CN102660733A - Silver nanoparticle film with mixed valent state, preparation method thereof and application thereof - Google Patents
Silver nanoparticle film with mixed valent state, preparation method thereof and application thereof Download PDFInfo
- Publication number
- CN102660733A CN102660733A CN2012101407124A CN201210140712A CN102660733A CN 102660733 A CN102660733 A CN 102660733A CN 2012101407124 A CN2012101407124 A CN 2012101407124A CN 201210140712 A CN201210140712 A CN 201210140712A CN 102660733 A CN102660733 A CN 102660733A
- Authority
- CN
- China
- Prior art keywords
- film
- silver
- preparation
- silver nano
- grain
- 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.)
- Granted
Links
Images
Landscapes
- Physical Vapour Deposition (AREA)
Abstract
The invention belongs to the technical field of nano materials and electric storage films, and in particular relates to a silver nanoparticle film with a mixed valent state, a preparation method thereof and application thereof. The preparation method comprises the following steps of: depositing a silver film with the nano thickness in vacuum environment by taking a smooth solid surface as a substrate, and annealing at the temperature of between 150 and 180 DEG C to form the silver nanoparticle film which is uniform in distribution and has the mixed valent state on the surface of a substrate. The preparation method is simple and low in annealing temperature, and is particularly suitable for the preparation and batch production of the large-area silver nanoparticle film. The silver nanoparticle film is embedded between two electrodes, so that electric storage film devices with high performance are formed.
Description
Technical field
The invention belongs to nano material and electric memory films technical field, be specifically related to a kind of silver nano-grain film and preparation method thereof with mixed valence.The present invention also with this nanometer particle film as a kind of electric storage media, be used to prepare electric memory films device.
Background technology
Silver (Ag) nano-particle material has characteristics such as unusual heat, light, electricity, magnetic, catalysis and sensitivity.The silver-colored particle of nanoscale also has antibiotic, deodorization functions, and very strong sterilizing ability is arranged, in the existing application widely of medicine and antibiotic field.In recent years, the Application Areas of silver nano-grain material is further expanded, such as: also have in surface plasma photonics field application [(1) Wei Hong, Xu Hongxing, the new development of surface plasma photonics research,
Science Bulletin,
53(18): 2263 (2008)].
Different with argent; Silver suboxide is a kind of important broad stopband (2.5-3.1eV) semiconductor material. silver suboxide is of many uses; Such as: as the novel storage battery electrode; Also can be used as catalyzer uses. and people such as calendar year 2001 Dickson find the silver suboxide nanoparticle behind blue light illumination, can send coloury Dynamic Fluorescence.[(2)?Smith?D.?F.,?
et?al.,?
J?Power?Sources,?
65:?47?(1997);?(3)?Eley?D.?D.,?Pines?H.,?Weisz?P.?B.?Advances?in?catalysis.?New?York:?Academic?Press,?1987:?265;?(4)?Peyser?L.?A,?
et?al.,?Photoactivated?Fluorescence?from?Individual?Silver?Nanoclusters.?
Science, 291:?103?(2001)]。
Recently, the scientific research personnel in Taiwan is deposited on the silverskin of 3 ~ 10 nanometer thickness on silicon oxide (SiO2) film surface, and anneal under 450 ~ 650 ℃ of temperature has prepared more uniform silver nano-grain film.But, because annealing temperature is higher, be unfavorable for the preparation of big area silver nano-grain film, also be unfavorable for producing in batches.[（5）Hsieh?J.?H.?
et?al.,?Optoelectronic?properties?of?sputter-deposited?Ag-SiO2?nanoparticle?films?by?rapid?thermal?annealing.?
Current?Appl?Phys,?
11:?S328?(2011)]。
The low-temperature annealing research of alloy is engaged in contriver's laboratory always, once adopts pellet Films Prepared with Vacuum Evaporation Deposition copper gold (Cu-Au) alloy film, in atmospheric environment, adopts lower temperature to anneal, and prepares the nano-hole golden film of self-supporting again with chemical etching method.[(6) xuwei, Zhou Hui, Jin Lan. a kind of transplantable ultrathin nano-porous gold film and preparation method thereof.
