Method for nanopatterning surface of dielectric substrate using near-field lithography

FIELD: physics.

SUBSTANCE: method includes forming a near-field mask on the surface of a dielectric substrate and irradiating the obtained structure with a femtosecond laser pulse. The laser radiation is first passed through a nonlinear optical crystal with a coefficient of transformation into a second harmonic equal to 5-7%. The dielectric substrate coated with the near-field mask is irradiated with the obtained bichromatic femtosecond pulse with energy density in the range of 25-40 mJ/cm2, which is less than the laser radiation energy density normally used in similar nanopatterning.

EFFECT: high resolution and low laser radiation energy consumption.

6 dwg

 

The invention relates to methods of laser nanostructuring of surfaces using an ordered array collects microscopic lenses (dielectric micron-sized beads), forming the peaks of the intensity distribution of the laser field, where the formation of structures with a scale less than the wavelength of the source radiation used. The method may be used to create ordered structures on the surface of the dielectric substrates of large area per one pulse of laser radiation. Manufactured elements with said structures can be used to nanometrology, filtering, recording, and conversion of optical signals, texturing materials as substrates in the catalytic processes.

If you create an array of structures immediately on large surface nanostructuring with laser-assisted has significant advantages compared to electron beams, which are preferred when creating individual nano-objects on a solid surface. There are two basic approaches to laser nanostructuring of the surface over large areas, is the use of the interference of laser beams and structuring using near-field masks, i.e. masks, working in near-field diffraction. If it �children on the modification of solid surfaces with femtosecond laser pulses, the second approach is preferred because such pulses interfere badly on large areas. The simplest form of a near-field mask is a layer of dielectric microparticles (microlenses). Typically, such a layer is applied to the surface of the material from the colloidal solution and forms a dense packing in the process of self-organization. Layers of colloidal particles deposited on the surface of a solid body, used for surface nanostructuring with laser radiation. This method nanomodifikatsii surface (sometimes referred to as laser Nanosphere lithography) devoted a number of works published in the literature [1-5], including with the participation of the authors of the invention [6-9].

On the other hand, in the literature there is considerable discussion about the possibility of increasing the efficiency of the influence of femtosecond laser pulse with matter by changing the shape of the pulse at the expense of spectral phase modulation [10-12]. When this high-frequency portion is located on the front edge, providing an efficient multiphoton ionization, while the low-frequency portion is quite effective for impact ionization.

Among patent documents to a method of laser nanostructuring of solid surfaces using near-field system mi�Rollins closest bid US 20030129545 "Method and apparatus for use of plasmon printing in near-field lithography", IPC G03F 7/00, B82Y, publ. 10.07.2003 in which to structure the surface as microlenses used metal nanoparticles irradiated with a laser beam with a wavelength in the region of their plasmon resonance. The disadvantages of this method is that the metal nanoparticles are not arranged on the surface of the substrate, and that the plasmon resonance imposes restrictions on the wavelength of the laser radiation to irradiate the near-field system of microlenses.

As a prototype the selected method of laser nanostructuring of the surface of a dielectric substrate using near-field lithography, described in work [1]. In the prototype we treat the production of structures with a characteristic scale (diameter) of 100 nm, which is 2/5 of the used wavelength of the laser radiation of the excimer laser (248 nm) laser beams are monochromatic. Prototype method is that initially, on the surface of a dielectric substrate form a near-field mask as a layer of silica beads with a diameter of 0.5 μm, and then irradiated structure formed by nanosecond pulse laser, receiving the ordered structure of the relief on a dielectric substrate with a characteristic size of 100 nm. The energy density of incident laser pulse is 340 MJ/cm2.

Lack�Adami of the prototype method are the low resolution (the size of the structures is 2/5 of the used wavelength) and the need to use laser radiation with high energy density (340 MJ/cm 2).

The problem solved by the present invention is to provide a method of obtaining an ordered nanoscale structures on the surface of a dielectric substrate of a large area by using near-field lithography, providing better resolution at lower energy density of the laser radiation.

The technical result in the proposed method is achieved by the fact that in it, as in the prototype method of nanostructuring the surface of a dielectric substrate using near-field lithography, initially form a near-field mask on the surface of the dielectric substrate and is irradiated with the pulse structure of the laser.

