CN101983914A - Method for preparing micro number density or size gradient metal nano-particle lattice - Google Patents
Method for preparing micro number density or size gradient metal nano-particle lattice Download PDFInfo
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Abstract
The invention provides a method for preparing a micro number density or size gradient metal nano-particle lattice. The method comprises the following steps: (a) adhering a mask to a substrate coated by a polymer film or an amorphous carbon film, and fixing the substrate on a substrate seat; (b) assembling the substrate seat in a high-vacuum settling chamber to ensure that the substrate is in the center of a metal nano-particle beam; (c) clustering the beam source by a gas-phase aggregation method to generate metal target nano-particles, and leading the nano-particles through a nozzle along with buffer gas to form a collimated nano-particle beam with directed height and accurately controllable equivalent deposition rate; and (d) rotating the substrate seat and depositing the beam, and controlling the rotating angle range and rotating mode of the substrate seat to prepare continuous gradient nano-particle lattice or stepped gradient nano-particle lattice. The method has high efficiency, controllability, low cost and simple process, is convenient for scale production and other characteristics.
Description
One, technical field
The present invention relates to nano material and nano-device, micro-nano processing, self assembly, technical fields such as biological/chemical sensor specifically relate to the controlled preparation of microcosmic gradient nano particle dot matrix.
Two, background technology
Gradient nano particle dot matrix has the extra free degree than traditional homogeneous nano particle dot array.Because the structure of gradient nano particle dot matrix can change on its gradient direction continuously, thereby gradient nano particle dot matrix provides the more structural variable than homogeneous nano particle dot array, for example forms the number density gradient of nano particle or the size gradient of nano particle along gradient direction.This character at research and nano particle dot array structure connection has significant values with using.For example, gradient nano particle dot matrix has bigger tolerance and response range as sensor; For gradient noble metal nano particles dot matrix, but, there is important use to be worth in fields such as phasmon enhanced spectrum and photovoltaic cells along the plasmon resonance frequency in the different package assembly wide regions regulation and control nano particle dot array locals zone of gradient direction; In addition, on mass transport, storage, medical science detected and diagnoses, gradient nano particle dot matrix had higher efficient and sensitivity than traditional homogeneous nano particle dot array.Yet the controlled preparation of gradient nano particle dot matrix is never solved effectively.Though in the preparation of gradient nano particle dot matrix, carried out certain research both at home and abroad, for example the method absorption colloidal nanoparticles by the surface organic matter grafting prepares the several millimeters gradient colloid nano particle dot array (R.R.Bhat to the number centimeter scale, J.Genzer, B.N.Chaney, H.W.Sugg, A.Liebmann-Vinson, Nanotechnology, 14,1145 (2003)), block the wedge shape substrate deposits several millimeters of preparations in atom gas thickness gradient film (T.W.H.Oates by slit, S.Noda, Applied Physics Letters, 94,053106 (2009)) and by nano particle in the mask shade freely spread the preparation submicron-scale gradient nano particle dot matrix (M.Han, C.H.Xu, D.Zhu, L.Yang, J.L.Zhang, Y.P.Chen, K.Ding, F.Q.Song, G.H.Wang, Adv Mater, 19,2979 (2007)), but these class methods are difficult to accurately control the number density of nano particle, the gradient span also can only be at macro-size or at submicron-scale, can't effectively prepare gradient nano particle lattice structure at micron to the microscopic dimensions of hundreds of micrometer ranges, thereby be difficult to make up micro-nano device, largely limit the application of gradient nano particle dot matrix; On the other hand, electron beam lithography and ion beam etching also possess the ability of preparation gradient nano particle dot matrix in theory, but its cost height, efficient are low, especially the preparation diameter less than the nano particle dot array of 30nm on cost expensive more, be difficult to satisfy industrial requirements.In the controlled preparation of microcosmic gradient nano particle dot matrix, currently still lack effective preparation means, especially for the regulation and control of microcosmic gradient nano particle dot matrix gradient feature (the granule number density or the average-size of nano particle dot array), currently remain blank.In a word, the preparation of the microcosmic gradient nano particle dot matrix that can independently regulate and control for gradient feature (granule number density or particle mean size) does not have the general preparation method of high efficiency, low cost at present as yet.
