CN100379892C - Optical thin-membrane production of dispersion oxide from copper-golden nanometer particle - Google Patents
Optical thin-membrane production of dispersion oxide from copper-golden nanometer particle Download PDFInfo
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- CN100379892C CN100379892C CNB2005100117340A CN200510011734A CN100379892C CN 100379892 C CN100379892 C CN 100379892C CN B2005100117340 A CNB2005100117340 A CN B2005100117340A CN 200510011734 A CN200510011734 A CN 200510011734A CN 100379892 C CN100379892 C CN 100379892C
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Abstract
The present invention provides a method for preparing optical films of dispersion oxides of copper-gold nanometer particles. A Cu sputtering target, an Au sputtering target and an oxide sputtering target are simultaneously arranged in a sputtering device, and shielding plates are respectively arranged in front of each sputtering target and a base plate. A composite film of dispersion oxides of copper-gold pure metal nanometer particles, which has nanometer lamellar characteristics, is prepared by the independent control of settling parameters of metal and oxides and power and flow quantity of argon gas of sputtering targets. The present invention comprises the following steps: firstly preparing a Cu nanometer particle single film or an Au nanometer particle single film; settling an oxide film; settling the Cu nanometer particle single film or the Au nanometer particle single film; settling the oxide film. A film of dispersion oxides of copper-gold pure metal nanometer particles, which has nanometer lamellar characteristics, is prepared by alternately settling in the order. The present invention has the advantages that copper nanometer particles and gold nanometer particles exist in a pure metal state not in an alloy state in the lamellar film of dispersion oxides of copper-gold nanometer particles. The film can be observed of absorption peaks at specific wavelengths, and has goodnonlinear optical characteristics.
Description
Technical field
The invention belongs to metal nanoparticle and ceramic field of compound material, a kind of design and preparation technology of copper gold pure metal nanometer particle and dispersal oxide multilayered nonlinear optical thin film particularly are provided, have related to the design and the preparation technology of multiple metal nanoparticle dispersion oxide multilayer optical film material.
Background technology
Because the good nonlinear optical properties of nano-metal particle dispersion oxide film is subjected to extensive concern recently.When metallic particles is of a size of nano level, the surface effects of metallic particles and quantum size effect are very remarkable, metallic particles and oxide matrix on every side interact, thereby make metallic particles internal electron and ion-transfer to the interface, have formed plasma body.Metallic particles generation surface plasma resonance (SPR) phenomenon under the effect of incident light produces selectivity to incident light wave and absorbs and see through.Function film with this nonlinear optical properties has broad application prospects at optical communication field as light wave separator, photoswitch etc.
Be to obtain stronger non-linear optical effect, generally the size by changing metallics, shape, dispersion concentration with and method such as microtexture realize.Most of system of research is a kind of pure metal particles dispersion oxide film at present, such as report more having (Au, Ag, Cu)/(SiO
2, TiO
2, Al
2O
3, MgF
2, BaTiO
3, Nd
2O
3, BaO, LiNbO
3, La
2O
3) etc., adopted technology of preparing has fusion quench, ion implantation, sol-gel method, sputtering method etc.Utilize fusion quench, ion implantation, sol-gel method to be difficult to improve and control the volume fraction of metal discrete particles; Utilize single target sputtering method, because the sedimentation velocity of metal and oxide compound differs greatly, the volume fraction that improves metallic particles is also difficult.Recently, the applicant utilizes the multi-target magnetic control sputtering method, making progress aspect the volume fraction research that improves metallic particles, by in laminated film, introducing laminate structure, realized that to the regulation and control of the wide region of metallographic phase content the national patent of preparing craft application is authorized [license number: ZL03156142.X].In conjunction with the later stage thermal treatment process, metallographic phase content with precursor thin-film of nano lamellar feature still can be had good dispersed texture and surface plasma resonance absorption peak under up to 85% situation, yet there are no and close the report that metallographic phase dispersion content is higher than this result.Also not about the report of copper gold composite nanometer particle dispersion oxide film, has only (Au, Ag)/SiO at present in multi-element metal dispersion oxide film field
2(Cu, Ag)/SiO
2Two kinds of systems were studied.At present the report about these two kinds of systems has: Huazhong Shi, Lide Zhang and Weiping Cai:JOURNAL OF APPLIED PHYSICS, 87[3] (2002) 1572～1574, they with Prepared by Sol Gel Method Ag
xAu
1-x/ SiO
2(0.2＜x＜0.8) disperses film, and through 973K, after the 2h anneal, Ag and Au form alloying pellet, observe a surface plasma resonance absorption peak on optical absorption spectra, with the increase absorption peak position of Ag content by 524 nanometers to 400 nanometer generation red shifts; B.Prevel, J.Lerme, M.Gaudry, E.Cottancin, M.Pellarin, M.Treilleux, P.Melinon, A.Perez, J.L.Vialle and M.Broyer:Scripta mater.44 (2001) 1235～1238, they have prepared (Au with low energy particle light beam deposition technique
