CN104152861A - Method of using applied magnetic field and laser to prepare transparent conductive film - Google Patents
Method of using applied magnetic field and laser to prepare transparent conductive film Download PDFInfo
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- CN104152861A CN104152861A CN201410378095.0A CN201410378095A CN104152861A CN 104152861 A CN104152861 A CN 104152861A CN 201410378095 A CN201410378095 A CN 201410378095A CN 104152861 A CN104152861 A CN 104152861A
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Abstract
The invention provides a method of using an applied magnetic field and laser to prepare a transparent conductive film. The method comprises following steps: TCO (transparent conductive oxide) glass is used as a substrate, and high vacuum DC magnetic control sputtering apparatus is adopted to sputter a metal M layer to acquire an M/TCO transparent conductive film; and the M/TCO transparent conductive film is placed a magnetic field, and the surface of the M/TCO transparent conductive film is subjected to laser irradiation with an ultrashort pulse laser. The thermal effect of the laser irradiation produces an annealing effect on the surface of the M/TCO transparent conductive film to enlarge the grain size of the film, thereby improving the photoelectric property of the film. During the laser irradiation, the magnetic field is applied to attract the metal M layer to enable the crystals on the surface of the film to be more compact and uniform while being recrystallized, thereby effectively promoting the light transmittance and electrical conductivity of the transparent conductive film.
Description
Technical field
The present invention relates to laser micro/nano processing technology and field of semiconductor materials, refer in particular to a kind of method of utilizing externally-applied magnetic field auxiliary laser to prepare transparent conductive film.
Background technology
Because transparent conductive oxide (TCO) film has good electroconductibility, and in visible-range, there are higher light transmission and the advantages such as highly reflective within the scope of infrared light, as window material, are widely used in the field of photoelectric devices such as thin-film solar cells and liquid-crystal display.Yet along with the development of field of photoelectric devices, the photoelectric properties of the transparent conductive film material that these are traditional can not meet far away.
Research shows that transparent conductive film has micro nano surface structure, and as optical grating construction, pyramid structure and honeycomb structure etc., because these structures have the surface that outstanding diversification structure can reduce luminous reflectance, therefore can improve the transmittance of film.Method for the preparation of film surface micro-nano structure mainly contains at present: electron beam lithography, plasma etching method, electrochemical deposition method and nanometer embossing etc.But because these method preparation process are complicated, the cycle is long, have also need to use poisonous and hazardous chemical reagent, often bring preparation efficiency lowly, easily to pollute the series of problems such as bad border.In addition, while adopting these methods to prepare structure of transparent conductive film, controllability is also difficult to guarantee, pattern and the size of products therefrom are inhomogeneous.And laser surface micro-processing technology has that process velocity is fast, environmentally safe and the good advantages such as dimensional controllability, but still very limited for the raising of transparent conductive film optics and electric property.Therefore it is very important, wanting at present simple to operate, efficient a, low cost and the good method of controllability to improve laser processing efficiency.
Summary of the invention
The object of the invention is to overcome the deficiency in prior art, a kind of method of utilizing externally-applied magnetic field auxiliary laser to prepare transparent conductive film is provided, without special gas or liquid as surrounding medium, by magnetic field booster action, improve the crystalline structure of transparent conductive film inside, improve transmittance and electroconductibility.
The present invention realizes above-mentioned technical purpose by following technique means.
Externally-applied magnetic field auxiliary laser is prepared a method for transparent conductive film, it is characterized in that, comprises the following steps:
(1) prepare M/TCO transparent conductive film: take TCO glass as substrate, after ultrasonic cleaning, drying, adopt high vacuum magnetically controlled DC sputtering instrument splash-proofing sputtering metal M layer, wherein sputtering current is 100～150mA, sputtering time is 10～40 seconds, sputter gas is argon gas, and operating pressure is 0.035MPa, obtains M/TCO transparent conductive film;
(2) externally-applied magnetic field auxiliary laser induction M/TCO transparent conductive film: M/TCO transparent conductive film is placed in magnetic field, utilize ultrashort pulse laser, the pulse width of take is less than 20ns, wavelength is 0.50～1.60J/cm at 300～1000nm, laser energy density
2, sweep velocity is 5～30mm/s, and laser irradiation processing is carried out in M/TCO transparent conductive film surface, obtains transparent conductive film.
