CN1448733A - Process for the manufacture of precious metal nanometer micro-structure grating - Google Patents
Process for the manufacture of precious metal nanometer micro-structure grating Download PDFInfo
- Publication number
- CN1448733A CN1448733A CN 03116343 CN03116343A CN1448733A CN 1448733 A CN1448733 A CN 1448733A CN 03116343 CN03116343 CN 03116343 CN 03116343 A CN03116343 A CN 03116343A CN 1448733 A CN1448733 A CN 1448733A
- Authority
- CN
- China
- Prior art keywords
- glass
- laser
- irradiation
- noble metal
- grating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Diffracting Gratings Or Hologram Optical Elements (AREA)
Abstract
The preparation process of nanometer microstructure noble metal grating includes the following steps: selecting ultrashort pulse laser of femto second level pulse width, splitting via the beam splitter into two beams being focused with two lens and cohered in the focus; selecting noble oxide doped glass; controlling the energy of the emitted laser beam to make the laser beam in the glass produce coherent phase with lasting energy density greater than the multiphoton reaction threshold but smaller than the damage threshold of the glass; focusing the two laser beams onto the glass and radiating the glass with femto second level coherent laser single pulse to form glass sample; heat treatment of the glass sample at 500-600 deg.c, cooling naturally to room temperature to induction produce the nanometer microstructure noble metal grating in the noble oxide doped glass.
Description
Technical field:
The present invention relates to the microstructured bodies grating, particularly a kind of inducing in being mixed with the glass of metal oxide containing precious metals forms the preparation method who contains noble metal nano microstructured bodies grating.
Background technology:
The metal Nano structure material receives much concern because of its exclusive photoelectric characteristic.Common metal mixed nanometer glass is made of methods such as fusion, ion injection, ion-exchange, sputter and colloidal sol-gels, and these methods have a common shortcoming, and that is exactly that nano particle in the glass is difficult to the implementation space and optionally arranges in order.Formerly in the technology, people such as Qiu Jianrong are aided with thermal treatment with femtosecond pulse, in being mixed with the glass of metal oxide containing precious metals, induce and produced noble metal nano particles, and make nano particle in glass, arrange (Appl.Phys.Lett. in order, J.Qiu, M.Shiral and T.Nakaya et al., American Institute of Physics, 2002,18:3040～3042).But this line width that in glass, obtains by laser scanning generally at several micron to tens microns, be difficult to break through a micron limit, and the space scale that has metal nanoparticle to separate out on the whole is bigger, scope is generally greater than several millimeters.If in several microns to tens microns scope, metal nanoparticle is separated out on the live width of nanoscale, produce periodic nano-micro structure array, to make for the integrated micro element in optical information storage and micro-optic field possibility will be provided, as: micro elements such as low-light grid, quantum line, photonic crystal.
Summary of the invention:
The objective of the invention is to overcome the deficiency of technology formerly, a kind of preparation method of noble metal nano microstructured bodies grating be provided, several microns to tens micrometer ranges, the preparation nano-scale nano-micro structure, array, the organizator grating.
Basic thought of the present invention is: adopts femtosecond laser to be aided with thermal treatment, mixing the on glass of metal oxide containing precious metals, and the relevant microstructured bodies grating that forms the containing metal nano particle of inducing, the method also can be used for optical storage and photonic crystal preparation.
The essence of method of the present invention is to adopt the monopulse femtosecond laser to focus on after beam splitting, and implementation space and temporal relevant superposition are by interference field and be aided with thermal treatment produces the containing metal nano particle in glass microstructured bodies grating.Concrete steps are as follows:
(1) selecting pulse width for use is the ultra-short pulse laser of femtosecond, is divided into two bundles through beam splitting chip, then by two convex lens focus, in strict implementation space, focus place and temporal relevant;
(2) select the suitable glass of mixing metal oxide containing precious metals for use;
(3) energy of control emission of lasering beam, laser beam is produced interfere the energy density that reaches when long mutually the multi-photon threshold of reaction greater than glass in glass, but damage threshold less than glass, the relevant femtosecond pulse of above-mentioned two bundles is focused on above-mentioned on glass, in the microcell that two light beams intersect, produce the periodic micro structure that contains precious metal atom, form the glass irradiation sample;
(4) with the glass irradiation sample of above-mentioned relevant femtosecond pulse effect after thermal treatment a period of time under the temperature that is higher than 500 degree Celsius (being lower than 600 degree), cool to room temperature, in the microcell of two beam interferences, just produce the periodic micro structure that contains noble metal nano particles, organizator grating.
Described laser pulse width is 50fs～500fs.
The heat treatment temperature of described glass irradiation sample is 500 ℃～600 ℃, and corresponding heat treatment time is half an hour.
