CN101949004A - Preparation method of nano copper film-based copper nano structure - Google Patents
Preparation method of nano copper film-based copper nano structure Download PDFInfo
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- CN101949004A CN101949004A CN 201010278840 CN201010278840A CN101949004A CN 101949004 A CN101949004 A CN 101949004A CN 201010278840 CN201010278840 CN 201010278840 CN 201010278840 A CN201010278840 A CN 201010278840A CN 101949004 A CN101949004 A CN 101949004A
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Abstract
The invention discloses a preparation method of a nano copper film-based copper nano structure, which relates to a preparation and assembly method of a nano structure. The method comprises the following steps: cleaning glass substrates, placing in a magnetron sputtering chamber, depositing a nano copper film of an appropriate thickness at room temperature, slicing the glass substrates into multiple pieces, carrying out high vacuum annealing of different time lengths, controlling the annealing time to directly form copper nano structures of various shapes on the surface of the nano copper film, and using a field emission scanning electronic microscope to photograph and record the surface topography of the nano copper film in multiple positions on one glass substrate so as to obtain the characteristics of the typical nano copper film and the copper nano structure on the surface thereof. From the perspective of nano curvature effect and thermal activation effect for the first time, the invention realizes the direct controllable preparation of various nano copper film-based copper nano structures on the surface of the nano copper film by carrying out annealing of different time lengths on the nano copper film of an appropriate thickness.
Description
Technical field
The present invention relates to a kind of preparation method of nanostructure, especially a kind of preparation method of nanometer copper film base copper nanostructure.
Background technology
Copper is owing to have than low resistivity of aluminium and good deelectric transferred performance, and the main flow interconnection material that becomes microelectronic device such as VLSI gradually is (referring to document: 1.Murarka S P, Mater.Sci.Engineer, 1997,19 (3-4): 85).Along with the progressively raising of the integrated degree of microelectronic device, inevitable requirement further reduces the size of copper product and in the nanoscale scope copper product is carried out controlledly synthesis and assembling.Many correlative studys about various low-dimensional copper nanostructure preparations have been arranged at present.Such as,
Pass through to improve depositing temperature at SiO Deng the people
2Prepared island copper particle on the surface (referring to document: 1.
J, Polcak J, Kolibal M et al, Appl.Surf.Sci., 2010,256:3636); People such as Bachmann carry out anneal to the carbon back copper film of different thickness and SiO base copper film respectively and have obtained the copper particle of various size (referring to document: 1.Bachmann L on respective substrate, Sawyer D L, Siegel B M, J.Appl.Phys., 1965,36 (1): 304); People such as Wang utilize the MOCVD method on the GaN substrate, prepared pentagon copper nanometer rod (referring to document: 1.Wang J H, Yang T H, Wu W W et al.Nanotech., 2006,17:719); People such as Wang utilize the electron beam irradiation copper powder on carbon film, prepared the single crystal Cu nanometer rod (referring to document: 1.Wang P I, Zhao Y P, Wang GC et al.Nanotech., 2004,15:218); Or the like.But in present document, we still find no similar relevant report of the present invention.The present invention first from the nanometer curvature effect (referring to document: 1.Zhu X F, Wang ZG, Int.J.Nanotech., 2006,3 (4): 492) and hot activation effect angle set out, by the nanometer copper film being carried out the high vacuum anneal of different time, various copper nanostructures directly on nanometer copper film surface, have been prepared, thereby realized comprising copper nano particles, copper nanometer rod, and synthesized and assembling interior various different dimension copper nanostructures by various X-Y schemes, the nanometer copper film that they are formed.
Summary of the invention
The purpose of this invention is to provide a kind of method that directly prepares various copper nanostructures on nanometer copper film surface.
Technical scheme of the present invention is from nanometer curvature effect and hot activation effect angle, carries out the high vacuum anneal of different time by the nanometer copper film to magnetron sputtering method preparation, directly prepares various copper nanostructures on nanometer copper film surface.