Further, described in step (1), metal M is Fe, Co, Ni and alloy thereof.
Further, TCO described in step (1) is zinc oxide (ZnO), Indium sesquioxide (In
2o
3), stannic oxide (SnO
2), Al-Doped ZnO (AZO), tin-doped indium oxide (ITO), fluorine doped tin oxide (FTO).
Further, described in step (2), magnetic field is produced by the permanent magnet that is positioned at sample table both sides or bottom.
Further, when laser irradiation described in step (2) is processed, laser beam is done unidirectional by line sweep, and the Duplication of adjacent two sweep traces is controlled at 40～70%.
Further, the surface of M/TCO transparent conductive film described in step (2) lay respectively at before the focus of the laser beam that described laser apparatus sends, three positions after focus or focus.
In the present invention, because the heat effect of laser irradiation has produced annealing effect to M/TCO transparent conductive film surface, grain-size in described film is increased, and then improve the photoelectric properties of film.The sucking action of magnetic field to metal M layer, makes the crystal of described film surface in recrystallization, become finer and close, even simultaneously.And in film, crystal structure degree, compactness and inhomogeneity raising contribute to the raising of film transmittance and electroconductibility more.
The method of preparing transparent conductive film of the present invention has the following advantages:
1) introducing in magnetic field in laser irradiation treating processes, can effectively improve transmittance and the conductivity of transparent conductive film.
2) laser irradiation treating processes is simple to operate, and preparation time is short, controllability good, only needs room temperature condition, in air, just can complete.And do not need to introduce the harsh envrionment conditions such as other special gas or liquid medium.
3) do not need to use any poisonous and corrosive chemical, can effectively reduce environmental pollution.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of permanent magnet placement location embodiment 1 in step (2).
Fig. 2 is the schematic diagram of permanent magnet placement location embodiment 2 in step (2).
Fig. 3 is that sample surfaces is positioned at laser beam different positions schematic diagram.
Fig. 4 is the transmittance spectrogram of prepared transparent conductive film when permanent magnet is placed on different positions in step (2).
Fig. 5 is the SEM figure of untreated Ni/FTO.
Fig. 6 processes the SEM figure of Ni/FTO sample without magnetic field laser irradiation.
Fig. 7 is the SEM figure of embodiment 1 sample in step (2).
Fig. 8 is the SEM figure of embodiment 2 samples in step (2).
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
In the present invention, product transparent conductive film to be prepared is harsher to light transmittance requirement, thus the present invention all to adopt the TCO glass with good transmittance be substrate, described TCO comprises ZnO, In
2o
3, SnO
2and a kind of in doping system AZO, ITO, FTO.Because method of the present invention is utilized laser irradiation processing in additional magnetic field environment, its principle is to utilize the reactive force of magnetic field to magneticmetal, make the crystal of described film surface in recrystallization, become finer and close, even, improve transmittance and electroconductibility, therefore, described metal level M is necessary for magneticmetal, for example Fe, Co, Ni and alloy thereof.
Embodiment 1:
Using FTO glass as substrate, after ultrasonic cleaning, drying, then use high vacuum magnetically controlled DC sputtering instrument sputtering sedimentation Ni layer in FTO substrate of glass, obtain Ni/FTO transparent conductive film.Ni target purity is 99.99%, and sputtering current is 100mA, and sputtering time is 30 seconds, and sputter gas is argon gas, and operating pressure is 0.035MPa.
