CN102000912B - Laser micro-nano machining system and method - Google Patents
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Abstract
The invention provides a laser micro-nano processing system and a laser micro-nano processing method. The system according to the invention comprises: a laser light source for providing a first laser beam having a first wavelength and a second laser beam having a second wavelength, pulse widths of the first laser beam and the second laser beam being respectively in a range from nanoseconds to femtoseconds and the first wavelength being different from the second wavelength; the optical delay assembly is used for adjusting the optical path of the first laser beam or the second laser beam so that the time difference of the first laser beam and the second laser beam reaching a focus is not more than the energy level life of the photosensitive material to be processed excited to an excited state; an optical focusing assembly for focusing the first laser beam and the second laser beam to the same focal point; and a computer-controlled micro-motion stage for adjusting the photosensitive material placed thereon to the focal point.
Description
Technical Field
The invention relates to a laser micro-nano processing method and a laser micro-nano processing system, in particular to a laser micro-nano processing method and a laser micro-nano processing system, wherein the processing resolution and the processing precision can be accurately controlled.
Background
For more than half a century, photolithography has dominated micro-nano fabrication techniques. When the laser technology is used for processing materials, the processing resolution which can be achieved by the laser technology is always limited by the limit of classical optical diffraction, and the processing of nanometer scale is difficult to be carried out, which is a core scientific problem which needs to be solved first for developing the nanometer photon processing technology and is also a focus of attention of scientists in the field.
The femtosecond laser micro-nano processing is a novel ultra-fine processing technology integrating an ultra-fast laser technology, a microscopic technology, an ultra-high precision positioning technology, a three-dimensional graph CAD manufacturing technology and a photochemical material technology, and has the characteristics of simplicity, low cost, high resolution, true three-dimension and the like. The technology utilizes the two-photon absorption effect, can limit the action range of laser and substances in a small area, and thus achieves the processing resolution below the diffraction limit. In 2001, Satoshi Kawata et al obtained 120nm processing resolution with 780nm femtosecond pulsed laser and produced three-dimensional nano-bovine structures, see Nature, Satoshi Kawata et al, 2001, 412 (6848): 697-698. In 2008, Xian-Zi Dong et al achieved 50nm processing resolution by controlling laser parameters, see appl.phys.lett., Xian-Zi Dong et al, american institute of physics, 2008, 92: 091113. dengfeng Tan et al utilize the shrinkage effect of polymers to achieve suspended polymer nanowires with 15nm line widths between pre-processed cuboids, see appl. phys. lett., Dengfeng Tan et al, american institute of physics, 2007, 90: 071106. the work related to breaking through the diffraction limit is performed by using a single light beam, and a method capable of accurately controlling the processing resolution and the processing precision is needed.
In order to further improve the processing resolution, some scientists propose to utilize one laser beam to initiate photopolymerization, and another laser beam to limit the reaction area, so that only the center of the focus of the excitation light reacts with the material, thereby greatly breaking through the diffraction limit. Timothy f.scott et al, with 473nm wavelength laser light generated by an all-solid-state laser, excited radicals to initiate photopolymerization, and another 365nm wavelength laser light generated by an argon ion laser, consumed radicals near the excitation light focal point, thereby limiting the reaction region to a very small range of the excitation light focal point, resulting in a processing resolution below the diffraction limit, see Science, Timothy f.scott et al, 2009, 324(5929), 913. Linie Li et al, see Science, Linjie Li et al, 2009, 324(5929), 910, use a femtosecond pulse laser to generate near-infrared laser with a wavelength of 800nm and a pulse width of 200fs to induce photopolymerization of a material by a two-photon process, and use another pulse laser with the same wavelength and a pulse width of 50ps to suppress the degree of reaction near the focal point of excitation light by a single photon process, thereby obtaining a processing resolution of 40nm in the longitudinal direction. The photoresist is covered by a photochromic film, which allows the laser with 325nm wavelength generated by the He-Cd laser to transmit, and the laser with 325nm wavelength to be absorbed in the laser action region with 633nm wavelength generated by the He-Ne laser, and the Loader mirror interferometer is used to make the interference fringes of the two beams alternate in light and shade, and only the laser with 325nm wavelength in the tiny region is allowed to transmit the photochromic film to act on the photosensitive material, so as to obtain the processing resolution of 36nm in the transverse direction, see Science, Trisha L.Andrew et al, 2009, 324(5929), 917. However, the above-described technique is limited to processing of a material having a property that can be quenched by light excitation and excited state light, and it is difficult to process other types of materials.
Therefore, there is a need for a laser micro-nano machining system and method for precisely controlling the machining resolution and machining precision of a photosensitive material to be machined by selecting a wavelength matched with the absorption characteristics of the photosensitive material to be machined.
Disclosure of Invention
The invention aims to provide a laser micro-nano processing method and a laser micro-nano processing system, wherein the processing resolution and the processing precision can be accurately controlled. The laser beam with the wavelength matched with the absorption characteristic of the photosensitive material to be processed is utilized to process various functional materials, and the material range of micro-nano processing is expanded.
The invention provides a laser micro-nano processing system, which comprises:
a laser light source for providing a first laser beam having a first wavelength and a second laser beam having a second wavelength, pulse widths of the first laser beam and the second laser beam being respectively in a range from nanoseconds to femtoseconds and the first wavelength being different from the second wavelength;
the optical delay assembly is used for adjusting the optical path of the first laser beam or the second laser beam so that the time difference of the first laser beam and the second laser beam reaching a focus is not more than the energy level life of the photosensitive material to be processed excited to an excited state;
an optical focusing assembly for focusing the first laser beam and the second laser beam to the same focal point; and
a computer controlled micro-motion stage for adjusting the photosensitive material placed thereon to said focal point.
Preferably, the repetition frequency of the first laser beam and the second laser beam is 1Hz to 100MHz, the wavelength adjusting range is 157nm to 1064nm, and the polarization state is linear polarization, circular polarization or elliptical polarization.
Preferably, the laser light source comprises a first laser providing a first laser beam and a second laser providing a second laser beam.
Preferably, the laser light source includes:
a first laser for providing a first laser beam,
a beam splitter for splitting the first laser beam into two parts,
a frequency multiplier for forming one of the two parts of the first laser beam into a second laser beam having a frequency which is a multiple of the frequency of the first laser beam, an
A filter for transmitting the second laser beam.
