CN102185107B - Resistance-type random storage component and preparation method thereof - Google Patents
Resistance-type random storage component and preparation method thereof Download PDFInfo
- Publication number
- CN102185107B CN102185107B CN 201110119804 CN201110119804A CN102185107B CN 102185107 B CN102185107 B CN 102185107B CN 201110119804 CN201110119804 CN 201110119804 CN 201110119804 A CN201110119804 A CN 201110119804A CN 102185107 B CN102185107 B CN 102185107B
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- China
- Prior art keywords
- nife
- film
- preparation
- type random
- random access
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- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000003860 storage Methods 0.000 title abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 238000000224 chemical solution deposition Methods 0.000 claims abstract description 8
- 238000001771 vacuum deposition Methods 0.000 claims abstract description 7
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 81
- 239000002243 precursor Substances 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004549 pulsed laser deposition Methods 0.000 claims description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000012362 glacial acetic acid Substances 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 229910003264 NiFe2O4 Inorganic materials 0.000 abstract 2
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 abstract 2
- 238000005137 deposition process Methods 0.000 abstract 1
- 239000010408 film Substances 0.000 description 46
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 210000000352 storage cell Anatomy 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Abstract
The invention discloses a resistance-type storage component and a preparation method thereof, belonging to the technical field of a novel nonvolatile memory. The resistance-type random storage component is composed of a conducting substrate, a NiFe2O4 film and a conducting top electrode. According to the preparation method, a vacuum coating technology is used to plate a conducting top electrode on the surface of a Nife2O4 film to prepare the resistance-type storage component. In the preparation method of the NiFe2O4 film, chemical solution deposition process or pulse laser deposition process and the like is used. The Nife2O4 resistance-type random storage component disclosed by the invention shows excellent high-low resistance state variation characteristic in a voltage continuous scanning mode, has stable variable voltage of high-low resistance state and excellent maintaining characteristic and continuous cycle reading and writing capacity. The excellent characteristics show that the resistance-type storage component has potential application value in the technical field of nonvolatile memory.
Description
Technical field
The present invention relates to the non-volatile memory technologies field, be specifically related to a kind of based on NiFe
2O
4The film resistor formula is the non-volatile memory device and preparation method thereof of storage characteristics at random.
Background technology
At present, Flashmemory (flash memory) is along with the raising of electronic device technology integrated level, and it is more and more obvious that the operating voltage height that it had, writing speed are slow, endurance difference etc. levels off to the shortcoming of this device physics limit.Simultaneously, novel nonvolatile memory is subjected to scientific circles and industrial quarters is more and more paid close attention to.Resistor type random access memory is a kind of novel nonvolatile memory, it have simple in structure, non-destructive reads, read or write speed is fast, storage density is high, low in energy consumption, retention time long, with the compatible characteristic such as good of semiconductor technology, have a good application prospect in the non-volatile RAM field.
Have the characteristic of bistable state change in resistance in the materials such as some transition metal oxides, sulfide and perovskite compound, can be developed to resistor type random access memory, be subjected to extensive studies.
NiFe
2O
4Be a kind of important soft magnetic ferrite, in catalyst, transducer, microwave device and magnetic material, have important purposes.Yet, now yet there are no relevant NiFe
2O
4The research report of the non-volatile resistor type random access storage characteristics of film.
At present, the preparation method of thin-film material mainly is divided into chemical deposition and physical deposition method, and the former is as chemical vapour deposition technique, chemical solution deposition etc.; The latter such as thermal evaporation, sputtering method, molecular beam epitaxy etc.
Summary of the invention
The objective of the invention is to provides a kind of NiFe according to above-mentioned defective of the prior art
2O
4The resistor type random access memory element.
Another object of the present invention provides above-mentioned NiFe
2O
4The preparation method of resistor type random access memory element.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of resistor type random access memory element is made of conductive substrates, resistive memory film and conducting top electrode, and described resistive memory film is NiFe
2O
4Film.