The preparation method of nanometer copper film base copper nanostructure of the present invention is as follows:
1) preparation of glass substrate: get glass substrate and place organic solvent for ultrasonic to clean, wash repeatedly with deionized water then, again that the glass substrate tow sides are residual moisture dries up, at last with the glass substrate oven dry, as the substrate of depositing nano copper film;
2) preparation of nanometer copper film: earlier ready glass substrate is placed the magnetron sputtering chamber, load onto the high purity copper target, pumping high vacuum, logical then sputter gas also keeps chamber pressure certain, regulate sample disc rotating speed and sputtering power, remove baffle plate and at room temperature begin depositing copper film, utilize the quartz crystal oscillator film thickness gauge that thickness and sedimentation rate are monitored in real time simultaneously, deposit certain thickness nanometer copper film;
3) anneal of nanometer copper film: place high vacuum annealing furnace to anneal the above-mentioned glass substrate that deposits the nanometer copper film, prepare various nanometer copper film base copper nanostructure by changing annealing time;
4) electron microscopic observation of copper nanostructure: the nanometer copper film after will anneal preceding and the annealing places field emission scanning electron microscope to observe piecewise, and on the same glass substrate of Taking Pictures recording under the suitable magnification surface topography of many places nanometer copper film, thereby obtain the feature that the copper nanostructure is gone up on typical nanometer copper film and surface thereof.
In step 1), described glass substrate is a microslide, described organic solvent is alcohol or acetone, the scavenging period of described ultrasonic cleaning is more than 10min, the described moisture that the glass substrate tow sides are residual dries up and refers to dry up along a direction with about 20 ° the grazing angle moisture that the glass substrate tow sides are residual with electric fan, and described oven dry refers to place 100 ℃ baking oven to toast 15min glass substrate.
In step 2) in, described high purity copper target is that purity is the copper target more than 99.99%, described high vacuum is meant that chamber pressure is 10
-4The Pa order of magnitude or even lower, described sputter gas is that flow is that 5～30sccm, purity are the high-purity Ar gas more than 99.99%, described chamber pressure is 0.1～5Pa, described sample disc rotating speed is 1～10r/min, described sputtering power is direct current 100W, and described nanometer copper film thickness is 20～40nm.
In step 3), described high vacuum is meant that chamber pressure is 10
-4The Pa order of magnitude or even lower, described annealing is to anneal at 400 ℃, annealing time is 5～30min.
In step 4), described suitable magnification is 10,000～100,000 times.
The present invention is first from nanometer curvature effect and hot activation effect angle, by the nano level copper film of suitable thickness being carried out the anneal of different time, directly controlledly on nanometer copper film surface prepared various nanometer copper film base copper nanostructures.With respect to other preparation method, the present invention: (1) mechanism is clear and definite, i.e. peculiar nanometer curvature effect of nano material or structure self (belonging to non-hot activation effect) and the extraneous hot activation effect of introducing; (2) annealing method that is adopted is simple relatively, only needs to change annealing time and can obtain various copper nanostructure on nanometer copper film surface; (3) need not catalyzer and participate in, avoided in prepared copper nanostructure, introducing unnecessary catalyst impurities; (4) various copper nanostructures, particularly copper nanometer rod " lie low " on nanometer copper film surface, and go out nanometer copper film surface unlike the distal process that has of conventional bibliographical information; (5) various copper nanostructure can simultaneously and be stored in nanometer copper film surface, has realized comprising copper nano particles, copper nanometer rod, and is synthesized and assembling interior various different dimension copper nanostructures by various X-Y schemes, the nanometer copper film that they are formed.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 be the prepared nanometer copper film of embodiment 1 and under different annealing times the forming process of various copper nanostructures: (a) 0min; (b) 5min; (c) 10min; (d) 20min; (e) 30min.Illustration is the intensified image at respective dashed frame place among the figure, and scale is 100nm among the figure.
