CN1320560C - Method for preparing conductive material using femtosecond laser double photon - Google Patents
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- CN1320560C CN1320560C CNB2004100430006A CN200410043000A CN1320560C CN 1320560 C CN1320560 C CN 1320560C CN B2004100430006 A CNB2004100430006 A CN B2004100430006A CN 200410043000 A CN200410043000 A CN 200410043000A CN 1320560 C CN1320560 C CN 1320560C
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Abstract
The present invention relates to a method for preparing conductive materials with femtosecond laser double photon, and relates to the technical field of processing conductive materials. The present invention comprises the procedure that a) the light source utilized by the present invention is blue femtosecond laser which is generated by the method that femtosecond laser with the wavelength of 750 to 850 nm and the pulse width of 60 to 100 fs is made into the blue femtosecond laser with the wavelength of 375 to 425 nm after frequency multiplication, or the present invention utilizes other femtosecond laser which can directly generate blue light as the processing light source; b) the blue femtosecond light with the wavelength of 375 to 425 nm is focused on non-conductive materials waiting for processing by a lens; c) the present invention controls the positions of samples or the irradiation position of the laser focal point in the non-conductive materials through a computer so that the laser is interacted with the materials for double-photon absorption, and the non-conductive materials are made into conductive functional materials at optical exposed positions. Compared with the existing methods for processing MEMS microelectronic devices, the present invention has the characteristics of real three dimensions, high resolution, electrical conductivity, once processing, etc.
Description
Technical field
The present invention relates to the electric conducting material processing technique field, relate to the method for the Fs laser double photon machining 3 D electric conducting material of blue light.The method has very characteristics such as three-dimensional, high-resolution, conductivity, disposable processing than the processing method of existing MEMS microelectronic device.
Technical background
The fast development of microelectronic has changed our scientific technological advance history and daily life.The research of microelectronic device and application level have become the important symbol of weighing a national science and technology level.Household electrical appliance, mobile electronic device, small-sized household computer and giant brain have been widely used in each and every one field of social life.1860s has been made first integrated circuit (ICs) in the world, indicate the beginning of electronics industry revolution. hereafter microelectronics industry has experienced unprecedented high speed development, and it is faster, littler, complicated and more cheap more that integrated circuit constantly becomes.
Microelectronic device mainly is made up of three kinds of materials, conductor, semiconductor and insulator. and current-carrying part mainly is to be used to provide electrode, electrostatic protection and electromagnetic shielding, and the insulation physical efficiency plays the effect of isolating and sealing current-carrying part.Conducting polymer is shown one's talent in numerous microelectronic materials with its exclusive characteristics.The first, eigenstate (attitude of not mixing) conducting polymer poor electric conductivity belongs to insulator. and change its electric conductivity by adding oxidant, reducing agent or Bronsted acid, make it to become semiconductor or conductor.In same system, just can have the electric conductivity different piece simultaneously like this by chemical reaction.The second, can regulate and control electric conductivity by the type and the doping level of controlled doping agent.The 3rd, conducting polymer also has light weight, easily makes and characteristics such as pliability height.Therefore, be that the microelectronic component that material is made will become the new growing point of microelectronic with the high polymer.
The method of processing conducting polymer microelectronic component mainly is to form printed circuit by electron beam exposure at present.Its process principle is with the Polymer Processing film forming, covers with photomask on it, places irradiation under electron beam or the high light then.Provide enough energy to make it to take place photochemical reaction in the place of illumination, thereby reach the difference of exposed portion and unexposed portion material electric conductivity, promptly conductor (or semiconductor) and insulator form microelectronic component.But since absorbed light (absorbed in electron beam exposure is electronics) from the etching agent surface up to substrate, so electron beam exposure is limited in the making of 2D or 2.5D structure.