0.5Ag
0.5)
N/ Al
2O
3Film, Ag and Au form alloying pellet, observe an independently plasma resonance absorption peak on the absorption spectrum between 420 nanometers and 500 nanometers; Xie Zibin, the king gets spring, straight state, Xiong Guiguang: Wuhan University's journal, 45[1] (1999) 84～86, they have prepared Ag with the method for rf magnetron sputtering
xAu
1-x/ SiO
2The composite metal particles film obtains the alloying pellet of Au and Ag after the annealing, find to have only an absorption peak to appear between 410 nanometers and 537 nanometers; Chen Haibo, Jiang Changzhong, Shi Ying pays strong: functional materials, 34[6] 714～718, they are Ag, and the Au ion successively is injected into SiO
2In the glass, obtain the Au and the Ag nano particle of alloy, have only an absorption peak in the optical absorption spectra, find to regulate by regulating the position that the ratio of injecting metal and suitable annealing conditions can the article on plasma resonance absorbing peak; In addition, J.Gonzalo, D.Babonneau, and C.N.Afonso:JOURNAL OF APPLIED PHYSICS, 96[9] (2004) 5164～5168, they have prepared CuAg/Al with pulsed laser deposition
2O
3Film, the Ag (Cu) of nucleocapsid structure or the particle of Cu (Ag) mixing element have been obtained, on optical absorption spectra, can only observe a surface plasma resonance absorption peak and appear in the scope that wavelength is 424～572 nanometers, find that by increasing Cu particulate volume content blue shift takes place in the position of absorption peak; F.Ren, C.Z.Jiang, L.zhang, Y.Shi, J.B.Wang, R.H.Wang:Micro 35 (2004) 489～493, and they have prepared AgCu/SiO with ion implantation
2Disperse film, having only an absorption peak to appear between 420～580 nanometers on the optical absorption spectra, analyze and point out that Cu and Ag have formed the particle of alloy.In above these several pieces of documents, the metal multicompentnt granular that is dispersed in the sull is alloying pellet, though the position of plasma resonance absorption peak can change to some extent, all is an independently plasma resonance absorption peak.And in all documents, all do not report the system of copper gold dispersion oxide laminated film.
Summary of the invention
The objective of the invention is to: design and preparation technology that the binary metal nanometer particle and dispersal oxide nonlinear optical film of a kind of copper and gold composition is provided.Utilize sputtering technology to carry out the preparation of copper-golden nanometer particles dispersed oxide optical 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.As mentioned above, in at present about copper gold composite nanometer particle dispersion oxide optical thin film research field, the investigator can only obtain the particle of the mixing element of copper gold, and nobody's report is prepared the film of two kinds of metals with the independent multilayered structure that exists mutually, and only there is an absorption peak in most of film in optical absorption spectra.
A kind of multiwalled dispersing technology of the present invention design can make copper and gold grain not with alloy form, and is dispersed in separately in the oxide compound with the form of pure metal respectively, and two plasma resonance absorption peaks appear in the film of preparation on optical absorption spectra.Copper, gold and three target sputters of oxide compound are installed in sputtering chamber simultaneously, shield is set respectively before each sputtering target and substrate, by to the power of the deposition parameter sputtering target of metal and oxide compound, the independent control of argon flow amount, thereby realize the copper-golden nanometer particles dispersed oxide compound complex optical film with nano lamellar feature is prepared in the isoparametric accurate control of granularity, dispersion state, the thicknesses of layers of copper gold grain.
The present invention takes to install simultaneously Cu, Au and three sputtering targets of oxide compound in sputtering equipment, shield is set respectively before each sputtering target and substrate, by independent control, prepare copper gold pure metal nanometer particle and dispersal oxide laminated film with nano lamellar feature to the deposition parameter (as power, the argon flow amount of sputtering target) of metal and oxide compound.
Concrete technical process of the present invention is, preparation Cu or Au nano-particle monolayer film earlier, and the deposition oxide film deposits Cu or Au nano-particle monolayer film then again, deposits one deck oxide film afterwards again.Press the said sequence alternating deposit, make copper gold pure metal nanometer particle and dispersal oxide film, make between Cu or the Au nano-particle monolayer film to separate with one deck sull with laminate structure feature.Copper and gold are existed with the state of pure metal and alloy can not be formed.Sedimentary copper gold pure metal nanometer particle and dispersal oxide laminated film with X and Y represent respectively individual layer Cu and Au nano-particular film the number of plies, represent the number of plies of oxide film with Z, X+Y=Z then, total number of plies of laminated film is X+Y+Z; Between 3～300, the value of Z is between 6～303 respectively for the value of X and Y, and total number of plies of laminated film is 12～606 layers; By changing X, Y, copper gold composition in the adjustable film of the value of Z.