Fig. 3 is prepared nanometer copper film and the XRD spectra under different annealing times thereof of embodiment 1.
Embodiment
The invention will be further described in conjunction with the accompanying drawings below by embodiment.
Embodiment 1:
1) preparation of glass substrate: get several microslides and place alcohol ultrasonic cleaning 15min, wash repeatedly with deionized water then, dry up along a direction with about 20 ° the grazing angle moisture that the slide glass tow sides are residual with electric fan again, at last slide glass is placed 100 ℃ of baking ovens to toast 15min, and select 1 wherein the cleanest slide glass to make the substrate of depositing nano copper film;
2) preparation of nanometer copper film: ready glass substrate is placed the magnetron sputtering chamber, load onto purity and be 99.99% copper target, pumping chamber vacuum to 5.0 * 10
-4Pa, through-current capacity is that 20sccm, purity are 99.999% high-purity Ar gas then, keeping chamber pressure is 0.5Pa, regulating the sample disc rotating speed is 2r/min, regulating d.c. sputtering power is 100W, remove baffle plate and at room temperature begin depositing copper film, utilize the quartz crystal oscillator film thickness gauge that thickness and sedimentation rate are monitored in real time simultaneously, the thick nanometer copper film of deposition 30nm;
3) anneal of nanometer copper film: with glass cutter the above-mentioned slide glass that deposits the nanometer copper film is cut into 5 small pieces, and will be wherein 4 to place vacuum tightness be 5.0 * 10
-4Pa, temperature are the 5min that anneals respectively in 400 ℃ the annealing furnace, 10min, 20min and 30min;
4) electron microscopic observation of copper nanostructure: place field emission scanning electron microscope to observe piecewise the nanometer copper film after above-mentioned 1 unannealed and 4 annealing, and 50, the surface topography of 000 times of following Taking Pictures recording different positions copper film, thus typical nanometer copper film and the surperficial feature that goes up the copper nanostructure thereof obtained.
Shown in Fig. 2 (a), the surface of Zhi Bei nanometer copper film is made up of the nano particle of many sizes between 15-30nm under these conditions.These nano particles have very strong nano surface curvature effect and very high surface energy, and the nano particle that suffers nearerly is easy to reunite together in deposition process; And the large particle surface after reuniting can be lower, and at room temperature mobility is lower, can not move freely on substrate surface, thereby form a nanometer copper film surface that shows slightly uneven and have many nano levels slit (seeing Fig. 2 (a) illustration).
Behind 400 ℃ of following high vacuum annealing 5min, shown in Fig. 2 (b), on the one hand, the copper film surface is fallen to seem level and smooth because of slit on it by the particles filled of vicinity, and the nano particle on composition copper film surface is fully together bonded to each other; On the other hand, the particle of some sizes about 30-130nm also appearred on the nanometer copper film surface.These particles may be exactly those particles far away apart from the slit, as to be difficult for moving to slit and blind of film surface, and perhaps they further with after the particles coalesce that is in contact with it form under high temperature annealing.They are broadly divided into three kinds of situations by relative position: (1) isolated single copper nano particles (seeing arrow 1); (2) several copper nano particles (seeing arrow 2) that suffer nearerly and be the wire arrangement; (3) several copper nano particles (seeing arrow 3) that suffer nearerly but distribute in a jumble.