The MEMS Micrometer-Nanometer Processing Technology of comparative maturity mainly comprises: the little processing of body silicon (mainly comprising dry method and wet etching), surperficial microfabrication (mainly comprising the preparation and the corrosion of structure sheaf and sacrifice layer), bonding techniques (mainly comprising electrostatic bonding and thermal bonding), high depth-to-width ratio micro process technology (mainly comprising LIGA and DEM technology) are in conjunction with the technology (photoetching, plating, diffusion, deposit etc.) of integrated circuit.Traditional optical exposure and electron beam exposure carry out the technology comparative maturity that two-dimensional structure is made.Yet (for example: photonic crystal, biotechnology, 3D guide technology etc.) needed the little processing of 3D during the generation of new unit and new material and MEMS used.Though multilayer technique can be realized by the long-pending 2D structure of treadle-operated tilt hammer for hulling rice in layer,, even simple structure, very big, the required fund of layer and the technique of alignment difficulty between the layer is costliness very.So, explore multiple material the 3 D complex figure Micrometer-Nanometer Processing Technology and be fit to the material of its processing request, be MEMS research deeply development be badly in need of the problem that solves.
Two-photon excitation is meant that medium absorbs two low-energy photons simultaneously and is excited to higher energy state, to speed rapidly to drive lower state and the process of launching a fluorescent photon from upper state then. the double photon three dimension process technology is based on such notion: atom or molecule absorb the rayed of sufficient intensity simultaneously, under the object lens focusing of higher numerical aperture, two photon absorption is limited in the spatial volume～λ at focus place
3(λ is a Wavelength of Laser) among a small circle in, chemistry and physical process just occur in the volume of this local, behind the absorbed two-photon in the volume of this local, material will become liquid or gas or contraction or expansion or solidify, and other possible variations take place, any variation does not then take place in other outer zones of focus, utilizes this characteristics, carries out three-dimensional any direction microfabrication by the position of accurate moving focal point in sample.Yet being fit to the two-photon material processed at present also only is the material of photoetching resinae, can not satisfy the requirement of microelectronic device processing.Recently developed the etching material of two-photon processing metal.But because the defective of metal material itself, cause the metal pattern lines that process discontinuous smooth, required working power is big.Therefore must develop and seek to be suitable for the novel conductive material and the processing method of two-photon processing characteristic.In recent years, utilize the two-photon laser technology to carry out the existing report of 3D microfabrication, but material processed and device all are by non electrically conductive material or nonconducting polymeric material, these materials and device all do not have actual application value in MEMS.
Summary of the invention
The objective of the invention is to propose a kind of new approaches of making miniature conducting function material, promptly use the method for the Fs laser double photon microfabrication of blue light, processing conducting function material and novel three-dimensional conducting function device.
For achieving the above object, technical solution of the present invention has proposed a kind of method of utilizing Fs laser double photon to prepare electric conducting material, it is characterized in that comprising:
A) in the step, the light source that uses as blue light femtosecond laser, the method for generation is: wavelength at 750-850nm, the pulse duration femtosecond laser at 60-100fs, is formed the femtosecond light of blue light 375-425nm after frequency multiplication;
B) step, the femtosecond light of blue light 375-425nm through lens focus to non-conducting material to be processed, carry out the two-photon excitation processing of blue light;
C) step is radiated at position in the non-conducting material by computer control sample position or laser spot, and laser and material are interacted, after main effect is material generation two photon absorption, and the functional material that formation is conducted electricity.
The described method for preparing electric conducting material, the light source in its described a) step, or use other directly to produce the light source of the femtosecond laser of 375-425nm blue light as processing.
The described method for preparing electric conducting material, the frequency multiplication in its described a) step is through bbo crystal or ktp crystal or lbo crystal frequency multiplication.
The described method for preparing electric conducting material, its described b) lens in the step are microscopical object lens.
The described method for preparing electric conducting material, its described initial raw materials is a non-conducting material, itself does not absorb near the wave-length coverage of blue light femtosecond laser incident light, and near the frequency multiplication position of the femtosecond laser wavelength (375-425nm) of blue light, absorption is arranged, and can after taking place, corresponding photon induced photochemical reaction form electric conducting material.
