CN103531360A - Sintering method for nanoscale semiconductor porous electrode material on flexible substrate - Google Patents
Sintering method for nanoscale semiconductor porous electrode material on flexible substrate Download PDFInfo
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- CN103531360A CN103531360A CN201310468445.8A CN201310468445A CN103531360A CN 103531360 A CN103531360 A CN 103531360A CN 201310468445 A CN201310468445 A CN 201310468445A CN 103531360 A CN103531360 A CN 103531360A
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Abstract
The invention discloses a sintering method for a nanoscale semiconductor porous electrode material on a flexible substrate. The sintering method comprises the following steps that the flexible substrate is plated with a transparent conducting thin film, the transparent conducting thin film is evenly coated with nanoscale semiconductor particle slurry, and manual or mechanical pressing is performed to form a nanoscale semiconductor thin film; a laser optical path is adjusted by selecting ultrashort pulse laser as a laser source, and is focused within proper depth of the nanoscale semiconductor thin film through an objective; multiphoton absorption ionization occurs in nanoscale semiconductor thin film when the intensity of the ultrashort pulse laser is not smaller than a multiphoton absorption threshold value, and valence band electrons jump to a conduction band to weaken crystal lattices; the surface of the nanoscale semiconductor thin film melts to connect adjacent nanoscale semiconductor particles together; all the nanoscale semiconductor particles are connected together along with the scanning of the focus of the ultrashort pulse laser on the whole nanoscale semiconductor thin film to form a network to realize sintering. According to the sintering method disclosed by the invention, the sintering quality of a nanoscale semiconductor porous electrode is improved, and the influence on the performance of the flexible substrate is avoided.
Description
Technical field
The present invention relates to electrode material sintering technology field, particularly the sintering method of Nano semiconductor porous electrode material in a kind of flexible substrate.
Background technology
It is light that flexible solar battery has quality, and can fold, the advantage such as curling, easy to carry, as long as photoelectric conversion rate reaches application level, market prospects will be very extensive.Nano semiconductor porous film electrode is as one of key components of dye-sensitized solar cells, its structure and performance not only affect absorption, the transmission of incident light in porous membrane of dye sensitizing agent, also bear the instrumentality that light induced electron transmits and shifts in porous membrane.For example, for example, but the thermal endurance that flexible substrate is lower (, the heat resisting temperature of PE plastics is about 150 ℃) has limited sintering (, the nano-TiO of Nano semiconductor porous film electrode
2sintering temperature be 450-500 ℃), therefore, mechanical stability is lower, a little less than being electrically connected to, a little less than being connected, causes cell integrated hydraulic performance decline with substrate between nano particle.
Utilize continuous laser/long pulse Ultra-Violet Laser sintering, can partly improve Nano semiconductor porous film electrode sintering quality, still, it is good not that Nano semiconductor particle connects, and affected electric transmission.This is that penetration depth due to the effect of continuous laser/Long Pulse LASER is about 1 micron, be that laser energy is to absorb in this 1 micrometer depth, and Nano semiconductor particle film thickness is greater than 10 microns, surperficial 1 micron is carried out sintering by thermal diffusion below completely, larger on the impact of flexible substrate.Keep flexible substrate unaffected, must reduce laser energy current density, cause sintering quality not reach desirable effect.
In sum, Nano semiconductor porous film electrode sintering quality becomes the bottleneck that flexible dye-sensitized solar cell performance improves.