Three, summary of the invention
1. goal of the invention
The object of the present invention is to provide a kind of preparation method who realizes the microcosmic graded metal nano particle dot array that granule number density or particle mean size are independently regulated and control.The method can be common in the vapor phase production technological process of common nano material and device, has that low cost, technology are simple, high efficiency, is easy to characteristics such as scale.
2. technical scheme
Technical scheme of the present invention is: a kind of method for preparing microcosmic number density or size gradient metal nanoparticle dot matrix is characterized in that preparation process is as follows:
(a) on substrate, apply layer of even high-polymer membrane or amorphous carbon film, for the mask of h pastes substrate (7) surface, then the substrate that has mask is fixed on the rotatable block substrate (6) highly;
(b) block substrate (6) is installed in the high vacuum settling chamber (11) of nanometer particle beam depositing system, makes that the substrate (7) on the block substrate (6) is in the center that collimates nanometer particle beam (5);
(c) utilize extract system Lodz pump (12) and molecular pump (13) that settling chamber (11) are vacuumized, and in the condensation chamber (9) of gas phase aggregation method cluster beam source, charge into argon gas from inert gas entrance (14), adopt the atomizer (1) in the gas phase aggregation method cluster beam source (10) to produce high desnity metal target atom gas, be grown to serve as metal nanoparticle in the inert gas of target atom gas in condensation chamber (9), metal nanoparticle forms metal nanoparticle line (5) with inert gas by nozzle (2) constant entropy expansion, the metal nanoparticle line enters in the high vacuum settling chamber (11) through collimater (4), forms the metal nanoparticle line (5) of high orientation;
(d) rotation connects the connecting rod (8) of the interior block substrate of vacuum deposition chamber (11) (6), makes substrate surface become angle theta with nanometer particle beam
1, the equivalent sedimentation rate of regulating the input power control metal nanoparticle line of shielding power supply is 0.1nm/s; Opening beam flow baffle plate (3) carries out angle that line deposition and rotation block substrate (6) make substrate surface be become with nanometer particle beam to substrate and at the uniform velocity reduces or progressively be reduced to θ
2After close beam flow baffle plate (3), promptly constituting span in mask edge is continuous gradient nano particle dot array or the stepped gradient nano particle dot matrix of L, and the deposition quality of gradient nano particle dot matrix zones of different is by the velocity of rotation or the control of rotation step-length of block substrate (6); The gradient nano particle dot matrix for preparing on the substrate that applies high-polymer membrane has number density gradient feature; The gradient nano particle dot matrix for preparing on the substrate that applies amorphous carbon film has the size gradient feature.
Magnificent film in the high-polymer membrane side of being preferably or PMMA film described in the step (a), more preferably side's magnificent film (polyvinyl formal).The magnificent membrane stability in side is good, prepares ultra-thin film easily.
The present invention utilizes height to decorate substrate for the mask of h and it at the uniform velocity or is progressively rotated in the nanometer particle beam of directionally aligning and deposits, the deposition quality that is controlled at the substrate zones of different by the angle between change substrate surface and the nanometer particle beam makes up microcosmic gradient nano particle dot matrix, regulate and control migration and the assembling of nano particle by high-polymer membrane or the film modified substrate surface of amorphous carbon, realize regulation and control the gradient feature (being the number density or the average-size of nano particle) of gradient nano particle dot matrix at substrate surface.Therefore, this method provides a kind of universal method of efficient, low-cost preparation microcosmic gradient nano particle dot matrix, and pass through the independent regulation and control of the modification realization of substrate surface to gradient feature (nano particle number density and average-size), be easy to realize functionalization and make up micro-nano device.