New in the present invention is that use of the femtosecond laser pulse, which is previously passed through a nonlinear optical crystal with a conversion rate of 5÷7% second harmonic radiation of a femtosecond laser, after which the irradiation of a dielectric substrate coated with a near-field mask is carried out obtained bichromatic femtosecond pulse with energy density in the range 25÷40 MJ/cm2that is less commonly used energy density of the laser radiation under similar nanostructuring of the surface.

As established by the authors of the present invention, the second accordion�radiation of the femtosecond laser is more effective when multiphoton ionization, what is the fundamental frequency, which, in turn, is effective in the process of multiplying the number of free electrons in the process of impact ionization. The authors have shown that the radiation of the second harmonic is better focused by a system of balls (microlenses). This may explain the decrease in the threshold of the modifications of substances and the decrease of the transverse size of the resulting structures (up to 1/7 of the wavelength of the used radiation at the fundamental frequency), i.e., improves the resolution of the method at lower energy density of the laser radiation.

The invention is illustrated by drawings.

Fig.1 is a schematic diagram of the proposed method.

Fig.2 shows a micrograph of spaced domains of ordered microspheres (near-field mask), obtained with an optical microscope Neophot 30 with magnification ×1000. In the box presents the diffraction pattern of the laser beam at the domain by using radiation at a wavelength of 532 nm. The symmetrical structure of the diffraction pattern corresponds to the hexagonal structure of ordered microspheres.

Fig.3 presents applied by the authors of the variant of the optical scheme of the setup for nanostructuring of dielectric substrate coated with an ordered monolayer of microparticles (near-field mask).

Fig.4 shows an image of nanostructure�agreed the surface of the dielectric substrate, obtained with a scanning probe microscope Solver Pro company NT-MDT. For research shows the profile of the formed nanostructures were used-sectional surface in straight lines.

Fig.5 presents the relative frequency distribution of diameters of nanostructures (full width (FWHM) at different conditions of irradiation of the substrate with pulses of the fundamental frequency (PTS), second harmonic (SH) and bichromatic (VE+VG) pulses.

Fig.6 presents the results of calculations of the distribution of the module of the amplitude of the electric field in the incident wave, |E|2near microspheres of polystyrene (n=1,59) on the substrate made of glass (n=1.46 in) when exposed to a normally incident plane wave, linearly polarized along the coordinate x. the Diameter of the ball is made of polystyrene 1 ám, the incident wave length of 800 nm (a, b, e) and 400 nm (b, g, e). The cases correspond to the cases: single bulb (a, b), hexagonal close-Packed-symmetric cluster of seven microspheres (b, g), and endless close-Packed monolayer (d, e). Distribution normalized to the value of the field in the incident wave.

On the concept of implementing the proposed method (see Fig.1) shows the bichromatic irradiation pulse 1 high-power femtosecond laser located on a structured substrate 2 microsc�microscopic dielectric balls forming a near-field mask 3. Structuring occurs under the centers of the balls directly to the substrate material 2 depending on the conditions in the form of a convex formations or cavities.

A variant of the device for implementing the proposed method, shown in Fig.3, comprises a substrate 2 formed on its surface near-field mask 3. The substrate 2 with the mask 3 is provided on the optical three-axis table 4 to change the position of the irradiated region on the substrate 2. Focusing of femtosecond laser radiation is plane-convex lens 5 with a focal length of 15 cm To obtain a bichromatic radiation 1 applies a thin (100 μm) nonlinear optical crystal 6 beta-barium borate (BBO), which is used for generating the 2nd harmonic (or indeed of the 2nd type) with a conversion rate of 5÷7% second harmonic radiation of the femtosecond laser. The orientation of the crystal 6 was varied to change the conversion efficiency (synchronism). For setting up and quality control of a laser beam is applied to the screen 7. Radiation 1 using a system of mirrors 8 with a high reflection coefficient comes from the complex femtosecond laser. Complex femtosecond laser includes a generator of femtosecond laser pulses with 10 laser pumped by a 1 manufactured by Spectra-Physics. Subsequent amplification of laser pulses occurs in the amplifier 12 with a laser-pumped 13 manufactured by Spectra-Physics. To control the laser output power is used, the optical power meter roaming scheme adopted by detector 9. For nanostructuring the surface of the dielectric substrate 2 laser system was used in the regime of single pulses was controlled by computer 14. The pulse duration was 50 femtoseconds (FS), the pulse energy was about 1.7 MJ, Central wavelength was 800 nm, the beam diameter was 7 mm. Blue glass filter 15 is used to select the radiation at the wavelength of 400 nm.