The described method for preparing electric conducting material, its described absorption is that two photon absorption takes place at the focus place of blue light femtosecond laser incident light, is equivalent to absorb the twice energy and photochemical reaction takes place.
The described method for preparing electric conducting material, its described photochemical reaction is conductivity and the dissolubility generation marked change that makes the non-conducting material itself at exposure and unexposed place.
The described method for preparing electric conducting material, its described photochemical reaction, mixing for photon induced photic iodine cancellation or the acid of photon induced light makes it form conducting polymer materials by non-conductive material polymerization or doping.
The described method for preparing electric conducting material, it also comprises d) step, select suitable solvent with c) go on foot unexposed part flush away in the conducting function material that obtains, the part of remaining conduction constitutes three-dimensional electric conducting material, can further be processed into three-dimensional conducting function device.
The described method for preparing electric conducting material, its described non-conducting material comprises: the poly-conducting polymer that forms along butadiene, polyaniline in eigenstate and pyrrole monomer of iodo.
The described method for preparing electric conducting material, it also comprises to the processing of non-conducting material before processing, that is:
A) will gather suitable butadiene and elemental iodine and be dissolved in cyclohexane, the room temperature nitrogen environment stirs down, behind certain hour, gets the mixed solution of poly-suitable butadiene of iodo and iodine; It is standby mixed solution to be dripped film again; Or
B) polyaniline in eigenstate is dissolved in the N-methyl pyrrolidone, forms saturated solution; Light acid agent is added the polyaniline saturated solution, fully stir and spend the night; The solution spin-coating film is standby; Or
C) with pyrroles and perchloric acid with
2: 1Mixing is dissolved in the oxolane, then mixed solution is added dropwise in the suitable miniature vessel standby.
The described method for preparing electric conducting material, its described poly-suitable butadiene is 185.5mg, and elemental iodine is 22.5mg, and cyclohexane is 25ml, about 162 hours of mixing time.
The described method for preparing electric conducting material, its described light acid agent is 0.05g, the polyaniline saturated solution is 2ml.
The described method for preparing electric conducting material, its described solvent is cyclohexane, N-methyl pyrrolidone and oxolane.
The present invention has very characteristics such as three-dimensional, high-resolution, conductivity, disposable processing than the processing method of existing MEMS microelectronic device.
Embodiment
The two-photon processing method: with wavelength at 750-850nm, the femtosecond light of the blue light 375-425nm that pulse duration forms after the bbo crystal frequency multiplication at the femtosecond laser of 60-100fs is through microscopical object lens 40x, 60x, perhaps 100x focuses on the non-conducting material to be processed, the position in non-conducting material by computer control sample or laser, laser and material are interacted, form the functional material of conduction, and utilize suitable solvent (to comprise that all that can dissolve the solvent of the unexposed portion in the rapidoprint, such as: cyclohexanes etc. can dissolve unexposed poly-along butadiene, the N-methyl pyrrolidone can dissolve unexposed intrinsic polyaniline, oxolane can the unpolymerized pyrrole monomer of flush away) with unexposed part flush away, form satisfactory three-dimensional conducting function device.
Concrete rapidoprint and Fs laser double photon method are:
(1), iodine replaces poly-along the butadiene photic iodine doping method of two-photon of (poly-along butadiene, English name cis-polybutadiene is called for short cis-pb).
Principle:
Iodo is poly-to issue iodine on the third contact of a total solar or lunar eclipse chemical reaction cancellation strand along butadiene in the illumination of Fs laser double photon, generates long conjugated structure.The iodine of cancellation simultaneously also can mix to material simultaneously.Thereby cause illumination place obviously to improve, reach the purpose of processing than without illumination place conductivity.
Concrete grammar:
The poly-preparation of iodo along butadiene
To gather suitable butadiene (cis-pb (Aldrich)) 185.5mg and elemental iodine 22.5mg and be dissolved in the 25ml cyclohexane, the room temperature nitrogen environment stirs down, approximately stirs 162 hours, can get the poly-mixed solution along butadiene and iodine of iodo.