The operation principle of this method is: by changing angle between substrate surface and the nanometer particle beam pasting highly for several microns to hundreds of microns mask on the substrate of modified and in nanometer particle beam, at the uniform velocity or progressively rotate block substrate, utilize mask in the shadow region of substrate surface formation the variation structure gradient nano particle dot matrix with angle.Thereby, promptly regulate and control the number density and the average-size of nano particle by on substrate, applying the regulation and control of ultra-thin high-polymer membrane or amorphous carbon film regulation and control nano particle in the migration realization gradient nano particle dot matrix gradient feature of substrate surface.Concrete principle is as shown in Figure 2: mask is pasted (can select high-polymer membrane or amorphous carbon film coated substrate surface for use with the migration of regulation and control nano particle at substrate surface) on the substrate and be placed in the collimation nanometer particle beam, shown in Fig. 2 (a), substrate surface and nanometer particle beam are had angle; There is certain shadow region can depositing nano particle along nanometer particle beam direction mask at substrate surface, shown in Fig. 2 (b), rotation (promptly changing the angle of substrate surface and nanometer particle beam) along with substrate, the shadow region of mask on substrate changes, and forms the gradient deposition quality in the shade span areas; For example, the angle when substrate surface and nanometer particle beam is θ
1The time (Fig. 2 (c)), be in the x in the mask shade
0The zone will be not can depositing nano particle, and be in x
1And remote area has deposition quality DM
X1=vt
1Sin θ
1, wherein v represents the sedimentation rate of nanometer particle beam, t
1The expression sedimentation time; When the angle of substrate surface and nanometer particle beam is θ
2The time, x
0And x
1The zone can depositing nano particle, is in x
2And remote area has deposition quality DM
X2=vt
2Sin θ
2+ DM
X1And the like, when the angle of substrate surface and nanometer particle beam is θ
iThe time, be in x
iThe zone have deposition quality DM
Xi=vt
iSin θ
i+ DM
X (i-1)Therefore, the deposition quality of the gradient nano particle lattice position correspondence of deposition preparation closes and is
DM
x(i+1)＝DM
xi+v·Δtsin(θ
1-iΔθ) (1)
xi＝h/tan(θ
1-iΔθ)-h/tanθ
1 (2)
Wherein h is the height of mask, and Δ θ is the stepping angle that block substrate rotates, i=0,1,2,3 Λ and θ
1-i Δ θ ≡ θ
2＞0, gradient span L=h/tan θ
2-h/tan θ
1Rotate when adopting progressively, the stepped band of gradient nano particle dot matrix of preparation, deposition quality in each band and strip width are by above-mentioned (1) and the decision of (2) formula; When adopting the continuously and smoothly to rotate, then prepare the continuous gradient nano particle dot array, the gradient span of the deposition quality of diverse location correspondence and gradient nano particle dot matrix is equally by above-mentioned (1) and the decision of (2) formula in the nano particle dot array.Adopt periodically mask manufacturing cycle gradient nano particle dot matrix, shown in Fig. 2 (d), periodically each gradient nano particle dot matrix all has highly consistent gradient feature in the gradient nano particle dot matrix.Thereby in this programme by mask and dynamically the method for the nanometer particle beam deposition spatial gradient that produces deposition quality to distribute be universality, promptly the orientation nanoparticle line for any materials can pass through this programme preparation quality thickness gradient film.For the metal nanoparticle line, when adopting the high-polymer membrane coated substrate, high-polymer membrane can effectively fetter and deposit to its surperficial nano particle, thereby metal nanoparticle keeps isolated each other in the dot matrix, rare migration, collision and growth, the graded metal nano particle dot array for preparing has granule number density gradient feature; When adopting the amorphous carbon film coated substrate, the metal nanoparticle that deposits to substrate surface is easily in the surface migration and the growth that bumps, thereby in the bigger zone of deposition quality, the probability of collision growth is big between the nano particle, nano particle after the collision growth has large-size, thereby the gradient nano particle dot matrix for preparing has the size gradient feature.In addition, on the basis of the one dimension gradient nano particle dot matrix for preparing, rotation mask certain angle (between the 5-90 degree) carries out gradient deposition once more, can prepare two-dimentional graded metal nano particle dot array.
3. beneficial effect
The present invention proposes a kind of method for preparing microcosmic number density or size gradient metal nanoparticle dot matrix: utilize mask to decorate substrate and it at the uniform velocity or is progressively rotated and deposit in the nanometer particle beam of collimation, the deposition quality that is controlled at the substrate zones of different by the angle between change substrate surface and the metal nanoparticle line makes up microcosmic graded metal nano particle dot array, regulate and control migration and the assembling of metal nanoparticle by high-polymer membrane or the film modified substrate surface of amorphous carbon, realize regulation and control gradient nano particle dot matrix gradient feature (being the number density or the average-size of nano particle) at substrate surface.But prepared gradient nano particle dot matrix accuracy controlling gradient feature and gradient span are easy to make up micro-nano device.Therefore the invention provides a kind of high efficiency, low cost, be easy to the universal method of scale preparation gradient nano particle dot matrix, filled up current microcosmic gradient nano particle dot matrix and be difficult to the blank of controlled preparation and have good compatibility with the modern device manufacture craft technically.