During described relevant femtosecond laser irradiation glass, every irradiation is the mobile glass in back once, and irradiation repeatedly moves repeatedly irradiation once more, to produce multilayer periodic micro structure body grating.
First point of above-mentioned specific practice, select for use the reason of femtosecond pulse to be: when the pulse width of laser is femtosecond, because of the femtosecond pulse very high power density that focuses on, fundamental frequency light and can make glass medium produce multi-photon from the super continuous white light that phase modulation (PM) causes to absorb.When femtosecond pulse focusing and crossing that two bundles are concerned with, in the microcell that intersects, the periodic coherent field of the relevant formation of femtosecond pulse, the periodic structural change of energy atarting material.
Second point of above-mentioned specific practice, the glass of mixing metal oxide containing precious metals plays two aspects.One, the multi-photon absorption that femtosecond pulse produces can inspire non-bridging oxygen electronics in the glass; Its two, the precious metal ion in the glass is caught the non-bridging oxygen electronic energy and is reduced into metallic atom.
Above-mentioned specific practice thirdly, when pulse width is that two bundle laser planoconvex lenses of femtosecond focus on and energy density after focus is relevant greater than the multi-photon threshold of reaction of glass but when being lower than the damage threshold of glass, coherent field will absorb by multi-photon, impel the precious metal ion in the glass to catch the non-bridging oxygen electronics and be reduced into precious metal atom, the periodic micro structure that contains precious metal atom like this forms (can in surface, inside) on glass.
The 4th of above-mentioned specific practice be because, under the effect of above-mentioned coherent field, what form in the glass microcell is the periodic micro structure array that contains precious metal atom, nano particle does not form as yet in this microcell, after thermal treatment a period of time under the temperature that is higher than 500 degree Celsius (being lower than 600 degree), the precious metal atom that has formed, diffusion taking place under the effect of heat energy and assembles forms nano particle (size 1～15nm), like this on glass several microns in the microcell of tens microns, formed the periodic micro structure array that contains noble metal nano particles, because the refractive index of noble metal nano particles is greater than the refractive index of glass, vertical degree of depth of periodic structure reaches tens microns, this nano-micro structure array is body grating, can be used as the low-light grid in the optical-fibre communications.
Advantage of the present invention:
Formerly utilize femtosecond pulse to act in the technology and induce the generation noble metal nano particles in the glass that is mixed with metal oxide containing precious metals, and nano particle is arranged in order in glass, and the inventive method is essentially different with it: first, this method is different with the mechanism of technology formerly, this method is to utilize single femtosecond pulse, in implementation space and temporal relevant back inducing periodic structure, rather than utilize the high-repetition-rate pulse inducing periodic structure of lining by line scan.The second, this method is utilized the coherent light of femtosecond pulse, makes the phase dry strength reach 4 times of single beam intensity, this means with technology formerly to compare, and the incident light energy can reduce by 4 times just can induce periodic micro structure.The 3rd, there is the difference on the order of magnitude in the area size of this method and the periodic structure of technology generation formerly, this method can produce periodic structure on several microns to tens microns microcell, site size can be controlled by the focal length that changes incident light diameter and condenser lens, and therefore this periodic micro structure is more suitable for the integrated needs of photoelectricity.The 4th, also be this method and the most essential difference of technology formerly, this method can produce periodic nano-micro structure and organizator grating in above-mentioned microcell, and structural cycle is easy to change by the angle of adjustment two-beam and the energy of incident beam, formerly the structural cycle of technology is difficult to break through micron dimension, does not also have the organizator grating.
The present invention is also included within and induces the multilayer periodic micro structure in the glass that is mixed with metal oxide containing precious metals, only computer-controlled three-dimensional loading mobile platform need be moved along the Z direction to get final product.
Description of drawings:
Fig. 1 is the preparation method's of noble metal nano microstructured bodies grating of the present invention light path synoptic diagram.
Fig. 2 is the observed microstructured bodies grating picture of embodiment 1 usefulness optical microscope (100 */0.9 object lens).
Fig. 3 is the observed microstructured bodies grating pictures of embodiment 2 usefulness optical microscopes (100 */0.9 object lens).
Fig. 4 is the observed microstructured bodies grating pictures of embodiment 3 usefulness optical microscopes (100 */0.9 object lens).
