs and the high resistant of generation and low-resistance all can be certain.This bigger discreteness will make device be difficult to accurate control, and this has become the obstruction organic resistive random access memory and has moved towards one of main difficult problem of practicability.
Summary of the invention
The present invention proposes a kind of stable organic resistive random access memory based on titanyl phthalocyanine.
Technical scheme of the present invention is following:
A kind of organic resistive random access memory comprises substrate, the hearth electrode on the substrate, and middle organic function layer and top electrode is characterized in that, said middle organic function layer is metal-doped titanyl phthalocyanine film.
A kind of preparation method of organic resistive random access memory, its step comprises
1) on substrate the deposit layer of metal as hearth electrode.
2) metal dust and organic titanyl phthalocyanine powder are ground stirring, then utilize the method for thermal evaporation film forming to form metal-doped titanyl phthalocyanine film;
3) deposit layer of metal above above-mentioned metal-doped titanyl phthalocyanine film realizes the preparation of top electrode.
The thickness of said functional layer is at 100-200nm.
Said top electrode and hearth electrode are W, (or Pt, Au).
Said top electrode and hearth electrode are W, (or Pt, thickness Au) is 100nm-200nm.
The metal of said doping is Al, any among Hf or the Mg.
The metal quality percentage of said doping is 0.1% to 1%.
The organic resistive random access film that the present invention adopts is the titanyl phthalocyanine film, adopts this organic film material to become functional layer mainly from following consideration as resistance:
1) experiment forms mechanism with the electric current of verified this organic film in theory and forms mechanism for the SCLC (space charge limited current) that receives trap control.This organic film can with the metal electrode generation redox reaction stronger than titanium activity, reaction result is to have formed the oxygen room, this oxygen room can be used as the SCLC that trap states hinders thin-film material and forms mechanism.Utilize the forward and reverse of redox reaction to carry out just can forming stable resistance and become bistable state.
2) this organic film chemical property is stable, has temperature stability preferably, both can stand temperature 450 ℃ with interior high-temperature technology, have again and utilize reliability and the ageing resistance that improves organic resistive random access memory.
3) preparation method of titanyl phthalocyanine film can adopt the method for thermal evaporation, is easy to realize.The technology that the titanyl phthalocyanine organic memory is relevant is simple, and the cost of material is low for being complementary with it of relating to, helps low-cost electronic device applications.
In the present invention, the method for in the organic film growth course, introducing the even metal doping realizes the redox reaction of metal impurities and organic film, and then realizes that resistance becomes bistable state.The artificial simultaneously even metal of introducing is mixed, and has realized uniform distribution of traps.Thereby the instability of the individual devices characteristic that the trap random distribution causes and the heterogeneity that resistance between the different components becomes characteristic have been effectively reduced.As shown in Figure 2, different on stability of the device of contrast the inventive method preparation and commonplace components.Be specially: do not have resistance change nature to titanyl phthalocyanine film itself; Organic resistive random access memory among Fig. 2 (a); In order to realize that resistance becomes bistable state; Just must introduce metal such as Al as some electrodes (for example top electrode), utilize the redox reaction between top electrode and the titanyl phthalocyanine to produce defective, change the SCLC mechanism of thin-film material.The interface conditions of electrode and titanyl phthalocyanine film is depended in the reaction of electrode and organic film, owing to the interface roughness out-of-flatness, causes reacting the main positions random distribution of generation.The titanyl phthalocyanine film is a non-crystalline material in addition, has the gap, and Al can be diffused in the organic film at random, has also caused reaction back trap uneven distribution spatially.Such random distribution is unfavorable for improving the stability and the homogeneity of device.Relative; The resistance-variable storing device of the present invention's preparation among Fig. 2 (b); Just artificially introducing is metal-doped in the organic film growth course, and electrode selects not take place the material of redox reaction, just can control the even distribution of trap in organic film; Thereby reduced the random distribution degree of trap, thereby can effectively improve the stability and the homogeneity of device.
Advantage of the present invention and good effect:
Organic material chemical property that the present invention relates to and temperature characterisitic are stable, and be with low cost, can on flexible substrate, prepare, and can be applicable to stable flexible electronic device cheaply.This stable organic resistive random access memory can improve the stability and the homogeneity of device simultaneously, and its preparation process that has improved is simple, helps low cost, the application of the memory device aspect of high stability.
Description of drawings
Fig. 1 is device architecture figure of the present invention;
The 1-substrate; The 2-hearth electrode; Evenly the mixed organic functional thin film of metal of 3-; The 4-hearth electrode is drawn; The 5-top electrode;
Fig. 2 has contrasted the stability and the homogeneity situation of two kinds of different organic resistive random access memories; Wherein Fig. 2 (a) is for adopting the device of active metal as electrode; The device of in organic film, introducing the even metal doping that Fig. 2 (b) proposes for the present invention;
The 2-hearth electrode; Evenly the mixed organic film of metal of 3-; The 5-top electrode; The trap that the 6-redox reaction forms; The top electrode of 7-active metal; 8-is the organic film of doping metals not.
