CN1485459A - Process for preparing nanometer metallic particles dispersion oxide optical thin film - Google Patents
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- CN1485459A CN1485459A CNA03156142XA CN03156142A CN1485459A CN 1485459 A CN1485459 A CN 1485459A CN A03156142X A CNA03156142X A CN A03156142XA CN 03156142 A CN03156142 A CN 03156142A CN 1485459 A CN1485459 A CN 1485459A
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Abstract
A method of preparing nonlinear optical film of nanometer-grade metal particles dispersed in oxides, which is characterized in, installing metal sputtering plate and oxide sputtering plate in ion sputtering device, baffles before each sputtering plate and base plate, controlling the sedimentation speed of metal and oxide, so controlling precisely the particles, dispersing state, thickness of film. It comprises the steps: preparing a monolayer film of nanometer-grade metal particles, a monolayer film of oxide particles, sedimentating the two member alternately, preparing stratified film; in sedimentating, dispersing uniformly metal particles with the size of 2-50nm into the oxide matrix. The nanometer-grade metal particles are Au, Ag or Cu. The oxides are SiO2, TiO2, BaTiO2. The stratified film has absorbing peaks in special wave lengths.
Description
Technical field:
The invention belongs to nano-metal particle and ceramic field of compound material, the design and the preparation technology of nano-metal particle dispersion oxide multilayered nonlinear optical thin film particularly are provided, relate to a kind of nano-metal particle (being mainly Au, Ag, Cu etc.) dispersion oxide (with SiO
2, TiO
2, BaTiO
2Be main) design and the preparation technology of multilayered nonlinear optical thin film material.
Background technology:
Nano-metal particle dispersion oxide film, because the surface effects and the quantum size effect of metal nanoparticle are very remarkable, the surface plasma resonance phenomenon takes place under the interaction of the electronics of nano-metal particle near surface and light, incident light wave is produced selectivity absorb and see through.Function film with this nonlinear optical properties has broad application prospects at optical communication field as light wave separator, photoswitch etc.
At present, the technology of preparing of nonlinear optical film has multiple, and adopted so far have fusion quench, ion implantation, sol-gel method, a sputtering method etc.Utilize the fusion quench, ion implantation, sol-gel method is difficult to improve and control the composition of metal discrete particles.Use single target sputtering method, because the sedimentation velocity of metal and oxide compound differs greatly the concentration of also difficult control metallic particles.For example, at relevant Au/SiO
2In the report of nonlinear optical film research, the dispersion content of Au is less than 10 usually, and also needs to make new sputter palladium when changing the composition of film.H.B.Liao and R.F.Xiao[H.B.Liao, R.F.Xiao, J.S.Fu, P.Yu, G.K.Wong andP.Sheng:Appl.Phys.Lett.70 (1997) 1-3.] etc. utilize the multi-target magnetic control sputtering method to prepare Au/SiO
2Composite material film brings up to 65% with the dispersion content of Au first, finds near 45% Au/SiO
2Film is maximum absorption intensity at the absorption peak of wavelength 560 nanometers performance.Therefore, improve the amount of nano metal discrete particles, can effectively improve the non-linear optical property of nano metal discrete particles sull.But, after the film that they make need be heat-treated, could show non-linear optical property.The relevant report with other of this result is identical.Up to now, because the restriction of technology of preparing is difficult to obtain nano-dispersed Au particle, many bibliographical informations, preparation Au/SiO
2During nonlinear optical film, normally at first prepare Au and SiO
2Noncrystalline membrane, make gold condense into particle by thermal treatment then, therefore, resulting metal particle size is inhomogeneous, dispersion range is also bigger, is reported as 50-100nm usually.
Summary of the invention:
The objective of the invention is to: design and preparation technology that a kind of nano-metal particle dispersion oxide nonlinear optical film is provided.Utilize the plasma sputtering technology to carry out the preparation of nano-metal particle dispersion oxide film.The principal feature of this technology is that working gas air pressure is lower, and is few to the pollution of film, and quality of forming film is stable, can accurately control film forming speed, is suitable for preparing the particle and the nano thin-film of nanoscale.