Summary of the invention
The invention provides the sintering method of Nano semiconductor porous electrode material in a kind of flexible substrate, the present invention has improved the sintering quality of Nano semiconductor porous film electrode, has avoided the impact on the performance of flexible substrate own, described below:
A sintering method for Nano semiconductor porous electrode material in flexible substrate, said method comprising the steps of:
In flexible substrate, be coated with transparent conductive film, even coated with nano semiconductor grain slurry on conductive film, by hand or the mode of mechanical compaction, forms Nanometer Semiconductor Films;
Select a kind of ultra-short pulse laser that can see through Nanometer Semiconductor Films as lasing light emitter, regulate laser optical path, ultra-short pulse laser is focused in Nanometer Semiconductor Films appropriate depth by object lens, make focal volume cover Nanometer Semiconductor Films and conductive film superficial layer;
When the intensity of ultra-short pulse laser is more than or equal to Multiphoton Absorbtion threshold value, Nanometer Semiconductor Films generation multiphoton absorption ionization, valence band electron transition is to conduction band, and lattice weakens;
Melt on Nanometer Semiconductor Films surface, and adjacent Nano semiconductor particle links together; Along with the scanning of ultra-short pulse laser focus on whole Nanometer Semiconductor Films, all Nano semiconductor particles are coupled together, form network and realized sintering.
The material of described flexible substrate is macromolecular material flexible substrate.
The material of described conductive film is transparent conductive semiconductor film.
Described ultra-short pulse laser is femtosecond pulse or picosecond pulse laser.
The beneficial effect of technical scheme provided by the invention is: the ultra-short pulse laser that the present invention adopts covers on Nano semiconductor particle film and transparent conductive film by object lens, after ultra-short pulse laser intensity is more than or equal to ionization threshold light intensity, by laser scanning, all Nano semiconductor particles are coupled together, form network and realized sintering; This invention has solved the sintering quality problem of Nano semiconductor porous film electrode in flexible substrate, has kept the performance of flexible substrate itself unaffected.
Accompanying drawing explanation
Fig. 1 is the structural representation between each device of adopting of the present invention;
Fig. 2 is flow chart of the present invention.
In accompanying drawing, being listed as follows of each parts:
1: laser beam; 2: object lens;
3: Nano semiconductor particle film; 4: transparent conductive film;
5: flexible substrate.
Embodiment
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing, embodiment of the present invention is described further in detail.
In order to improve the sintering quality of Nano semiconductor porous film electrode, avoid the impact on the performance of flexible substrate own, the embodiment of the present invention provides the sintering method of Nano semiconductor porous electrode material in a kind of flexible substrate, referring to Fig. 1 and Fig. 2, described below:
The light intensity at ultrashort pulse (pulse duration is less than 1 psec) laser spot place is high, can realize Multiphoton Absorbtion, and therefore, ultra-short pulse laser can enter transparent material inside, at focus place, carries out laser treatment.And the laser action time is short, heat affected area is little.In general, the heat accumulation effect of laser action, with laser pulse repetition rates, increase, heat affected area scope is also larger, but, when interpulse period, shortening to also short to required time of focus outdiffusion than laser heat action time, laser heat action only occurs in focal volume, that is to say, high-repetition-rate does not aggravate thermal diffusion.High-repetition-rate (being greater than 1MHz) femtosecond laser, shows as and take heat accumulation effect as main, greatly reduces laser processing required pulse energy, has effectively reduced heat affected area scope.Compare with Long Pulse LASER sintering technology, the required laser energy current density of high-repetition-rate femtosecond laser is lower, and thermal-diffusion length is shorter.
In addition, due to thermal coupling time (being typically several psecs) of electronics and lattice pulse duration much larger than ultra-short pulse laser, electronics does not have time enough that the energy absorbing is transferred to lattice, when laser energy current density is greater than semiconductor material surface damage threshold, valence band electronics is excited, transit to conduction band, weakened the chemical bond of lattice atoms, cause surface that ultrafast fusing occurs, this fusing just occurs in nano grain surface, do not damage granule interior, can realize the connection between nano particle.When forming good connection between nano particle, the existence of heat affected area also can strengthen being connected of the particle porous film of this Nano semiconductor and transparent conductive film in flexible substrate.
Therefore, high-repetition-rate femtosecond laser sintering, can realize the connection of Nano semiconductor particle, and the quality of the lower sintering that reaches a high temperature has realized again the good bonding with substrate, and kept flexible substrate unaffected.