Specific embodiment
Further specify the present invention below in conjunction with an embodiment, but purposes of the present invention is not limited in following practical implementation example.
Among the present invention, the technological process for preparing polymorphic organic resistive random access memory is:
1) on glass substrate, vacuum degree is 4.5 * 10
-4Under the Pa, vapor deposition one deck W is as hearth electrode.
2) before organic titanyl phthalocyanine thin film was grown in thermal evaporation, earlier with metal A l, the powder of Hf or Mg and organic titanyl phthalocyanine thing powder ground and stir, and the mass percent of metal is 0.1% to 1%.Then using mask is 4.5 * 10 in vacuum degree
-4Under the Pa, temperature is at the mixed titanyl phthalocyanine film (thickness is at 100-200nm) of metal of 200 ℃ of-250 ℃ of following vapor deposition one decks, and forms the fairlead of hearth electrode.
3) mask is placed the organic film top, deposit one deck W realizes the preparation of top electrode on mask, and drawing hearth electrode.
Though this specification is described resistance variation memory structure of the present invention in detail through concrete embodiment; Material and preparation method thereof, but it should be appreciated by those skilled in the art that implementation of the present invention is not limited to the description scope of embodiment; In not breaking away from essence of the present invention and spirit; Can carry out various modifications and replacement to the present invention, for example bottom electrode can change inert metal Pt or Au common in the technology into, and the thickness range of top electrode and hearth electrode is 100nm-200nm.
More than through specific embodiment organic resistive random access memory provided by the present invention and preparation method thereof has been described, it will be understood by those of skill in the art that in the scope that does not break away from essence of the present invention, can make certain conversion or modification to the present invention; Be not limited to disclosed content among the embodiment.
Claims (5)
1. organic resistive random access memory; Comprise substrate, substrate is provided with hearth electrode, middle organic function layer and top electrode, it is characterized in that; Said top electrode and hearth electrode are W, Pt or Au; Organic function layer is metal-doped titanyl phthalocyanine film in the middle of said, and the metal of doping is a kind of among Al, Hf or the Mg, and the mass percent of the metal of doping is 0.1% to 1%.
2. organic resistive random access memory as claimed in claim 1 is characterized in that, the thickness range of said functional layer is 100-200nm.
3. organic resistive random access memory as claimed in claim 1 is characterized in that the thickness range of said top electrode and hearth electrode is 100nm-200nm.
4. organic resistive random access memory as claimed in claim 1 is characterized in that, substrate is glass or flexible substrates.
5. the preparation method of an organic resistive random access memory, its step comprises
1) the deposit layer of metal is as hearth electrode on substrate, and hearth electrode is W, Pt or Au;
2) metal dust and organic titanyl phthalocyanine powder are ground stir, then utilize the method for thermal evaporation film forming to form metal-doped titanyl phthalocyanine film, the metal of doping is a kind of among Al, Hf or the Mg, and the mass percent of the metal of doping is 0.1% to 1%;
3) deposit one deck W, Pt or Au metal above above-mentioned metal-doped titanyl phthalocyanine film are realized the preparation of top electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101614229A CN101826597B (en) | 2010-05-04 | 2010-05-04 | Organic resistive random access memory and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101614229A CN101826597B (en) | 2010-05-04 | 2010-05-04 | Organic resistive random access memory and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101826597A CN101826597A (en) | 2010-09-08 |
| CN101826597B true CN101826597B (en) | 2012-08-29 |
Family
ID=42690390
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101614229A Active CN101826597B (en) | 2010-05-04 | 2010-05-04 | Organic resistive random access memory and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101826597B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103219464B (en) * | 2013-04-28 | 2015-08-26 | 桂林电子科技大学 | A kind of MMA/BMI copolymer organic resistive random access memory and preparation method thereof |
| CN103219466B (en) * | 2013-04-28 | 2015-07-15 | 桂林电子科技大学 | Organic resistive random access memory and preparation method thereof |
| CN104993047A (en) * | 2015-03-11 | 2015-10-21 | 中国科学院宁波材料技术与工程研究所 | Soft resistive random access memory |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101174673A (en) * | 2007-08-31 | 2008-05-07 | 南京大学 | Double-layer compound film non-volatile memory device and method for producing the same |
