CN113223969A - Ultrafast laser annealing technology of flexible p/n type semiconductor - Google Patents

Ultrafast laser annealing technology of flexible p/n type semiconductor Download PDF

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Publication number
CN113223969A
CN113223969A CN202110443539.4A CN202110443539A CN113223969A CN 113223969 A CN113223969 A CN 113223969A CN 202110443539 A CN202110443539 A CN 202110443539A CN 113223969 A CN113223969 A CN 113223969A
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China
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flexible
flexible substrate
type semiconductor
laser annealing
annealing technique
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王学文
陈襄玉
柴年垚
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/34—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies not provided for in groups H01L21/0405, H01L21/0445, H01L21/06, H01L21/16 and H01L21/18 with or without impurities, e.g. doping materials
    • H01L21/42—Bombardment with radiation
    • H01L21/423—Bombardment with radiation with high-energy radiation
    • H01L21/428—Bombardment with radiation with high-energy radiation using electromagnetic radiation, e.g. laser radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring

Abstract

The invention discloses an ultrafast laser annealing technology of a flexible p/n type semiconductor, which is characterized in that a transparent conductive semiconductor material is deposited on a flexible substrate by using a chemical solution method, a sputtering method and other methods, and then high-power femtosecond pulse laser is utilized to act on a conductive film, so that the crystallinity, the microstructure and the chemical composition of the semiconductor film can be adjusted and improved, and the defects are eliminated, thereby obtaining the flexible semiconductor material with excellent performance.