Preferably, the system according to the present invention further comprises a shutter for adjusting the exposure time and an optical attenuator for adjusting the exposure energy.
Preferably, the optical delay assembly comprises four reflecting mirrors on a one-dimensional micro-moving platform, and the optical path of the first laser beam or the second laser beam is changed by adjusting the one-dimensional micro-moving platform.
Preferably, the optical delay assembly comprises two right-angle prisms located on a one-dimensional micro-moving platform, and the optical path of the first laser beam or the second laser beam is changed by adjusting the one-dimensional micro-moving platform.
Preferably, the moving range of the one-dimensional micro-moving stage is 0.1 μm to 1 m.
Preferably, the optical focusing assembly comprises;
a beam expanding lens for expanding the first laser beam and the second laser beam respectively,
a dichroic mirror and a reflecting mirror for superimposing the first laser beam and the second laser beam into a superimposed laser beam traveling along the same optical path, and
an objective lens for focusing the superimposed laser beams.
Preferably, the objective lens is a dry objective lens, a water immersion objective lens or an oil immersion objective lens.
Preferably, the laser micro-nano processing system of the invention further comprises:
a first wave plate for changing a polarization state of the first laser beam;
a second wave plate for changing the polarization state of the second laser beam.
Preferably, the computer-controlled micro-motion stage is a three-dimensional micro-motion stage, and the moving range of the three-dimensional micro-motion stage in the x, y and z directions is 1nm-200 mm.
The invention provides a laser micro-nano processing method, which comprises the following steps:
adjusting a laser light source, adjusting a first laser beam and a second laser beam output by the laser light source to a first wavelength and a second wavelength which can enable the photosensitive material to be processed to generate a two-photon effect respectively, wherein the pulse widths of the first laser beam and the second laser beam are respectively in a range from nanosecond to femtosecond, and the first wavelength is different from the second wavelength,
adjusting an optical path of the first laser beam or the second laser beam such that a time difference between arrival of the first laser beam and the second laser beam at the photosensitive material is not more than an energy level lifetime of the photosensitive material excited to an excited state,
focusing the first laser beam and the second laser beam to the same focal point, an
And adjusting the micro-moving platform to enable the photosensitive material on the micro-moving platform to be positioned at the focus so as to carry out micro-nano processing.
Preferably, the exposure time of the first laser beam and the exposure time of the second laser beam are respectively adjusted to be 1ms-10min, and the exposure energy of the first laser beam and the second laser beam is respectively adjusted to be 0.1 muW-1W of the average laser power acting on the photosensitive material.
Preferably, the photosensitive material is selected from the group consisting of an organic photosensitive material, an inorganic photosensitive material, and a photosensitive material containing metal ions.
Preferably, the organic photosensitive material is selected from the group consisting of an organic material that can undergo a photopolymerization reaction, an organic material that can undergo a photodecomposition reaction, an organic material containing a molecule that can undergo a photocrosslinking reaction, and an organic material containing a molecule that can undergo a photoisomerization reaction.
Preferably, the inorganic photosensitive material is selected from the group consisting of an inorganic material that can undergo a photopolymerization reaction, an inorganic material that can undergo a photodecomposition reaction, an inorganic material that contains a molecule that can undergo a photocrosslinking reaction, an inorganic material that contains a molecule that can undergo a photoreduction reaction, and an inorganic material that contains a molecule that can undergo a photooxidation reaction.
Preferably, the photosensitive material containing metal ions is selected from the group consisting of an inorganic material containing metal ions of molecules capable of undergoing photoreduction reaction, an organic material containing metal ions of molecules capable of undergoing photoreduction reaction, an inorganic material containing molecules capable of undergoing photooxidation reaction, and an organic material containing molecules capable of undergoing photooxidation reaction.
The invention has the advantages that:
1. the system and the method of the invention realize the superposition of two beams of laser in space and time, can process in nanometer scale in photosensitive material, and obtain the processing resolution ratio higher than that of single beam laser beam.
2. The method can accurately control the processing resolution and the processing precision by respectively adjusting the exposure energy and the exposure time of the two beams of light acting with the photosensitive material.
3. The method can expand the range of the processing materials and realize the processing of various functional materials by selecting the wavelength of the used laser to be matched with the characteristics of different materials.
Drawings
FIG. 1 shows a calculated intensity profile for focusing two laser beams having wavelengths of 800nm and 500nm, respectively, at the same focal point and for focusing one 800nm laser beam at the focal point;
FIG. 2 is a graph showing a calculated intensity distribution of two laser beams having wavelengths of 800nm and 400nm, respectively, focused at the same focal point and one 800nm laser beam focused at the focal point;
FIG. 3 is a schematic view of a laser machining system according to one embodiment of the present invention;
FIG. 4 is a schematic view of a laser machining system according to another embodiment of the present invention;
FIG. 5 is a schematic view of an optical delay assembly of one embodiment of the present invention;
FIG. 6 is a schematic view of an optical delay element according to another embodiment of the present invention;
FIG. 7 is a scanning electron microscope photomicrograph of a line array structure obtained using the system of FIG. 3 with a single 800nm laser beam (a) and a superimposed laser beam of two 800nm and 400nm lasers (b), respectively;
FIG. 8 is a scanning electron microscope photograph of a suspended line structure obtained using the system of FIG. 3;
FIG. 9 is a scanning electron micrograph of a two-dimensional spot array structure obtained using the system of FIG. 3 with a single 800nm laser (a) and a superimposed laser beam (b) of the 800nm and 400nm lasers, respectively;
FIG. 10 is a scanning electron micrograph of a polymerization site prepared using the system of FIG. 3.