| CN101179109A (en) * | 2007-12-17 | 2008-05-14 | 中国科学院长春应用化学研究所 | Stacking organic photovoltaic power cell taking three layers organic hetero-junction thin film as middle electric pole |
| CN101630718A (en) * | 2009-07-24 | 2010-01-20 | 北京大学 | Resistive random access memory and manufacturing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101151106B1 (en) * | 2006-09-15 | 2012-06-01 | 삼성전자주식회사 | Organic Insulating Polymer and Organic Insulating Layer and Organic Thin Film Transistor Prepared by using the Same |
-
2010
- 2010-05-04 CN CN2010101614229A patent/CN101826597B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101174673A (en) * | 2007-08-31 | 2008-05-07 | 南京大学 | Double-layer compound film non-volatile memory device and method for producing the same |
| CN101179109A (en) * | 2007-12-17 | 2008-05-14 | 中国科学院长春应用化学研究所 | Stacking organic photovoltaic power cell taking three layers organic hetero-junction thin film as middle electric pole |
| CN101630718A (en) * | 2009-07-24 | 2010-01-20 | 北京大学 | Resistive random access memory and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101826597A (en) | 2010-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lin et al. | Transient resistive switching memory of CsPbBr3 thin films | |
| Kim et al. | Nanofilamentary resistive switching in binary oxide system; a review on the present status and outlook | |
| CN101826598B (en) | Polymorphic organic resistive random access memory and preparation method | |
| Wang et al. | Fabrication and characterization of extended arrays of Ag2S/Ag nanodot resistive switches | |
| JP7020690B2 (en) | Memristor element and its manufacturing method | |
| JP2007311798A (en) | Nonvolatile memory element using oxygen deficient metal oxide and manufacturing method of the same | |
| JP2008022007A (en) | Non-volatile memory element containing variable resistance substance, and its manufacturing method | |
| CN104795493A (en) | Nanowire array based memristor and manufacturing method thereof | |
| US8115282B2 (en) | Memory cell device and method of manufacture | |
| Chen et al. | Multilevel resistive switching effect in sillenite structure Bi12TiO20 thin films | |
| CN101630718B (en) | Resistive random access memory and manufacturing method thereof | |
| Hu et al. | High speed and multi-level resistive switching capability of Ta2O5 thin films for nonvolatile memory application | |
| Kim et al. | Resistive-switching behavior in Ti/Si3N4/Ti memory structures for ReRAM applications | |
| Wei Zhou et al. | Interface engineering for improving reliability of resistance switching in Cu/HfO2/TiO2/Pt structure | |
| CN101872836A (en) | Resistor-type nonvolatile storage device and manufacturing method thereof | |
| CN101826597B (en) | Organic resistive random access memory and preparation method thereof | |
| CN102005536A (en) | Improved NiO-based resistive random access memory (RRAM) and manufacturing method thereof | |
| Li et al. | Ferroelectric Hafnium Oxide Films for In‐Memory Computing Applications | |
| CN109411600A (en) | A kind of method and its resistance-variable storing device reducing resistance-variable storing device operation voltage | |
| KR101054465B1 (en) | Variable resistance layer manufacturing method of resistive memory | |
| Luo et al. | Phase-dependent memristive behaviors in FAPbI3-based memristors | |
| TWI549263B (en) | Memory structure and preparation method thereof | |
| Liu et al. | Memristive properties of transparent $({\rm La},\,{\rm Sr}){\rm MnO} _ {3} $ thin films deposited on ITO glass at room temperature | |
| Lata et al. | An overview of current trends in hafnium oxide–based resistive memory devices | |
| Yu et al. | Flexible nanoscale memory device based on resistive switching in nickel oxide thin film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C53 | Correction of patent for invention or patent application | ||
| CB03 | Change of inventor or designer information |
Inventor after: Huang Ru Inventor after: Yu Zhe Inventor after: Kuang Yongbian Inventor after: Zhang Lijie Inventor after: Gao Dejin Inventor before: Yu Zhe Inventor before: Huang Ru Inventor before: Kuang Yongbian Inventor before: Zhang Lijie Inventor before: Gao Dejin |
|
| COR | Change of bibliographic data |
Free format text: CORRECT: INVENTOR; FROM: YU ZHE HUANG RU KUANG YONGBIAN ZHANG LIJIE GAO DEJIN TO: HUANG RU YU ZHE KUANG YONGBIAN ZHANG LIJIE GAO DEJIN |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: BEIJING UNIV. Effective date: 20130530 Owner name: SEMICONDUCTOR MANUFACTURING INTERNATIONAL (BEIJING Free format text: FORMER OWNER: BEIJING UNIV. Effective date: 20130530 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 100871 HAIDIAN, BEIJING TO: 100176 DAXING, BEIJING |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130530 Address after: 100176 No. 18, Wenchang Avenue, Beijing economic and Technological Development Zone Patentee after: Semiconductor Manufacturing International (Beijing) Corporation Patentee after: Peking University Address before: 100871 Beijing the Summer Palace Road, Haidian District, No. 5 Patentee before: Peking University |