Patent of invention: 200510111258.X (mandate on November 4th, 2009); (7) Zhou H., Jin L., Xu W., New approach to fabricate nanoporous gold film.
Chinese Chemical Letters,
18: 365-368 (2007)].
We believe that the low-temperature annealing technology should have more applications aspect the preparation of nano material.
Summary of the invention
The objective of the invention is to silver nano-grain film and the methods and applications thereof that adopt relatively low temperature to prepare with mixed valence.
The present invention proposes to prepare the method for mixed valence silver nano-grain film, and concrete steps are following: at pressure is 2 * 10
-3In the Vakuumkammer of Pa, through the vacuum thermal evaporation method, the silver-colored film of deposition 3-6 nanometer thickness on cleaning, smooth substrate surface.Let silver-colored film sample then under 150 ~ 180 ℃ of temperature, in the atmospheric environment, annealed 5 minutes to 5 hours, promptly on substrate surface, form be evenly distributed, particle size is at silver nano-grain film 10 ~ 60 nanometers, that have mixed valence.
Among the present invention, said base material specifically can adopt a kind of of mica, aluminium film, silicon chip.
Observe the silverskin sample with sem (SEM), confirm to have formed be evenly distributed, particle size is at the silver nano-grain film of 10-60 nanometer.X-ray photoelectric spectrum (XPS) analysis shows, in the silver nano-grain valence state of silver have 0 valency ,+1 valency and+divalent, explain that this silver nano-grain is a kind of silver nano-grain of mixed valence.Except argent, also has silver suboxide etc. in the nano particle.The component ratio of three kinds of valence states is relevant with annealing time and annealing temperature.
Need to prove, growing metal nano particle on substrate surface, the particulate size and dimension all can receive the substrate lattice effect on structure usually.But, discover that under identical annealing temperature, although the material character of mica, aluminium film and silicon chip is obviously different with surface micro-structure, its shape and size difference of silver nano-grain that forms is not obvious.
Crucial part of the present invention is to adopt lower temperature to anneal, and annealing temperature is 150 ~ 180 ℃.In addition, silver suboxide at high temperature decomposes easily, and relatively low annealing temperature (150 ~ 180 ℃) makes that silver suboxide is able to exist.In addition, from angle of practical application, in the atmospheric environment, 150 ~ 180 ℃ annealing temperature is more favourable for the preparation of big area silver nano-grain film.Such as, can large area film be placed on and carry out anneal in the bigger baking oven, use more convenient, easily mass-produced.
The present invention also proposes the silver nano-grain film of above-mentioned mixed valence as a kind of electric storage media; Be used to prepare electric memory films device; Specifically the silver nano-grain film with said mixed valence is clipped between two membrane electrodes, constitutes the electric memory films device that once writes, repeatedly reads.
Such as: with the aluminium film is substrate; Deposit the silver-colored film of 3-6 nanometer thickness from the teeth outwards; In atmospheric environment, under 150 ~ 180 ℃ of temperature, anneal, after the cooling, more from the teeth outwards deposited copper as upper current conducting cap; So just constituted a two-terminal device, that is: aluminium/silver nano-grain film/copper (Al/Nano-Ag Film/Cu) device.Research confirms that this aluminium/silver nano-grain film/brass ware is a kind of non-volatile electrically memory device of excellent property, can once write repeatedly read operation (write-once read-many-times memories is called for short WORM).Research confirms that also adopt this technology to prepare the WORM device, the threshold voltage between the different components is very stable, and consistence is better.This WORM device has been widely used at the aspects such as storage of books, archives and space flight data.
Description of drawings
After Fig. 1 anneals and handled in 10 minutes, the SEM image of silver nano-grain film on the mica surface.
After Fig. 2 anneals and handled in 90 minutes, the SEM image of silver nano-grain film on the mica surface.