Described conductive substrates is preferably ITO or Pt, perhaps prepares some conductive film substrates voluntarily, and the conducting top electrode is preferably Pt, Au or Cu electrode.
Described NiFe
2O
4Film thickness is 1～1000nm.
The preparation method of above-mentioned resistor type random access memory element is to prepare NiFe on conductive substrates
2O
4Film adopts vacuum coating technology, again at NiFe
2O
4Film surface plates the conducting top electrode, constitutes NiFe
2O
4The resistor type random access memory element of film sandwich structure.
Described NiFe
2O
4Method for manufacturing thin film is chemical solution deposition or pulsed laser deposition.
Described chemical solution deposition is made up of following steps: preparation NiFe
2O
4Precursor liquid is coated on its rotation on the conductive substrates, preparation NiFe
2O
4Precursor film is heat-treated precursor film, and treatment temperature is 400～800 ℃, and preferred temperature is 500～800 ℃, and the time is 1～60 minute.
Described NiFe
2O
4Precursor liquid is by Fe (NO
3)
39H
2O and C
4H
6NiO
44H
2O is a solute, adds in the mixed solution of being made up of by the 2:1 volume ratio EGME and glacial acetic acid, and stirring at room is dissolved extremely fully and obtained.
Described pulsed laser deposition is to prepare NiFe on conductive substrates
2O
4Film, underlayer temperature are 400～800 ℃, and sedimentation time is 1～60 minute.
Compared with prior art, the present invention has following beneficial effect:
Resistor type random access memory element of the present invention has excellent high low resistance state conversion characteristic, and the shift voltage of high low resistance state is stable, and has excellent memory retention performance and continuous circulation literacy.
NiFe
2O
4The resistor type random access memory element of film has stable resistor type random access storage opening and closing voltage, the selection of voltage when helping the memory element read-write;
NiFe with resistor type random access memory property of the present invention
2O
4Method for manufacturing thin film is many, and excellent performance is easy to scientific research and industrial production.
Description of drawings
Fig. 1. based on the NiFe of Pt substrate
2O
4The sandwich structure schematic diagram of film resistor formula random storage element;
Fig. 2. based on the NiFe of ITO substrate
2O
4The sandwich structure schematic diagram of film resistor formula random storage element;
Fig. 3 .Pt/NiFe
2O
4The storage characteristics schematic diagram of/Pt resistor type random access memory element;
Fig. 4 .Pt/NiFe
2O
4/ Pt resistor type random access memory element read high low resistance state schematic diagram repeatedly continuously.
Specific embodiments
Further specify technical scheme of the present invention by the following examples.
1.NiFe
2O
4The preparation of precursor liquid: NiFe
2O
4The solvent of precursor liquid is the mixed solution of 32ml EGME and 16ml glacial acetic acid, and solute is 8.2030g nine nitric hydrate iron (Fe (NO
3)
39H
2O) and 2.5392g four hydration nickel acetate (C
4H
6NiO
44H
2O), stir 6 hours under the room temperature, promptly obtain the NiFe of the 0.2mol/L of 50ml to dissolving fully
2O
4Precursor liquid.
2.NiFe
2O
4The preparation of precursor film: with NiFe
2O
4The precursor liquid rotation is coated on the Pt substrate, and regulating the rotation coating parameters is 3000rpm, and the pretreatment temperature that each rotation applies is 300 ℃, and the number of times that rotation applies is 8 times, promptly obtains NiFe
2O
4Precursor film.
3.NiFe
2O
4Precursor film heat treatment: with the NiFe of preparation
2O
4Precursor film was heat-treated 1 hour at 700 ℃, promptly finished NiFe
2O
4The preparation of film, film thickness are 450nm.
4. prepare NiFe
2O
4Film sandwich structure: adopt vacuum coating and mask technique, at NiFe
2O
4Film surface plates the Pt electrode, promptly prepares NiFe
2O
4The film memory element, Pt/NiFe
2O
4/ Pt resistor type random access storage cell as shown in Figure 1.