Because the sedimentation velocity of metal and oxide compound differs greatly, how nano-metal particle being distributed to oxide compound uniformly has very big difficulty.At this, we have designed a kind of multilayer dispersing technology.At ion sputtering equipment metal and oxide sputtering target are installed simultaneously, shield is set respectively before each sputtering target and substrate, by independent control to the sedimentation velocity of metal and oxide compound, thereby realize the nano-metal particle dispersion oxide nanocomposite films with nano lamellar feature is prepared in the isoparametric accurate control of granularity, dispersion state, the thicknesses of layers of metallic particles.Specifically be, prepare nano-particle monolayer film respectively, the oxide particle unitary film, afterwards, both alternating deposits are made the laminate structure film; Direct metallic particles with diameter 2～50nm is evenly dispersed in the oxide matrix in deposition process.Realization is without thermal treatment process, and direct metallic particles with diameter 2～50nm is evenly dispersed in the oxide matrix in deposition process.Wherein nano-metal particle is Au, Ag, and Cu etc., dispersion oxide are SiO
2, TiO
2, BaTiO
2Deng; The nano-metal particle diameter is at 2～50nm, and is uniformly dispersed; Oxide skin thickness is between 5～500 nanometers; The metallic particles volume percent is between 5%～30%; Nano-metal particle layer and oxide skin are for replacing nanometer laminated structure.See Fig. 1.
The preparation technology parameter of above-mentioned nano-metal particle material multilayered nonlinear optical thin film is specially: matrix pressure is 1 * 10
-5～5 * 10
-4Pa, the one-tenth film pressure is 0.1～1Pa; Nano-metal particle layer film-forming process parameter be for argon flow amount be 5～30 cc/min, oxygen flow is 5～10 cc/min, the power of sputtering target is 50～300W, and high frequency telefault power is 50～300W, and film formation time is 50～300 seconds; Oxidate nano layer film-forming process parameter is that oxygen flow is 5～10 cc/min for argon flow amount is 5～30 cc/min, and the power of sputtering target is 50～300W, and high frequency telefault power is 50～300W, and film formation time is 5～60 minutes.
Treatment process of the present invention is intended to by the independent control to the sedimentation velocity of metal and oxide compound, directly in film process, realize the nano-metal particle dispersion oxide nanocomposite films with nano lamellar feature is prepared in the isoparametric accurate control of granularity, dispersion state, volume percent, the thicknesses of layers of metallic particles without thermal treatment process.
The invention has the advantages that: adopt the nano-metal particle dispersion oxide nonlinear optical film of the present invention's preparation, have nanometer laminated structure, littler than the nano-metal particle size of report, particle diameter is at 2～50nm, and is uniformly dispersed.The place can be observed absorption peak in certain wavelengths, has good non-linear property.
Description of drawings:
The mode chart of the nano-metal particle dispersion oxide multilayer film that Fig. 1 designs for the present invention.The mode chart of nano-metal particle dispersion oxide multilayer film.Wedge 1 nano-metal particle layer, wedge 2 oxide skins, wedge 3 substrates.
The section transmission electron micrograph of Fig. 2 nano-metal particle dispersion oxide multilayer film.Wedge 1 substrate, wedge 2 nanometer Au granular layers, particle diameter is 6-8nm, wedge 3 SiO
2Layer, SiO
2The thickness of layer is about 10nm.
Embodiment:
Au/SiO of the present invention
2System nano-metal particle dispersion oxide multilayer film are made up of which floor even hundreds of layer nano-metal particle layer and oxide compound, and the nano-metal particle diameter is at 2～50nm, and oxide skin thickness is in several nanometer to tens nanometers.Fig. 2 represents nano lamellar pattern (the nanometer Au layer and the SiO of 11 layer films
2The layer be respectively 11 layers) the section transmission electron micrograph.Shown in Fig. 2 a, the nano-metal particle layer is parallel fully in the big area scope, and evenly, the thickness of whole film is 150nm at interval.We can observe Au and SiO from Fig. 2 b
2Nanometer laminated structure, SiO wherein
2The thickness of layer is 10nm, and the diameter of gold grain is 6-8nm.This film adopts the ion sputtering preparation.