By using the device shown in Fig.3, the inventive method of nanostructuring the surface of the dielectric substrate 2 using near-field lithography as follows.

First of all, on a dielectric substrate 2, prepare the close-Packed monolayer of polystyrene microspheres with a diameter of 1 μm, which form a near-field mask 3 (see Fig.1, 2, 3). Then using the complex femtosecond laser and the nonlinear optical crystal 6 beta-barium borate (BBO) form a bichromatic pulse 1, most of the energy which falls on the fundamental frequency of the laser radiation, and a small proportion ene�GII - for the second harmonic. Then the irradiation of the dielectric substrate 2 with the applied near-field mask 3 is carried out obtained bichromatic femtosecond pulse 1 with energy density in the range 25÷40 MJ/cm2that is less commonly used energy density of the laser radiation under similar nanostructuring of the surface.

Irradiation of the dielectric substrate 2 with the applied near-field mask 3 bichromatic femtosecond pulse with 1 total energy density in the range 25÷40 MJ/cm2leads to the formation of periodic nanostructures, consisting of ablation craters or hillocks depending on the irradiation conditions, for example depending on the material of the irradiated substrate.

Essentially, a simple method of increasing sensitivity and resolution of one of the main methods of laser nanostructuring of the surface of a dielectric substrate by using laser pulses, which allowed to solve the task, i.e. to obtain the best resolution (the minimum size of nanostructures comprise 1/7 of the wavelength of the radiation used instead of 2/5 of the radiation wavelength in the implementation of the prototype method) at lower energy density (bichromatic irradiation of femtosecond pulse 1 was carried out with the total energy density � the range 25÷40 MJ/cm 2instead of 340 MJ/cm2declared in the prototype method in [1]).

In particular examples, the realization of the specimen substrate 2 was irradiated single femtosecond pulses of the fundamental frequency (PTS), second harmonic (SH) and bichromatic (VE+VG) pulses 1. Crystal 6 was placed behind the lens 5 to avoid time division PTS and SH pulses. Blue glass filter 15 (optical thickness And400<0.02, A800>20) of 3 mm thickness was used to select the radiation SH. Falling energy density in the laser spot was varied by moving the substrate 2 along the axis of the focused beam. Atomic force microscope was used for surface analysis.

When the energy density per pulse was increased above a certain threshold, the balls of the near-field mask 3 flew from the surface of the dielectric substrate 2 irradiated area. With increasing energy density by 15% against the threshold of the fly balls were obtained nanostructures are of good quality. On substrates of poly (methyl methacrylate) (PMMA) were ablative craters (see Fig.4), and on glass substrates that were hillocks. For glass substrates the threshold of the departure of balls and consequently the energy density required for the formation of structures, was almost two times lower than in the case of bichromatic irradiation beam 1 compared to obleceni�bunch of PTS. For PMMA substrates, this difference was even greater. In both cases, the energy density per pulse required for the formation of structures of the bichromatic pulse was less significant than the energy density required for laser cleaning when exposed to a pulse PTS.

The addition of VG leads to the formation of more localized structures on glass and PMMA substrates with a diameter of ablation craters of the order of 100 nm. The results of statistical processing shown in Fig.5, indicate that when irradiated PMMA bichromatic pulse and only the momentum of the SH get the craters of similar diameter, and this diameter is smaller than in the case of irradiation with one pulse PTS. If we filter out the fundamental frequency and only use GV patterns appear only if the sample stood parallel and closer to the focus of the beam than in the case when the patterns are observed when exposed to a bichromatic pulse 1. This displacement of the sample indicates that the threshold energy density when exposed to only the SH several times higher than the partial energy density of SH in the bichromatic beam at the threshold of formation of structures. This means that the fundamental frequency (PTS) in bichromatic pulse makes a significant contribution to the process of surface modification.