Four, description of drawings
Fig. 1: the generation and the precipitation equipment that are used to realize preparation method's of the present invention nanometer particle beam.
Reference numeral:
1-atomizer (magnetron sputtering, high temperature evaporation etc.);
2-aerodynamics nozzle;
3-nanometer particle beam baffle plate moving up and down;
The 4-collimater;
5-metal nanoparticle line;
The rotatable block substrate of 6-;
7-pastes the substrate of mask;
8-block substrate connecting rod;
The condensation chamber of 9-growing metal nano particle;
10-gas phase aggregation method cluster beam source;
11-high vacuum settling chamber;
12-Lodz pump;
The 13-molecular pump;
The 14-inert gas entrance.
Fig. 2: the principle schematic of deposition preparation gradient nano array of particles: (a) collimation nanometer particle beam and the substrate that has mask, (b) the rotation substrate obtains the gradient deposition quality, deposition region when (c) substrate surface is with the different angle of nanometer particle beam (d) utilizes cycle mask manufacturing cycle gradient nano array of particles.
Fig. 3: the gradient span is the optical microphotograph mirror image of the continuous gradient nano particle dot array of 25 μ m.
Fig. 4: (a) relation of nano particle dot array number density, average-size and coverage rate in the gradient Nano silver grain dot matrix for preparing on the magnificent film substrate in coating side (c)-(h) is followed successively by the transmission electron microscope structure chart of corresponding coverage rate Nano silver grain dot matrix in (a); (b) relation of nano particle dot array number density, average-size and coverage rate in the gradient Nano silver grain dot matrix for preparing on applying the amorphous carbon film substrate (i)-(n) is followed successively by the transmission electron microscope structure chart of corresponding coverage rate Nano silver grain dot matrix in (b).
Fig. 5: respectively at (a) on the substrate of the magnificent film in coating side with apply the optical microphotograph picture of the stepped gradient Nano silver grain dot matrix of (b) preparation on the substrate of amorphous carbon film.
Fig. 6: the transmission electron microscope structure chart of each band in the stepped gradient Nano silver grain dot matrix (Fig. 5 (a)) that (a) on the magnificent film substrate in coating side, prepares; (b) the transmission electron microscope structure chart of each band in the stepped gradient Nano silver grain dot matrix (Fig. 5 (b)) that on applying the amorphous carbon film substrate, prepares.
Fig. 7: the optical microphotograph picture of the two-dimentional stepped gradient Nano silver grain dot matrix that the angle for preparing on the magnificent film substrate in coating side is 70 °.
Fig. 8: (a) the optical microphotograph picture of continuous gradient Nano silver grain dot matrix, (b) the rhodamine 6G molecule 610 wave number Raman peaks mean intensity curves of position correspondence in the gradient Nano silver grain dot matrix, (c) spatial distribution of rhodamine 6G molecule 610 wave number Raman peaks rectangle frame zone leveling intensity in (a), (d) the structure scale of gradient Nano silver grain dot matrix.
Five, the specific embodiment
Below be example to prepare various graded metal nano particles arrays, the basic procedure of this method is described.Described metal targets is gold, silver, copper, chromium etc. for example, and the pairing sputtering power difference of different metal targets is selected silver-colored target herein for use.
Prepare the method for microcosmic number density or size gradient metal nanoparticle dot matrix, the thickness of the magnificent film in side described in the invention preparation process (1) is 8-15nm; The thickness of described amorphous carbon film is 5-8nm; Described mask height is 10 μ m≤h≤100 μ m; Described substrate is any smooth non-metal base, as quartz glass plate or silicon chip etc.
The angle of divergence of the collimation nanometer particle beam described in the invention preparation process (2) is less than 5 °.