The XPS analysis of Fig. 3 silver nano-grain (the samples using mica is done substrate, anneals 90 minutes).
After Fig. 4 anneals and handled in 90 minutes, the SEM image of silver nano-grain film on the silicon chip surface.
After Fig. 5 anneals and handled in 90 minutes, the SEM image of silver nano-grain film on the aluminium film surface.
After Fig. 6 anneals and handled in 90 minutes, the SEM image of silver nano-grain film on the mica surface.
The electronically written process of Fig. 7 aluminium/silver nano-grain/brass ware.
Two kinds of states of Fig. 8 aluminium/silver nano-grain/brass ware are read with 0.1 volt of voltage signal.
Embodiment
Silver nano-grain film and application thereof that the invention is further illustrated by the following examples proposes with mixed valence:
At pressure is 2 * 10
-3In the Vakuumkammer of Pa, through the vacuum thermal evaporation method, the silverskin of about 4.5 nanometer thickness of deposition on cleaning, smooth mica surface.Then with film sample under about 150 ℃ of temperature, anneal in the atmospheric environment.After the cooling, use sem (SEM) to observe again.The SEM image of 10 minutes samples of annealing is as shown in Figure 1; The SEM image of 90 minutes samples of annealing is as shown in Figure 2.Two width of cloth images all show, even particle distribution, most of particulate sizes be in 20 ~ 40 nanometers, about 50 nanometers that minority is bigger, about 10 nanometers that minority is less.
90 minutes sample of annealing is done XPS analysis, as shown in Figure 3.Show that simple substance silver accounts for 56.3% in this sample, monovalence silver accounts for 33.2%, and divalence silver accounts for 10.5%.Silver in this explanation nano particle is in mixed valence.
At pressure is 2 * 10
-3In the Vakuumkammer of Pa, through the vacuum thermal evaporation method, at the silverskin of about 4.5 nanometer thickness of deposition on cleaning, smooth silicon chip surface.Then with film sample under about 150 ℃ of temperature, anneal in the atmospheric environment.After the cooling, use sem (SEM) to observe again.The SEM image of 90 minutes samples of annealing is as shown in Figure 4.Pictorial display, even particle distribution, most of particulate sizes be in 20 ~ 40 nanometers, about 50 nanometers that minority is bigger, about 10 nanometers that minority is less.
At pressure is 2 * 10
-3In the Vakuumkammer of Pa,,, place subsequent use at the aluminium film of deposition 200 nanometer thickness on cleaning, smooth slide glass through the vacuum thermal evaporation method.On aluminium film surface, deposit the silverskin of about 4.5 nanometer thickness again.Then with film sample under about 150 ℃ of temperature, anneal in the atmospheric environment.After the cooling, use sem (SEM) to observe again.The SEM image of 90 minutes samples of annealing is as shown in Figure 5.Pictorial display, even particle distribution, most of particulate sizes be in 20 ~ 40 nanometers, about 50 nanometers that minority is bigger, about 10 nanometers that minority is less.
At pressure is 2 * 10
-3In the Vakuumkammer of Pa, through the vacuum thermal evaporation method, the silverskin of about 4.5 nanometer thickness of deposition on cleaning, smooth mica surface.Then with film sample under about 180 ℃ of temperature, anneal in the atmospheric environment.After the cooling, use sem (SEM) to observe again.The SEM image of 90 minutes samples of annealing is as shown in Figure 6.Pictorial display, even particle distribution, most of particulate sizes be in 20 ~ 45 nanometers, about 60 nanometers that minority is bigger, about 10 nanometers that minority is less.