In the figure, the position of the upper end of the main shaft,
1. a first pulse laser; 2. A second pulse laser; 3. A semi-transparent semi-reflective mirror;
4. a first reflector; 5. Frequency doubling crystals; 6. A filter;
7. a first shutter; 8. A second shutter; 9. An optical delay element;
10. a first lens; 11. A second lens; 12. A third lens;
13. a fourth lens; 14. A first wave plate; 15. A second wave plate;
16. a first light gradual change attenuator; 17. A second light gradual change attenuator;
18. a dichroic mirror; 19. A second reflector; 20. An objective lens;
21. a computer-operated three-dimensional micro-mobile station; 22. A one-dimensional micro-motion platform;
23. a third reflector; 24. A fourth mirror; 25. A fifth mirror;
26. a sixth mirror; 27. A first right-angle prism; 28. A second right-angle prism;
Detailed Description
The invention will now be described in connection with preferred embodiments thereof with reference to the accompanying drawings. It should be understood that in the following description, numerous specific details are provided, such as examples of optical components, to provide a thorough understanding of embodiments of the invention. However, it will be understood by those of ordinary skill in the art that the present invention is applicable not only to one or more of the specific details, but also to other structural elements, wavelengths, materials, etc. The embodiments set forth below in the specification are illustrative and not restrictive.
Two beams of laser with different wavelengths are superposed and the superposed laser beams act on the same focus, and the light intensity distribution at the focus is determined by the product of the light intensity distribution functions of the two beams of laser at the focus. By comparing the full width at half maximum (FWHM) of the intensity distribution function characterizing the diameter of the spot of the laser beam, it can be seen that the FWHM of the product of the intensity distribution functions of the superimposed laser beams is smaller than the FWHM of the square of the intensity of a conventional laser beam. Therefore, the superposed laser beam obtained by superposing two beams of laser beams with different wavelengths is used for acting on the photosensitive material with the two-photon absorption effect, and the high-resolution micro-nano processing higher than the resolution of the photosensitive material with the two-photon absorption effect acted by a single laser beam can be realized. The light intensity distribution function of the superposed light beam obtained by superposing two laser beams with different wavelengths at the same focus and the relationship between the light intensity distribution function and the processing resolution ratio are specifically analyzed.
According to the Debye method, see J.Stammers, Waves in Focal Regions, Adam Hilger, Bristol, 1986, the intensity distribution function for a beam of light of wavelength λ and polarization phi after being focused by an objective lens with an aperture angle α is:
Wherein,
(formula 1-1)
(formula 1-2)
(formulae 1 to 3)
Wherein u and v are optical coordinates, respectively, and u ═ znk sin2α，v＝rnk sinα；k＝2π/λ，
NA is the numerical aperture of the objective lens, and n is the refractive index of the material to be processed; j. the design is a square0、J1、J2Are all a class of Bessel functions; phi 0 or pi/2 means the polarization directions of the laser light are x and y, respectively.
It can be seen from the above formula that the light intensity distribution functions are different when the wavelength λ of the laser beam is different and the polarization direction is different. For two beams of laser with different wavelengths focused on the same focus by the same objective lens, the respective light intensity distribution function I is calculated1And I2And then the product is made to calculate the light intensity distribution of the superposed light beam at the focal point.
To be propagated in the z-direction1First laser and λ of 800nm2A second laser beam of 500nm, focused by an objective lens of NA 1.45, for example, in a material of refractive index n 1.515, the intensity distribution function I transverse to the propagation direction of the laser beam at the focal point is calculated1And I2The obtained results are shown in fig. 1.
In fig. 1, I1 and I2 respectively indicate the laser intensities of 800nm laser light and 500nm laser light, and Ix and Iy respectively indicate that the laser light used is linearly polarized light in the x and y directions. From the full width at half maximum (FWHM) of the light intensity distribution, it can be seen that the FWHM of the product of the light intensity distribution functions at the focus of the superimposed laser beams formed by superimposing two laser beams with different wavelengths is smaller than the FWHM of the square of the light intensity distribution function at the focus of one laser beam of 800nm, and the polarization direction of the laser also has an influence on the FWHM.
To be propagated in the z-direction1First laser and λ of 800nm2A second laser beam of 400nm, focused by an objective lens of NA 1.45, for example, in a material of refractive index n 1.515, the distribution function I of the intensity of the light at the focal point transverse to the propagation direction of the laser beam is calculated1And I2The obtained result is shown in fig. 2.
In fig. 2, I1 and I2 represent the intensities of laser light at 800nm and 400nm, respectively, and Ix and Iy represent the laser light used as linearly polarized light polarized in the x and y directions, respectively. It can be seen from the FWHM of the light intensity distribution that the FWHM of the product of the light intensity distribution functions of the superposed laser beams formed by superposing two laser beams with different wavelengths at the focal point is less than the FWHM of the square of the light intensity distribution function of one laser beam with 800nm at the focal point, and the polarization direction of the laser also has an influence on the FWHM.
As can be seen from the calculation results shown in equation 1 and fig. 1 and 2, the diameter of the beam spot formed by focusing two laser beams having different wavelengths to the same focal point is smaller than that of the conventional beam spot formed by the two-photon effect of one laser beam. In other words, when a photosensitive material having a two-photon absorption effect is processed by a superimposed beam formed by two laser beams of different wavelengths, the resolution is higher than that of the conventional processing using the two-photon effect of a single laser. Further, by adjusting the polarization directions of the two laser beams, respectively, the processing resolution can be further improved.
The laser micro-nano processing system of the present invention will be further described with reference to the preferred embodiments.