Embodiment:
Embodiment 1:
As above-mentioned specific practice, selecting pulse width for use is 50fs (5 * 10
-14Second) femtosecond pulse, wavelength is 800nm, pulse recurrence rate is 1Hz, pulse energy is 50 μ J, by beam splitting chip light beam is divided into two bundles with 1: 1 ratio, beam diameter is 5mm, and the relevant second harmonic that produces by means of frequency-doubling crystal of two-beam is realized, the angle of two-beam is 20 °, is that two condenser lenses of 20cm focus on two light beams and mix Au with focal length
2On the silicate glass of O, application point is apart from surperficial 50 μ m, and the three-dimensional mobile platform that sample is handled by computing machine is controlled, and focus place spot diameter is about 40 μ m.Again with the glass irradiation sample of coherent light effect thermal treatment half an hour under 580 degree Celsius, in interfering long mutually light action district, the Au nano particle just can be separated out, color becomes aubergine, and interfere the zone that disappears mutually not have change color, induce the district to form the microstructured bodies grating that contains noble metal nano particles at laser coherence like this.Focus on the induced with laser district in the glass irradiation sample with optical microscope (100 */0.9 object lens), observe optical grating construction as shown in Figure 2, structural cycle is 2.3 μ m, and the dimension that the Au nano particle is separated out is about 300nm.Use He-Ne laser acquisition, observe diffraction light on the first-order diffraction direction of Prague, diffraction efficiency is greater than 5%.
Embodiment 2:
Similar to the way of embodiment 1, selecting pulse width for use is 120fs (1.2 * 10
-13Second) ultrashort pulse, wavelength is 800nm, and pulse recurrence rate is 10Hz, and pulse energy is 60 μ J, and beam diameter is 5mm, the angle of two-beam is 45 °.Be that two condenser lenses of 15cm focus on two relevant light beams and mix Ag with focal length
2100 μ m places under the silicate glass surface of O, focus place spot diameter is about 30 μ m.Again with the glass irradiation sample of coherent light effect thermal treatment half an hour under 510 degree Celsius, in interfering long mutually light action district, (2～8nm) just can separate out the Ag nano particle, color is orange-yellow, and interfere the zone disappear mutually not have change color, what obtain like this contains Ag nano particle microstructured bodies grating.Focus on the induced with laser district in the glass irradiation sample with optical microscope (100 */0.9 object lens), observe the optical grating construction cycle and be about 1 μ m, the dimension that the Ag nano particle is separated out is about 300nm, as shown in Figure 3.Use He-Ne laser acquisition, Prague first-order diffraction efficient is greater than 3%.
Embodiment 3:
As the way of embodiment 1, selecting pulse width for use is 500fs (5 * 10
-13Second) ultrashort pulse, wavelength is 800nm, pulse recurrence rate is 5Hz, pulse energy is 40 μ J, the angle of two-beam is 60 °, is that two condenser lenses of 10cm focus on two light beams and mix Cu with focal length
2Intersect at the focus place at 150 μ m places under the silicate glass surface of O, and the spot diameter of joining is about 25 μ m.With the glass irradiation sample of coherent light effect thermal treatment half an hour under 580 degree Celsius, in interfering long mutually light action district, the Cu nano particle just can be separated out again, and color is a peony, and interferes the zone that disappears mutually not have change color.Focus on the induced with laser district in the glass irradiation sample with optical microscope (100 */0.9 object lens), observing the microstructured bodies grating cycle that contains the Cu nano particle is 0.8 μ m, and the dimension that the Cu nano particle is separated out is about 200nm.Use He-Ne laser acquisition, Bragg diffraction first-order diffraction efficient is greater than 4%.
Claims (4)
1, a kind of preparation method of noble metal nano microstructured bodies grating is characterized in that this method comprises the following steps:
1.. selecting pulse width for use is the ultra-short pulse laser of femtosecond, is divided into two bundles through beam splitting chip, uses two convex lens focus then, forms relevant at the focus place;
2.. select the glass of mixing metal oxide containing precious metals for use;
3.. the energy of control emission of lasering beam, laser beam is produced interfere the energy density that reaches when growing mutually the multi-photon threshold of reaction greater than glass in glass, but less than the damage threshold of glass; The relevant femtosecond pulse of above-mentioned two bundles is focused on above-mentioned on glass,, form the glass irradiation sample with femtosecond coherent laser monopulse irradiation glass;
4.. the glass irradiation sample is heat-treated under 500 ℃～600 ℃ temperature, naturally cools to room temperature.
2, the preparation method of noble metal nano microstructured bodies grating according to claim 1 is characterized in that described laser pulse width is 50fs～500fs.
3, the preparation method of noble metal nano microstructured bodies grating according to claim 1, the heat treatment temperature that it is characterized in that described glass irradiation sample are 500 ℃～600 ℃, and corresponding heat treatment time is half an hour.