At pressure is 2 * 10
-3In the Vakuumkammer of Pa, through the vacuum thermal evaporation method, as lower conducting dome, lower conducting dome is horizontal strip, and is evenly distributed at the aluminium film that on cleaning, smooth slide glass, deposits 200 nanometer thickness.On aluminium film surface, deposit the silverskin of about 4.5 nanometer thickness again.Then with film sample under about 150 ℃ of temperature, anneal annealing time 90 minutes in the atmospheric environment.Like this, formed mixed valence silver nano-grain film (result of similar embodiment 3) on the strip aluminium film surface.The copper film of vapor deposition 200 nanometer thickness is done upper current conducting cap on the silver nano-grain film then, and upper current conducting cap is longitudinal strip, and is evenly distributed.Laterally strip aluminium film and longitudinal strip copper film juxtaposition part has just constituted the interlayer device of silver nano-grain embedding, that is: aluminium/silver nano-grain/brass ware.The about 0.1mm of the area of this device
2
Be connected when aluminium electrode and external signal source are anodal, under the situation of copper electrode ground connection, add the forward voltage signal and can be easy to make thin-film device to be end Resistance states from the high-resistance state transition, as shown in Figure 7.The threshold voltage of device is more stable, 2.8 ~ 3.4 volts of scopes.State and the state after the transition before the transition are all very stable, can read with 0.1 volt voltage signal respectively, and be as shown in Figure 8.In the signal process of reading and in the process of device placement, the state of device does not change.Adopt the technology of present embodiment to prepare thin-film device, the yield rate of WORM device is more than 95%.
Claims (4)
1. the preparation method of the silver nano-grain film of a mixed valence is characterized in that concrete steps are: at first, through the vacuum thermal evaporation method, on substrate surface, deposit the silver-colored film of 3 ~ 6 nanometer thickness; Let silver-colored film then under 150 ~ 180 ℃ of temperature, in the atmospheric environment, annealed 5 minutes ~ 5 hours, on substrate surface, form be evenly distributed, particle size is at silver nano-grain film 10 ~ 60 nanometers, that have mixed valence.
2. the preparation method of the silver nano-grain film of mixed valence according to claim 1 is characterized in that said base material is a kind of of mica, aluminium film, silicon chip.
3. silver nano-grain film of the mixed valence of preparation method preparation according to claim 1, in the said silver nano-grain valence state of silver have 0 valency ,+1 valency and+divalent.
4. the application of the silver nano-grain film of a mixed valence as claimed in claim 3 in the electric memory films device of preparation; It is characterized in that the silver nano-grain film of said mixed valence is clipped between two membrane electrodes, constitute the electric memory films device that once writes, repeatedly reads.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101407124A CN102660733B (en) | 2012-05-09 | 2012-05-09 | Silver nanoparticle film with mixed valent state, preparation method thereof and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101407124A CN102660733B (en) | 2012-05-09 | 2012-05-09 | Silver nanoparticle film with mixed valent state, preparation method thereof and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102660733A true CN102660733A (en) | 2012-09-12 |
| CN102660733B CN102660733B (en) | 2013-11-27 |
Family
ID=46770307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101407124A Expired - Fee Related CN102660733B (en) | 2012-05-09 | 2012-05-09 | Silver nanoparticle film with mixed valent state, preparation method thereof and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102660733B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818464A (en) * | 2015-04-17 | 2015-08-05 | 河南科技大学 | Method for template-free preparation of nano-silver particle and film composite material with large specific surface area |
| CN109280890A (en) * | 2018-09-11 | 2019-01-29 | 合肥工业大学 | A method of enhancing nano silver film photoelectric properties |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04382A (en) * | 1990-04-14 | 1992-01-06 | Nisshin Steel Co Ltd | Production of silver cobalt superlattice film |