The vacuum of the high vacuum settling chamber 11 described in the invention preparation process (3) is 10
-4Pa～10
-5Pa charges into the inert gas of 90～200Pa to condensation chamber 9; The average diameter of nano particle is 8-20nm in the described metal nanoparticle line, and its size is by changing the distance between atomizer 1 and the aerodynamics nozzle 2, or changes the air pressure that charges into condensation chamber 9 interior inert gases and control.
The substrate surface described in the invention step (4) and the angle theta of nanometer particle beam
1It is 60 °-90 °; The angle theta of described substrate surface and nanometer particle beam
2Be 0＜θ
2＜θ
1Described gradient span L is subjected to h, θ
1And θ
2Decision, 1 μ m＜L＜380 μ m.
Continuous gradient nano grain of silver subarray with number density gradient feature or size gradient feature
(1) applying layer of even side's China's film (thickness is 8-15nm) on the quartz glass plate and on another pieces of quartz glass sheet, applying layer of even amorphous carbon film (thickness 5-8nm), the mask that highly is 25 μ m is pasted the quartz glass plate surface of magnificent film in coating side and amorphous carbon film respectively, then four jiaos of the quartz glass plates that has mask are smeared 704 vacuum silicon rubber and be fixed on the rotatable block substrate 6;
(2) block substrate 6 that will have a substrate is fixedly installed in the high vacuum settling chamber 11 of nanometer particle beam depositing system by screw, makes the substrate on the block substrate 7 be in the center of Nano silver grain line 5;
(3) utilize 13 pairs of settling chambers 11 of extract system Lodz pump 12 and molecular pump to vacuumize, vacuum is 5 * 10
-5Pa, in the condensation chamber 9 of gas phase aggregation method cluster beam source, charge into the 100Pa argon gas from inert gas entrance 14, the atomizer of assembling mutually in body corporate's bunch beam source 10 in this air pressure therapeutic method to keep the adverse qi flowing downward 1 produces high density silver atoms gas by magnetron sputtering, be grown to serve as Nano silver grain in the inert gas of silver atoms gas in condensation chamber 9, Nano silver grain is with the nozzle 2 generation constant entropy expansion of inert gas by the 2mm diameter, form the Nano silver grain line, it is 5 * 10 that the collimater 4 of Nano silver grain line process 2mm diameter enters vacuum
-5In the high vacuum settling chamber 11 of Pa, form the Nano silver grain line 5 of high orientation;
(4) close beam flow baffle plate 3, the connecting rod 8 of rotation block substrate 6 makes substrate surface become 60 ° of angles with nanometer particle beam, and the equivalent sedimentation rate of regulating the input power control Nano silver grain line of shielding power supply is 0.1nm/s; For the substrate of the magnificent film in coating side, open that 3 pairs of substrates of beam flow baffle plate carry out line deposition and at the uniform velocity rotate and close beam flow baffle plate 3 after angle that block substrate 6 makes substrate surface be become with nanometer particle beam at the uniform velocity is reduced to 30 ° with the angular speed of 0.2 °/s; For the substrate that applies amorphous carbon film, block substrate heating is also kept 200 ℃, closes beam flow baffle plate 3 after opening that 3 pairs of substrates of beam flow baffle plate carry out the line deposition and at the uniform velocity being reduced to 30 ° with the angle that the angular speed rotation block substrate 6 of 0.05 °/s makes substrate surface be become with nanometer particle beam; Constituting span in mask edge is the gradient Nano silver grain dot matrix of 25 μ m; Optical microscope photograph as shown in Figure 3.Figure 4 shows that the gradient Nano silver grain lattice structure of two kinds of different gradient features of preparation and the relation between the nano particle coverage.On the substrate of the magnificent film in covering side, along with the average-size of increase (Fig. 4 (c)-(the h)) Nano silver grain of coverage is kept 10nm constant (Fig. 4 (a) orbicular spot) substantially, and the Nano silver grain number density becomes dull increase (square point among Fig. 4 (a)), thereby gradient nano particle dot matrix has number density gradient feature; On the substrate that covers amorphous carbon film, along with the average-size of increase (Fig. 4 (i)-(the n)) Nano silver grain of coverage adds to 28nm (Fig. 4 (b) orbicular spot) from the 10nm monotone increasing, and the nano particle number density does not increase (square point among Fig. 4 (b)), thereby gradient Nano silver grain dot matrix has the size gradient feature.