The authors suggested that the surface modification was �through ionization. Second harmonic is more effective when multiphoton ionization than the fundamental frequency, which, in turn, is effective in the process of multiplying the number of free electrons in the process of impact ionization. This leads to a decrease of the threshold modification substances. The radiation of the second harmonic is better focused by a system of balls near-field mask 3. This can explain the decrease of the transverse size of the resulting structures during the transition to bichromatic irradiation.

Thus, the presented method of nanostructuring of solid surfaces, such as polymers and glass by a femtosecond laser pulse through a layer of colloidal particles as a near-field mask. We are talking about single-pulse exposure to high-power femtosecond laser. The fundamental frequency of these lasers is in the near-infrared range. A typical example is the laser on sapphire from titanium with a wavelength of about 800 nm. The authors experimentally confirmed that the conversion of the energy of the initial laser pulse second harmonic by using a nonlinear crystal 6, the use of bichromatic pulses leads to the decrease of the threshold of laser nanostructuring about two times and to reduce the transverse dimensions of elementary structures of the relief, such as ablative craters in sluchivsheisya on polymers. The radius of the craters when exposed bichromatic pulses was 30% less than when exposed to radiation of the fundamental frequency, with an absolute value less than 100 nm. In the experiment we used pulses with energy of 1.7 MJ, the second harmonic was converted 5% of the radiation energy of the fundamental frequency.

Modification of the surface (ablation, swelling) at intensities corresponding to the threshold modification occurs through ionization. Thus the second harmonic is more effective when multiphoton ionization, i.e. it is more effective than radiation of the fundamental frequency, creates a source of electrons in the conduction band, while the radiation of the fundamental frequency effectively with impact ionization, leading to the multiplication of the number of initial electrons. Thus, second harmonic creates the seeds for the formation of structures, while the radiation of the fundamental frequency is used for energy impact. The authors have shown that the radiation of the second harmonic is better focused by a system of colloidal particles (near-field mask 3) than the radiation of the fundamental frequency. The calculations were performed for cases of irradiation plane monochromatic wave at wavelengths of 800 nm (the fundamental frequency of the laser on sapphire with titanium) and 400 nm (second harmonic). The results of calculations (see Fig.6) show that for the three rassmotren�x cases: single bulb, close-Packed hexagonal symmetric cluster of seven microspheres and endless close-Packed monolayer of second harmonic is better focused by a system of balls (near-field mask 3) than the radiation of the fundamental frequency. In addition, in the case of the ball in the final cluster, and in the case of infinite monolayer noticeable influence of collective effects on the focusing - intensity reduction and the formation of long focus. The calculation was carried out by the finite-difference time-domain (the conventional designation method FDTD) with a drill grid spacing of 10 nm. To simulate an infinite monolayer of microspheres applied periodic boundary conditions in the directions x and y (Fig.1). As the seed radiation of the second harmonic is better focused by a layer of microparticles, near the threshold impact localization bichromatic radiation corresponds to the location of the second harmonic.

Thus, the authors have proved that the conversion of some part of the pulse energy of the fundamental frequency of the femtosecond laser radiation into the second harmonic gives the best resolution in the fabrication of ordered nanostructures on the surface of the dielectric substrate at a lower energy density of the laser radiation.

References

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2. Langer G., Brodoceanu D., and D. Bauerle Appl. Phys. Lett. 89, 261104 (2006).

3. Wu W., A. Katsnelson, O. G. Memis, and H. Mohseni Nanotechnology 18, 485302 (2007).

4. Khan A., Wang, Z. V., M. A. Sheikh, D. J. Whitehead, L. and Li Appl. Surf. Sci. 258, 774 (2011).

5. Chong T. C., Hong M. H., and Shi L. P. Laser Photon. Rev. 4, 123 (2010).

6. Pikulin A., Bityurin N., Langer G., Brodoceanu D., and D. Bäuerle Appl. Phys. Lett. 91, 191106 (2007).

7. Pikulin A., Afanasiev A., Agareva N., A. P. Alexandrov, V. Bredikhin, and N. Bityurin Optics Express 20, 9052, (2012).