Fig. 3 shows a schematic diagram of a laser micro-nano machining system according to an embodiment of the invention. The laser micro-nano machining system 100 includes: a laser 1, a half-mirror 3, a frequency multiplier, such as a frequency multiplying crystal 5, an optical delay assembly 9, an optical focusing assembly and a moving stage 21. The laser 1 is used to generate pulsed laser light with pulse widths ranging from nanoseconds to femtoseconds. A half mirror 3 is placed on the output light path of the laser 1 for forming transmitted light and reflected light. And a frequency doubling crystal 5 and a filter 6 are sequentially arranged on the transmission light path along the main axis. The filter 6 is used for filtering the frequency doubling light beam, and the ratio of the energy of frequency doubling laser in the output energy to the output energy of the filter is not less than 99.5%. The system 100 may further include, for example, lenses 12, 13 in the transmission-doubled optical path after the filters for expanding the doubled light. A reflecting mirror 4 is arranged on a reflecting light path of the semi-transmitting and semi-reflecting mirror 3 along a main shaft to enable a reflecting fundamental frequency light path to be parallel to a transmitting frequency doubling light path, an optical delay assembly 9 is arranged behind the reflecting light path to adjust the optical path to enable the time difference of two laser beams reaching a focus to be not more than the energy level life of a photosensitive material to be processed excited to be in an excited state, and then lenses 10 and 11 for expanding the fundamental frequency light are arranged behind the reflecting light path. The system 100 may further include wave plates 15, 14 respectively positioned in the transmission path and the reflection path for adjusting the polarization state of the laser light in the transmission path and the reflection path, respectively. The wave plate is preferably a full wave plate, a half wave plate and a quarter wave plate with the working wavelength of the laser wavelength of the optical path. The optical focusing assembly of system 100 includes, for example, a dichroic mirror 18 and a mirror 19 for superimposing two laser beams into one laser beam, and an objective lens 20 for focusing the laser beam on a photosensitive material placed on a three-dimensional micro-motion stage 21 manipulated by a computer. The objective lens is preferably a dry objective lens, a water immersion objective lens or an oil immersion objective lens, the numerical aperture is 0.7-1.65, and the amplification factor is 10-100. The computer-operated three-dimensional micromovement stage preferably has a movement range of 1nm to 200mm in the x, y and z directions. The system 100 may further comprise shutters 8, 7 in the transmission and reflection paths, respectively, for adjusting the exposure time, and optical attenuators 17, 16 in the transmission and reflection paths, respectively, for adjusting the exposure energy. Preferably, the focal lengths of the lenses 10, 12, 12 and 13 are in the range of 1mm to 500mm, respectively. According to the laser micro-nano processing system of the preferred embodiment, the fundamental frequency laser beam and the frequency doubling laser beam form the superposed laser beam which is transmitted along the same optical path, and the superposed laser beam is focused on the same focus for processing the photosensitive material to be processed, so that the method for carrying out micro-nano processing on the photosensitive material with high resolution and high processing precision is provided.
Fig. 4 shows a schematic diagram of a laser micro-nano machining system according to another embodiment of the invention. The laser micro-nano machining system 200 includes: a laser 1, a laser 2, an optical delay assembly 9, an optical focusing assembly and a translation stage 21. The laser 1 is used to generate a first pulsed laser having a first wavelength with a pulse width in the range from nanoseconds to femtoseconds. The laser 2 replaces the half mirror 3, the reflector 4, the frequency doubling crystal 5, and the filter 6 shown in fig. 3, and is used for generating second pulse laser light having a second wavelength different from the first wavelength and having a pulse width ranging from nanoseconds to femtoseconds. In the system 200, the other structure of the system except the laser 2 is the same as that of the system 100 shown in fig. 3.
The method for performing micro-nano processing by using laser is performed in the system, and comprises the following steps:
1) and (2) turning on a laser light source, respectively adjusting the first laser beam and the second laser beam to a first wavelength and a second wavelength which can enable the photosensitive material to be processed to generate a two-photon effect, wherein the output average power is within the range of 1mW-10W, and the wavelength is within the range of 157nm-1064nm, and constructing the system.
2) Adjusting an optical path of the first laser beam or the second laser beam such that a time difference between arrival of the first laser beam and the second laser beam at the photosensitive material is not more than an energy level lifetime of the photosensitive material excited to an excited state,
3) adjusting a lens in the beam expanding system in a direction parallel to the main shaft, and focusing two beams of light on the same focal plane through an objective lens by using a three-dimensional micro-moving platform controlled by a computer;
4) the reflector, the semi-transparent and semi-reflective mirror, the right-angle prism and the dichroic mirror in the system are adjusted to enable the two beams of light to be focused on the same point on the same focal plane through the objective lens.
5) Placing a photosensitive material on a sample platform on a three-dimensional micro-moving platform operated by a computer, controlling the polarization state of laser through a wave plate, controlling the exposure time to be 1ms-10 minutes through a shutter, and controlling the average power of the laser acted on the photosensitive material to be within the range of 0.1 muW-1W through a light gradient attenuator;
6) the movement of a three-dimensional mobile station controlled by a computer is utilized to realize the scanning processing of the focus after the superposition of the two beams of light in the photosensitive material.
Obtaining a machined structure by a post-treatment process: washing, heating, decomposing, ablating, etching, developing and the like the photosensitive material subjected to the action of the two beams of light obtained in the step 3), and selecting corresponding process conditions according to the type of the material; portions of the photosensitive material that do not interact with light are removed to obtain a negative-type structure, or portions of the photosensitive material that interact with light are removed to obtain a positive-type structure.
In the above technical solution, the photosensitive material is an organic photosensitive material, an inorganic photosensitive material, or a photosensitive material containing metal ions.
In the above technical solution, the organic photosensitive material is an organic material capable of generating photopolymerization reaction, an organic material capable of generating photolysis reaction, an organic material containing a molecule capable of generating photocrosslinking reaction, or an organic material containing a molecule capable of generating photoisomerization reaction.
In the above-mentioned technical solution, the inorganic photosensitive material is an inorganic material capable of generating photopolymerization reaction, an inorganic material capable of generating photodecomposition reaction, an inorganic material containing a molecule capable of generating photocrosslinking reaction, an inorganic material containing a molecule capable of generating photoreduction reaction, or an inorganic material containing a molecule capable of generating photooxidation reaction.
In the above-mentioned technical means, the photosensitive material containing metal ions is an inorganic material containing metal ions capable of generating molecules of photoreduction reaction, an organic material containing metal ions capable of generating molecules of photoreduction reaction, an inorganic material containing molecules capable of generating molecules of photooxidation reaction, or an organic material containing molecules capable of generating molecules of photooxidation reaction.
The high processing resolution obtained by the laser micro-nano processing system and method according to the invention is described below with reference to specific examples.
Example 1
The following is a detailed description of the laser micro-nano processing system according to the present invention and the specific implementation steps for preparing the line array structure in the photoresist with the trade name of SCR500 placed on the glass substrate using the system.