| CN101172573A (en) * | 2006-11-01 | 2008-05-07 | 国家纳米技术与工程研究院 | Silver nano-grain array mould plate and preparation method thereof |
| CN101985741A (en) * | 2009-07-29 | 2011-03-16 | 中国科学院福建物质结构研究所 | Method for improving conductivity of indium-doped zinc oxide transparent conductive film |
-
2012
- 2012-05-09 CN CN2012101407124A patent/CN102660733B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04382A (en) * | 1990-04-14 | 1992-01-06 | Nisshin Steel Co Ltd | Production of silver cobalt superlattice film |
| CN101172573A (en) * | 2006-11-01 | 2008-05-07 | 国家纳米技术与工程研究院 | Silver nano-grain array mould plate and preparation method thereof |
| CN101985741A (en) * | 2009-07-29 | 2011-03-16 | 中国科学院福建物质结构研究所 | Method for improving conductivity of indium-doped zinc oxide transparent conductive film |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818464A (en) * | 2015-04-17 | 2015-08-05 | 河南科技大学 | Method for template-free preparation of nano-silver particle and film composite material with large specific surface area |
| CN109280890A (en) * | 2018-09-11 | 2019-01-29 | 合肥工业大学 | A method of enhancing nano silver film photoelectric properties |
| CN109280890B (en) * | 2018-09-11 | 2023-10-27 | 合肥工业大学 | Method for enhancing photoelectric performance of nano silver film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102660733B (en) | 2013-11-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jun et al. | Architectural control of magnetic semiconductor nanocrystals | |
| Yu et al. | Catalytic synthesis and structural characteristics of high-quality tetrapod-like ZnO nanocrystals by a modified vapor transport process | |
| Venkateswaran et al. | Nano silicon from nano silica using natural resource (RHA) for solar cell fabrication | |
| Zou et al. | Well-aligned arrays of CuO nanoplatelets | |
| Si et al. | Controlled-synthesis, self-assembly behavior, and surface-dependent optical properties of high-quality rare-earth oxide nanocrystals | |
| Lao et al. | Hierarchical ZnO nanostructures | |
| Wu et al. | Room-temperature synthesis of single-crystalline anatase TiO2 nanowires | |
| Nguyen et al. | Shape-and size-controlled synthesis of monoclinic ErOOH and cubic Er2O3 from micro-to nanostructures and their upconversion luminescence | |
| Lu et al. | Perfect orientation ordered in-situ one-dimensional self-assembly of Mn-doped PbSe nanocrystals | |
| Hu et al. | Large-scale and rapid synthesis of ultralong ZnO nanowire films via anodization | |
| Ma et al. | Self-assembly of copper sulfide nanoparticles into nanoribbons with continuous crystallinity | |
| Kenanakis et al. | Growth of c-axis oriented ZnO nanowires from aqueous solution: the decisive role of a seed layer for controlling the wires’ diameter | |
| CN102234111B (en) | Comprise silicon nanowires of high desnity metal nanocluster and preparation method thereof | |
| CN104003353B (en) | The preparation method of metal not close arrangement spherical nanoparticle array | |
| JP6968057B2 (en) | A memory structure used for a resistance-change memory device and a method used for manufacturing a data storage device. | |
| Tsai et al. | Water-driven formation of luminescent Zn2GeO4 nanorods from Zn-containing Ge nanoparticles | |
| CN101266919A (en) | A method for selectively etching silicon nano line | |
| Xu et al. | Cu-doped ZnO hemispherical shell structures: synthesis and room-temperature ferromagnetism properties | |
| Wang et al. | Facile synthesis of ultralong and thin copper nanowires and its application to high-performance flexible transparent conductive electrodes | |
| Ai et al. | Ligand‐triggered self‐assembly of flexible carbon dot nanoribbons for optoelectronic memristor devices and neuromorphic computing | |
| Howard et al. | High-throughput continuous hydrothermal synthesis of transparent conducting aluminum and gallium Co-doped zinc oxides | |
| Abbasi et al. | Biomaterial-induced stable resistive switching mechanism in TiO2 thin films: the role of active interstitial sites/ions in minimum current leakage and superior bioactivity | |
| Yu et al. | Shape-controlled copper selenide nanocubes synthesized by an electrochemical crystallization method | |
| CN102660733B (en) | Silver nanoparticle film with mixed valent state, preparation method thereof and application thereof | |
| CN104818463A (en) | Method for preparing nano platinum-coated gold particles film composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131127 Termination date: 20180509 |