Its concrete technical process is:
1, Au and SiO
2The diameter of sputtering target material is 50mm, and purity is 99.99%.
2, with quartz base plate in acetone after ultrasonic cleaning 5-10 minute, in the sputtering chamber of packing into.
3, treat that sputtering chamber endobasal-body pressure is less than 1 * 10
-5～5 * 10
-4Behind the Pa, import oxygen and argon gas, its flow is respectively 5～10 cc/min, and 5～30 cc/min, becomes film pressure to remain between 0.1～1Pa, and the power of Au sputtering target and high frequency telefault fixes on 50-300W.SiO
2The power of sputtering target and high frequency telefault fixes on 50-300W.Treated plasma stability 3～10 minutes.
4, open the preceding shield of Au sputtering target and substrate, deposition Au film, depositing time is 5～300 seconds.Then, close the preceding shield of Au sputtering target and substrate.
5, open SiO
2Shield before sputtering target and the substrate, deposition SiO
2Film, depositing time are 5～60 minutes.Then, close SiO
2Shield before sputtering target and the substrate.
6, repeating step (4) (5), alternating deposit Au film and SiO
2Film, preparation multilayer Au/SiO
2Film.
Table 1 has provided several preferred embodiments of the present invention:
Table 1 preferred embodiment
| Preferred embodiment | Embodiment 1 | | | |
| Sputtering target | ??Au，SiO 2 | ??Au，SiO 2 | ??Ag，SiO 2 | |
| Substrate | Quartzy | Quartzy | Quartzy | |
| Matrix pressure (Pa) | ??＜5×10 -4 | ??＜5×10 -4 | ??＜6×10 -4 | |
| Become film pressure (Pa) | ??1.6×10 -1 | ??1.6×10 -1 | ??1.2×10 -1 | |
| Temperature (℃) | Room temperature | Room temperature | Room temperature | |
| Nano-metal particle layer film-forming process parameter | Argon flow amount (cc/min) | ??5 | ??5 | ??5 |
| Oxygen flow (cc/min) | ??10 | ??10 | ??10 | |
| The power of sputtering target (W) | ??50 | ??100 | ??100 | |
| High frequency telefault power (W) | ??50 | ??100 | ??100 | |
| Film formation time, (second) | ??5 | ??50 | ??30 | |
| Oxidate nano layer film-forming process parameter | Argon flow amount (cc/min) | ??5 | ??5 | ??5 |
| Oxygen flow (cc/min) | ??10 | ??10 | ??10 | |
| The power of sputtering target (W) | ??200 | ??200 | ??200 | |
| High frequency telefault power (W) | ??200 | ??200 | ??200 | |
| Film formation time, (minute) | ??5 | ??60 | ??60 | |
| The nano-metal particle layer or the oxide skin alternating deposit number of plies, | ??11 | ??5 | ??5 | |
| Absorption peak position wavelength (nm) | ??560 | ??560 | ??430 | |
In sum, preparation technology's method of the present invention's design can prepare the nano-metal particle dispersion oxide nonlinear optical film with nanometer laminated structure.