The laser micro-nano machining system 100 includes: the laser device comprises a laser 1, a half-transmitting and half-reflecting mirror 3, a frequency doubling crystal 5, an optical delay assembly 9, an optical focusing assembly and a mobile station 21. The laser 1 is, for example, a titanium sapphire femtosecond pulse laser, and outputs a laser beam having a wavelength of 800nm, a pulse width of 100fs, a pulse repetition frequency of 82MHz, a beam diameter of 1.8mm, and a polarization state of linear polarization. A half mirror 3 made of BK7 glass, for example, is placed on the output light path of the titanium sapphire femtosecond pulse laser 1, and the transflective ratio thereof is 7: 3, for example, to form transmitted light and reflected light. The frequency doubler on the transmitted light path comprises, for example, a BBO type I frequency doubling crystal 5, for example, 1mm thick, and an interference filter 6 for filtering wavelengths of 800nm, placed in succession along the principal axis. The transmitted light passes through a frequency doubling crystal to obtain pure 400nm wavelength frequency doubling light with the beam diameter of 1.2mm, wherein the ratio of the energy of the 400nm wavelength laser to the energy of the laser output by the filter is not less than 99.5%. The system 100 may further include, for example, a lens 12 having a focal length of 60mm and a lens 13 having a focal length of 150mm on the transmission path as beam expanding lenses for expanding the doubled light. A reflecting mirror 4 made of BK7 glass, for example, is placed along the principal axis on the reflecting path of the half mirror 3 so that the reflecting path is parallel to the transmitting path, and then an optical delay assembly 9 is placed for adjusting the optical path so that the time difference of the two laser beams reaching the focal point is not more than the energy level life of the photosensitive material excited to the excited state. The optical delay assembly 9 comprises, for example, a one-dimensional micro-motion stage 22 and four mirrors 23, 24, 25 and 26 made of BK7 glass, as shown in fig. 5. Behind the optical delay assembly are placed, for example, a lens 10 with a focal length of 35mm and a lens 11 with a focal length of 150mm for expanding the fundamental light. After which a half-wave plate 14 having an operating wavelength equal to 800nm is placed, the optical axis direction of which coincides with the polarization direction of the fundamental frequency light. The optical focusing assembly comprises a dichroic mirror 18 made of BK7 glass and a reflecting mirror 19 made of BK7 glass and used for combining two beams of light into one path after a frequency doubling optical path, and the two beams of light pass through an oil immersion objective lens 20 with the numerical aperture of 1.45 and the magnification of 100 times and are focused inside a photosensitive material placed on a three-dimensional micro-moving platform 21 operated by a computer. A computer-operated, for example, three-dimensional micromovement stage 21 is adjusted to bring the focal point of the superimposed two beams of light to the interface of the glass substrate and the photosensitive material and set the speed of movement thereof to 10 nm/ms. The light-gradation attenuator 17 was adjusted so that the average power of light having a wavelength of 400nm became 2.3 μ W, the light-gradation attenuator 16 was adjusted so that the average power of light having a wavelength of 800nm became in the range of 14.91 to 11.19mW, exposure was performed in the photosensitive material, the portion of the photosensitive material which did not interact with light was removed with an anhydrous ethanol solution, and the line array structure obtained on the surface of the glass substrate was as shown in fig. 7 (b). The average power of the 800nm wavelength laser light of each line from left to right in the line array structure of FIG. 7(b) was 14.91mW, 14.50mW, 14.09mW, 13.73mW, 13.36mW, 13.02mW, 12.68mW, 12.36mW, 12.06mW, 11.77mW, 11.48mW and 11.19mW in this order. It can be seen that the processing resolution of the photosensitive material can be improved by reducing the processing power of the laser beam with the wavelength of 800nm while keeping the processing power of the laser beam with the wavelength of 400nm unchanged. This example can obtain a line structure having a processing resolution of less than 100nm under the processing conditions of 2.3 μ W as an average power of a 400nm wavelength laser and 11.19mW as an average power of an 800nm wavelength laser.
Comparative example 1
For example 1 above, the photosensitive material was exposed with only a single 800nm laser beam, and the other experimental conditions were kept the same, to obtain comparative experimental results. The light graded attenuator 17 was adjusted so that the power of light of 400nm wavelength was 0W, the light graded attenuator 16 was adjusted so that the average power of light of 800nm wavelength was varied in the range of 14.91mW to 13.36mW, exposure was performed in the photosensitive material, the portion of the photosensitive material which did not interact with light was removed with an anhydrous ethanol solution, and the line array structure obtained on the surface of the glass substrate was as shown in FIG. 7 (a). The average power of the laser light having a wavelength of 800nm in the line array structure of FIG. 7(a) was 14.91mW, 14.50mW, 14.09mW, 13.73mW, and 13.36mW in this order from left to right. Further reduction of the laser power will not result in the desired line structure. This example can achieve line structures with a processing resolution of 120nm under the processing conditions of an average power of 13.36mW of a 800nm wavelength laser.
It can be seen that the laser micro-nano processing system and method according to the present invention can obtain a processing resolution of less than 100nm by changing the processing power of 800nm laser, which is superior to the 120nm resolution obtained by using a conventional one-beam 800nm laser, and the processing energy according to using two laser beams is lower than that using a single laser beam.
Example 2
The system of the present invention and the steps for implementing the system to fabricate suspended line structures in a photoresist, which is commercially available as SCR500, placed on a glass substrate are described in detail below with reference to fig. 3:
the system comprises: the laser 1 is a titanium gem femtosecond pulse laser, the output wavelength of the laser 1 is 800nm, the pulse width is 100fs, the pulse repetition frequency is 82MHz, the beam diameter is 1.8mm, and the polarization state is linear polarization; firstly, turning on a titanium gem femtosecond pulse laser 1, and placing a semi-transparent semi-reflecting mirror 3 made of BK7 glass on an output light path, wherein the transflective ratio is 7: 3; placing an I-type BBO frequency doubling crystal 5 with the thickness of 1mm and an interference filter 6 for filtering the 800nm wavelength on a transmission light path along a main shaft in sequence to obtain pure 400nm wavelength frequency doubling light with the beam diameter of 1.2mm, and expanding the frequency doubling light through a lens 12 with the focal length of 60mm and a lens 13 with the focal length of 150 mm; a reflecting mirror 4 made of BK7 glass is placed along the main shaft on the reflection optical path of the half-transmitting and half-reflecting mirror 3 to be parallel to the other optical path, then an optical delay assembly 9 consisting of a one-dimensional micro-moving platform 22 and two right-angle prisms 27 and 28 made of BK7 glass is placed, as shown in FIG. 6, the basic frequency light is expanded through a lens 10 with the focal length of 35mm and a lens 11 with the focal length of 150mm, then a half-wave plate 14 with the working wavelength of 800nm is placed, and the optical axis direction of the half-wave plate is consistent with the polarization direction of the basic frequency light; a dichroic mirror 18 made of BK7 glass and a reflecting mirror 19 made of BK7 glass, which are arranged behind a fundamental frequency light path, are used for combining two beams of light into one path, and the two beams of light are focused inside a photosensitive material arranged on a three-dimensional micro-moving platform 21 operated by a computer through an oil immersion objective lens 20 with the numerical aperture of 1.45 and the magnification of 100 times; setting the moving speed of the three-dimensional micro-moving table 21 operated by the computer to be 170nm/ms, adjusting the light gradual change attenuators 16 and 17 to ensure that the average power of light with the wavelength of 400nm is 2.5 muW and the average power of light with the wavelength of 800nm is 12.23mW, carrying out exposure in the photosensitive material, removing the part of the photosensitive material which does not interact with the light by using absolute ethyl alcohol solution, and obtaining a suspended line structure between pre-processed cuboids with the interval of 1 mu m as shown in figure 8, wherein the resolution is less than 25 nm.