The preparation of conductive devices
The poly-suitable butadiene solution of iodo is dripped film, because sample does not have absorption and at the 200nm place stronger absorption arranged at the 400nm place.Can with wavelength be the femtosecond laser of 800nm by bbo crystal, frequency multiplication produces the femtosecond laser of 400nm material is processed.Sample absorbs two 400nm photons (being equivalent to a 200nm photon) simultaneously photochemical reaction takes place at the focus place, generate conducting polymer composite.Thereby make exposure and the conductivity generation marked change of unexposed place, and utilize the unexposed non-conductive material part of cyclohexane flush away, reach the purpose of machining 3 D conductive devices.
(2), the double-photon optical of polyaniline acid doping method.
Principle:
Mainly utilize light acid agent (being generally the salt of triphenylsulfonium or diphenyl iodine) under the double-photon optical of femtosecond laser shines, to discharge the characteristics of Bronsted acid, polyaniline in eigenstate carried out light acid mix, make its conduction.
Concrete grammar:
Polyaniline in eigenstate is dissolved in NMP (N-methyl pyrrolidone) forms saturated solution.0.05g light acid agent is added 2ml polyaniline saturated solution, fully stir and spend the night.With the solution spin-coating film, can carry out the two-photon microfabrication.Can with wavelength be the femtosecond laser of 800nm by bbo crystal, frequency multiplication produces 400nm laser material is carried out two-photon processing.Photochemical reaction takes place in sample absorbs two femtoseconds simultaneously at the focus place 400nm photon (being equivalent to a 200nm photon), and acid is separated out in light acid agent, generates conducting polymer composite.Thereby make exposure and the conductivity generation marked change of unexposed place, and utilize the unexposed non-conductive material part of N-methyl pyrrolidone flush away, reach the purpose of machining 3 D conductive devices.
(3), photon induced pyrrole monomer forms the method for conducting polymer.
Principle:
Utilize the pyrroles that the characteristics of polymerization take place under double-photon optical shines, mix with acid simultaneously, generate the electric polypyrrole polymer at the focus place that femtosecond laser focuses on.
Concrete grammar:
With pyrroles and perchloric acid with certain proportion,
BestPyrroles more (such as 2: 1) mixing is dissolved in the oxolane, then mixed solution is added dropwise in the suitable miniature vessel, can carry out the Fs laser double photon microfabrication.Can with wavelength be the femtosecond laser of 800nm by bbo crystal, frequency multiplication produces 400nm laser material is processed.Photochemical reaction takes place in sample absorbs two femtoseconds simultaneously at the focus place 400nm photon (being equivalent to a 200nm photon), generates conducting polymer composite.Thereby make exposure and the conductivity generation marked change of unexposed place, and utilize the unexposed non-conductive material part of oxolane flush away, reach the purpose of machining 3 D conductive devices.
More than the characteristics of three kinds of materials be that this does not absorb material near in the wave-length coverage of femtosecond laser incident light, and absorption is arranged near the frequency multiplication wavelength of laser, and corresponding photochemical reaction can take place its conduction property is changed.In the process of two-photon processing, photochemical reaction takes place in the non-conducting material generation two photon absorption (being equivalent to absorb the twice energy) at the focus place, forms the polymer of conduction, reaches the purpose of processing.
Claims (13)
1. method of utilizing the blue light Fs laser double photon to prepare electric conducting material is characterized in that comprising:
A) in the step, the light source that uses as blue light femtosecond laser, the method for generation is: wavelength at 750-850nm, the pulse duration femtosecond laser at 60-100fs, is formed the femtosecond light of blue light 375-425nm after frequency multiplication;
B) step, the femtosecond light of blue light 375-425nm through lens focus to non-conducting material to be processed; Described non-conducting material comprises: iodo is poly-along butadiene, polyaniline in eigenstate and pyrrole monomer;
C) step is radiated at position in the non-conducting material by computer control sample position or laser spot, and laser and material are interacted, and mainly is two photon absorption takes place the functional material that conducts electricity in the position formation that exposed.