Behind 400 ℃ of following high vacuum annealing 10min, shown in Fig. 2 (c) and illustration thereof, nanometer copper film surface is covered by the tiny particle of one deck fully.XRD (see figure 3) as a result shows that this moment, the nanometer copper film began to occur the diffraction peak in (111) crystal orientation, so each fine particle on copper film surface just comprises one or several crystal grain probably.These small grains or particulate exist to the formation of various copper nanostructures next with grow up most important because the copper nano particles of above-mentioned three kinds of situations at high temperature can change their shape or/and size gradually by the small grains around the continuous absorption.At first, for isolated single copper nano particles, because isotropy, basically be same to the absorption of small grains on every side on the different directions, therefore, along with the increase of annealing time, isolated single copper nano particles grows up into a bigger copper particle (seeing arrow 4 and 9) gradually.Secondly, for several copper nano particles that suffer nearerly and be the wire arrangement, they will contact with each other and at high temperature be bonded together (seeing arrow 5 and 6) after the small grains around the absorption, form the copper nanometer rod of wire.Because free-ended nano surface curvature of copper nanometer rod and surface energy are all much bigger than the side, the speed of two free end absorption small grains is just faster than the side, therefore, increase along with annealing time, only otherwise run into other larger-size structure, the copper nanometer rod will be grown up gradually, elongated (seeing arrow 8 and 10).In a single day the copper nanometer rod runs into other larger-size structure, and they will form various X-Y schemes, than situation as shown in arrow 7.Once more, suffer nearerly but the mixed and disorderly copper nano particles that distributes for several, they form a macrobead in irregular shape will contacting with each other and be bonded together after the small grains around the absorption.Because the nanometer curvature difference of this macrobead on all directions, will be preferential on the bigger direction of nanometer curvature small grains and elongated around the absorption quickly, thereby be an irregular macrobead in the middle of final the formation, grow the X-Y scheme (seeing arrow 11) of some copper nanometer rod on every side.
Therefore, as mentioned above, can be by the control annealing time directly in the copper nanostructure of preparing different shape on the nanometer copper film surface: (1) can prepare some copper nano particles on nanometer copper film surface about 400 ℃ of following high vacuum annealing 5min; (2) about 400 ℃ of following high vacuum annealing 10min, can on nanometer copper film surface, prepare bigger copper nano particles and some copper nanometer rod than weak point; (3) more than 400 ℃ of following high vacuum annealing 20min, can on nanometer copper film surface, prepare bigger copper nano particles, longer copper nanometer rod and some other X-Y scheme of forming by nanometer rod and nanometer rod or particle and nanometer rod etc.
In addition, it should be noted that the further increase along with annealing time, as Fig. 2 (d-e) and shown in Figure 3, the small grains on nanometer copper film surface is also grown up gradually, and several little crystal grain may be merged into big crystal grain or particle.Relatively little crystal grain, the curvature of these big crystal grain is less, and surface energy is lower, and reactivity is relatively poor, relatively is not easy to be adsorbed.Therefore, these increasing crystal grain can cause to a certain degree restraining effect to the formation of above-mentioned various copper nanostructures and growth process.
Claims (4)
1. the preparation method of a nanometer copper film base copper nanostructure, step is as follows:
1) preparation of glass substrate: get glass substrate and place organic solvent for ultrasonic to clean, wash repeatedly with deionized water then, again that the glass substrate tow sides are residual moisture dries up, at last with the glass substrate oven dry, as the substrate of depositing nano copper film;
2) preparation of nanometer copper film: earlier ready glass substrate is placed the magnetron sputtering chamber, load onto the high purity copper target, pumping high vacuum, logical then sputter gas also keeps chamber pressure certain, regulate sample disc rotating speed and sputtering power, remove baffle plate and at room temperature begin depositing copper film, utilize the quartz crystal oscillator film thickness gauge that thickness and sedimentation rate are monitored in real time simultaneously, deposit certain thickness nanometer copper film;
3) anneal of nanometer copper film: place high vacuum annealing furnace to anneal the above-mentioned glass substrate that deposits the nanometer copper film, prepare various nanometer copper film base copper nanostructure by changing annealing time.
2. preparation method according to claim 1, it is characterized in that: in the step (1), described glass substrate is a microslide, described organic solvent is alcohol or acetone, the scavenging period of described ultrasonic cleaning is more than 10min, the described moisture that the glass substrate tow sides are residual dries up and refers to dry up along a direction with about 20 ° the grazing angle moisture that the glass substrate tow sides are residual with electric fan, and described oven dry refers to place 100 ℃ baking oven to toast 15min glass substrate.