Example 3
The system of the present invention and the specific implementation steps for using the system to prepare a two-dimensional spot array structure in a photoresist, which is commercially available under the name SCR500, placed on a glass substrate are described in detail below with reference to fig. 3:
the system comprises: the laser 1 is a titanium gem femtosecond pulse laser, the output wavelength of the laser 1 is 800nm, the pulse width is 100fs, the pulse repetition frequency is 82MHz, the beam diameter is 1.8mm, and the polarization state is linear polarization; firstly, turning on a titanium gem femtosecond pulse laser 1, and placing a semi-transparent semi-reflecting mirror 3 made of BK7 glass on an output light path, wherein the transflective ratio is 7: 3; placing an I-type BBO frequency doubling crystal 5 with the thickness of 1mm and an interference filter 6 for filtering the 800nm wavelength on a transmission light path along a main shaft in sequence to obtain pure 400nm wavelength frequency doubling light with the beam diameter of 1.2mm, and expanding the frequency doubling light through a lens 12 with the focal length of 60mm and a lens 13 with the focal length of 150 mm; a reflector 4 made of BK7 glass is arranged on a reflection light path of the half-transmitting and half-reflecting mirror 3 along a main shaft to enable the reflection light path to be parallel to another light path, an optical delay assembly 9 consisting of a one-dimensional micro-moving platform 22 and four reflectors made of BK7 glass is arranged behind the reflector, fundamental frequency light is expanded through a lens 10 with the focal length of 35mm and a lens 11 with the focal length of 150mm, a half-wave plate 14 with the working wavelength of 800nm is arranged behind the reflector, and the included angle between the optical axis direction of the half-wave plate and the polarization direction of the fundamental frequency light is 45 degrees; a dichroic mirror 18 made of BK7 glass and a reflecting mirror 19 made of BK7 glass, which are arranged behind a frequency doubling optical path, are used for combining two beams of light into one path, and the two beams of light are focused inside a photosensitive material arranged on a three-dimensional micro-moving platform 21 operated by a computer through an oil immersion objective lens 20 with the numerical aperture of 1.45 and the magnification of 100 times; adjusting a three-dimensional micro-moving table 21 operated by a computer to enable a focus point of the two superposed lights to be on an interface of the glass substrate and the photosensitive material; the exposure times of the two beams are 100ms each by adjusting the shutters 7 and 8. The light graded attenuator 16 was adjusted so that the average power of light with a wavelength of 400nm varied from 6.0. mu.W to 4.2. mu.W, and the light graded attenuator 16 was adjusted so that the average power of light with a wavelength of 800nm varied from 15.02mW to 10.34mW, exposure was performed in the photosensitive material, and the portion of the photosensitive material that did not interact with light was removed with an anhydrous ethanol solution, and a two-dimensional dot array structure obtained on the surface of the glass substrate was as shown in FIG. 9 (b). In FIG. 9(b), the average power of the laser beam having a wavelength of 800nm was adjusted to 15.02mW, 14.12mW, 13.20mW, 12.34mW, 11.50mW, 10.84mW, and 10.34mW, respectively, while maintaining the average power at a wavelength of 400nm from left to right; the average power of the laser beam with the wavelength of 400nm was adjusted to 6.0. mu.W, 5.8. mu.W, 5.6. mu.W, 5.4. mu.W, 5.2. mu.W, 5.0. mu.W, 4.8. mu.W, and 4.6. mu.W, while keeping the average power at the wavelength of 800nm constant from top to bottom. This example can achieve a resolution of less than 130nm under the processing conditions of 4.6 μ W average power of a 400nm wavelength laser and 10.84mW average power of an 800nm wavelength laser.
Comparative example 3
For example 3 above, the photosensitive material was exposed with only a single 800nm laser beam, and the other experimental conditions were kept the same, to obtain comparative experimental results. The light-graded attenuator 17 was adjusted so that the power of light having a wavelength of 400nm became 0W, the light-graded attenuator 16 was adjusted so that the average power of light having a wavelength of 800nm became in the range of 15.02mW to 13.20mW, exposure was performed in the photosensitive material, the portion of the photosensitive material which did not interact with light was removed with an anhydrous ethanol solution, and a dot array structure obtained on the surface of the glass substrate was as shown in FIG. 9 (a). In FIG. 9(a), the average power of the laser beam having a wavelength of 800nm was 15.02mW, 14.12mW and 13.20mW in this order, and the processing resolution was 155nm at an average power of 13.20 mW. With a laser beam at 800nm below an average power of 13.20mW, no spot structure can be obtained.
It can be seen that the laser micro-nano processing system and method according to the present invention obtains a processing resolution of less than 130nm by changing the processing power of two laser beams, respectively, which is superior to a 155nm resolution obtained by using a conventional one 800nm laser, and the processing energy according to using two laser beams is lower than that using a single laser beam.