101: in flexible substrate, be coated with transparent conductive film, even coated with nano semiconductor grain slurry on conductive film, by hand or the mode of mechanical compaction, forms certain thickness Nanometer Semiconductor Films;
Wherein, in order to improve the effect of sintering, this flexible substrate is preferably PET macromolecular material flexible substrate.The thickness of semiconductive thin film determines according to the needs in practical application, and the embodiment of the present invention does not limit this.
For example, at PET(PETG) flexible substrate be coated with on tin indium oxide (ITO) conductive film evenly coated with nano semiconductor grain slurry, naturally dry, then through 100 ℃ of oven dry 30min, formed certain thickness Nanometer Semiconductor Films.
102: select a kind of ultra-short pulse laser that can see through Nanometer Semiconductor Films as lasing light emitter, regulate laser optical path, ultra-short pulse laser is focused in Nanometer Semiconductor Films appropriate depth by object lens, make focal volume cover Nanometer Semiconductor Films and conductive film superficial layer;
Wherein, because making ultra-short pulse laser effect, the effect of ultra-short pulse laser accumulation is only confined near scope focus center.
103: when the intensity of ultra-short pulse laser is more than or equal to Multiphoton Absorbtion threshold value, Nanometer Semiconductor Films generation multiphoton absorption ionization, valence band electron transition is to conduction band, and lattice weakens;
104: weakened the chemical bond of lattice atoms, caused Nanometer Semiconductor Films surface to be melted, adjacent Nano semiconductor particle (and the transparent conductive film in nano particle and flexible substrate) links together; Along with the scanning of ultra-short pulse laser focus on whole Nanometer Semiconductor Films, all Nano semiconductor particles (and in flexible substrate transparent conductive film) are coupled together, form network and realized sintering.
During specific implementation, according to the Nano semiconductor particle in practical application, need to determine the power of laser, it is femtosecond or picosecond level that ultra-short pulse laser is chosen pulse duration conventionally, can be both femtosecond pulse or picosecond pulse laser, and the embodiment of the present invention does not limit this.
The specific operation process of the method is described with specific embodiment below:
First, to being coated with PET (PETG) flexible substrate of tin indium oxide (ITO) transparent conductive film, clean; Then, the nano-TiO that preparation mass ratio is 20%
2particle (diameter 10～30 nanometers) alcohol suspending liquid, electromagnetic agitation 2h, forms slurries, and slurries are evenly coated on tin indium oxide (ITO) conductive film, and by operation skill in using a kitchen knife in cookery film forming, thickness is 10～15 microns; Secondly, adopting pulse duration is that 1～100 femtosecond, repetition rate are that 2～50.0MHz, power are that 1～20W, the wavelength femtosecond amplifier that is 1040nm is as lasing light emitter; Making femtosecond pulse is that 0.05～0.20 object lens 5 focus on nano-TiO by numerical aperture
2in semiconductive thin film, in appropriate depth, make focal volume cover nano-TiO
2semiconductive thin film and conductive film superficial layer below.When femtosecond pulse intensity is more than or equal to the multiphoton absorption ionization threshold value light intensity of Nanometer Semiconductor Films, near Nano semiconductor particle surface generation multiphoton absorption ionization focus center, valence band electron transition is to conduction band, weakened the chemical bond of lattice atoms, cause the fusing of surface electronic, by adjacent nano-TiO
2particle, and nano-TiO
2particle and electric conductive oxidation indium tin thin film link together.Along with laser scans with suitable speed, whole nano-TiO
2nano particle in film (and indium tin oxide films) links together.