2. the method for preparing electric conducting material as claimed in claim 1 is characterized in that: the light source in the described a) step, use other directly to produce the light source of the femtosecond laser of 375-425nm blue light as processing.
3. the method for preparing electric conducting material as claimed in claim 1 is characterized in that: the frequency multiplication in the described a) step is through bbo crystal or ktp crystal or lbo crystal frequency multiplication.
4. the method for preparing electric conducting material as claimed in claim 1 is characterized in that: the lens in the step described b) are microscopical object lens.
5. the method for preparing electric conducting material as claimed in claim 1, it is characterized in that: described non-conducting material, itself does not absorb in the wave-length coverage of femtosecond laser incident light, and in femtosecond laser wavelength frequency multiplication position absorption is arranged, and corresponding photon induced photochemical reaction can take place.
6. the method for preparing electric conducting material as claimed in claim 5 is characterized in that: described absorption is that two photon absorption takes place at the focus place of femtosecond laser incident light, is equivalent to absorb the twice energy and photochemical reaction takes place.
7. the method for preparing electric conducting material as claimed in claim 5 is characterized in that: described photochemical reaction is that exposure and the conductivity and the dissolubility of the non-conducting material at unexposed place itself are changed.
8. as claim 5, the 6 or 7 described methods that prepare electric conducting material, it is characterized in that: described photochemical reaction, mixing for photon induced photic iodine cancellation or the acid of photon induced light makes it by the non-conductive material polymerization or be doping to conducting polymer materials.
9. the method for preparing electric conducting material as claimed in claim 1, it is characterized in that: also comprise d) step, selective solvent is with c) and go on foot unexposed part flush away in the conducting function material that obtains, be left the part of conduction, constitute three-dimensional electric conducting material, can further be processed into three-dimensional conducting function device.
10. the method for preparing electric conducting material as claimed in claim 9 is characterized in that: also comprise to the processing of non-conducting material before processing, that is:
A) will gather suitable butadiene and elemental iodine and be dissolved in cyclohexane, the room temperature nitrogen environment stirs down, behind certain hour, gets the mixed solution of poly-suitable butadiene of iodo and iodine; It is standby mixed solution to be dripped film again; Or
B) polyaniline in eigenstate is dissolved in the N-methyl pyrrolidone, forms saturated solution; Light acid agent is added the polyaniline saturated solution, fully stir and spend the night; The solution spin-coating film is standby; Or
C) pyrroles is mixed with 2: 1 volume ratios with perchloric acid be dissolved in the oxolane, then mixed solution is added dropwise in the suitable miniature vessel standby.
11. the method for preparing electric conducting material as claimed in claim 10 is characterized in that: described poly-suitable butadiene is 185.5mg, and elemental iodine is 22.5mg, and cyclohexane is 25ml, mixing time 162 hours.
12. the method for preparing electric conducting material as claimed in claim 10 is characterized in that: described light acid agent is 0.05g, and the polyaniline saturated solution is 2ml.
13. the method for preparing electric conducting material as claimed in claim 9 is characterized in that: described solvent is cyclohexane, N-methyl pyrrolidone and oxolane.
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| CN1320560C true CN1320560C (en) | 2007-06-06 |
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| CN102320553B (en) * | 2011-07-04 | 2014-11-26 | 中国科学院理化技术研究所 | Method for making micro nanometer structure device by laser two-photon direct writing technology |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465075A (en) * | 2001-08-09 | 2003-12-31 | 松下电器产业株式会社 | Method for producing nanocomposite magnet using atomizing method |
| EP1420439A2 (en) * | 2002-11-14 | 2004-05-19 | Air Products And Chemicals, Inc. | Non-thermal process for forming porous low dielectric constant films |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1465075A (en) * | 2001-08-09 | 2003-12-31 | 松下电器产业株式会社 | Method for producing nanocomposite magnet using atomizing method |
| EP1420439A2 (en) * | 2002-11-14 | 2004-05-19 | Air Products And Chemicals, Inc. | Non-thermal process for forming porous low dielectric constant films |
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