Example 4
The system of the present invention and the steps for performing the system to prepare a polymerization site in a photoresist, which is commercially available as SCR500, placed on a glass substrate are described in detail below with reference to the accompanying drawings:
the system comprises: the laser 1 is a titanium gem femtosecond pulse laser, the output wavelength of the laser 1 is 800nm, the pulse width is 100fs, the pulse repetition frequency is 82MHz, the beam diameter is 1.8mm, and the polarization state is linear polarization; firstly, turning on a titanium gem femtosecond pulse laser 1, and placing a semi-transparent semi-reflecting mirror 3 made of BK7 glass on an output light path, wherein the transflective ratio is 7: 3; placing an I-type BBO frequency doubling crystal 5 with the thickness of 1mm and an interference filter 6 for filtering the 800nm wavelength on a transmission light path along a main shaft in sequence to obtain pure 400nm wavelength frequency doubling light with the beam diameter of 1.2mm, and expanding the frequency doubling light through a lens 12 with the focal length of 60mm and a lens 13 with the focal length of 150 mm; a reflecting mirror 4 made of BK7 glass is placed along a main shaft on a reflecting light path of the semi-transparent semi-reflecting mirror 3 to be parallel to another light path, then an optical delay assembly 9 consisting of a one-dimensional micro-moving platform 22 and four reflecting mirrors made of BK7 glass is placed, fundamental frequency light is expanded through a lens 10 with the focal length of 35mm and a lens 11 with the focal length of 150mm, then a half-wave plate 14 with the working wavelength of 800nm is placed, and the optical axis direction of the half-wave plate is adjusted to enable the included angles of the polarization directions of the fundamental frequency light and the frequency doubling light to be 0 degree, 45 degrees and 90 degrees respectively; a dichroic mirror 18 made of BK7 glass and a reflecting mirror 19 made of BK7 glass, which are arranged behind a frequency doubling optical path, are used for combining two beams of light into one path, and the two beams of light are focused inside a photosensitive material arranged on a three-dimensional micro-moving platform 21 operated by a computer through an oil immersion objective lens 20 with the numerical aperture of 1.45 and the magnification of 100 times; adjusting a three-dimensional micro-moving table 21 operated by a computer to enable a focus point of the two superposed lights to be on an interface of the glass substrate and the photosensitive material; the light shutters 7 and 8 were adjusted so that the exposure time of both beams was 100ms, the light gradual attenuators 16 and 17 were adjusted so that the average power of light of 400nm wavelength was 5.8 μ W and the average power of light of 800nm wavelength was 12.34mW, 13.20mW, and 11.79mW respectively for the three polarization directions, exposure was performed in the photosensitive material, the portion of the photosensitive material that did not interact with light was removed with an anhydrous ethanol solution, and a polymerized spot was obtained on the surface of the glass substrate with a resolution of less than 135nm as shown in fig. 10. It follows that the processing accuracy of the laser processing system according to the embodiment of the present invention can be improved by changing the polarization direction of the laser beam.
While the invention has been illustrated and described herein in the context of a limited number of embodiments, the present invention can be embodied in many different forms without departing from the spirit of the essential characteristics of the invention. Accordingly, the illustrated and described embodiments are to be considered in all respects as illustrative and not restrictive. The above detailed description can be given, for example, based on adjustment of the exposure time. However, the above-described technique can be equally applied to gain control. For example, instead of increasing or decreasing the exposure amount, the gain amount may be similarly increased or decreased. In addition, the number of exposure times and gains may be increased or decreased as needed. The scope of the invention is, therefore, indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
The invention was funded by the national 973 program (2010CB 934103).
Claims (24)
1. A laser micro-nano processing system comprises:
the laser processing device comprises a laser light source, a laser processing device and a processing device, wherein the laser light source is used for providing a first laser beam with a first wavelength and a second laser beam with a second wavelength, the pulse widths of the first laser beam and the second laser beam are respectively in a range from nanosecond to femtosecond, and the first wavelength is different from the second wavelength, and the first wavelength and the second wavelength can enable a photosensitive material to be processed to generate a two-photon effect;
the optical delay assembly is used for adjusting the optical path of the first laser beam or the second laser beam so that the time difference of the first laser beam and the second laser beam reaching a focus is not more than the energy level life of the photosensitive material to be processed excited to an excited state;
an optical focusing assembly for focusing the first laser beam and the second laser beam to the same focal point; and
and a micro-moving stage controlled by a computer for adjusting the photosensitive material placed thereon to the focus, wherein the repetition frequency of the first laser beam and the second laser beam is 1Hz-100MHz, the wavelength adjustment range is 157nm-1064nm, and the polarization state is linear polarization, circular polarization or elliptical polarization.
2. A laser micro-nano machining system according to claim 1, wherein the laser light source comprises a first laser providing a first laser beam and a second laser providing a second laser beam.
3. The laser micro-nano machining system according to claim 1, wherein the laser light source comprises:
a first laser for providing a first laser beam,
a beam splitter for splitting the first laser beam into two parts,
a frequency multiplier for forming one of the two parts of the first laser beam into a second laser beam having a frequency which is a multiple of the frequency of the first laser beam, an
A filter for transmitting the second laser beam.
4. The laser micro-nano machining system according to claim 1, further comprising an optical shutter for adjusting exposure time and an optical attenuator for adjusting exposure energy.
5. A laser micro-nano machining system according to claim 1, wherein the optical delay assembly comprises four reflecting mirrors on a one-dimensional micro-moving platform, and the optical path of the first laser beam or the second laser beam is changed by adjusting the one-dimensional micro-moving platform.
6. A laser micro-nano machining system according to claim 1, wherein the optical delay assembly comprises two right-angle prisms on a one-dimensional micro-moving platform, and the optical path of the first laser beam or the second laser beam is changed by adjusting the one-dimensional micro-moving platform.
7. The laser micro-nano processing system according to claim 5 or 6, wherein the moving range of the one-dimensional micro-moving stage is 0.1 μm-lm.
8. The laser micro-nano machining system according to claim 1, wherein the optical focusing assembly comprises;
a beam expanding lens for expanding the first laser beam and the second laser beam respectively,
a dichroic mirror and a reflecting mirror for superimposing the first laser beam and the second laser beam into a superimposed laser beam traveling along the same optical path, and
an objective lens for focusing the superimposed laser beams.
9. The laser micro-nano machining system according to claim 8, wherein the objective lens is a dry objective lens, a water immersion objective lens or an oil immersion objective lens.
10. The laser micro-nano machining system according to claim 1, further comprising:
a first wave plate for changing a polarization state of the first laser beam;
a second wave plate for changing the polarization state of the second laser beam.
11. The laser micro-nano machining system according to claim 1, wherein the micro-moving stage controlled by the computer is a three-dimensional micro-moving stage, and the moving range of the three-dimensional micro-moving stage in x, y and z directions is 1nm-200 mm.