Dispersion oxide of the present invention is SiO
2, TiO
2, Al
2O
3, BaTiO
3, Nd
2O
3, BaO, LiNbO
3, La
2O
3Deng; Copper-golden nanometer metallic particles diameter is in 2～100 nanometers, and is uniformly dispersed; Oxide skin thickness is between 5～500 nanometers; Copper gold composition is pressed chemical formula Cu
xAu
1-x/ SiO
2Describe, x represents copper particle volume per-cent, between 5%～85%; Membrane structure is the alternating laminated structure that copper nano particles layer, gold nano grain layer and oxide skin are formed.
The preparation technology parameter of above-mentioned nano-metal particle material multilayered nonlinear optical thin film is specially: film forming matrix pressure is 1 * 10
-5～5 * 10
-4Pa, the one-tenth film pressure is 0.1～1Pa; Copper nano particles layer film-forming process parameter is that argon flow amount is 5～30 cc/min, and oxygen flow is 5～10 cc/min, and the power of sputtering target is 50～300W, and high frequency telefault power is 50～300W, and film formation time is 50～300 seconds; Gold nano grain layer film-forming process parameter is that argon flow amount is 5～30 cc/min, and oxygen flow is 5～10 cc/min, and 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: for argon flow amount is 5～30 cc/min, oxygen flow is 5～10 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 to the power of the deposition parameter sputtering target of copper-golden nanometer metallic particles and oxide compound, the independent control of argon flow amount, directly in film process, realize the isoparametric accurate control of granularity, dispersion state, volume percent, the thicknesses of layers of metallic particles without thermal treatment process, and prepare copper-golden nanometer particles dispersed oxide optical laminated film on the basis of the above with nano lamellar feature.
The invention has the advantages that: the copper-golden nanometer particles dispersed oxide optical laminated film that adopts the present invention's preparation, has nanometer laminated structure, two kinds of metallic particles of copper gold exist with pure metallic state rather than with the state of alloy, two kinds of particle diameters of copper gold are all in 2～100 nanometer range, and be uniformly dispersed, institute's made membrane can be observed two absorption peaks in absorption spectrum, have 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.Wedge 1 is a substrate, and wedge 2 and wedge 3 are respectively Au or Cu nano-particle layer, and wedge 4 is oxide skins.
Embodiment
Cu of the present invention
xAu
1-x/ SiO
2The oxide multilayered film of copper-golden nanometer particles dispersed of system is made up of which floor even hundreds of layer copper-golden nanometer metallic particles layer and oxide compound, and the copper-golden nanometer particle diameter is in 2～100 nanometers, and oxide skin thickness is in several nanometer to tens nanometers.The mode chart of the nano-metal particle dispersion oxide multilayer film that Fig. 1 designs for the present invention.Wedge 1 is a substrate, and wedge 2 and wedge 3 are respectively Cu or Au nano-particle layer, and wedge 4 is oxide skins.This film adopts the sputtering technology preparation.
Its concrete technical process is:
1, Cu, Au and SiO
2The diameter of sputtering target material is 50mm, and purity is 99.99%.
2, with quartz base plate ultrasonic cleaning after 5～10 minutes, in the sputtering chamber of packing in acetone.
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 the sputtering target of Cu and Au 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 Cu or Au sputtering target and substrate, deposition Cu or Au film, depositing time is 5～300 seconds.Then, close the preceding shield of Cu or 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, open the preceding shield of Cu or Au sputtering target and substrate, deposition Cu or Au film, depositing time is 5～300 seconds.Then, close the preceding shield of Cu or Au sputtering target and substrate.
7, repeating step 5.
8, repeating step (4) (5) (6) (7), alternating deposit Cu or Au film and SiO
2Film, preparation multi-layer C u
xAu
1-x/ SiO
2Film.
Table 1 has provided several preferred embodiments of the present invention:
Table 1 preferred embodiment
The continuous table of going up
In sum, preparation technology's method of the present invention's design can prepare the copper gold pure metal nanometer particle and dispersal oxide multilayered nonlinear optical thin film with nanometer laminated structure.