Stepped gradient nano grain of silver subarray with number density gradient feature or size gradient feature
(1) applying layer of even side's China's film (thickness is 8-15nm) on the quartz glass plate and on another pieces of quartz glass sheet, applying layer of even amorphous carbon film (thickness 5-8nm), the mask that highly is 35 μ m is pasted the quartz glass plate surface of magnificent film in coating side and amorphous carbon film respectively, then four jiaos of the quartz glass plates that has mask are smeared 704 vacuum silicon rubber and be fixed on the rotatable block substrate 6;
(2) block substrate 6 that will have a substrate is fixedly installed in the high vacuum settling chamber 11 of nanometer particle beam depositing system by screw, makes the substrate on the block substrate 6 be in the center of Nano silver grain line 5;
(3) utilize 13 pairs of settling chambers 11 of extract system Lodz pump 12 and molecular pump to vacuumize, vacuum is 5 * 10
-5Pa, in the condensation chamber 9 of gas phase aggregation method cluster beam source, charge into the 150Pa argon gas from inert gas entrance 14, the atomizer of assembling mutually in body corporate's bunch beam source 10 in this air pressure therapeutic method to keep the adverse qi flowing downward 1 produces high density silver atoms gas by magnetron sputtering, be grown to serve as Nano silver grain in the inert gas of silver atoms gas in condensation chamber 9, Nano silver grain is with the nozzle 2 generation constant entropy expansion of inert gas by the 2mm diameter, form the Nano silver grain line, it is 5 * 10 that the collimater 4 of Nano silver grain line process 2mm diameter enters vacuum
-5In the high vacuum settling chamber 11 of Pa, form the Nano silver grain line 5 of high orientation;
(4) close beam flow baffle plate 3, the connecting rod 8 of rotation block substrate 6 makes substrate surface become 70 ° of angles with the Nano silver grain line, and the equivalent sedimentation rate of regulating the input power control Nano silver grain line of shielding power supply is 0.1nm/s; Substrate for the magnificent film in coating side, close beam flow baffle plate 3 after opening 3 couples of substrate deposition 30s of beam flow baffle plate, rotation block substrate 6 makes substrate surface and Nano silver grain line angle reduce 6 ° and open beam flow baffle plate 3 and deposit 30s, closing beam flow baffle plate once more and rotating block substrate 6 makes substrate surface and nanometer particle beam angle reduce 6 ° of depositions once more, carry out 7 circulations successively, final substrate surface and nanometer particle beam angle are 28 °, on substrate, constitute the stepped gradient nano particle dot matrix of 8 different deposition qualities, shown in Fig. 5 (a); For the substrate that applies amorphous carbon film, the block substrate heating is also kept 200 ℃, close beam flow baffle plate 3 after opening 3 couples of substrate deposition 60s of beam flow baffle plate, rotation block substrate 6 makes substrate surface and Nano silver grain line angle reduce 6 ° and open beam flow baffle plate 3 and deposit 60s, closing beam flow baffle plate once more and rotating block substrate 6 makes substrate surface and nanometer particle beam angle reduce 6 ° of depositions once more, carry out 7 circulations successively, final substrate surface and nanometer particle beam angle are 28 °, on substrate, constitute the stepped gradient nano particle dot matrix of 8 different deposition qualities, shown in Fig. 5 (b); The stepped gradient nano particle dot matrix for preparing on the substrate of the magnificent film in coating side has number density gradient feature, and the structure of its each band is shown in Fig. 6 (a); The stepped gradient nano particle dot matrix for preparing on coating amorphous carbon film substrate has the size gradient feature, and the structure of its each band is shown in Fig. 6 (b).