12. The laser micro-nano machining system according to claim 1, comprising:
a pulsed laser for generating a first laser beam having a first wavelength,
a half mirror for splitting the first laser beam into a first laser beam traveling along a first optical path and a second laser beam traveling along a second optical path,
a first reflector, a first shutter, an optical delay assembly, a first lens, a second lens, a first wave plate and a first light gradual change attenuator which are sequentially positioned on the first light path,
a frequency doubling crystal, a filter, a second optical gate, a third lens, a fourth lens, a second wave plate and a second light gradual change attenuator which are positioned on a second light path in sequence,
a dichroic mirror, a second reflecting mirror and an objective lens for focusing the first laser beam and the second laser beam to the same focal point, an
A three-dimensional micro-mobile station controlled by a computer.
13. The laser micro-nano processing system according to claim 1, wherein the photosensitive material is selected from organic photosensitive materials, inorganic photosensitive materials and photosensitive materials containing metal ions.
14. A laser micro-nano machining system according to claim 13, wherein the organic photosensitive material is selected from organic materials capable of photopolymerization, organic materials capable of photolysis, organic materials containing molecules capable of photocrosslinking, and organic materials containing molecules capable of photoisomerization.
15. The laser micro-nano machining system according to claim 13, wherein the inorganic photosensitive material is selected from inorganic materials capable of photopolymerization, inorganic materials capable of photolysis, inorganic materials containing molecules capable of photocrosslinking, inorganic materials containing molecules capable of photoreduction, and inorganic materials containing molecules capable of photooxidation.
16. The laser micro-nano processing system according to claim 13, wherein the photosensitive material containing metal ions is selected from an inorganic material containing metal ions capable of generating molecules for photo-reduction reaction, an organic material containing metal ions capable of generating molecules for photo-reduction reaction, an inorganic material containing molecules capable of generating molecules for photo-oxidation reaction, and an organic material containing molecules capable of generating molecules for photo-oxidation reaction.
17. A laser micro-nano processing method is characterized by comprising the following steps:
adjusting a laser light source, adjusting a first laser beam and a second laser beam output by the laser light source to a first wavelength and a second wavelength which can enable the photosensitive material to be processed to generate a two-photon effect respectively, wherein the pulse widths of the first laser beam and the second laser beam are respectively in a range from nanosecond to femtosecond, and the first wavelength is different from the second wavelength,
adjusting an optical path of the first laser beam or the second laser beam such that a time difference between arrival of the first laser beam and the second laser beam at the photosensitive material is not more than an energy level lifetime of the photosensitive material excited to an excited state,
focusing the first laser beam and the second laser beam to the same focal point, an
And adjusting the micro-moving platform to enable the photosensitive material on the micro-moving platform to be positioned at the focus to carry out micro-nano processing, wherein the repetition frequency of the first laser beam and the second laser beam is 1Hz-100MHz, the wavelength adjusting range is 157nm-1064nm, and the polarization state is linear polarization, circular polarization or elliptical polarization.
18. A laser micro-nano machining method according to claim 17, wherein the focusing the first laser beam and the second laser beam to a same focus further comprises:
expanding the first laser beam and the second laser beam, respectively;
overlapping the expanded first laser beam and the expanded second laser beam to obtain an overlapped laser beam advancing along the same optical path;
and focusing the superposed laser beams to the same focus, and processing the photosensitive material at the focus.
19. The laser micro-nano machining method according to claim 17, further comprising the steps of:
changing exposure times of the first laser beam and the second laser beam by adjusting shutters located on a first laser beam optical path and a second laser beam optical path, respectively; and
the exposure energy of the first laser beam and the second laser beam is changed by adjusting optical attenuators located on the first laser beam optical path and the second laser beam optical path, respectively.
20. A laser micro-nano processing method according to claim 17, characterized in that the exposure time of the first laser beam and the second laser beam is respectively adjusted to 1ms-10min, and the exposure energy of the first laser beam and the second laser beam is respectively adjusted to an average laser power of 0.1 μ W-1W acting on the photosensitive material.
21. A laser micro-nano machining method according to claim 17, characterized in that the photosensitive material is selected from organic photosensitive materials, inorganic photosensitive materials and photosensitive materials containing metal ions.
22. A laser micro-nano machining method according to claim 17, wherein the organic photosensitive material is selected from an organic material capable of performing a photopolymerization reaction, an organic material capable of performing a photodecomposition reaction, an organic material containing a molecule capable of performing a photocrosslinking reaction, and an organic material containing a molecule capable of performing a photoisomerization reaction.
23. A laser micro-nano machining method according to claim 17, wherein the inorganic photosensitive material is selected from an inorganic material capable of photopolymerization, an inorganic material capable of photolysis, an inorganic material containing a molecule capable of photocrosslinking, an inorganic material containing a molecule capable of photoreduction, and an inorganic material containing a molecule capable of photooxidation.
24. The laser micro-nano machining method according to claim 17, wherein the photosensitive material containing metal ions is selected from an inorganic material containing metal ions capable of generating molecules of photo-reduction reaction, an organic material containing metal ions capable of generating molecules of photo-reduction reaction, an inorganic material containing molecules capable of generating molecules of photo-oxidation reaction, and an organic material containing molecules capable of generating molecules of photo-oxidation reaction.
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| CN201010290490.5A CN102000912B (en) | 2010-09-21 | 2010-09-21 | Laser micro-nano machining system and method |
| JP2013528496A JP5814371B2 (en) | 2010-09-21 | 2011-09-15 | Laser micro / nano processing method |
| PCT/CN2011/001567 WO2012037780A1 (en) | 2010-09-21 | 2011-09-15 | Laser micro/nano processing system and method |
| EP19214556.3A EP3650162B1 (en) | 2010-09-21 | 2011-09-15 | Laser micro/nano fabricating system and method of processing a metal ion solution |
| US13/824,634 US9187318B2 (en) | 2010-09-21 | 2011-09-15 | Laser micro/nano processing system and method |
| EP11826307.8A EP2620249B1 (en) | 2010-09-21 | 2011-09-15 | Laser micro/nano processing system and method |
| US14/930,856 US9636777B2 (en) | 2010-09-21 | 2015-11-03 | Laser micro/nano processing system and method |
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