Claims (2)
1, a kind of nano-metal particle optical thin-membrane production of dispersion oxide, it is characterized in that: metal and oxide sputtering target are installed simultaneously at ion sputtering equipment, shield is set respectively before each sputtering target and substrate, by independent control, realize granularity, the dispersion state to metallic particles, the precision control of thicknesses of layers parameter to the sedimentation velocity of metal and oxide compound; Concrete steps are: prepare nano-particle monolayer film respectively, and the oxide particle unitary film, afterwards, both alternating deposits are made the laminate structure film; Direct metallic particles with diameter 2～50nm is evenly dispersed in the oxide matrix in deposition process; Preparation technology parameter is:
The preparation technology parameter of a, nano-metal particle material multilayered nonlinear optical thin film: matrix pressure is 1 * 10
-5～5 * 10
-4Pa, the one-tenth film pressure is 0.1～1Pa; Nano-metal particle layer film-forming process parameter be for argon flow amount be 5～30 cc/min, oxygen flow is 5～10 cc/min, the power of sputtering target is 50～300W, and high frequency telefault power is 50～300W, and film formation time is 50～300 seconds;
B, oxidate nano layer film-forming process parameter: for argon flow amount is 5～30 cc/min, oxygen flow is 5～10 cc/min, the power of sputtering target is 50～300W, and high frequency telefault power is 50～300W, and film formation time is 5～60 minutes.
2, according to the described preparation method of claim 1, it is characterized in that: described nano-metal particle is Au, Ag, and Cu, dispersion oxide are SiO
2, TiO
2, BaTiO
2The nano-metal particle diameter is at 2～50nm, and is uniformly dispersed; Oxide skin thickness is between 5～500 nanometers; The metallic particles volume percent is between 5%～30%; Nano-metal particle layer and oxide skin are alternating structure.
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|---|---|---|---|
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|---|---|---|---|
| CNB03156142XA CN1208497C (en) | 2003-09-01 | 2003-09-01 | Process for preparing nanometer metallic particles dispersion oxide optical thin film |
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| CN1208497C CN1208497C (en) | 2005-06-29 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100379891C (en) * | 2005-05-18 | 2008-04-09 | 北京科技大学 | Optical thin-membrane production of dispersion oxide from copper-silver nanometer particle |
| CN100379892C (en) * | 2005-05-18 | 2008-04-09 | 北京科技大学 | Optical thin-membrane production of dispersion oxide from copper-golden nanometer particle |
| CN100383275C (en) * | 2005-04-11 | 2008-04-23 | 北京科技大学 | Method for preparing optical thin film with gold silver nanometer particle and dispersal oxide |
| CN107916407A (en) * | 2017-11-14 | 2018-04-17 | 辽宁大学 | A kind of preparation method of the uniform SERS substrate of surface particles |
| CN108455698A (en) * | 2017-02-22 | 2018-08-28 | 南方科技大学 | Photocatalysis component and preparation method thereof |
| CN111926298A (en) * | 2020-07-13 | 2020-11-13 | 钢铁研究总院 | Nonlinear optical noble metal/silicon dioxide nanocluster film and preparation method thereof |
-
2003
- 2003-09-01 CN CNB03156142XA patent/CN1208497C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383275C (en) * | 2005-04-11 | 2008-04-23 | 北京科技大学 | Method for preparing optical thin film with gold silver nanometer particle and dispersal oxide |
| CN100379891C (en) * | 2005-05-18 | 2008-04-09 | 北京科技大学 | Optical thin-membrane production of dispersion oxide from copper-silver nanometer particle |
| CN100379892C (en) * | 2005-05-18 | 2008-04-09 | 北京科技大学 | Optical thin-membrane production of dispersion oxide from copper-golden nanometer particle |
| CN108455698A (en) * | 2017-02-22 | 2018-08-28 | 南方科技大学 | Photocatalysis component and preparation method thereof |
| CN108455698B (en) * | 2017-02-22 | 2020-12-25 | 南方科技大学 | Photocatalytic component and preparation method thereof |
| US11179699B2 (en) | 2017-02-22 | 2021-11-23 | Southern University Of Science And Technology | Photocatalytic assembly and its preparation method |
| CN107916407A (en) * | 2017-11-14 | 2018-04-17 | 辽宁大学 | A kind of preparation method of the uniform SERS substrate of surface particles |
| CN111926298A (en) * | 2020-07-13 | 2020-11-13 | 钢铁研究总院 | Nonlinear optical noble metal/silicon dioxide nanocluster film and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1208497C (en) | 2005-06-29 |
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