The stepped gradient nano grain of silver subarray of two dimension
(1) on quartz glass plate, applies layer of even side China film (thickness is 8-15nm), the mask that highly is 30 μ m is pasted the quartz glass plate surface of the magnificent film in coating side, then four jiaos of the quartz glass plates that has mask are smeared 704 vacuum silicon rubber and be fixed on the rotatable block substrate 6;
(2) block substrate 6 that will have a substrate is fixedly installed in the high vacuum settling chamber 11 of nanometer particle beam depositing system by screw, makes the substrate on the block substrate 6 be in the center of Nano silver grain line 5;
(3) utilize 13 pairs of settling chambers 11 of extract system Lodz pump 12 and molecular pump to vacuumize, vacuum is 5 * 10
-5Pa, in the condensation chamber 9 of gas phase aggregation method cluster beam source, charge into the 120Pa argon gas from inert gas entrance 14, the atomizer of assembling mutually in body corporate's bunch beam source 10 in this air pressure therapeutic method to keep the adverse qi flowing downward 1 produces high density silver atoms gas by magnetron sputtering, be grown to serve as Nano silver grain in the inert gas of silver atoms gas in condensation chamber 9, Nano silver grain is with the nozzle 2 generation constant entropy expansion of inert gas by the 2mm diameter, form the Nano silver grain line, it is 5 * 10 that the collimater 4 of Nano silver grain line process 2mm diameter enters vacuum
-5In the high vacuum settling chamber 11 of Pa, form the Nano silver grain line 5 of high orientation;
(4) close beam flow baffle plate 3, the connecting rod 8 of rotation block substrate 6 makes substrate surface become 60 ° of angles with the Nano silver grain line, and the equivalent sedimentation rate of regulating the input power control Nano silver grain line of shielding power supply is 0.1nm/s; Opening 3 pairs of substrates of beam flow baffle plate carries out closing beam flow baffle plate 3 behind the line deposition 30s, rotation block substrate 6 makes substrate surface and nanometer particle beam angle reduce 6 ° and open beam flow baffle plate 3 and deposit 30s, closing beam flow baffle plate once more and rotating block substrate 6 makes substrate surface and nanometer particle beam angle reduce 6 ° of depositions once more, carry out 4 circulations successively, final substrate surface and nanometer particle beam angle are 36 °, constitute the stepped gradient Nano silver grain dot matrix of 5 different deposition qualities on substrate; Take out substrate and take off and paste the original place after mask rotates 70 °, repeating step (2) and (3), close beam flow baffle plate, the connecting rod 8 of rotation block substrate 6, make substrate surface become 60 ° of angles with the Nano silver grain line, the equivalent sedimentation rate of regulating the input power control Nano silver grain line of shielding power supply is 0.1nm/s; Opening 3 pairs of substrates of beam flow baffle plate carries out closing beam flow baffle plate behind the line deposition 30s, rotation block substrate 6 makes substrate surface and Nano silver grain line angle reduce 6 ° and open beam flow baffle plate 3 and deposit 30s, closing beam flow baffle plate once more and rotating block substrate 6 makes substrate surface and Nano silver grain line angle reduce 6 ° of depositions then, carry out 3 circulations successively, final substrate surface and nanometer particle beam angle are 42 °, on the other direction of substrate, constitute the stepped gradient Nano silver grain dot matrix of 4 different deposition qualities, promptly obtain angle and be 70 ° two-dimentional stepped gradient Nano silver grain dot matrix, as shown in Figure 7.
Six, application examples
Continuous gradient Nano silver grain dot matrix is used to survey the best group assembling structure and realizes that maximum Raman strengthens
Shown in Figure 8 is to utilize the continuous gradient Nano silver grain dot matrix with number density gradient feature for preparing to survey the application example of optimum Raman substrat structure.By the rhodamine 6G molecule being adsorbed onto equably on the gradient Nano silver grain dot matrix, the dotted rectangle zone of selection shown in Fig. 8 (a) obtains (the light color expression intensity height of the raman scattering intensity spatial distribution map shown in Fig. 8 (c) to the Raman peaks mean intensity tracking measurement of rhodamine 6G 610 wave numbers, dark-coloured expression intensity is low), the intensity curve shown in the white straight line is shown in Fig. 8 (b) among Fig. 8 (c), become maximum at 9.7 μ m places, the optimum nano grain of silver minor structure that corresponding maximum Raman strengthens.By demarcating " the structure chi " of gradient Nano silver grain dot matrix, (short-term represents that spacing is less than the right relative amount of neighbour's Nano silver grain of Nano silver grain mean radius shown in Fig. 8 (d), stain is represented the local plasmon resonance wavelength that gradient nano particle dot matrix should the zone), can obtain the architectural feature of the Nano silver grain dot matrix that the maximum Raman of corresponding rhodamine 6G molecule strengthens fast.