8. H. M. bityurin Quantum electronics, 40, 955 (2010).

9. Bityurin N., Afanasiev A., Bredikhin V., Alexandrov A., Agareva N., A. Pikulin, Ilyakov I., Shishkin V., and Akhmedzhanov R., Optics Express, 21, 21485 (2013).

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12. Englert L., M. Wollenhaupt, C. Sarpe, Otto D., and T. Baumert J. Laser Appl. 24, 042002 (2012).

Method of nanostructuring the surface of a dielectric substrate using near-field lithography, which includes the formation of a near-field mask on the surface of a dielectric substrate and radiation patterns obtained by the laser pulse, characterized in that the use of the femtosecond laser pulse, which is previously passed through a nonlinear optical crystal with a conversion rate of 5÷7% second harmonic radiation of a femtosecond laser, after which the irradiation of a dielectric substrate coated with a near-field mask is carried out obtained bichromatic�Kim femtosecond pulse with energy density in the range 25÷40 MJ/cm 2that is less commonly used energy density of the laser radiation under similar surface nanostructuring.



 

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5 cl, 4 dwg

FIELD: physics.

SUBSTANCE: drawing is converted to raster in digital form and information on the amplitude and phase, characterising each raster point, is recorded. The required parameters of elements of the hologram are calculated, for which elements of the digital raster of the image of the drawing are converted to digital raster of the future hologram. A diffraction pattern is calculated at each point of the future hologram. An interference pattern resulting from interaction of the calculated diffraction pattern with the calculated wave front from a virtual reference radiation source is calculated. The transmission function of the hologram is calculated and regions are selected therein, which, after binarisation, yield transparent elements of an unallowable small size, which physically do not transmit light, after which the transmission function is changed to increase the size of said elements. The result is used to form a diffraction structure of the hologram on a carrier and the hologram is created in the form of a set of transparent discrete elements in an opaque layer deposited on a transparent substrate. Optical correction of the enlarged elements is performed to allow the enlarged elements to transmit an amount of light according to the primary transmission function. Correction is performed by placing on the opaque layer a layer of absorbent substance with a known absorption coefficient for the image reconstructing radiation, and the region over the non-enlarged elements is made transparent.

EFFECT: obtaining a drawing with improved process parameters, high contrast of the obtained drawing and low noise level.

13 cl

FIELD: radio engineering, communication.

SUBSTANCE: invention relates to electronics and a method of forming a channel for transmitting an optical signal between electronic modules on one printed-circuit board. The method employs a head which contains a transparent polymer, placing a photoresist over a suitable area on the head and applying a die on said area. UV radiation exposure is carried out through the transparent mask of the die and the outer surface of the optical path of the hardened photoresist is coated with a light-reflecting metal layer by sputtering.

EFFECT: simple method of forming a channel and improved performance of products.

5 dwg

FIELD: physics, optics.

SUBSTANCE: invention relates to the field of optical instrument making and the method of image recording. The method includes formation of a light sensitive layer on a substrate from nanodiamond film and radiation of a nanodiamond film with focused radiation of laser according to the specified program with the purpose to produce a required image. The image on the nanodiamond film arises due to blackening of radiated sections of the film as a result of conversion of nanodiamond particles into amorphous carbon in the field of focused laser radiation.

EFFECT: technical result consists in simplification of the recording method and reduction of power inputs.

3 cl, 3 dwg

Information carrier // 2533821

FIELD: chemistry.

SUBSTANCE: invention relates to information carriers. Claimed is an information carrier, successively including a substrate, selected from a polymer-covered paper, synthetic paper and plastic films, the first ink-receiving layer and the second ink-receiving layer, with the ink-receiving layer containing at least one substance, selected from aluminium oxide, aluminium oxide hydrate and highly dispersive silicon oxide, polyvinyl alcohol and boric acid, with a weight ratio of the boric acid and polyvinyl alcohol content in the first ink-receiving layer constituting 2.0 wt % or more and 7.9 wt % or less, with the second ink-receiving layer containing highly-dispersive silicon dioxide, polyvinyl alcohol and boric acid, and a weight ratio of the boric acid and polyvinyl alcohol content in the second ink-receiving layer constitutes 10.0 wt % or more and 30.0 wt % or less.