3. preparation method according to claim 1 is characterized in that: in the step (2), described high purity copper target is that purity is the copper target more than 99.99%, and described high vacuum is meant that chamber pressure is 10
-4The Pa order of magnitude or even lower, described sputter gas is that flow is that 5～30sccm, purity are the high-purity Ar gas more than 99.99%, described chamber pressure is 0.1～5Pa, described sample disc rotating speed is 1～10r/min, described sputtering power is direct current 100W, and described nanometer copper film thickness is 20～40nm.
4. preparation method according to claim 1 is characterized in that: in the step (3), described high vacuum is meant that chamber pressure is 10
-4The Pa order of magnitude or even lower, described annealing is to anneal at 400 ℃, annealing time is 5～30min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345096A (en) * | 2011-06-29 | 2012-02-08 | 常州大学 | Copper nanowire / copper film composite structure and preparation method thereof |
| CN103640282A (en) * | 2013-12-12 | 2014-03-19 | 安徽工程大学 | Textile and preparation method and application thereof |
| CN111926299A (en) * | 2020-08-05 | 2020-11-13 | 北京信息科技大学 | Multi-level Cu film with surface interface regulation and control function and preparation method thereof |
| CN115029769A (en) * | 2022-06-28 | 2022-09-09 | 江苏科技大学 | Preparation method for transforming nano twin crystal copper film into single crystal copper film |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1712556A (en) * | 2005-05-18 | 2005-12-28 | 北京科技大学 | Optical thin-membrane production of dispersion oxide from copper-silver nanometer particle |
| CN2789934Y (en) * | 2005-03-09 | 2006-06-21 | 南开大学 | Special heating device for large-area solar cell nano transparent conductive film production |
| CN1837288A (en) * | 2005-03-25 | 2006-09-27 | 浙江工业大学 | Temperature sensitive composite materials and preparing process thereof |
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| CN2789934Y (en) * | 2005-03-09 | 2006-06-21 | 南开大学 | Special heating device for large-area solar cell nano transparent conductive film production |
| CN1837288A (en) * | 2005-03-25 | 2006-09-27 | 浙江工业大学 | Temperature sensitive composite materials and preparing process thereof |
| CN1712556A (en) * | 2005-05-18 | 2005-12-28 | 北京科技大学 | Optical thin-membrane production of dispersion oxide from copper-silver nanometer particle |
Non-Patent Citations (1)
| Title |
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| 《中国优秀硕士学位论文全文数据库》 20100702 顾家方 "飞秒激光作用下铜薄膜的超快动力学研究" 16-19 1-4 , 第8期 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102345096A (en) * | 2011-06-29 | 2012-02-08 | 常州大学 | Copper nanowire / copper film composite structure and preparation method thereof |
| CN102345096B (en) * | 2011-06-29 | 2014-02-05 | 常州大学 | Copper nanowire/copper film composite structure and preparation method thereof |
| CN103640282A (en) * | 2013-12-12 | 2014-03-19 | 安徽工程大学 | Textile and preparation method and application thereof |
| CN103640282B (en) * | 2013-12-12 | 2016-01-20 | 安徽工程大学 | A kind of textile, its preparation method and application |
| CN111926299A (en) * | 2020-08-05 | 2020-11-13 | 北京信息科技大学 | Multi-level Cu film with surface interface regulation and control function and preparation method thereof |
| CN111926299B (en) * | 2020-08-05 | 2022-07-26 | 北京信息科技大学 | Multi-level Cu film with surface interface regulation and control function and preparation method thereof |
| CN115029769A (en) * | 2022-06-28 | 2022-09-09 | 江苏科技大学 | Preparation method for transforming nano twin crystal copper film into single crystal copper film |
| CN115029769B (en) * | 2022-06-28 | 2023-11-21 | 江苏科技大学 | Preparation method for converting nano twin crystal copper film into single crystal copper film |
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