It will be appreciated by those skilled in the art that accompanying drawing is the schematic diagram of a preferred embodiment, the invention described above embodiment sequence number, just to describing, does not represent the quality of embodiment.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. a sintering method for Nano semiconductor porous electrode material in flexible substrate, is characterized in that, said method comprising the steps of:
In flexible substrate, be coated with transparent conductive film, even coated with nano semiconductor grain slurry on conductive film, by hand or the mode of mechanical compaction, forms Nanometer Semiconductor Films;
Select a kind of ultra-short pulse laser that can see through Nanometer Semiconductor Films as lasing light emitter, regulate laser optical path, ultra-short pulse laser is focused in Nanometer Semiconductor Films appropriate depth by object lens, make focal volume cover Nanometer Semiconductor Films and conductive film superficial layer;
When the intensity of ultra-short pulse laser is more than or equal to Multiphoton Absorbtion threshold value, Nanometer Semiconductor Films generation multiphoton absorption ionization, valence band electron transition is to conduction band, and lattice weakens;
Melt on Nanometer Semiconductor Films surface, and adjacent Nano semiconductor particle links together; Along with the scanning of ultra-short pulse laser focus on whole Nanometer Semiconductor Films, all Nano semiconductor particles are coupled together, form network and realized sintering.
2. the sintering method of Nano semiconductor porous electrode material in a kind of flexible substrate according to claim 1, is characterized in that, the material of described flexible substrate is macromolecular material flexible substrate.
3. the sintering method of Nano semiconductor porous electrode material in a kind of flexible substrate according to claim 1, is characterized in that, the material of described conductive film is transparent semiconductor conductive film.
4. the sintering method of Nano semiconductor porous electrode material in a kind of flexible substrate according to claim 1, is characterized in that, described ultra-short pulse laser is femtosecond pulse or picosecond pulse laser.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336399A (en) * | 2018-02-08 | 2018-07-27 | 天津瑞晟晖能科技有限公司 | Solid electrolyte film and preparation method thereof and secondary cell and preparation method thereof |
| CN108365173A (en) * | 2018-02-08 | 2018-08-03 | 天津瑞晟晖能科技有限公司 | Electrode for secondary battery and preparation method thereof and secondary cell and preparation method thereof |
| CN108598562A (en) * | 2018-03-27 | 2018-09-28 | 电子科技大学 | A kind of heat treatment method and lithium cell structure of solid electrolyte film |
| CN115260567A (en) * | 2022-08-24 | 2022-11-01 | 天津大学 | Preparation method of micron/nano-pore polymer film |
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| CN102013332A (en) * | 2010-11-24 | 2011-04-13 | 华中科技大学 | Method and device for preparing photo anode in flexible solar cell through selective laser sintering |
| CN102601522A (en) * | 2012-03-30 | 2012-07-25 | 天津大学 | Method for assisting supercritical fluid in micromachining of high polymer materials through femtosecond laser |
| CN103085274A (en) * | 2013-01-09 | 2013-05-08 | 天津大学 | Method for welding glass fiber cloth |
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Patent Citations (3)
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| CN102013332A (en) * | 2010-11-24 | 2011-04-13 | 华中科技大学 | Method and device for preparing photo anode in flexible solar cell through selective laser sintering |
| CN102601522A (en) * | 2012-03-30 | 2012-07-25 | 天津大学 | Method for assisting supercritical fluid in micromachining of high polymer materials through femtosecond laser |
| CN103085274A (en) * | 2013-01-09 | 2013-05-08 | 天津大学 | Method for welding glass fiber cloth |
Non-Patent Citations (1)
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| 贾威等: "飞秒激光在材料微加工中的应用", 《量子电子学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108336399A (en) * | 2018-02-08 | 2018-07-27 | 天津瑞晟晖能科技有限公司 | Solid electrolyte film and preparation method thereof and secondary cell and preparation method thereof |
| CN108365173A (en) * | 2018-02-08 | 2018-08-03 | 天津瑞晟晖能科技有限公司 | Electrode for secondary battery and preparation method thereof and secondary cell and preparation method thereof |
| CN108598562A (en) * | 2018-03-27 | 2018-09-28 | 电子科技大学 | A kind of heat treatment method and lithium cell structure of solid electrolyte film |
| CN115260567A (en) * | 2022-08-24 | 2022-11-01 | 天津大学 | Preparation method of micron/nano-pore polymer film |
| CN115260567B (en) * | 2022-08-24 | 2023-05-05 | 天津大学 | Method for preparing micrometer/nanometer pore polymer film |
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