5. utilize Keithley236 analyzer test Pt/NiFe
2O
4I-E characteristic, cycle characteristics and the retention performance of/Pt resistor type random access memory element.Two test probes are connected respectively to the top electrode and the hearth electrode of above-mentioned memory element, and under voltage continuous sweep pattern, test draws the current-voltage storage characteristics curve of memory element, as shown in Figure 3.The employing pulsed test signal goes out the cycle characteristics and the retention performance of this memory element, as shown in Figure 4.
Embodiment 2 chemical solution depositions prepare NiFe
2O
4The resistor type random access memory element
1.NiFe
2O
4The preparation of precursor liquid: NiFe
2O
4The solvent of precursor liquid is the mixed solution of 32ml EGME and 16ml glacial acetic acid, and solute is 8.2030g nine nitric hydrate iron (Fe (NO
3)
39H
2O) and 2.5392g four hydration nickel acetate (C
4H
6NiO
44H
2O), stir 6 hours under the room temperature, promptly obtain the NiFe of the 0.2mol/L of 50ml to dissolving fully
2O
4Precursor liquid.
2.NiFe
2O
4The preparation of precursor film: with NiFe
2O
4The precursor liquid rotation is coated on the Pt substrate, and regulating the rotation coating parameters is 3000rpm, and the pretreatment temperature that each rotation applies is 300 ℃, and the number of times that rotation applies is 4 times, promptly obtains NiFe
2O
4Precursor film.
3.NiFe
2O
4Precursor film heat treatment: with the NiFe of preparation
2O
4Precursor film was heat-treated 1 hour at 400 ℃, promptly finished NiFe
2O
4The preparation of film, thickness are 280nm.
4. prepare NiFe
2O
4Film sandwich structure: adopt vacuum coating and mask technique, at NiFe
2O
4Film surface plates the Au electrode, promptly prepares Au/NiFe
2O
4/ Pt film memory element.
5. utilize Keithley236 analyzer test Au/NiFe
2O
4I-E characteristic, cycle characteristics and the retention performance of/Pt resistor type random access memory element.The NiFe of preparation
2O
4The I-E characteristic of film memory element and this element, cycle characteristics and retention performance and Fig. 1, Fig. 3 and Fig. 4 are similar.
1.NiFe
2O
4NiFe is selected in the preparation of film
2O
4Ceramic target utilizes pulsed laser deposition to prepare NiFe on conductive substrates Pt
2O
4Film.Laser energy is 300mJ/cm
2, frequency is 5Hz, and air pressure is 50Pa, and temperature is 500 ℃, and sedimentation time is 1 hour, promptly is prepared into NiFe
2O
4Film, thickness are 300nm.
2. prepare NiFe
2O
4Film sandwich structure: adopt vacuum coating and mask technique, at NiFe
2O
4Film surface plates the Cu electrode, promptly prepares Cu/NiFe
2O
4/ Pt resistor type random access memory element.
3. utilize Keithley236 analyzer test Cu/NiFe
2O
4I-E characteristic, cycle characteristics and the retention performance of/Pt resistor type random access memory element.The NiFe of preparation
2O
4The I-E characteristic of film memory element and this element, cycle characteristics and retention performance and Fig. 1, Fig. 3 and Fig. 4 are similar.
1.NiFe
2O
4NiFe is selected in the preparation of film
2O
4Ceramic target utilizes pulsed laser deposition to prepare NiFe on conductive substrates ITO
2O
4Film.Laser energy is 300mJ/cm
2, frequency is 5Hz, and air pressure is 50Pa, and temperature is 700 ℃, and sedimentation time is 1 hour, promptly is prepared into NiFe
2O
4Film, thickness are 300nm.
2. prepare NiFe
2O
4Film sandwich structure: adopt vacuum coating and mask technique, at NiFe
2O
4Film surface plates the Pt electrode, promptly prepares Pt/NiFe
2O
4/ ITO resistor type random access memory element.
3. utilize Keithley236 analyzer test Pt/NiFe
2O
4I-E characteristic, cycle characteristics and the retention performance of/ITO resistor type random access memory element.The NiFe of preparation
2O
4The I-E characteristic of film memory element and this element, cycle characteristics and retention performance and Fig. 2, Fig. 3 and Fig. 4 are similar.