Claims (3)
1. copper gold pure metal nanometer particle and dispersal oxide multilayered nonlinear method for preparing optical thin film, it is characterized in that: three sputtering targets of Cu, Au and oxide compound are installed in sputtering equipment simultaneously, shield is set respectively before each sputtering target and substrate, by to the power of the deposition parameter sputtering target of metal and oxide compound, the independent control of argon flow amount, prepare copper gold pure metal nanometer particle and dispersal oxide laminated film with nano lamellar feature; Concrete steps are: prepare Cu or Au nano-particle monolayer film earlier, the deposition oxide film deposits Cu or Au nano-particle monolayer film then again, deposits one deck oxide film afterwards again; By above-mentioned alternating deposit pattern, make copper gold pure metal nanometer particle and dispersal oxide laminated film with laminate structure feature, make between Cu or the Au nano-particle monolayer film to separate with one deck sull, copper and gold are existed with the state of pure metal; Membrane structure is the alternating laminated structure that copper nano particles layer, gold nano grain layer and oxide skin are formed; Sedimentary copper gold pure metal nanometer particle and dispersal oxide laminated film with X and Y represent respectively individual layer Cu and Au nano-particular film the number of plies, represent the number of plies of oxide film with Z, X+Y=Z then, total number of plies of laminated film is X+Y+Z; Between 3～300, the value of Z is between 6～303 respectively for the value of X and Y, and total number of plies of laminated film is 12～606 layers; By changing X, Y, copper gold composition in the adjustable film of the value of Z; Processing parameter is: film forming matrix pressure is 1 * 10
-5～5 * 10
-4Pa, the one-tenth film pressure is 0.1～1Pa; Copper nano particles layer film-forming process parameter is that argon flow amount is 5～30 cc/min, and oxygen flow is 5～10 cc/min, and the power of sputtering target is 50～300W, and high frequency telefault power is 50～300W, and film formation time is 50～300 seconds; Gold nano grain layer film-forming process parameter is that argon flow amount is 5～30 cc/min, and oxygen flow is 5～10 cc/min, and the power of sputtering target is 50～300W, and high frequency telefault power is 50～300W, and film formation time is 50～300 seconds.
2. it is characterized in that in accordance with the method for claim 1: described oxide compound is SiO
2, TiO
2, Al
2O
3, BaTiO
3, Nd
2O
3, BaO, LiNbO
3, La
2O
3The copper nano particles diameter is in 2～100 nanometers, and is uniformly dispersed; The gold nano grain diameter is in 2～100 nanometers, and is uniformly dispersed; Oxide skin thickness is between 5～500 nanometers; Copper gold composition is pressed chemical formula Cu
xAu
1-x/ SiO
2Describe, x represents copper particle volume per-cent, between 5%～85%.
3. according to claim 1 or 2 described methods, it is characterized in that: oxide skin 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, high frequency telefault power is 50～300W, and film formation time is 5～60 minutes.
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|---|---|---|---|
| CNB2005100117340A CN100379892C (en) | 2005-05-18 | 2005-05-18 | Optical thin-membrane production of dispersion oxide from copper-golden nanometer particle |
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|---|---|
| CN1712557A CN1712557A (en) | 2005-12-28 |
| CN100379892C true CN100379892C (en) | 2008-04-09 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000117871A (en) * | 1998-10-09 | 2000-04-25 | Suzutora:Kk | Selective light transmitting film |
| CN1485459A (en) * | 2003-09-01 | 2004-03-31 | 北京科技大学 | Process for preparing nanometer metallic particles dispersion oxide optical thin film |
| CN1523641A (en) * | 2003-09-09 | 2004-08-25 | 山东大学 | Method for preparing zinc oxide base magnetic semiconductor material using sub-nanometer composite method |
| CN1564336A (en) * | 2004-04-16 | 2005-01-12 | 北京航空航天大学 | Preparing high giant magnetic resistance effect nano multiplayer membrane on silicon-based chip by sputtering process and its prepn. method |
-
2005
- 2005-05-18 CN CNB2005100117340A patent/CN100379892C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000117871A (en) * | 1998-10-09 | 2000-04-25 | Suzutora:Kk | Selective light transmitting film |
| CN1485459A (en) * | 2003-09-01 | 2004-03-31 | 北京科技大学 | Process for preparing nanometer metallic particles dispersion oxide optical thin film |
| CN1523641A (en) * | 2003-09-09 | 2004-08-25 | 山东大学 | Method for preparing zinc oxide base magnetic semiconductor material using sub-nanometer composite method |
| CN1564336A (en) * | 2004-04-16 | 2005-01-12 | 北京航空航天大学 | Preparing high giant magnetic resistance effect nano multiplayer membrane on silicon-based chip by sputtering process and its prepn. method |
Non-Patent Citations (1)
| Title |
|---|
| 贵金属纳米粒子/无机复合材料的制备及性能. 李钱陶，何峰，张兆艳.硅酸盐通报，第23卷第1期. 2004 * |
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|---|---|
| CN1712557A (en) | 2005-12-28 |
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