Claims (8)
1. method for preparing microcosmic number density or size gradient metal nanoparticle dot matrix is characterized in that preparation process is as follows:
(a) on substrate, apply layer of even high-polymer membrane or amorphous carbon film, for the mask of h pastes substrate (7) surface, then the substrate that has mask is fixed on the rotatable block substrate (6) highly;
(b) block substrate (6) is installed in the high vacuum settling chamber (11) of nanometer particle beam depositing system, makes that the substrate (7) on the block substrate (6) is in the center that collimates nanometer particle beam (5);
(c) utilize extract system Lodz pump (12) and molecular pump (13) that settling chamber (11) are vacuumized, and in the condensation chamber (9) of gas phase aggregation method cluster beam source, charge into argon gas from inert gas entrance (14), produce high desnity metal target atom gas by the atomizer (1) in the gas phase aggregation method cluster beam source (10), be grown to serve as metal nanoparticle in the inert gas of target atom gas in condensation chamber (9), metal nanoparticle forms metal nanoparticle line (5) with inert gas by nozzle (2) constant entropy expansion, the metal nanoparticle line enters in the high vacuum settling chamber (11) through collimater (4), forms the metal nanoparticle line (5) of high orientation;
(d) the be rotatably connected connecting rod (8) of the interior block substrate of vacuum deposition chamber (11) (6) makes substrate surface become angle theta with nanometer particle beam
1, the equivalent sedimentation rate of regulating the input power control metal nanoparticle line of shielding power supply is 0.1nm/s; Opening beam flow baffle plate (3) carries out angle that line deposition and rotation block substrate (6) make substrate surface be become with nanometer particle beam to substrate and at the uniform velocity reduces or progressively be reduced to θ
2After close beam flow baffle plate (3), promptly constituting span in mask edge is continuous gradient nano particle dot array or the stepped gradient nano particle dot matrix of L, and the deposition quality of gradient nano particle dot matrix zones of different is by the velocity of rotation or the control of rotation step-length of block substrate (6); The gradient nano particle dot matrix for preparing on the substrate that applies high-polymer membrane has number density gradient feature; The gradient nano particle dot matrix for preparing on the substrate that applies amorphous carbon film has the size gradient feature.
2. the method for preparing microcosmic number density or size gradient metal nanoparticle dot matrix according to claim 1, the thickness that it is characterized in that the high-polymer membrane described in the step (a) is 8-15nm; The thickness of described amorphous carbon film is 5-8nm; Described mask height is 10 μ m≤h≤100 μ m; Described substrate is the substrate of any smooth nonmetallic materials.
3. the method for preparing microcosmic number density or size gradient metal nanoparticle dot matrix according to claim 2 is characterized in that the high-polymer membrane described in the step (a) is magnificent film in side or PMMA film.
4. the method for preparing microcosmic number density or size gradient metal nanoparticle dot matrix according to claim 3 is characterized in that the high-polymer membrane described in the step (a) is the magnificent film in side.
5. substrate according to claim 2 is any smooth substrate, and wherein said any smooth substrate is selected from quartz glass plate or silicon chip.
6. the method for preparing microcosmic number density or size gradient metal nanoparticle dot matrix according to claim 1 is characterized in that the metal nanoparticle line (5) described in the step (b) is the orientation nanoparticle line and can accurately regulates the line size.
7. the method for preparing microcosmic number density or size gradient metal nanoparticle dot matrix according to claim 1 is characterized in that the vacuum of the high vacuum settling chamber (11) described in the step (c) is 10
-4Pa～10
-5Pa; The average diameter of nano particle is 8-20nm in the described metal nanoparticle line, by the regulation and control of the air pressure in the control condensation chamber (9).
8. the method for preparing microcosmic number density or size gradient metal nanoparticle dot matrix according to claim 1 is characterized in that the substrate surface described in the step (d) and the angle theta of nanometer particle beam
1It is 60 °-90 °; The angle theta of described substrate surface and nanometer particle beam
2Be 0＜θ
2＜θ
1Described gradient span L is subjected to h, θ
1And θ
2Decision, 1 μ m＜L＜380 μ m.
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| CN102560384A (en) * | 2012-02-23 | 2012-07-11 | 成都精密光学工程研究中心 | Method for depositing nano dot matrix on surface of substrate |
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