EFFECT: claimed carrier makes it possible to prevent cracking after the application of ink-receiving layers, possesses the high ink-absorbing ability and a resistance to cracking in bending.

6 cl, 4 tbl, 68 ex

FIELD: physics.

SUBSTANCE: disclosed is a light-sensitive negative polymer composition comprising (a) an epoxy group-containing compound, (b) a first onium salt containing a structure of a cationic part of formula (b1) , and a structure of an anionic part of formula (b2) , and (c) a second onium salt containing a structure of a cationic part of formula (c1) , and a structure of an anionic part of formula (c2) . The invention also discloses a thin structure obtained from said composition and a method for making said thin structure, as well as a liquid ejector head in which said thin structure is used.

EFFECT: composition reduces variability and provides excellent reproducibility of a three-dimensional shape when using a photolithographic process.

11 cl, 5 dwg, 1 tbl, 12 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a polyurethane composition for producing holographic media, which includes: (A) a polyisocyanate component containing at least one polyurethane prepolymer with a terminal isocyanate group with isocyanate group functionality of 1.9-5.0, for which the isocyanate group is attached to a primary aliphatic residue and which is based on compounds with hydroxyl functional groups with hydroxyl group functionality of 1.6-2.05, (B) polyether polyols which react with isocyanates, (C) urethane acrylates and/or urethane methacrylates with at least one aromatic structural unit and with a refraction index greater than 1.50 at 405 nm, which are free of isocyanate groups and hydroxyl groups, (D) radical stabilisers, (E) photoinitators based on combinations of borate salts and one or more dyes with absorption bands which at least partially overlap the spectral region from 400 to 800 nm, (F) optionally catalyst and (G) optionally auxiliary substances and additives. The invention also describes a method of producing media for recording visual holograms, media for recording visual holograms, use of such a medium and a method of recording holograms.

EFFECT: producing polyurethane compositions for producing holographic media having high surface quality, good processing properties and good contrast with respect to refraction index.

14 cl, 2 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for hydroconversion of heavy oil fractions - feed stock, the method including a zero step and subsequent N steps. The zero step includes feeding, into a reactor, material, a catalyst precursor - aqueous solution of a Mo (VI) salt or salts of Mo and Ni, and hydrogen at pressure of 4-9 MPa under normal conditions; reacting the material and hydrogen at 420-450°C in the presence of a precursor of a suspended nanosize molybdenum or molybdenum-nickel catalyst formed in the reactor; atmospheric or atmospheric-vacuum distillation of the hydrogenation product; removing the low-boiling fraction with a boiling point not higher than 500°C as a product and returning the high-boiling fraction or part thereof into the reactor. The next steps include feeding, into the reactor, material, a catalyst precursor, the returned part of the high-boiling fraction and hydrogen; reaction thereof; said atmospheric distillation of the hydrogenation product; removing the low-boiling fraction as a product; returning part of the high-boiling fraction into the reactor; burning at 1000-1300°C or gasification of the remaining part of the high-boiling fraction, after which trapped ash-slag residues are subjected to further oxidising burning at 800-900°C and the obtained ash product, which is carbon-free, is used to regenerate the catalyst precursor and produce an industrial concentrate of vanadium and nickel. The number of steps N is determined using formulae: bd(nn+nm+1)=a+i=1nmbi+benm, N=nn+nm+1, where nn is the number of steps with recirculation, after which equilibrium output of the low-boiling fractions is achieved; nm is the number of steps with recirculation after achieving equilibrium output of the low-boiling fractions, which enables to achieve a given output of low-boiling fractions from the feed stock; bd is the given output of low-boiling fractions, wt %; a is the output of low-boiling fractions at the zero step, wt %; bi is the output of low-boiling fractions at the i-th step before achieving equilibrium, wt %; be is the output of low-boiling fractions after achieving equilibrium, wt %, be>bd.

EFFECT: high output of low-boiling fractions, low molybdenum consumption, high degree of extraction of molybdenum, vanadium and nickel from the solution, enabling calculation of the required reactor volume, obtaining an industrial concentrate of vanadium and nickel, low hydrogen consumption.

3 cl, 1 dwg, 2 tbl, 2 ex

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