In the present embodiment, use a block permanent magnet as the generating unit in magnetic field, by permanent magnet be positioned over sample table under, Ni/FTO transparent conductive film is placed in sample table, be positioned at magnet directly over, as shown in Figure 1.Adopt ultrashort pulse laser to take pulsewidth, as 1～2ns, wavelength as the nanosecond laser that 532nm, repetition rate are 1kHz, Ni/FTO transparent conductive film is carried out to laser irradiation processing.
When laser irradiation is processed, the position of adjusting sample table makes the surface of Ni/FTO transparent conductive film be positioned at 2.0mm place after the laser spot after planoconvex lens focuses on, and the position after described laser spot as shown in Figure 3; Control laser energy density is 0.95J/cm
2, sweep velocity is 10mm/s; According to laser energy, determine that the line width of laser beam is 90 μ m, setting accordingly distance between centers of tracks is 40 μ m, and setting each line sweep number of times is 1 time; The motion of control laser beam, makes laser beam scan perpendicular to film surface, scans the whole surface of described Ni/FTO transparent conductive film.The SEM figure of gained sample, as shown in Figure 7.Compare with the SEM figure that processes Ni/FTO sample without magnetic field laser irradiation shown in SEM figure, the Fig. 6 of untreated Ni/FTO shown in Fig. 5, the crystal grain of the sample that the present embodiment is prepared slightly increases, and become finer and close, evenly, this is all very favorable to the raising of the transmittance of film and electroconductibility.
Embodiment 2:
Using FTO glass as substrate, after ultrasonic cleaning, drying, then use high vacuum magnetically controlled DC sputtering instrument sputter Ni layer, Ni target purity is 99.99%, and sputtering current is 100mA, and sputtering time is 30 seconds, and sputter gas is argon gas, and operating pressure is 0.035MPa.Metal Ni is deposited in FTO substrate of glass, obtains Ni/FTO transparent conductive film.
In the present embodiment, use two block permanent magnets as the generating unit in magnetic field, two blocks of magnet are placed on the both sides of sample table, and as shown in Figure 2, Ni/FTO transparent conductive film is placed in sample table, be positioned at the centre of two block permanent magnets.Adopt ultrashort pulse laser to take pulsewidth, as 1～2ns, wavelength as the nanosecond laser that 532nm, repetition rate are 1kHz, Ni/FTO transparent conductive film is carried out to laser irradiation processing.
When laser irradiation is processed, the position of adjusting sample table makes Ni/FTO transparent conductive film surface be positioned at 2.0mm place after the laser spot after planoconvex lens focuses on; Control laser energy density is 0.95J/cm
2, sweep velocity is 10mm/s; According to laser energy, determine that the line width of laser beam is 90 μ m, setting accordingly distance between centers of tracks is 40 μ m, and setting each line sweep number of times is 1 time; The motion of control laser beam, makes laser beam scan perpendicular to film surface, scans the whole surface of described Ni/FTO transparent conductive film.The SEM figure of gained sample, as shown in Figure 8.Compare with the SEM figure that processes Ni/FTO sample without magnetic field laser irradiation shown in SEM figure, the Fig. 6 of the untreated Ni/FTO shown in Fig. 5, the crystal grain of gained sample slightly increases, and become finer and close, evenly, this is all very favorable to the raising of the transmittance of film and electroconductibility.
Fig. 4 is embodiment 1, embodiment 2 and the transmittance spectrogram of assisting the transparent conductive film of processing in situation without magnetic field.As can be seen from Figure 4, under the booster action in magnetic field, no matter sample is directly over magnet or in the middle of two blocks of magnet, and both transmittances are all higher than the sample without processing in the auxiliary situation in magnetic field, this absolutely proves, very important effect has been played in magnetic field in laser processing procedure.
Described embodiment is preferred embodiment of the present invention; but the present invention is not limited to above-mentioned embodiment; in the situation that not deviating from flesh and blood of the present invention, any apparent improvement, replacement or modification that those skilled in the art can make all belong to protection scope of the present invention.