Claims (8)
1. a resistor type random access memory element is made of conductive substrates, resistive memory film and conducting top electrode, it is characterized in that described resistive memory film is NiFe
2O
4Film.
2. resistor type random access memory element according to claim 1 is characterized in that described NiFe
2O
4Film thickness is 1 ~ 1000nm.
3. resistor type random access memory element according to claim 1 is characterized in that described conductive substrates is ITO or Pt, and the conducting top electrode is Pt, Au or Cu electrode.
4. the preparation method of the described resistor type random access memory element of claim 1 is to prepare NiFe on conductive substrates
2O
4Film adopts vacuum coating technology, again at NiFe
2O
4Film surface plates the conducting top electrode, constitutes NiFe
2O
4The resistor type random access memory element of film sandwich structure.
5. preparation method according to claim 4 is characterized in that described NiFe
2O
4The preparation method of film is chemical solution deposition or pulsed laser deposition.
6. preparation method according to claim 5 is characterized in that described chemical solution deposition is made up of following steps: preparation NiFe
2O
4Precursor liquid is coated on its rotation on the conductive substrates, preparation NiFe
2O
4Precursor film is heat-treated precursor film, and treatment temperature is 400 ~ 800 ℃, and the time is 60 minutes.
7. preparation method according to claim 6 is characterized in that described NiFe
2O
4Precursor liquid is by Fe (NO
3)
39H
2O and C
4H
6NiO
44H
2O is a solute, adds in the mixed solvent of being made up of by the 2:1 volume ratio EGME and glacial acetic acid, and stirring at room is dissolved extremely fully and obtained.
8. preparation method according to claim 5 is characterized in that described pulsed laser deposition is to prepare NiFe on conductive substrates
2O
4Film, underlayer temperature are 400 ~ 800 ℃, and sedimentation time is 1 ~ 60 minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110119804 CN102185107B (en) | 2011-05-10 | 2011-05-10 | Resistance-type random storage component and preparation method thereof |
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|---|---|---|---|
| CN 201110119804 CN102185107B (en) | 2011-05-10 | 2011-05-10 | Resistance-type random storage component and preparation method thereof |
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| CN102185107A CN102185107A (en) | 2011-09-14 |
| CN102185107B true CN102185107B (en) | 2013-07-31 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106601906B (en) * | 2016-12-02 | 2019-08-20 | 北京有色金属研究总院 | The preparation method and application of InP resistance-change memory material |
| CN111129300A (en) * | 2020-01-10 | 2020-05-08 | 新疆大学 | CuFe2O4 film resistance type random access memory device and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501849A (en) * | 2006-08-25 | 2009-08-05 | 松下电器产业株式会社 | Storage element, memory device and semiconductor integrated circuit |
| CN101569011A (en) * | 2006-12-28 | 2009-10-28 | 松下电器产业株式会社 | Resistance variable element, resistance variable storage device and resistance variable device |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6881993B2 (en) * | 2002-08-28 | 2005-04-19 | Micron Technology, Inc. | Device having reduced diffusion through ferromagnetic materials |
| WO2008047711A1 (en) * | 2006-10-16 | 2008-04-24 | Panasonic Corporation | Non-volatile storage element array, and its manufacturing method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101501849A (en) * | 2006-08-25 | 2009-08-05 | 松下电器产业株式会社 | Storage element, memory device and semiconductor integrated circuit |
| CN101569011A (en) * | 2006-12-28 | 2009-10-28 | 松下电器产业株式会社 | Resistance variable element, resistance variable storage device and resistance variable device |
Non-Patent Citations (2)
| Title |
|---|
| NiFe2O4纳米粒子的水热合成及表征;赵红晓 等;《化工新型材料》;20060630;第34卷(第6期);39-41 * |
| 赵红晓 等.NiFe2O4纳米粒子的水热合成及表征.《化工新型材料》.2006,第34卷(第6期),39-41. |
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