Description

Ultrafast laser annealing technology of flexible p/n type semiconductor
Technical Field
The invention relates to the technical field of laser annealing, in particular to an ultrafast laser annealing technology of a flexible p/n type semiconductor.
Background
Since the 90 s of the 20 th century, inorganic flexible electronic devices began to enter the human field of vision, and scientists integrated electronic devices on flexible substrates, and obtained the ductility of the devices and maintained the electrical characteristics of the devices through structural design. By the 21 st century, flexible electronic devices have been widely varied in the fields of biomedicine, nanoscience, communication engineering, consumer electronics, and the like, with their unique ductility and their efficient and low-cost manufacturing processes, resulting in a series of emerging technologies and novel electronic devices such as flexible circuits, transfer technologies, electronic eye cameras, flexible batteries, and flexible skin electronics.
Key materials required for flexible electronics include flexible conductive materials and flexible semiconducting materials, where the semiconducting materials need to undergo an annealing process to eliminate tissue defects. However, the conventional furnace annealing, even at up to 1150 ℃, does not completely eliminate the crystal defects and may result in the deterioration of material properties, decomposition of the matrix, precipitation of dopant or contamination of the surface, etc. The defects can be thoroughly eliminated by laser annealing, but the traditional laser annealing technology is a thermal processing technology, the annealing mechanism belongs to a thermal process, and the performance of the device can be remarkably reduced by higher annealing temperature; and the pulse laser is longer, the heat diffusion area is larger in the processing process, and the method is not suitable for the field of fine processing.
Disclosure of Invention
Based on the defects of the prior art, the technical problem solved by the invention is to provide an ultrafast laser annealing technology of a flexible p/n type semiconductor with good processing effect, in the femtosecond laser processing process, the energy deposition speed is far higher than the thermal diffusion speed, the energy can be effectively concentrated in a focused three-dimensional space, and the fine degree of micromachining is greatly improved. Meanwhile, the pulse time of the femtosecond laser is short, the energy is highly concentrated, and the peak power of the femtosecond laser is more than 100 times of that of the nanosecond laser under the same average power. When a sample is irradiated with femtosecond laser, a multiphoton absorption process occurs, which causes destruction of an electronic bond while almost no heat is transferred to the sample, and is a non-thermal process. Therefore, the femtosecond laser can realize non-thermal low-temperature annealing, which leads the laser to have excellent development prospect in the annealing field. The ultrafast laser annealing technology of the flexible p/n type semiconductor deposits the transparent conductive semiconductor material on the flexible substrate by using methods such as a chemical solution method, a sputtering method and the like, and then utilizes high-power femtosecond pulse laser to act on the conductive film, so that the crystallinity, the microstructure and the chemical composition of the semiconductor film can be adjusted and improved, the defects are eliminated, and the flexible semiconductor material with excellent performance is obtained.
In order to solve the above technical problems, the present invention provides an ultrafast laser annealing technique for a flexible p/n type semiconductor, comprising the steps of:
1) depositing an amorphous film of transparent conductive semiconductor material on a flexible substrate;
2) and scanning the transparent conductive film at a high speed by using a femtosecond laser and controlling parameters of the femtosecond laser to enable the temperature of the flexible substrate to be in a range from room temperature to the softening temperature of the substrate.
Preferably, the ultrafast laser annealing technology for the flexible p/n type semiconductor further includes some or all of the following technical features:
as an improvement of the technical scheme, the flexible substrate is made of an organic synthetic polymer material, flexible ultrathin glass or a graphene material.
As an improvement of the above technical solution, the organic synthetic polymer material is an organic synthetic polymer material with good heat resistance, such as nanocellulose, milar, polyethylene terephthalate, polycarbonate, polypropylene, polyimide, polypropylene diester, polytetrafluoroethylene, polymethyl methacrylate, and polyethylene terephthalate.
As an improvement of the above technical solution, the transparent conductive semiconductor material is indium tin oxide, zinc aluminum oxide, a nano silver wire, a carbon nanotube, graphene, or a carbon fiber.
As an improvement of the above technical solution, the method for depositing the amorphous film of the transparent conductive semiconductor material on the flexible substrate is a chemical solution method, a pulsed laser sputtering method, a magnetron sputtering method, or a sol-gel method.
As an improvement of the above technical solution, the chemical solution method is that the flexible substrate which is cleaned and treated by ultraviolet irradiation is placed in Sn2+Sealing in the diluent, heating, washing the flexible substrate after precipitation occurs, and repeating the above process for three times or more.
As an improvement of the technical scheme, the heating temperature is 70 ℃, and the heating time is 90 min; the process for cleaning the flexible substrate is specifically that the flexible substrate is cleaned by deionized water, then the flexible substrate is subjected to ultrasonic treatment for 5min in the deionized water, and then the surface of the glass is cleaned by the deionized water.
As an improvement of the technical scheme, the pulse laser sputtering method is that laser is irradiated on a target, the target is heated and melted in a very short time and then gasified until becoming plasma, the plasma is transmitted from a target flexible substrate, and finally, the plasma is condensed and nucleated on the flexible substrate to form a thin film.
As an improvement of the technical scheme, in the step 2), the scanning speed of the femtosecond laser is 400-.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the pulse duration is shorter than the relaxation time of the electron-lattice collision, so that only the electrons absorb energy under the action of the pulse, while the lattice is in a cooled state. After the pulse is finished, the energy is transferred to the crystal lattice, and the electron temperature and the crystal lattice temperature are in a non-equilibrium state.
2. The femtosecond laser has extremely high peak power, when irradiating a sample, a multiphoton absorption process occurs, which causes destruction of an electronic bond, while hardly transferring heat to the sample, and is a non-thermal process, thereby minimizing damage to a flexible substrate.
3. The temperature of the flexible substrate during annealing is lower, so that the requirement on the substrate material is lower, and the preparation cost is reduced.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the contents of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following detailed description is given in conjunction with the preferred embodiments.
Drawings
FIG. 1a is a photograph of an unprocessed conductive film according to an embodiment of the present invention;
FIG. 1b is a diagram of a conductive film after high temperature annealing at 170 ℃ according to an embodiment of the present invention;
FIG. 1c is a photograph of an embodiment of the present invention after femtosecond laser annealing with a power of 0.12 microfocus;
FIG. 1d is a photograph of an embodiment of the present invention after femtosecond laser annealing with a power of 0.43 microfocus;
FIG. 1e is a photograph of an embodiment of the present invention after femtosecond laser annealing with a power of 0.73 microjoules;
FIG. 1f is a photograph of an embodiment of the present invention after femtosecond laser annealing at a power of 1.04 microfocus.
Detailed Description
Other aspects, features and advantages of the present invention will become apparent from the following detailed description, which, when taken in conjunction with the drawings, illustrate by way of example the principles of the invention.
Example 1
1. Preparing a transparent conductive film precursor solution, sequentially adding 5g of urea, 100 mu L of thioglycollic acid, 5 ml of concentrated hydrochloric acid, 400 ml of pure water and 1.096g of stannous chloride into a glass container, shaking until the solution is transparent, and standing the prepared solution at a low temperature for 3 days.
2. And ultrasonically cleaning the flexible substrate for 15min by using a detergent, deionized water and absolute ethyl alcohol respectively, blow-drying by using dry compressed air, and treating for 10min by using ultraviolet-ozone to remove organic residues on the surface.
3. Preparing a transparent conductive film by adopting a chemical solution method: 120mL of 0.27% g/mL Sn was taken2+The diluted solution was poured into a clean glass container, and the flexible substrate which was cleaned and treated with ultraviolet irradiation for 15min was put in and sealed. The glass was heated in an oven at 70 ℃ for 90min until a slightly white precipitate appeared, after which the glass surface was rinsed clean with deionized water. And after washing, putting the glass into an ultrasonic machine for ultrasonic treatment for 5min, washing the surface of the substrate by using deionized water, and repeating the step for three times.
4. The femtosecond laser is used for sweeping the transparent conductive film at a high speed, and the temperature of the flexible substrate is controlled within the range from room temperature to the softening temperature of the substrate by controlling the energy, power, scanning speed and other parameters of the femtosecond laser. The scanning speed is controlled to be about 500mm/s, and the femtosecond laser energy is 0.14-1.04 microjoule.
Example 2
1. And ultrasonically cleaning the flexible substrate for 15min by using a detergent, deionized water and absolute ethyl alcohol respectively, blow-drying by using dry compressed air, and treating for 10min by using ultraviolet-ozone to remove organic residues on the surface.
2. Preparing a transparent conductive film by adopting a pulse laser sputtering method: when laser is irradiated on the target, the target is heated and melted in a very short time, then is gasified until becoming plasma, the plasma is transported from the target flexible substrate, and finally is condensed and nucleated on the flexible substrate to form a thin film.
3. The femtosecond laser is used for sweeping the transparent conductive film at a high speed, and the temperature of the flexible substrate is controlled within the range from room temperature to the softening temperature of the substrate by controlling the energy, power, scanning speed and other parameters of the femtosecond laser. The scanning speed is controlled to be about 500mm/s, and the femtosecond laser energy is 0.14-1.04 microjoule.
FIG. 1a is a picture of a conductive film without any treatment, FIG. 1b is a picture of a conductive film after high temperature annealing at 170 ℃, and FIGS. 1c-f are pictures after femtosecond laser annealing, and the energy of the femtosecond laser is sequentially increased to 0.14-1.04 micro-focus. The conductive films in the two schemes are tin oxide conductive films, the scanning speeds of the lasers in fig. 1c-f are 500mm/s, the femtosecond laser power in fig. 1c is 0.12 micro-focus, the femtosecond laser power in fig. 1d is 0.43 micro-focus, the femtosecond laser power in fig. 1e is 0.73 micro-focus, and the femtosecond laser power in fig. 1f is 1.04 micro-focus.
As can be seen from the figure: femtosecond laser annealing has an effect, but the laser energy cannot be too large, otherwise the grains are melted and then recrystallized into larger particles. Therefore, the smaller the femtosecond laser energy is, the better the femtosecond laser energy is in a certain range.
The raw materials listed in the invention, the upper and lower limits and interval values of the raw materials of the invention, and the upper and lower limits and interval values of the process parameters (such as temperature, time and the like) can all realize the invention, and the examples are not listed.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.

Claims (9)

1. An ultrafast laser annealing technique for flexible p/n type semiconductor, comprising the steps of:
1) depositing an amorphous film of transparent conductive semiconductor material on a flexible substrate;
2) and scanning the transparent conductive film at a high speed by using a femtosecond laser and controlling parameters of the femtosecond laser to enable the temperature of the flexible substrate to be in a range from room temperature to the softening temperature of the substrate.
2. The ultra-fast laser annealing technique of a flexible p/n-type semiconductor according to claim 1, wherein: the flexible substrate is made of an organic synthetic polymer material, flexible ultrathin glass or a graphene material.
3. The ultra-fast laser annealing technique for flexible p/n-type semiconductors of claim 2, wherein: the organic synthetic polymer material is nano-cellulose, milar, polyethylene terephthalate, polycarbonate, polypropylene, polyimide, polypropylene diester, polytetrafluoroethylene, polymethyl methacrylate and polyethylene glycol terephthalate.
4. The ultra-fast laser annealing technique of a flexible p/n-type semiconductor according to claim 1, wherein: the transparent conductive semiconductor material is indium tin oxide, zinc aluminum oxide, nano silver wire, carbon nano tube, graphene or carbon fiber.
5. The ultra-fast laser annealing technique of a flexible p/n-type semiconductor according to claim 1, wherein: the method for depositing the amorphous film of the transparent conductive semiconductor material on the flexible substrate is a chemical solution method, a pulse laser sputtering method, a magnetron sputtering method or a sol-gel method.
6. The ultrafast laser annealing technique of a flexible p/n-type semiconductor of claim 5, wherein: the chemical solution method is to place the cleaned flexible substrate after the ultraviolet irradiation treatment on Sn2+Sealing in the diluent, heating, washing the flexible substrate after precipitation occurs, and repeating the above process for three times or more.
7. The ultrafast laser annealing technique of a flexible p/n-type semiconductor of claim 6, wherein: the heating temperature is 70 ℃, and the heating time is 90 min; the process for cleaning the flexible substrate is specifically that the flexible substrate is cleaned by deionized water, then the flexible substrate is subjected to ultrasonic treatment in the deionized water for 5min, and then the surface of the substrate is cleaned by the deionized water.
8. The ultrafast laser annealing technique of a flexible p/n-type semiconductor of claim 5, wherein: the pulse laser sputtering method is that laser is irradiated onto a target, the target is heated and melted in a very short time, then is gasified until becoming plasma, the plasma is transmitted from a target flexible substrate, and finally is condensed and nucleated on the flexible substrate to form a thin film.
9. The ultra-fast laser annealing technique of a flexible p/n-type semiconductor according to claim 1, wherein: in the step 2), the femtosecond laser scanning speed is 400-800mm/s, and the femtosecond laser energy is 0.14-1.04 microjoule.
CN202110443539.4A 2021-04-23 2021-04-23 Ultrafast laser annealing technology of flexible p/n type semiconductor Pending CN113223969A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101425467A (en) * 2008-11-25 2009-05-06 中国科学院安徽光学精密机械研究所 Method for preparing transparent conductive film and transparent hetero-junction on flexible substrate
CN103268852A (en) * 2013-05-02 2013-08-28 中国科学院半导体研究所 Method for preparing supersaturated-doping semiconductor thin film
CN108831827A (en) * 2018-07-31 2018-11-16 山东大学 A kind of device of heat auxiliary femtosecond laser annealing amorphous silicon
CN108831930A (en) * 2018-06-22 2018-11-16 福州大学 A kind of flexible thin-film transistor and preparation method thereof based on laser technology
CN112670212A (en) * 2020-12-24 2021-04-16 武汉理工大学 Large-area printing and laser annealing manufacturing device and semiconductor manufacturing method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101425467A (en) * 2008-11-25 2009-05-06 中国科学院安徽光学精密机械研究所 Method for preparing transparent conductive film and transparent hetero-junction on flexible substrate
CN103268852A (en) * 2013-05-02 2013-08-28 中国科学院半导体研究所 Method for preparing supersaturated-doping semiconductor thin film
CN108831930A (en) * 2018-06-22 2018-11-16 福州大学 A kind of flexible thin-film transistor and preparation method thereof based on laser technology
CN108831827A (en) * 2018-07-31 2018-11-16 山东大学 A kind of device of heat auxiliary femtosecond laser annealing amorphous silicon
CN112670212A (en) * 2020-12-24 2021-04-16 武汉理工大学 Large-area printing and laser annealing manufacturing device and semiconductor manufacturing method

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