Claims (6)
1. externally-applied magnetic field auxiliary laser is prepared a method for transparent conductive film, it is characterized in that, comprises the following steps:
(1) prepare M/TCO transparent conductive film: take TCO glass as substrate, after ultrasonic cleaning, drying, adopt high vacuum magnetically controlled DC sputtering instrument splash-proofing sputtering metal M layer, wherein sputtering current is 100～150mA, sputtering time is 10～40 seconds, sputter gas is argon gas, and operating pressure is 0.035MPa, obtains M/TCO transparent conductive film;
(2) externally-applied magnetic field auxiliary laser induction M/TCO transparent conductive film: M/TCO transparent conductive film is placed in magnetic field, utilize ultrashort pulse laser, the pulse width of take is less than 20ns, wavelength is 0.50～1.60J/cm at 300～1000nm, laser energy density
2, sweep velocity is 5～30mm/s, and laser irradiation processing is carried out in M/TCO transparent conductive film surface, obtains transparent conductive film.
2. the method for preparing transparent conductive film according to claim 1, is characterized in that, described in step (1), metal M is Fe, Co, Ni and alloy thereof.
3. the method for preparing transparent conductive film according to claim 1, is characterized in that, TCO described in step (1) is zinc oxide (ZnO), Indium sesquioxide (In
2o
3), stannic oxide (SnO
2), a kind of in Al-Doped ZnO (AZO), tin-doped indium oxide (ITO), fluorine doped tin oxide (FTO).
4. the method for preparing transparent conductive film according to claim 1, is characterized in that, described in step (2), magnetic field is produced by the permanent magnet that is positioned at sample table both sides or bottom.
5. the method for preparing transparent conductive film according to claim 1, is characterized in that, when laser irradiation described in step (2) is processed, laser beam is done unidirectional by line sweep, and the Duplication of adjacent two sweep traces is controlled at 40～70%.
6. the method for preparing transparent conductive film according to claim 1, is characterized in that, the surface of M/TCO transparent conductive film described in step (2) is positioned at before the focus of the laser beam that described laser apparatus sends, position after focus or focus.
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Cited By (2)
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| CN105734523A (en) * | 2016-02-24 | 2016-07-06 | 西安工业大学 | Method and device capable of improving laser damage resistance capacity of diamond-like thin film |
| CN110453183A (en) * | 2019-08-01 | 2019-11-15 | 上海理工大学 | Nearly controllable substrate of zero dielectric constant of one kind and preparation method thereof |
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| US20110200414A1 (en) * | 2010-02-12 | 2011-08-18 | Samsung Mobile Display Co., Ltd | Transfer apparatus for cell made organic light-emitting diode display device |
| CN102634754A (en) * | 2011-02-15 | 2012-08-15 | 鸿富锦精密工业（深圳）有限公司 | Coated piece and preparation method thereof |
| CN103606389A (en) * | 2013-10-28 | 2014-02-26 | 中国科学院长春光学精密机械与物理研究所 | Preparation method for high-conductivity inorganic metal-doped multi-layer-structure transparent conductive film |
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2014
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Patent Citations (3)
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| US20110200414A1 (en) * | 2010-02-12 | 2011-08-18 | Samsung Mobile Display Co., Ltd | Transfer apparatus for cell made organic light-emitting diode display device |
| CN102634754A (en) * | 2011-02-15 | 2012-08-15 | 鸿富锦精密工业（深圳）有限公司 | Coated piece and preparation method thereof |
| CN103606389A (en) * | 2013-10-28 | 2014-02-26 | 中国科学院长春光学精密机械与物理研究所 | Preparation method for high-conductivity inorganic metal-doped multi-layer-structure transparent conductive film |
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Cited By (2)
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| CN105734523A (en) * | 2016-02-24 | 2016-07-06 | 西安工业大学 | Method and device capable of improving laser damage resistance capacity of diamond-like thin film |
| CN110453183A (en) * | 2019-08-01 | 2019-11-15 | 上海理工大学 | Nearly controllable substrate of zero dielectric constant of one kind and preparation method thereof |
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