4, according to the preparation method of claim 1 or 2 or 3 described noble metal nano microstructured bodies gratings, when it is characterized in that described relevant femtosecond laser irradiation glass, every irradiation is back mobile glass, irradiation once more once, repeatedly move repeatedly irradiation, to produce multilayer periodic micro structure body grating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03116343 CN1448733A (en) | 2003-04-11 | 2003-04-11 | Process for the manufacture of precious metal nanometer micro-structure grating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03116343 CN1448733A (en) | 2003-04-11 | 2003-04-11 | Process for the manufacture of precious metal nanometer micro-structure grating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1448733A true CN1448733A (en) | 2003-10-15 |
Family
ID=28684163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03116343 Pending CN1448733A (en) | 2003-04-11 | 2003-04-11 | Process for the manufacture of precious metal nanometer micro-structure grating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1448733A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100495081C (en) * | 2005-11-04 | 2009-06-03 | 中国科学院上海光学精密机械研究所 | Device and method for preparing nanometer optical grating |
| CN101798179A (en) * | 2010-04-02 | 2010-08-11 | 华东理工大学 | Dichroic nanogold-particle-doped glass and preparation method thereof |
| CN102097314A (en) * | 2010-12-27 | 2011-06-15 | 清华大学 | Laser heat treatment device and method for accurately controlling cooling process |
| CN104625420A (en) * | 2014-12-29 | 2015-05-20 | 中自高科（苏州）光电有限公司 | Machining method for non-vacuum maskless high-conductivity metal nanowire |
-
2003
- 2003-04-11 CN CN 03116343 patent/CN1448733A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100495081C (en) * | 2005-11-04 | 2009-06-03 | 中国科学院上海光学精密机械研究所 | Device and method for preparing nanometer optical grating |
| CN101798179A (en) * | 2010-04-02 | 2010-08-11 | 华东理工大学 | Dichroic nanogold-particle-doped glass and preparation method thereof |
| CN102097314A (en) * | 2010-12-27 | 2011-06-15 | 清华大学 | Laser heat treatment device and method for accurately controlling cooling process |
| CN102097314B (en) * | 2010-12-27 | 2012-12-26 | 清华大学 | Laser heat treatment device and method for accurately controlling cooling process |
| CN104625420A (en) * | 2014-12-29 | 2015-05-20 | 中自高科（苏州）光电有限公司 | Machining method for non-vacuum maskless high-conductivity metal nanowire |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yang et al. | Rapid two‐photon polymerization of an arbitrary 3D microstructure with 3D focal field engineering | |
| Mills et al. | Embedded anisotropic microreflectors by femtosecond-laser nanomachining | |
| Liu et al. | Three-dimensional self-organization in nanocomposite layered systems by ultrafast laser pulses | |
| Miwa et al. | Femtosecond two-photon stereo-lithography | |
| US20070091977A1 (en) | Method and system for forming periodic pulse patterns | |
| CN107790887A (en) | The femtosecond laser direct write preparation method of two-dimentional rhombus cycle micro-nano metal structure | |
| CN102285635A (en) | System and method for making metal micro-nano structure by using laser | |
| Zhang et al. | Transmission volume phase holographic gratings in photo-thermo-refractive glass written with femtosecond laser Bessel beams | |
| CN1448755A (en) | Method for preparing periodic microstructure on metallic film by femto second laser | |
| Ning et al. | Femtosecond laser-induced anisotropic structure and nonlinear optical response of yttria-stabilized zirconia single crystals with different planes | |
| Zhao et al. | Controllable precipitation and dissolution of silver nanoparticles in ultrafast laser pulses irradiated Ag+-doped phosphate glass | |
| Wang et al. | Nanoscale material redistribution induced by spatially modulated femtosecond laser pulses for flexible high-efficiency surface patterning | |
| CN1448733A (en) | Process for the manufacture of precious metal nanometer micro-structure grating | |
| Matushiro et al. | Femtosecond laser processing of polymethyl methacrylate with an axicon | |
| Kulchin et al. | Modification of a new polymer photorecording material based on PMMA doped with 2, 2-difluoro-4-(9-antracyl)-6-methyl-1, 3, 2-dioxaborine by ultrashort pulses | |
| Phelan et al. | Two-photon polymerisation of novel shapes using a conically diffracted femtosecond laser beam | |
| Quentin et al. | Optical trap assisted laser nanostructuring in the near-field of microparticles | |
| Messaddeq et al. | Formation of cross-superposed LIPSSs on bulk chalcogenide glasses using fs-laser | |
| Itoh et al. | Generation of glass nanofibers from back surface of substrate using pulsed UV 355 nm laser | |
| Kondo et al. | Three-dimensional recording by femtosecond pulses in polymer materials | |
| Abou Khalil | Direct laser writing of a new type of optical waveguides and components in silver containing glasses | |
| Zambon et al. | Fabrication of photonic devices directly written in glass using ultrafast Bessel beams | |
| Paipulas et al. | Volumetric modifications in fused silica using Gaussian and Bessel femtosecond laser beams | |
| Ihlemann et al. | Periodic Surface Structures by Laser Interference Ablation | |
| Jung-Kyu et al. | Optical diffraction gratings embedded in BK-7 glass by low-density plasma formation using femtosecond laser |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |