WO2019196025A1 - Azo transparent conductive thin film, and preparation method therefor and application thereof - Google Patents

Azo transparent conductive thin film, and preparation method therefor and application thereof Download PDF

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Publication number
WO2019196025A1
WO2019196025A1 PCT/CN2018/082599 CN2018082599W WO2019196025A1 WO 2019196025 A1 WO2019196025 A1 WO 2019196025A1 CN 2018082599 W CN2018082599 W CN 2018082599W WO 2019196025 A1 WO2019196025 A1 WO 2019196025A1
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Prior art keywords
zinc oxide
transparent conductive
conductive film
substrate
azo
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PCT/CN2018/082599
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French (fr)
Chinese (zh)
Inventor
刘荣跃
丁庆
冯军正
杨旻蔚
张翠
许奔
孙竹
Original Assignee
深圳市太赫兹科技创新研究院
深圳市太赫兹科技创新研究院有限公司
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Priority to PCT/CN2018/082599 priority Critical patent/WO2019196025A1/en
Publication of WO2019196025A1 publication Critical patent/WO2019196025A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the invention belongs to the field of new energy, and particularly relates to an AZO transparent conductive film and a preparation method and application thereof.
  • Photovoltaic solar cells have the advantages of clean energy, renewable energy and inexhaustible energy. In addition, their industrialized manufacturing is becoming more and more mature and the cost is getting lower and lower, which makes it gradually become an effective way to solve the energy crisis and environmental crisis. At present, research on solar cells is mainly focused on improving the conversion efficiency of batteries and saving manufacturing costs, as well as improving the effective use time of batteries. There are two main ways to improve the efficiency of photovoltaic solar cells: one is to make full use of the solar spectrum energy of each band; the other is to improve the collection efficiency of photogenerated carriers. Among them, the transparent conductive film is one of the key materials in the solar cell.
  • the commercial transparent conductive film is mainly made of indium-doped tin oxide (ITO), but due to its high production cost, limited raw materials and toxic reasons, it is urgent to develop a new transparent conductive film substitute material.
  • ITO indium-doped tin oxide
  • Aluminum-doped zinc oxide (AZO) film raw materials are widely used, non-toxic, and good photoelectric properties, and have gradually become an ideal substitute for ITO transparent conductive film materials.
  • AZO transparent conductive films with excellent photoelectric properties can be prepared by vacuum method and solution method, and have been widely applied.
  • the area of the AZO film prepared by the vacuum method is limited by the size of the vacuum chamber, and the complicated vacuum equipment greatly increases the film production cost.
  • the AZO film prepared by the solution method needs to be annealed at a high temperature of 600 ° C or higher for a long time, and then post-annealed under a hydrogen atmosphere of 550 ° C to obtain a resistivity of 1.7 ⁇ 10 -3 to 7.2 ⁇ 10 -3 ⁇ . ⁇ AZO film between cm.
  • AZO transparent conductive films are deposited on top of the cell, and excessive annealing temperatures cause excessive cadmium or zinc.
  • the object of the present invention is to provide an AZO transparent conductive film and a preparation method thereof, aiming at solving the high cost of the preparation method of the existing AZO film, and the diffusion of metal atoms in the deposited film due to the high annealing temperature, which affects the device. It is a problem of thin film solar cell performance (especially photoelectric conversion efficiency).
  • Another object of the present invention is to provide a thin film solar cell comprising an AZO transparent conductive film.
  • An aspect of the invention provides a method for preparing an AZO transparent conductive film, comprising the following steps:
  • the AZO pre-formed film is subjected to ultraviolet irradiation treatment to prepare an AZO transparent conductive film.
  • Another aspect of the present invention provides an AZO transparent conductive film comprising a zinc oxide seed layer, and an array of AZO thin films bonded to the surface of the zinc oxide seed layer.
  • a thin film solar cell comprising the above AZO transparent conductive film or an AZO transparent conductive film prepared by the above method is provided.
  • the method for preparing an AZO transparent conductive film provided by the invention adopts an aqueous solution method, first preparing a zinc oxide seed layer on a substrate, then depositing aluminum-doped zinc oxide on the zinc oxide seed layer, and finally performing ultraviolet irradiation treatment.
  • An AZO transparent conductive film was prepared.
  • the method uses an aqueous solution method to deposit a film, and does not require high-temperature annealing treatment. Therefore, the diffusion of metal atoms in the deposited functional layer during high-temperature annealing can be avoided, and the influence on other functional layers can be avoided.
  • the AZO transparent conductive film is used in a thin film solar cell, cadmium or zinc in the functional layer can be prevented from diffusing into the absorption layer of the thin film solar cell during high temperature annealing, thereby improving the photoelectric conversion efficiency of the battery.
  • the AZO transparent conductive film is used as a conductive window layer of a copper zinc tin sulfide (CZTS) thin film solar cell, and the photoelectric conversion efficiency of the battery can reach 5.47%.
  • CZTS copper zinc tin sulfide
  • the AZO transparent conductive film provided by the present invention can remove excess carbon impurities in the film by ultraviolet irradiation treatment of the AZO pre-formed film, improve carrier concentration and conductivity of the film, and obtain AZO transparent excellent in electrical conductivity. Conductive film.
  • the conditions for preparing the AZO transparent conductive film are mild, and it is not necessary to use complicated and expensive equipment, which is advantageous for reducing the production cost of the AZO transparent conductive film.
  • the AZO transparent conductive film provided by the invention has excellent electrical conductivity and low manufacturing cost, and is an ideal substitute for the ITO transparent conductive film, and can be widely used in CIGS and CZTS thin film solar cells, and has better photoelectric conversion efficiency of the battery.
  • the thin film solar cell provided by the present invention can not only reduce the cost but also improve the photoelectric conversion efficiency of the battery because the AZO transparent conductive film is contained.
  • an aqueous solution of zinc oxide seed layer is prepared, a zinc oxide seed layer is uniformly deposited on the surface of the glass, and then an aqueous solution of aluminum-doped zinc oxide is prepared, and a dense and uniform columnar aluminum-doped zinc oxide nano-array is deposited on the surface of the seed layer, followed by UV.
  • an aluminum-doped zinc oxide transparent conductive film excellent in photoelectric properties can be obtained.
  • FIG. 1 is a flow chart of a process for preparing an AZO transparent conductive film according to an embodiment of the present invention
  • FIG. 2 is a plan view showing an AZO transparent conductive film provided in Embodiment 1 of the present invention.
  • Figure 3 is a cross-sectional view showing an AZO transparent conductive film provided in Example 1 of the present invention.
  • Example 4 is a view showing the effect of detecting light transmittance of the AZO transparent conductive film provided in Example 1 of the present invention
  • FIG. 5 is a schematic structural view of a CZTA thin film solar cell according to Embodiment 2 of the present invention.
  • FIG. 6 is a cross-sectional view showing the structure of a CZTA thin film solar cell according to Embodiment 2 of the present invention.
  • FIG. 7 is a graph showing current and voltage curves of a CZTA thin film solar cell structure according to Embodiment 2 of the present invention.
  • first and second are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated.
  • features defining “first” and “second” may include one or more of the features either explicitly or implicitly.
  • the meaning of "a plurality" is two or more unless specifically and specifically defined otherwise.
  • an embodiment of the present invention provides a method for preparing an AZO transparent conductive film, which includes the following steps:
  • the AZO pre-formed film is subjected to ultraviolet irradiation treatment to prepare an AZO transparent conductive film.
  • the method for preparing an AZO transparent conductive film adopts an aqueous solution method, first preparing a zinc oxide seed layer on a substrate, then depositing aluminum-doped zinc oxide on the zinc oxide seed layer, and finally passing ultraviolet irradiation.
  • the AZO transparent conductive film was prepared by treatment.
  • the method uses an aqueous solution method to deposit a film, and does not require high-temperature annealing treatment. Therefore, the diffusion of metal atoms in the deposited functional layer during high-temperature annealing can be avoided, and the influence on other functional layers can be avoided.
  • the AZO transparent conductive film is used in a thin film solar cell, cadmium or zinc in the functional layer can be prevented from diffusing into the absorption layer of the thin film solar cell during high temperature annealing, thereby improving the photoelectric conversion efficiency of the battery.
  • the AZO transparent conductive film is used as a conductive window layer of a copper zinc tin sulfide (CZTS) thin film solar cell, and the photoelectric conversion efficiency of the battery can reach 5.47%.
  • CZTS copper zinc tin sulfide
  • the AZO transparent conductive film provided by the embodiment of the present invention can remove excess carbon impurities in the film by ultraviolet irradiation treatment on the AZO pre-formed film, improve carrier concentration and conductivity of the film, and obtain excellent electrical conductivity.
  • AZO transparent conductive film can remove excess carbon impurities in the film by ultraviolet irradiation treatment on the AZO pre-formed film, improve carrier concentration and conductivity of the film, and obtain excellent electrical conductivity.
  • the conditions for preparing the AZO transparent conductive film are mild, and it is not necessary to use complicated and expensive equipment, which is advantageous for reducing the production cost of the AZO transparent conductive film.
  • the substrate used as the AZO transparent conductive film is not strictly limited, and a substrate commonly used in the art, such as ultra-white glass, may be selected.
  • a substrate commonly used in the art such as ultra-white glass
  • the substrate needs to be surface cleaned prior to deposition of the zinc oxide seed solution.
  • the method of surface cleaning treatment is as follows:
  • a glass cleaner preferably an aqueous alkaline detergent solution having a volume concentration of 5%, an alkaline detergent and deionized water at a volume ratio of 5:95. Remove the oil that is difficult to remove on the glass surface.
  • the substrate was rinsed in clean deionized water, placed in acetone, and the organic impurities on the surface of the glass were removed, followed by ultrasonic cleaning in isopropanol for 10 min.
  • the substrate is washed in a low-concentration glass cleaning agent to remove particulate impurities on the surface of the substrate, washed again with deionized water, and finally ultrasonically cleaned in anhydrous ethanol. Min after use.
  • the surface of the substrate after the surface cleaning treatment by the above method is as clean as new, which is advantageous for deposition of an aqueous zinc oxide solution.
  • a large substrate can be cut and cut according to the specifications of the formed AZO transparent conductive film to obtain a desired substrate size, such as 25 mm ⁇ 25 mm. It should be understood that the large substrate may be first cut and then subjected to surface cleaning; or the large substrate may be surface-cleaned before cutting and cutting. Preferably, in order to avoid the introduction of impurities or dirt during the cutting and cutting process, it is preferred to cut the cutting after the surface cleaning treatment.
  • step S02 since the bonding strength of the aluminum-doped zinc oxide to the surface of the substrate, particularly the glass substrate, is not strong, the bonding is not strong, and it is even difficult to nucleate the surface of the substrate, and therefore, the aluminum-doped zinc oxide is deposited.
  • a layer of zinc oxide seed was deposited on the substrate for subsequent formation and growth of zinc oxide nanoarrays. Specifically, a zinc oxide seed solution is used to nucleate the surface of the substrate to form a transition layer, that is, a zinc oxide seed layer. Further, aluminum-doped zinc oxide is deposited on the substrate by using the zinc oxide seed layer as a medium.
  • the zinc oxide seed solution is an aqueous solution of zinc oxide added with excess ammonia water, and the addition of excess ammonia water is beneficial to increase the solubility of zinc oxide.
  • the zinc oxide seed solution is prepared by dispersing zinc oxide powder in deionized water, and then adding ammonia water to stir well to promote dissolution of the oxidative powder. Further, the dissolved solution is subjected to a filtration treatment to remove excess zinc oxide impurities, and the clear solution remains. Specifically, the filtration treatment was carried out by using a filter having a diameter of 0.45 ⁇ m.
  • the zinc oxide seed solution is deposited on the substrate, and as the ammonia water in the zinc oxide seed solution is volatilized, the dissolution property of the zinc oxide is lowered, and further adhered to the surface of the substrate to form a film layer.
  • the concentration of zinc oxide in the zinc oxide seed solution is 20-50 mmol/L to form a dense and uniform zinc oxide seed layer. If the concentration of zinc oxide in the zinc oxide seed solution is too low, the formed film layer is not dense. If the concentration of zinc oxide in the zinc oxide seed solution is too high, the zinc oxide particles deposited on the substrate are not uniform, and the obtained surface film layer is not uniform in thickness, which affects the thickness of the subsequent deposition of the zinc oxide film. Uniformity further affects the stability of film properties.
  • the concentration of zinc oxide in the zinc oxide seed solution is too high, the thickness of the obtained zinc oxide seed layer is too thick, which affects the performance of the AZO transparent conductive film.
  • the concentration of zinc oxide in the zinc oxide seed solution is 30-40 mmol/L.
  • a method of depositing the zinc oxide seed solution on the substrate to prepare a zinc oxide seed layer bonded to the surface of the substrate preferably using a spin coating method.
  • the method for preparing a zinc oxide seed layer by spin coating is as follows:
  • the cleaned substrate was taken out, blown under a nitrogen stream, and placed on the sample stage of the homogenizer.
  • Set the pre-rotation number and pre-rotation time, rotation rotation number and rotation time of the homogenizer absorb the zinc oxide ammonia aqueous solution and drip it onto the first surface to ensure that the zinc oxide seed layer solution completely covers the sample surface.
  • the spin-coated substrate is placed on a thermostatic table, and heated at a constant temperature for a certain period of time to be cooled in the air to form a zinc oxide seed layer.
  • the embodiment of the present invention prepares an AZO transparent conductive film by a solution method.
  • a zinc oxide deposition solution for deposition is first provided.
  • the zinc oxide deposition solution contains zinc oxide, ammonia water and deionized water, wherein the ammonia water is used to increase the solubility of the zinc oxide, and at the same time, in the preparation of the AZO pre-formed film, zinc oxide is realized by volatilization of ammonia water.
  • the ammonia water is added in an amount such that the pH of the zinc oxide deposition solution is 9-12.
  • the solubility of zinc oxide in deionized water can be improved, the deposition rate of zinc oxide can be controlled, and the density of the obtained film layer can be improved.
  • the present invention reduces the solubility of zinc oxide by the evaporation of ammonia water, and further the growth of zinc oxide after aluminum doping on the surface of the zinc oxide seed layer.
  • the zinc oxide deposition solution further contains ammonium citrate and ammonium nitrate.
  • the ammonium citrate and ammonium nitrate can control the crystal structure and morphology of the aluminum-doped zinc oxide on the surface of the zinc oxide seed layer, thereby obtaining an AZO transparent conductive film of an array structure.
  • the array structure is a columnar structure. Compared with the AZO transparent conductive film which does not have the array structure, the AZO transparent conductive film of the array structure transmits electrons directly along the array during charge, such as electron transport, which can reduce the barrier effect of the grain boundary and thereby improve the photoelectric effect.
  • the concentration of each constituent substance is preferably:
  • the concentration of ammonium nitrate is 0.01 ⁇ 2 mmol/L.
  • a suitable concentration of the above substances can be doped with an aluminum zinc oxide nano-array, and the aluminum-doped zinc oxide nano-array is uniformly dense. Specifically, if the concentration of the zinc oxide is too high, the growth rate of the zinc oxide is fast, and the doping speed of the aluminum cannot keep up with the growth rate of the zinc oxide, so that the aluminum doping content of the finally obtained AZO transparent conductive film does not meet the requirements. . In addition, the concentration of zinc oxide is too high, the zinc oxide particles formed during the deposition process are coarse, and pores are formed between the zinc oxide particles, thereby lowering the properties of the finally obtained AZO transparent conductive film. If the concentration of the zinc oxide is too low, the growth rate of zinc oxide is slow.
  • the content of the ammonium citrate and ammonium nitrate is related to the formation of the aluminum-doped zinc oxide nano-array, that is, whether the AZO transparent conductive film has an array structure.
  • the ammonium citrate and ammonium nitrate are used as an additive in the form of citrate ions, nitrate ions and ammonium ions in an aqueous solution. Due to electrostatic attraction, citrate ions and nitrate ions are strongly adsorbed to the oxidation.
  • the crystal plane of zinc which occupies most of the growth position of zinc and oxygen, inhibits the growth of zinc oxide nanorods along the c-axis direction, while the lateral growth of nanorods is less affected, so the nanorods tend to grow laterally.
  • the aspect ratio is reduced, and the nanorods can contact each other to form a dense film.
  • the introduced ammonium ions are present in the solution itself and therefore do not affect the chemical properties of the solution. If the concentration of the ammonium citrate and the ammonium nitrate is too high, the longitudinal growth limitation of the zinc oxide nanorods is severe, and the rod-shaped zinc oxide will grow into a sheet shape, which is disadvantageous to the increase of carrier mobility, resulting in thin film electrical power. Reduced performance.
  • the zinc oxide deposition solution is prepared by taking a clean container such as a beaker, weighing a certain amount of deionized water, and adding the desired ammonium citrate, ammonium nitrate, and oxidation to the beaker. Zinc powder and ammonia reagent. After stirring for 24 h at room temperature, excess zinc oxide impurities in the solution were removed by filtration using a filter having a diameter of 0.45 ⁇ m, leaving a clear solution for use.
  • a substrate on which a zinc oxide seed layer is deposited is placed in the zinc oxide deposition solution, the zinc oxide deposition solution is immersed in the substrate, and zinc oxide seeds are deposited in the substrate.
  • the surface of the layer is not adhered to grow aluminum-doped zinc oxide on the surface of the zinc oxide seed layer.
  • the substrate is placed vertically in the zinc oxide deposition solution.
  • impurities may be prevented from falling into the surface of the zinc oxide seed layer during sedimentation, and space saving is facilitated, and deposition of a plurality of substrates is simultaneously achieved.
  • a plurality of substrates are simultaneously placed in the zinc oxide deposition solution to prepare an AZO transparent conductive film.
  • the substrate is placed vertically in the zinc oxide deposition solution, which can be realized by means of a mold, and the selection of the mold is not specifically required.
  • the zinc oxide is deposited by heating (volatile ammonia water to supersaturate the zinc oxide in the solution); at the same time, the aluminum ion is continuously introduced into the zinc oxide deposition solution.
  • a peristaltic pump is used to continuously add aluminum nitrate nonahydrate or immersed in an aluminum flake to the zinc oxide deposition solution, and aluminum ions are continuously introduced into the zinc oxide deposition solution to achieve uniform doping.
  • the step of introducing aluminum nitrate into the aluminum oxide by continuously adding the aluminum nitrate nonahydrate in the zinc oxide deposition solution by using a peristaltic pump satisfies the introduction condition of the aluminum ion: the rotational speed of the peristaltic pump is ⁇ 0.1 rpm.
  • the concentration of aluminum nitrate in the zinc oxide deposition solution is 10 to 300 mmol/L.
  • the step of continuously immersing the aluminum sheet into the aluminum ion in the zinc oxide deposition solution by using a peristaltic pump the introduction condition of the aluminum ion is satisfied: the rotational speed of the peristaltic pump is ⁇ 0.1 rpm, The immersion area of the aluminum sheet is 1 to 10 cm 2 .
  • the rotational speed of the peristaltic pump is ⁇ 0.1 rpm
  • the immersion area of the aluminum sheet is 1 to 10 cm 2 .
  • the aluminum ion will exist in the form of [Al(OH) 4 ] ⁇ in the alkaline solution, so most of it will adsorb to the crystal plane of the zinc oxide columnar crystal, which will cause the columnar surface to accept a large decrease in the position of zinc.
  • the growth of the columnar crystal lateral direction is suppressed, resulting in a decrease in grain size and an increase in aspect ratio.
  • the concentration of the aluminum nitrate nonahydrate is too high or the area of the immersed aluminum sheet is too large, the growth of the zinc oxide columnar grain is limited, the film cannot grow on the substrate; if the concentration of the aluminum nitrate nonahydrate is too low Or the area of the immersed aluminum sheet is too small, the aluminum doping concentration in the zinc oxide is decreased, and the conductive property of the zinc oxide film is decreased.
  • the purpose of the heating is to volatilize the ammonia water in the zinc oxide deposition solution, and the heating temperature has a great influence on the preparation of the AZO pre-formed film in the embodiment of the invention.
  • the zinc oxide deposition solution contains zinc oxide, ammonia water and deionized water, the zinc oxide deposition solution has a pH of 9-12, and the heating temperature is 60-90 °C.
  • the ammonia water can ensure a proper evaporation rate, which is beneficial to the formation of AZO prefabricated film with good crystal structure.
  • the heating temperature is too low, the volatilization speed is slow; if the heating temperature is too high, the ammonia water volatilizes too fast, the zinc oxide grows fast, and the doping speed of aluminum cannot keep up with the growth rate of zinc oxide.
  • the aluminum doping content in the finally obtained AZO transparent conductive film is not satisfactory.
  • the zinc oxide particles formed by the deposition are coarse, and pores are formed between the zinc oxide particles, thereby lowering the properties of the finally obtained AZO transparent conductive film.
  • the zinc oxide deposition solution is added to the heating vessel, and the substrate on which the zinc oxide seed layer is deposited is placed in the zinc oxide deposition solution, and the zinc oxide deposition solution is immersed in the lining. a bottom, and a surface of the substrate in which the zinc oxide seed layer is deposited is not adhered; the heating vessel is placed in a water bath, and aluminum ions are continuously introduced into the zinc oxide deposition solution under heating
  • the AZO pre-formed film was prepared by growing on the surface of the zinc oxide seed layer by stirring.
  • the sample from which the AZO pre-formed film was grown was taken out from the aqueous solution, rinsed with a large amount of deionized water, and then blown dry under a nitrogen stream.
  • the AZO pre-formed film is subjected to ultraviolet irradiation treatment, and then the surface of the sample is irradiated with a UV irradiation lamp for 5 to 10 minutes to complete preparation of the AZO film sample. Excess carbon impurities in the film are removed to increase the carrier concentration and conductivity of the film.
  • the ultraviolet irradiation treatment condition is: the UV lamp has an effective area of 100 cm 2 and a radiation time of 1 to 20 min.
  • Embodiments of the present invention provide an AZO transparent conductive film, including a zinc oxide seed layer, and an array of AZO thin films bonded to the surface of the zinc oxide seed layer.
  • the AZO transparent conductive film provided by the embodiment of the invention has excellent electrical conductivity and low manufacturing cost, and is an ideal substitute for the ITO transparent conductive film, and can be widely used in CIGS and CZTS thin film solar cells, and has better photoelectric conversion efficiency of the battery.
  • the AZO transparent conductive film provided by the embodiment of the invention can be obtained by the above method.
  • the AZO transparent conductive film of the array structure transmits electrons directly along the array during charge, such as electron transport, which can reduce the barrier effect of the grain boundary and is beneficial to the collection of carriers. , thereby improving the photoelectric conversion efficiency of the solar cell.
  • the array of the array of AZO thin films is a columnar nano array.
  • a thin film solar cell comprising the above AZO transparent conductive film or an AZO transparent conductive film prepared by the above method is provided.
  • the thin film solar cell provided by the embodiment of the invention can not only reduce the cost but also improve the photoelectric conversion efficiency of the battery because the AZO transparent conductive film is contained.
  • the thin film solar cell may be a copper indium gallium selenide (CIGS) or a copper zinc tin sulfide (CZTS) thin film solar cell.
  • the thin film solar cell is a CZTA thin film solar cell, including a glass substrate, and a molybdenum metal layer, a CATS light absorbing layer, a cadmium sulfide buffer layer, and an AZO transparent layer sequentially disposed on the glass substrate.
  • Conductive film and silver electrode can be prepared by the following method:
  • the cleaning method can refer to the surface cleaning treatment method of the substrate, and then continuously adopting the sol-gel technique and the high-temperature tempering two-step method to prepare the CZTS light absorbing layer, and chemical bath deposition vulcanization
  • the cadmium buffer layer is tempered at 200 ° C for 10 min, and then the AZO transparent conductive film is prepared on the surface of the sample by using the preparation method of the AZO transparent conductive film, and the top electrode (wiring electrode) is prepared by using the conductive silver paste to complete the CZTS thin film solar energy. Battery preparation.
  • a method for preparing an AZO transparent conductive film comprising the steps of:
  • Providing a zinc oxide seed solution spin-depositing the zinc oxide seed solution on the substrate to prepare a zinc oxide seed layer bonded to a surface of the substrate, wherein a solution composition of the zinc oxide seed solution is : zinc oxide nanoparticles, high purity water, excess ammonia water, wherein the concentration of zinc oxide is 20 ⁇ 50 Mmmol/L;
  • the AZO pre-formed film is subjected to ultraviolet irradiation treatment under the following conditions: the UV lamp has an effective area of 100 cm 2 and the irradiation time is 1 to 20 min, and an AZO transparent conductive film is prepared.
  • the plan view and the cross-sectional view of the AZO transparent conductive film prepared in the first embodiment of the present invention are as shown in FIG. 2 and FIG. 3, and the AZO transparent conductive film prepared in the first embodiment of the present invention is tested for light transmittance, and the result is shown in FIG.
  • the light rate is 85%-95%.
  • a method for preparing a CZTA thin film solar cell comprising the steps of:
  • the soda lime glass deposited with metal Mo is cleaned, and then the CZTS light absorbing layer is prepared by a sol gel technique and a high temperature tempering two-step method, and the cadmium sulfide buffer layer is deposited by a chemical bath, tempered at 200 ° C for 10 min, and then The method of Example 1 prepared an AZO transparent conductive film on the surface of the sample, and prepared a top electrode (wiring electrode) using a conductive silver paste to complete the preparation of the CZTS thin film solar cell.
  • the structure of the CZTA thin film solar cell prepared in Example 2 is shown in Fig. 5, and a cross-sectional view of the structure of the CZTA thin film solar cell is shown in Fig. 6.
  • the CZTA thin film solar cell prepared in Example 2 and the AZO thin film prepared by high temperature annealing were subjected to long-time annealing at a high temperature of 600 ° C or higher, followed by post-annealing under a hydrogen atmosphere at 550 ° C to obtain a resistivity of 1.7 ⁇ 10 -3 .
  • the CZTS thin film solar cell obtained by the AZO thin film of ⁇ 7.2 ⁇ 10 -3 ⁇ cm and the other layer method is the same) is subjected to photoelectric performance test, and the current-voltage curve obtained by the test is shown in Fig. 7.
  • the photoelectric conversion efficiency of the CZTA thin film solar cell prepared in Example 2 was significantly improved compared to the CZTS thin film solar cell obtained by the AZO film prepared by high temperature annealing.

Abstract

A preparation method for an AZO transparent conductive thin film, comprising the following steps: providing a substrate and performing cleaning treatment on the surface of the substrate; providing a zinc oxide seed solution, and depositing the zinc oxide seed solution on the substrate to prepare a zinc oxide seed layer combined on the surface of the substrate; providing a zinc oxide deposition solution, placing the substrate deposited with the zinc oxide seed layer in the zinc oxide deposition solution, and enabling the substrate to be completely immersed in the zinc oxide deposition solution, wherein the surface of the substrate deposited with the zinc oxide seed layer is not adhered to wall; under a heating condition, introducing aluminum ions to the zinc oxide deposition solution continuously and stirring to grow and prepare an AZO pre-fabricated thin film on the surface of the zinc oxide seed layer; and performing ultraviolet radiation treatment on the AZO pre-fabricated thin film to prepare the AZO transparent conductive thin film.

Description

AZO透明导电薄膜及其制备方法和应用AZO transparent conductive film and preparation method and application thereof 技术领域Technical field
本发明属于新能源领域，尤其涉及一种AZO透明导电薄膜及其制备方法和应用。The invention belongs to the field of new energy, and particularly relates to an AZO transparent conductive film and a preparation method and application thereof.
背景技术Background technique
光伏太阳能电池具有能源清洁、可再生和用之不竭等优点，加之其产业化制造越来越成熟，成本越来越低，使其逐渐成为解决能源危机和环境危机的有效途径之一。目前，太阳能电池的研究主要集中在提高电池的转换效率和节约生产制造成本，以及提高电池有效使用时间上。提高光伏太阳能电池效率的主要途径有两个：一是要使各波段的太阳光谱能量得到充分的利用；二是要提高光生载流子的收集效率。其中，透明导电薄膜是太阳能电池中的关键材料之一。通过增加透明导电薄膜的透过率，可以使得更多的太阳光到达电池的吸收层，进而产生更多的光生载流子；通过降低透明导电薄膜的电阻率，可以使得更多的光生载流子通过薄膜，进而有效提高能量转换效率；通过优化透明导电薄膜结构，可以提高太阳能电池的化学和力学稳定性。因此，透明导电薄膜材料的发展必定向着成本更低、透过率更高、电阻率更低、化学稳定性更好的方向进行。Photovoltaic solar cells have the advantages of clean energy, renewable energy and inexhaustible energy. In addition, their industrialized manufacturing is becoming more and more mature and the cost is getting lower and lower, which makes it gradually become an effective way to solve the energy crisis and environmental crisis. At present, research on solar cells is mainly focused on improving the conversion efficiency of batteries and saving manufacturing costs, as well as improving the effective use time of batteries. There are two main ways to improve the efficiency of photovoltaic solar cells: one is to make full use of the solar spectrum energy of each band; the other is to improve the collection efficiency of photogenerated carriers. Among them, the transparent conductive film is one of the key materials in the solar cell. By increasing the transmittance of the transparent conductive film, more sunlight can be reached to the absorption layer of the battery, thereby generating more photo-generated carriers; by reducing the resistivity of the transparent conductive film, more photo-generated carriers can be made. By passing through the film, the energy conversion efficiency is effectively improved; by optimizing the structure of the transparent conductive film, the chemical and mechanical stability of the solar cell can be improved. Therefore, the development of transparent conductive film materials must be oriented in a direction of lower cost, higher transmittance, lower resistivity, and better chemical stability.
目前，商用的透明导电薄膜以铟掺杂氧化锡（ITO）为主，但是由于其生产成本较高、原料有限且有毒的原因，因此急需开发新型的透明导电薄膜替代材料。铝掺氧化锌（AZO）薄膜原料来源广泛、无毒、良好的光电性能，逐渐成为ITO透明导电薄膜材料的理想替代者。目前采用真空法和溶液法都可制备出光电性能优异的AZO透明导电薄膜，并成功实现了其广泛应用。但是真空法制备的AZO薄膜的面积要受到真空室尺寸的限制，而且复杂的真空设备极大的增加了薄膜生产成本。而通过溶液法制备的AZO薄膜，需在600℃以上的高温长时间退火，随后在550℃的氢气气氛下进行后退火处理，才能得到电阻率在1.7×10 -3~7.2×10 -3 Ω·cm之间的AZO薄膜。对于薄膜太阳能电池来讲，例如铜铟镓硒(CIGS)或铜锌锡硫(CZTS)薄膜太阳能电池，AZO透明导电薄膜要沉积在电池的顶部，过高的退火温度会引起过量的镉或锌扩散到电池的吸收层中（pn结界面过量的元素扩散，从而破坏了pn结），造成电池吸收层形成多种缺陷，增加载流子复合机会，恶化电池性能，从而降低电池光电转化效率。因此，降低窗口层的退火温度，发展一种非真空、低温、低成本，且可大规模生产透明导电膜的方法成为当今的发展趋势。 At present, the commercial transparent conductive film is mainly made of indium-doped tin oxide (ITO), but due to its high production cost, limited raw materials and toxic reasons, it is urgent to develop a new transparent conductive film substitute material. Aluminum-doped zinc oxide (AZO) film raw materials are widely used, non-toxic, and good photoelectric properties, and have gradually become an ideal substitute for ITO transparent conductive film materials. At present, AZO transparent conductive films with excellent photoelectric properties can be prepared by vacuum method and solution method, and have been widely applied. However, the area of the AZO film prepared by the vacuum method is limited by the size of the vacuum chamber, and the complicated vacuum equipment greatly increases the film production cost. The AZO film prepared by the solution method needs to be annealed at a high temperature of 600 ° C or higher for a long time, and then post-annealed under a hydrogen atmosphere of 550 ° C to obtain a resistivity of 1.7 × 10 -3 to 7.2 × 10 -3 Ω. · AZO film between cm. For thin-film solar cells, such as copper indium gallium selenide (CIGS) or copper-zinc-tin-sulfur (CZTS) thin-film solar cells, AZO transparent conductive films are deposited on top of the cell, and excessive annealing temperatures cause excessive cadmium or zinc. Diffusion into the absorption layer of the battery (excessive element diffusion at the pn junction interface, thereby destroying the pn junction), causing various defects in the battery absorption layer, increasing carrier recombination opportunities, deteriorating battery performance, thereby reducing battery photoelectric conversion efficiency. Therefore, reducing the annealing temperature of the window layer, developing a non-vacuum, low temperature, low cost, and mass production of a transparent conductive film has become a current development trend.
技术问题technical problem
本发明的目的在于提供一种AZO透明导电薄膜及其制备方法，旨在解决现有AZO薄膜的制备方法成本高，以及因退火温度高导致已沉积好的薄膜中的金属原子扩散，影响器件特别是薄膜太阳能电池性能（特别是光电转化效率）的问题。The object of the present invention is to provide an AZO transparent conductive film and a preparation method thereof, aiming at solving the high cost of the preparation method of the existing AZO film, and the diffusion of metal atoms in the deposited film due to the high annealing temperature, which affects the device. It is a problem of thin film solar cell performance (especially photoelectric conversion efficiency).
本发明的另一目的在于提供一种含有AZO透明导电薄膜的薄膜太阳能电池。Another object of the present invention is to provide a thin film solar cell comprising an AZO transparent conductive film.
技术解决方案Technical solution
为实现上述发明目的，本发明采用的技术方案如下：In order to achieve the above object, the technical solution adopted by the present invention is as follows:
本发明一方面提供一种AZO透明导电薄膜的制备方法，包括以下步骤：An aspect of the invention provides a method for preparing an AZO transparent conductive film, comprising the following steps:
提供衬底，对所述衬底进行表面清洁处理；Providing a substrate, and performing surface cleaning treatment on the substrate;
提供氧化锌种子溶液，在所述衬底上沉积所述氧化锌种子溶液，制备结合在所述衬底表面的氧化锌种子层；Providing a zinc oxide seed solution, depositing the zinc oxide seed solution on the substrate to prepare a zinc oxide seed layer bonded to the surface of the substrate;
提供氧化锌沉积溶液，将沉积好氧化锌种子层的衬底置于所述氧化锌沉积溶液中，使所述氧化锌沉积溶液浸没所述衬底，且所述衬底中沉积有氧化锌种子层的表面不贴壁，在加热的条件下，在所述氧化锌沉积溶液中连续引入铝离子并搅拌处理，在所述氧化锌种子层表面生长制备AZO预制薄膜；Providing a zinc oxide deposition solution, placing a substrate on which the zinc oxide seed layer is deposited in the zinc oxide deposition solution, immersing the zinc oxide deposition solution in the substrate, and depositing zinc oxide seeds in the substrate The surface of the layer is not adhered to the wall, and under the heating condition, aluminum ions are continuously introduced into the zinc oxide deposition solution and stirred to form an AZO pre-formed film on the surface of the zinc oxide seed layer;
对所述AZO预制薄膜进行紫外照射处理，制备得到AZO透明导电薄膜。The AZO pre-formed film is subjected to ultraviolet irradiation treatment to prepare an AZO transparent conductive film.
本发明另一方面提供一种AZO透明导电薄膜，包括氧化锌种子层，以及结合在所述氧化锌种子层表面的阵列状AZO薄膜。Another aspect of the present invention provides an AZO transparent conductive film comprising a zinc oxide seed layer, and an array of AZO thin films bonded to the surface of the zinc oxide seed layer.
本发明再一方面提供一种薄膜太阳能电池，包括上述的AZO透明导电薄膜，或如上述方法制备的AZO透明导电薄膜。According to still another aspect of the present invention, a thin film solar cell comprising the above AZO transparent conductive film or an AZO transparent conductive film prepared by the above method is provided.
有益效果Beneficial effect
本发明提供的AZO透明导电薄膜的制备方法，采用水溶液法，先在衬底上制备氧化锌种子层，然后在所述氧化锌种子层上沉积铝掺杂的氧化锌，最后通过紫外照射处理，制备得到AZO透明导电薄膜。The method for preparing an AZO transparent conductive film provided by the invention adopts an aqueous solution method, first preparing a zinc oxide seed layer on a substrate, then depositing aluminum-doped zinc oxide on the zinc oxide seed layer, and finally performing ultraviolet irradiation treatment. An AZO transparent conductive film was prepared.
首先，该方法全程采用水溶液方法沉积薄膜，不需要高温退火处理，因此，可以避免高温退火过程中已沉积好的功能层中的金属原子扩散，对其他功能层的影响。特别的，当所述AZO透明导电薄膜用于薄膜太阳能电池时，可以避免在高温退火过程中功能层中的镉或锌扩散到薄膜太阳能电池的吸收层中，从而提高电池光电转化效率。将所述该AZO透明导电薄膜作为铜锌锡硫(CZTS)薄膜太阳能电池的导电窗口层，电池光电转化效率可达到5.47%。Firstly, the method uses an aqueous solution method to deposit a film, and does not require high-temperature annealing treatment. Therefore, the diffusion of metal atoms in the deposited functional layer during high-temperature annealing can be avoided, and the influence on other functional layers can be avoided. In particular, when the AZO transparent conductive film is used in a thin film solar cell, cadmium or zinc in the functional layer can be prevented from diffusing into the absorption layer of the thin film solar cell during high temperature annealing, thereby improving the photoelectric conversion efficiency of the battery. The AZO transparent conductive film is used as a conductive window layer of a copper zinc tin sulfide (CZTS) thin film solar cell, and the photoelectric conversion efficiency of the battery can reach 5.47%.
其次，本发明提供的AZO透明导电薄膜，通过对所述AZO预制薄膜进行紫外照射处理，可以除去薄膜中多余的碳杂质，提高薄膜的载流子浓度和导电性，获得导电性能优异的AZO透明导电薄膜。Next, the AZO transparent conductive film provided by the present invention can remove excess carbon impurities in the film by ultraviolet irradiation treatment of the AZO pre-formed film, improve carrier concentration and conductivity of the film, and obtain AZO transparent excellent in electrical conductivity. Conductive film.
再次，本发明中，制备AZO透明导电薄膜的条件温和，不需要使用复杂昂贵的设备，有利于降低AZO透明导电薄膜的生产成本。Further, in the present invention, the conditions for preparing the AZO transparent conductive film are mild, and it is not necessary to use complicated and expensive equipment, which is advantageous for reducing the production cost of the AZO transparent conductive film.
本发明提供的AZO透明导电薄膜导电性能优异，制造成本低廉，是ITO透明导电薄膜的理想替代者，可广泛用于CIGS和CZTS薄膜太阳能电池，并具有较好的电池光电转化效率。The AZO transparent conductive film provided by the invention has excellent electrical conductivity and low manufacturing cost, and is an ideal substitute for the ITO transparent conductive film, and can be widely used in CIGS and CZTS thin film solar cells, and has better photoelectric conversion efficiency of the battery.
本发明提供的薄膜太阳能电池，由于含有上述AZO透明导电薄膜，不仅可以降低成本，而且能够提高电池光电转化效率。The thin film solar cell provided by the present invention can not only reduce the cost but also improve the photoelectric conversion efficiency of the battery because the AZO transparent conductive film is contained.
先是制备氧化锌种子层水溶液，在玻璃表面沉积均匀沉积氧化锌种子层，接着制备铝掺杂氧化锌生长的水溶液，在种子层表面沉积致密均匀柱状的铝掺杂氧化锌纳米阵列，接着采用UV灯辐射，即可得到光电性能优异的铝掺杂氧化锌透明导电薄膜。First, an aqueous solution of zinc oxide seed layer is prepared, a zinc oxide seed layer is uniformly deposited on the surface of the glass, and then an aqueous solution of aluminum-doped zinc oxide is prepared, and a dense and uniform columnar aluminum-doped zinc oxide nano-array is deposited on the surface of the seed layer, followed by UV. When the lamp is irradiated, an aluminum-doped zinc oxide transparent conductive film excellent in photoelectric properties can be obtained.
附图说明DRAWINGS
图1是本发明实施例提供的AZO透明导电薄膜的制备工艺流程图；1 is a flow chart of a process for preparing an AZO transparent conductive film according to an embodiment of the present invention;
图2是本发明实施例1提供的AZO透明导电薄膜的平面图；2 is a plan view showing an AZO transparent conductive film provided in Embodiment 1 of the present invention;
图3是本发明实施例1提供的AZO透明导电薄膜的截面图；Figure 3 is a cross-sectional view showing an AZO transparent conductive film provided in Example 1 of the present invention;
图4是本发明实施例1提供的AZO透明导电薄膜的透光性检测效果图；4 is a view showing the effect of detecting light transmittance of the AZO transparent conductive film provided in Example 1 of the present invention;
图5是本发明实施例2提供的CZTA薄膜太阳能电池结构示意图；5 is a schematic structural view of a CZTA thin film solar cell according to Embodiment 2 of the present invention;
图6是本发明实施例2提供的CZTA薄膜太阳能电池结构的截面图；6 is a cross-sectional view showing the structure of a CZTA thin film solar cell according to Embodiment 2 of the present invention;
图7是本发明实施例2提供的CZTA薄膜太阳能电池结构的电流电压曲线图。7 is a graph showing current and voltage curves of a CZTA thin film solar cell structure according to Embodiment 2 of the present invention.
本发明的实施方式Embodiments of the invention
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clear, the present invention will be further described in detail below with reference to the embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
在本发明的描述中，需要理解的是，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本发明的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。In the description of the present invention, it is to be understood that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, features defining "first" and "second" may include one or more of the features either explicitly or implicitly. In the description of the present invention, the meaning of "a plurality" is two or more unless specifically and specifically defined otherwise.
结合图1，本发明实施例提供了一种AZO透明导电薄膜的制备方法，包括以下步骤：With reference to FIG. 1, an embodiment of the present invention provides a method for preparing an AZO transparent conductive film, which includes the following steps:
S01.提供衬底，对所述衬底进行表面清洁处理；S01. Providing a substrate, and performing surface cleaning treatment on the substrate;
S02.提供氧化锌种子溶液，在所述衬底上沉积所述氧化锌种子溶液，制备结合在所述衬底表面的氧化锌种子层；S02. Providing a zinc oxide seed solution, depositing the zinc oxide seed solution on the substrate to prepare a zinc oxide seed layer bonded to the surface of the substrate;
S03.提供氧化锌沉积溶液，将沉积好氧化锌种子层的衬底置于所述氧化锌沉积溶液中，使所述氧化锌沉积溶液浸没所述衬底，且所述衬底中沉积有氧化锌种子层的表面不贴壁，在加热的条件下，在所述氧化锌沉积溶液中连续引入铝离子并搅拌处理，在所述氧化锌种子层表面生长制备AZO预制薄膜；S03. Providing a zinc oxide deposition solution, placing a substrate on which the zinc oxide seed layer is deposited in the zinc oxide deposition solution, immersing the zinc oxide deposition solution in the substrate, and depositing oxidation in the substrate The surface of the zinc seed layer is not adhered to the wall, and under the heating condition, aluminum ions are continuously introduced into the zinc oxide deposition solution and stirred to form an AZO pre-formed film on the surface of the zinc oxide seed layer;
S04.对所述AZO预制薄膜进行紫外照射处理，制备得到AZO透明导电薄膜。S04. The AZO pre-formed film is subjected to ultraviolet irradiation treatment to prepare an AZO transparent conductive film.
本发明实施例提供的AZO透明导电薄膜的制备方法，采用水溶液法，先在衬底上制备氧化锌种子层，然后在所述氧化锌种子层上沉积铝掺杂的氧化锌，最后通过紫外照射处理，制备得到AZO透明导电薄膜。The method for preparing an AZO transparent conductive film provided by the embodiment of the invention adopts an aqueous solution method, first preparing a zinc oxide seed layer on a substrate, then depositing aluminum-doped zinc oxide on the zinc oxide seed layer, and finally passing ultraviolet irradiation. The AZO transparent conductive film was prepared by treatment.
首先，该方法全程采用水溶液方法沉积薄膜，不需要高温退火处理，因此，可以避免高温退火过程中已沉积好的功能层中的金属原子扩散，对其他功能层的影响。特别的，当所述AZO透明导电薄膜用于薄膜太阳能电池时，可以避免在高温退火过程中功能层中的镉或锌扩散到薄膜太阳能电池的吸收层中，从而提高电池光电转化效率。将所述该AZO透明导电薄膜作为铜锌锡硫(CZTS)薄膜太阳能电池的导电窗口层，电池光电转化效率可达到5.47%。Firstly, the method uses an aqueous solution method to deposit a film, and does not require high-temperature annealing treatment. Therefore, the diffusion of metal atoms in the deposited functional layer during high-temperature annealing can be avoided, and the influence on other functional layers can be avoided. In particular, when the AZO transparent conductive film is used in a thin film solar cell, cadmium or zinc in the functional layer can be prevented from diffusing into the absorption layer of the thin film solar cell during high temperature annealing, thereby improving the photoelectric conversion efficiency of the battery. The AZO transparent conductive film is used as a conductive window layer of a copper zinc tin sulfide (CZTS) thin film solar cell, and the photoelectric conversion efficiency of the battery can reach 5.47%.
其次，本发明实施例提供的AZO透明导电薄膜，通过对所述AZO预制薄膜进行紫外照射处理，可以除去薄膜中多余的碳杂质，提高薄膜的载流子浓度和导电性，获得导电性能优异的AZO透明导电薄膜。The AZO transparent conductive film provided by the embodiment of the present invention can remove excess carbon impurities in the film by ultraviolet irradiation treatment on the AZO pre-formed film, improve carrier concentration and conductivity of the film, and obtain excellent electrical conductivity. AZO transparent conductive film.
再次，本发明实施例中，制备AZO透明导电薄膜的条件温和，不需要使用复杂昂贵的设备，有利于降低AZO透明导电薄膜的生产成本。Further, in the embodiment of the present invention, the conditions for preparing the AZO transparent conductive film are mild, and it is not necessary to use complicated and expensive equipment, which is advantageous for reducing the production cost of the AZO transparent conductive film.
具体的，上述步骤S01中，用作AZO透明导电薄膜的衬底，没有严格限定，可选用本领域常用的衬底，如超白玻璃。为了提高材料在所述衬底上的附着力，在沉积氧化锌种子溶液之前，需要对所述衬底进行表面清洁处理。Specifically, in the above step S01, the substrate used as the AZO transparent conductive film is not strictly limited, and a substrate commonly used in the art, such as ultra-white glass, may be selected. In order to improve the adhesion of the material on the substrate, the substrate needs to be surface cleaned prior to deposition of the zinc oxide seed solution.
作为一种优选实施方式，所述表面清洁处理的方法如下：As a preferred embodiment, the method of surface cleaning treatment is as follows:
用去污粉初步清洗衬底表面污渍后，使用玻璃清洗剂（优选为体积浓度为5%的碱性洗涤剂水溶液，碱性洗涤剂和去离子水按体积比为5:95制备）进行清洗，去掉玻璃表面难以去除的油污。After preliminarily cleaning the surface surface stain with the decontamination powder, clean it with a glass cleaner (preferably an aqueous alkaline detergent solution having a volume concentration of 5%, an alkaline detergent and deionized water at a volume ratio of 5:95). Remove the oil that is difficult to remove on the glass surface.
接着，将所述衬底在干净的去离子水中冲洗后，放入丙酮中，除去玻璃表面的有机杂质，再在异丙醇中超声清洗10 min。Next, the substrate was rinsed in clean deionized water, placed in acetone, and the organic impurities on the surface of the glass were removed, followed by ultrasonic cleaning in isopropanol for 10 min.
然后，将所述衬底放入低浓度玻璃清洗剂中清洗，除去所述衬底表面颗粒杂质，再次使用去离子水冲洗，最后放入无水乙醇中超声清洗10 min后待用。Then, the substrate is washed in a low-concentration glass cleaning agent to remove particulate impurities on the surface of the substrate, washed again with deionized water, and finally ultrasonically cleaned in anhydrous ethanol. Min after use.
采用上述方法进行表面清洁处理后的所述衬底表面清洁如新，有利于氧化锌水溶液的沉积。The surface of the substrate after the surface cleaning treatment by the above method is as clean as new, which is advantageous for deposition of an aqueous zinc oxide solution.
本发明实施例中，可根据形成的AZO透明导电薄膜的规格，可对大片衬底进行切割裁剪，以获得满足要求的衬底尺寸，如25 mm×25 mm。应当理解的是，可先对大片衬底进行切割裁剪，然后进行表面清洁处理；也可以先对大片衬底进行表面清洁处理后再行切割裁剪。优选的，为了避免切割裁剪过程中引入杂质或污物，优选先表面清洁处理后切割裁剪的方式。In the embodiment of the present invention, a large substrate can be cut and cut according to the specifications of the formed AZO transparent conductive film to obtain a desired substrate size, such as 25 mm × 25 mm. It should be understood that the large substrate may be first cut and then subjected to surface cleaning; or the large substrate may be surface-cleaned before cutting and cutting. Preferably, in order to avoid the introduction of impurities or dirt during the cutting and cutting process, it is preferred to cut the cutting after the surface cleaning treatment.
上述步骤S02中，由于掺铝氧化锌与所述衬底特别是玻璃衬底表面的结合力不强，结合不牢固，甚至难以在所述衬底表面形核，因此，在沉积掺铝氧化锌之前，先在所述衬底上沉积一层氧化锌种子层，用于后续产率氧化锌纳米阵列的形成和生长。具体的，利用氧化锌种子溶液在所述衬底表面形核，沉积形成过渡层即氧化锌种子层。进一步的，以所述氧化锌种子层作为媒介，在所述衬底上沉积掺铝氧化锌。In the above step S02, since the bonding strength of the aluminum-doped zinc oxide to the surface of the substrate, particularly the glass substrate, is not strong, the bonding is not strong, and it is even difficult to nucleate the surface of the substrate, and therefore, the aluminum-doped zinc oxide is deposited. Previously, a layer of zinc oxide seed was deposited on the substrate for subsequent formation and growth of zinc oxide nanoarrays. Specifically, a zinc oxide seed solution is used to nucleate the surface of the substrate to form a transition layer, that is, a zinc oxide seed layer. Further, aluminum-doped zinc oxide is deposited on the substrate by using the zinc oxide seed layer as a medium.
本发明实施例中，所述氧化锌种子溶液为添加有过量氨水的氧化锌水溶液，通过添加过量的氨水，有利于提高氧化锌的溶解度。作为一个具体实施例，所述氧化锌种子溶液的制备方法为：将氧化锌粉末分散于去离子水中，然后加入氨水充分搅拌，促进氧化性粉末的溶解。进一步的，将溶解后的溶液进行过滤处理，去除过量的氧化锌杂质，澄清溶液留存。具体的，过滤处理采用直径为0.45μm的过滤器进行过滤。In the embodiment of the invention, the zinc oxide seed solution is an aqueous solution of zinc oxide added with excess ammonia water, and the addition of excess ammonia water is beneficial to increase the solubility of zinc oxide. As a specific embodiment, the zinc oxide seed solution is prepared by dispersing zinc oxide powder in deionized water, and then adding ammonia water to stir well to promote dissolution of the oxidative powder. Further, the dissolved solution is subjected to a filtration treatment to remove excess zinc oxide impurities, and the clear solution remains. Specifically, the filtration treatment was carried out by using a filter having a diameter of 0.45 μm.
具体的，在所述衬底上沉积所述氧化锌种子溶液，随着所述氧化锌种子溶液中氨水的挥发，氧化锌的溶解性能降低，进而附着在所述衬底表面形成膜层。优选的，所述氧化锌种子溶液中氧化锌的浓度为20-50mmol/L，以便形成致密均匀的氧化锌种子层。若所述氧化锌种子溶液中氧化锌的浓度过低，则形成的膜层不致密。若所述氧化锌种子溶液中氧化锌的浓度过高，则沉积在所述衬底上的氧化锌颗粒不均匀，得到的表面膜层厚度不均匀，影响后续沉积的产率氧化锌薄膜的厚度均一性，进一步影响薄膜性能的稳定性。此外，所述氧化锌种子溶液中氧化锌的浓度过高，也会造成得到的氧化锌种子层的厚度过厚，影响AZO透明导电薄膜的性能。进一步优选的，所述氧化锌种子溶液中氧化锌的浓度为30-40mmol/L。Specifically, the zinc oxide seed solution is deposited on the substrate, and as the ammonia water in the zinc oxide seed solution is volatilized, the dissolution property of the zinc oxide is lowered, and further adhered to the surface of the substrate to form a film layer. Preferably, the concentration of zinc oxide in the zinc oxide seed solution is 20-50 mmol/L to form a dense and uniform zinc oxide seed layer. If the concentration of zinc oxide in the zinc oxide seed solution is too low, the formed film layer is not dense. If the concentration of zinc oxide in the zinc oxide seed solution is too high, the zinc oxide particles deposited on the substrate are not uniform, and the obtained surface film layer is not uniform in thickness, which affects the thickness of the subsequent deposition of the zinc oxide film. Uniformity further affects the stability of film properties. In addition, if the concentration of zinc oxide in the zinc oxide seed solution is too high, the thickness of the obtained zinc oxide seed layer is too thick, which affects the performance of the AZO transparent conductive film. Further preferably, the concentration of zinc oxide in the zinc oxide seed solution is 30-40 mmol/L.
在所述衬底上沉积所述氧化锌种子溶液，制备结合在所述衬底表面的氧化锌种子层的方法，优选采用旋涂法。作为一个具体实施例，采用旋涂法制备氧化锌种子层的方法为：A method of depositing the zinc oxide seed solution on the substrate to prepare a zinc oxide seed layer bonded to the surface of the substrate, preferably using a spin coating method. As a specific embodiment, the method for preparing a zinc oxide seed layer by spin coating is as follows:
取出清洗干净的衬底，将其放入氮气气流下吹干后放在匀胶机的样品台上。设定好匀胶机的预转转数和预转时间、旋转转数和旋转时间，吸取氧化锌氨水溶液并将其滴涂到所述呈第上，确保氧化锌种子层溶液完全覆盖样品表面，然后打开真空泵以及匀胶机真空控制开关，按开始按钮进行旋涂。将旋涂后的衬底放在恒温台上，恒温加热一定时间后在空气中冷却，即形成氧化锌种子层。The cleaned substrate was taken out, blown under a nitrogen stream, and placed on the sample stage of the homogenizer. Set the pre-rotation number and pre-rotation time, rotation rotation number and rotation time of the homogenizer, absorb the zinc oxide ammonia aqueous solution and drip it onto the first surface to ensure that the zinc oxide seed layer solution completely covers the sample surface. , then turn on the vacuum pump and the vacuum control vacuum control switch, press the start button to spin. The spin-coated substrate is placed on a thermostatic table, and heated at a constant temperature for a certain period of time to be cooled in the air to form a zinc oxide seed layer.
上述步骤S03中，本发明实施例通过溶液法制备AZO透明导电薄膜。具体的，先提供用于沉积的氧化锌沉积溶液。所述氧化锌沉积溶液中含有氧化锌、氨水和去离子水，其中，所述氨水用于提高所述氧化锌的溶解度，同时，在制备AZO预制薄膜时，通过氨水的挥发，实现氧化锌的沉积。优选的，所述氨水的添加量满足：使所述氧化锌沉积溶液的pH值为9-12。在该pH范围内，可以提高氧化锌在去离子水中的溶解性能，有利于控制氧化锌的沉积速率，并提高得到的膜层的致密性。同时，本发明通过氨水的挥发，降低氧化锌的溶解度，进而掺铝后的氧化锌在氧化锌种子层表面的生长。In the above step S03, the embodiment of the present invention prepares an AZO transparent conductive film by a solution method. Specifically, a zinc oxide deposition solution for deposition is first provided. The zinc oxide deposition solution contains zinc oxide, ammonia water and deionized water, wherein the ammonia water is used to increase the solubility of the zinc oxide, and at the same time, in the preparation of the AZO pre-formed film, zinc oxide is realized by volatilization of ammonia water. Deposition. Preferably, the ammonia water is added in an amount such that the pH of the zinc oxide deposition solution is 9-12. In this pH range, the solubility of zinc oxide in deionized water can be improved, the deposition rate of zinc oxide can be controlled, and the density of the obtained film layer can be improved. At the same time, the present invention reduces the solubility of zinc oxide by the evaporation of ammonia water, and further the growth of zinc oxide after aluminum doping on the surface of the zinc oxide seed layer.
进一步优选的，所述氧化锌沉积溶液中还含有柠檬酸铵、硝酸铵。所述柠檬酸铵、硝酸铵可以控制掺铝的氧化锌在氧化锌种子层表面生长时的晶体结构和形貌，从而得到阵列结构的AZO透明导电薄膜，具体的，阵列结构为柱状结构。相较于不具备阵列结构的AZO透明导电薄膜，阵列结构的AZO透明导电薄膜在电荷如电子传输过程中，电子沿着阵列直接传输，可以减少晶界的阻碍作用，从而提高光电效果。Further preferably, the zinc oxide deposition solution further contains ammonium citrate and ammonium nitrate. The ammonium citrate and ammonium nitrate can control the crystal structure and morphology of the aluminum-doped zinc oxide on the surface of the zinc oxide seed layer, thereby obtaining an AZO transparent conductive film of an array structure. Specifically, the array structure is a columnar structure. Compared with the AZO transparent conductive film which does not have the array structure, the AZO transparent conductive film of the array structure transmits electrons directly along the array during charge, such as electron transport, which can reduce the barrier effect of the grain boundary and thereby improve the photoelectric effect.
更进一步地，所述氧化锌沉积溶液中，各组成物质的浓度优选为：Further, in the zinc oxide deposition solution, the concentration of each constituent substance is preferably:
氧化锌        20~60 mmol/L；Zinc oxide 20~60 mmol/L;
柠檬酸铵      0.01~4 mmol/L；Ammonium citrate 0.01~4 mmol/L;
硝酸铵浓度    0.01~2 mmol/L。The concentration of ammonium nitrate is 0.01~2 mmol/L.
合适的上述物质的浓度，能够掺铝氧化锌纳米阵列，且掺铝氧化锌纳米阵列均匀致密。具体的，若所述氧化锌的浓度过高，氧化锌的生长速度快，铝的掺杂速度跟不上氧化锌的生长速度，导致最终得到的AZO透明导电薄膜中铝掺杂含量不满足要求。此外，氧化锌的浓度过高，沉积过程中形成的氧化锌颗粒粗大，氧化锌颗粒之间形成孔隙，降低最终得到的AZO透明导电薄膜的性能。若所述氧化锌的浓度过低，氧化锌的生长速度慢。而所述柠檬酸铵、硝酸铵的含量关于着掺铝氧化锌纳米阵列的形成，即AZO透明导电薄膜是否具备阵列结构。所述柠檬酸铵、硝酸铵作为一种添加剂，在水溶液中以柠檬酸根离子、硝酸根离子和铵根离子的形式出现，由于静电吸引作用，柠檬酸根离子、硝酸根离子会强烈的吸附于氧化锌的晶面，从而占据大部分锌和氧的生长位置，使得氧化锌纳米棒沿c轴方向的生长受到抑制，而纳米棒横向的生长受到影响较小，因此纳米棒有向横向生长的趋势，长径比减小，纳米棒之间可以彼此接触形成致密薄膜。而同时，引入的铵根离子由于在溶液中本身就存在，因此不会对溶液化学性质产生影响。若所述檬酸铵和所述硝酸铵的浓度过高，氧化锌纳米棒纵向的生长限制严重，棒状氧化锌会长成片状，这样就不利于载流子迁移率的提高，造成薄膜电学性能的降低。作为一个具体实施例，所述氧化锌沉积溶液的制备方法为：取干净的容器如烧杯，称取一定量的去离子水，分别向该烧杯中加入所需的柠檬酸铵、硝酸铵、氧化锌粉末和氨水试剂。室温下搅拌24 h，再采用直径为0.45 μm的过滤器过滤除去溶液中过量的氧化锌杂质，留澄清溶液待用。A suitable concentration of the above substances can be doped with an aluminum zinc oxide nano-array, and the aluminum-doped zinc oxide nano-array is uniformly dense. Specifically, if the concentration of the zinc oxide is too high, the growth rate of the zinc oxide is fast, and the doping speed of the aluminum cannot keep up with the growth rate of the zinc oxide, so that the aluminum doping content of the finally obtained AZO transparent conductive film does not meet the requirements. . In addition, the concentration of zinc oxide is too high, the zinc oxide particles formed during the deposition process are coarse, and pores are formed between the zinc oxide particles, thereby lowering the properties of the finally obtained AZO transparent conductive film. If the concentration of the zinc oxide is too low, the growth rate of zinc oxide is slow. The content of the ammonium citrate and ammonium nitrate is related to the formation of the aluminum-doped zinc oxide nano-array, that is, whether the AZO transparent conductive film has an array structure. The ammonium citrate and ammonium nitrate are used as an additive in the form of citrate ions, nitrate ions and ammonium ions in an aqueous solution. Due to electrostatic attraction, citrate ions and nitrate ions are strongly adsorbed to the oxidation. The crystal plane of zinc, which occupies most of the growth position of zinc and oxygen, inhibits the growth of zinc oxide nanorods along the c-axis direction, while the lateral growth of nanorods is less affected, so the nanorods tend to grow laterally. The aspect ratio is reduced, and the nanorods can contact each other to form a dense film. At the same time, the introduced ammonium ions are present in the solution itself and therefore do not affect the chemical properties of the solution. If the concentration of the ammonium citrate and the ammonium nitrate is too high, the longitudinal growth limitation of the zinc oxide nanorods is severe, and the rod-shaped zinc oxide will grow into a sheet shape, which is disadvantageous to the increase of carrier mobility, resulting in thin film electrical power. Reduced performance. As a specific embodiment, the zinc oxide deposition solution is prepared by taking a clean container such as a beaker, weighing a certain amount of deionized water, and adding the desired ammonium citrate, ammonium nitrate, and oxidation to the beaker. Zinc powder and ammonia reagent. After stirring for 24 h at room temperature, excess zinc oxide impurities in the solution were removed by filtration using a filter having a diameter of 0.45 μm, leaving a clear solution for use.
本发明实施例中，将沉积好氧化锌种子层的衬底置于所述氧化锌沉积溶液中，使所述氧化锌沉积溶液浸没所述衬底，且所述衬底中沉积有氧化锌种子层的表面不贴壁，以便在所述氧化锌种子层表面生长掺铝氧化锌。优选的，所述衬底竖直放置在所述氧化锌沉积溶液中。所述衬底竖直放置在所述氧化锌沉积溶液时，沉降过程中可以防止杂质落入所述氧化锌种子层表面，且有利于节约空间，同时实现多个衬底的沉积。进一步优选的，将多份衬底同时放置在所述氧化锌沉积溶液中，制备AZO透明导电薄膜。将所述衬底竖直放置在所述氧化锌沉积溶液，可以借助模具实现，模具的选择没有具体要求。In an embodiment of the invention, a substrate on which a zinc oxide seed layer is deposited is placed in the zinc oxide deposition solution, the zinc oxide deposition solution is immersed in the substrate, and zinc oxide seeds are deposited in the substrate. The surface of the layer is not adhered to grow aluminum-doped zinc oxide on the surface of the zinc oxide seed layer. Preferably, the substrate is placed vertically in the zinc oxide deposition solution. When the substrate is placed vertically on the zinc oxide deposition solution, impurities may be prevented from falling into the surface of the zinc oxide seed layer during sedimentation, and space saving is facilitated, and deposition of a plurality of substrates is simultaneously achieved. Further preferably, a plurality of substrates are simultaneously placed in the zinc oxide deposition solution to prepare an AZO transparent conductive film. The substrate is placed vertically in the zinc oxide deposition solution, which can be realized by means of a mold, and the selection of the mold is not specifically required.
本发明实施例采用水溶液法制备AZO透明导电薄膜的过程中，通过加热实现氧化锌的沉积（挥发氨水，使溶液中的氧化锌出现过饱和）；同时，在氧化锌沉积溶液中连续引入铝离子，与沉积的氧化锌实现掺杂。具体优选的，采用蠕动泵向所述氧化锌沉积溶液中连续加入九水硝酸铝或浸入铝片的方式，在所述氧化锌沉积溶液中连续引入铝离子，从而实现均匀掺杂。作为一个具体优选实施例，采用蠕动泵在所述氧化锌沉积溶液中连续加入九水硝酸铝引入铝离子的步骤中，铝离子的引入条件满足：所述蠕动泵的转速为≥0.1 rpm，所述氧化锌沉积溶液中的九水硝酸铝浓度为10~300 mmol/L。作为另一个具体优选实施例，采用蠕动泵在所述氧化锌沉积溶液中连续浸入铝片引入铝离子的步骤中，铝离子的引入条件满足：所述蠕动泵的转速为≥0.1 rpm，所述铝片的浸入面积为1~10 cm 2。氧化锌柱状晶粒生长过程中，氧化锌的柱状面带有正电，其顶面带有负电，因此在静电吸附的作用下会使得不同的表面对溶液中离子的吸引能力不同。而铝离子在碱性溶液中会以[Al(OH) 4 ] −形式存在，因此大部分将吸附于氧化锌柱状晶的晶面，这样就会造成柱状面可以接受锌的位置大量减少，从而抑制柱状晶横向的生长，造成晶粒尺寸的减小，长径比增加。因此，若所述九水硝酸铝浓度过高或浸入的铝片面积过大，氧化锌柱状晶粒生长受到限制，则薄膜已不能在衬底上生长；若所述九水硝酸铝浓度过低或浸入的铝片面积过小，氧化锌中铝掺杂浓度下降，氧化锌薄膜导电性能下降。 In the process of preparing the AZO transparent conductive film by the aqueous solution method, the zinc oxide is deposited by heating (volatile ammonia water to supersaturate the zinc oxide in the solution); at the same time, the aluminum ion is continuously introduced into the zinc oxide deposition solution. Doping with deposited zinc oxide. Specifically, a peristaltic pump is used to continuously add aluminum nitrate nonahydrate or immersed in an aluminum flake to the zinc oxide deposition solution, and aluminum ions are continuously introduced into the zinc oxide deposition solution to achieve uniform doping. As a specific preferred embodiment, the step of introducing aluminum nitrate into the aluminum oxide by continuously adding the aluminum nitrate nonahydrate in the zinc oxide deposition solution by using a peristaltic pump satisfies the introduction condition of the aluminum ion: the rotational speed of the peristaltic pump is ≥0.1 rpm. The concentration of aluminum nitrate in the zinc oxide deposition solution is 10 to 300 mmol/L. As another specific preferred embodiment, the step of continuously immersing the aluminum sheet into the aluminum ion in the zinc oxide deposition solution by using a peristaltic pump, the introduction condition of the aluminum ion is satisfied: the rotational speed of the peristaltic pump is ≥0.1 rpm, The immersion area of the aluminum sheet is 1 to 10 cm 2 . During the growth of zinc oxide columnar grains, the columnar surface of zinc oxide is positively charged, and its top surface is negatively charged. Therefore, under the action of electrostatic adsorption, different surfaces may have different attracting abilities to ions in the solution. The aluminum ion will exist in the form of [Al(OH) 4 ] − in the alkaline solution, so most of it will adsorb to the crystal plane of the zinc oxide columnar crystal, which will cause the columnar surface to accept a large decrease in the position of zinc. The growth of the columnar crystal lateral direction is suppressed, resulting in a decrease in grain size and an increase in aspect ratio. Therefore, if the concentration of the aluminum nitrate nonahydrate is too high or the area of the immersed aluminum sheet is too large, the growth of the zinc oxide columnar grain is limited, the film cannot grow on the substrate; if the concentration of the aluminum nitrate nonahydrate is too low Or the area of the immersed aluminum sheet is too small, the aluminum doping concentration in the zinc oxide is decreased, and the conductive property of the zinc oxide film is decreased.
本发明实施例中，所述加热的目的在于挥发所述氧化锌沉积溶液中的氨水，而加热的温度对本发明实施例制备AZO预制薄膜的影响较大。优选的，所述氧化锌沉积溶液中含有氧化锌、氨水和去离子水，所述氧化锌沉积溶液的pH值为9-12，所述加热的温度为60-90℃。再次温度范围内，氨水能够保证合适的挥发速率，从而有利于形成晶体结构形貌较好的AZO预制薄膜。若所述加热的温度过低，则挥发速度慢；若所述加热的温度过高，则氨水挥发过快，氧化锌的生长速度快，铝的掺杂速度跟不上氧化锌的生长速度，导致最终得到的AZO透明导电薄膜中铝掺杂含量不满足要求。此外，沉积形成的氧化锌颗粒粗大，氧化锌颗粒之间形成孔隙，降低最终得到的AZO透明导电薄膜的性能。In the embodiment of the present invention, the purpose of the heating is to volatilize the ammonia water in the zinc oxide deposition solution, and the heating temperature has a great influence on the preparation of the AZO pre-formed film in the embodiment of the invention. Preferably, the zinc oxide deposition solution contains zinc oxide, ammonia water and deionized water, the zinc oxide deposition solution has a pH of 9-12, and the heating temperature is 60-90 °C. In the temperature range again, the ammonia water can ensure a proper evaporation rate, which is beneficial to the formation of AZO prefabricated film with good crystal structure. If the heating temperature is too low, the volatilization speed is slow; if the heating temperature is too high, the ammonia water volatilizes too fast, the zinc oxide grows fast, and the doping speed of aluminum cannot keep up with the growth rate of zinc oxide. The aluminum doping content in the finally obtained AZO transparent conductive film is not satisfactory. In addition, the zinc oxide particles formed by the deposition are coarse, and pores are formed between the zinc oxide particles, thereby lowering the properties of the finally obtained AZO transparent conductive film.
作为一种优选实施方式，在加热容器中加入所述氧化锌沉积溶液，将沉积好氧化锌种子层的衬底置于所述氧化锌沉积溶液中，使所述氧化锌沉积溶液浸没所述衬底，且所述衬底中沉积有氧化锌种子层的表面不贴壁；将所述加热容器置于水浴锅中，在加热的条件下，在所述氧化锌沉积溶液中连续引入铝离子并搅拌处理，在所述氧化锌种子层表面生长制备AZO预制薄膜。通过水浴加热所述氧化锌沉积溶液，可以更好地控制反应温度，使沉积匀速发生。As a preferred embodiment, the zinc oxide deposition solution is added to the heating vessel, and the substrate on which the zinc oxide seed layer is deposited is placed in the zinc oxide deposition solution, and the zinc oxide deposition solution is immersed in the lining. a bottom, and a surface of the substrate in which the zinc oxide seed layer is deposited is not adhered; the heating vessel is placed in a water bath, and aluminum ions are continuously introduced into the zinc oxide deposition solution under heating The AZO pre-formed film was prepared by growing on the surface of the zinc oxide seed layer by stirring. By heating the zinc oxide deposition solution by a water bath, the reaction temperature can be better controlled, and deposition can occur at a uniform rate.
将生长完AZO预制薄膜的样品从水溶液中取出，用大量的去离子水冲洗后，接着在氮气流下吹干。The sample from which the AZO pre-formed film was grown was taken out from the aqueous solution, rinsed with a large amount of deionized water, and then blown dry under a nitrogen stream.
上述步骤S04中，对所述AZO预制薄膜进行紫外照射处理，接着，采用UV照射灯对样品表面进行照射处理5~10 min，完成AZO薄膜样品的制备。除去薄膜中多余的碳杂质，提高薄膜的载流子浓度和导电性。优选的，所述紫外照射处理的条件为：UV灯辐射有效面积100 cm 2，辐射时间1~20 min。 In the above step S04, the AZO pre-formed film is subjected to ultraviolet irradiation treatment, and then the surface of the sample is irradiated with a UV irradiation lamp for 5 to 10 minutes to complete preparation of the AZO film sample. Excess carbon impurities in the film are removed to increase the carrier concentration and conductivity of the film. Preferably, the ultraviolet irradiation treatment condition is: the UV lamp has an effective area of 100 cm 2 and a radiation time of 1 to 20 min.
本发明实施例提供一种AZO透明导电薄膜，包括氧化锌种子层，以及结合在所述氧化锌种子层表面的阵列状AZO薄膜。Embodiments of the present invention provide an AZO transparent conductive film, including a zinc oxide seed layer, and an array of AZO thin films bonded to the surface of the zinc oxide seed layer.
本发明实施例提供的AZO透明导电薄膜导电性能优异，制造成本低廉，是ITO透明导电薄膜的理想替代者，可广泛用于CIGS和CZTS薄膜太阳能电池，并具有较好的电池光电转化效率。本发明实施例提供的AZO透明导电薄膜，可以通过上述方法制备获得。The AZO transparent conductive film provided by the embodiment of the invention has excellent electrical conductivity and low manufacturing cost, and is an ideal substitute for the ITO transparent conductive film, and can be widely used in CIGS and CZTS thin film solar cells, and has better photoelectric conversion efficiency of the battery. The AZO transparent conductive film provided by the embodiment of the invention can be obtained by the above method.
相较于不具备阵列结构的AZO透明导电薄膜，阵列结构的AZO透明导电薄膜在电荷如电子传输过程中，电子沿着阵列直接传输，可以减少晶界的阻碍作用，有益于载流子的收集，从而提高太阳电池的光电转化效率。优选的，所述阵列状AZO薄膜的阵列为柱状纳米阵列。Compared with the AZO transparent conductive film without the array structure, the AZO transparent conductive film of the array structure transmits electrons directly along the array during charge, such as electron transport, which can reduce the barrier effect of the grain boundary and is beneficial to the collection of carriers. , thereby improving the photoelectric conversion efficiency of the solar cell. Preferably, the array of the array of AZO thin films is a columnar nano array.
本发明再一方面提供一种薄膜太阳能电池，包括上述的AZO透明导电薄膜，或如上述方法制备的AZO透明导电薄膜。According to still another aspect of the present invention, a thin film solar cell comprising the above AZO transparent conductive film or an AZO transparent conductive film prepared by the above method is provided.
本发明实施例提供的薄膜太阳能电池，由于含有上述AZO透明导电薄膜，不仅可以降低成本，而且能够提高电池光电转化效率。The thin film solar cell provided by the embodiment of the invention can not only reduce the cost but also improve the photoelectric conversion efficiency of the battery because the AZO transparent conductive film is contained.
所述薄膜太阳能电池可以为铜铟镓硒(CIGS)或铜锌锡硫(CZTS)薄膜太阳能电池。作为一个具体优选实施例，所述薄膜太阳能电池为CZTA薄膜太阳能电池，包括玻璃衬底，以及依次设置在所述玻璃衬底上的钼金属层、CATS光吸收层、硫化镉缓冲层、AZO透明导电薄膜和银电极。所述CZTA薄膜太阳能电池可以采用下述方法制备获得：The thin film solar cell may be a copper indium gallium selenide (CIGS) or a copper zinc tin sulfide (CZTS) thin film solar cell. As a particularly preferred embodiment, the thin film solar cell is a CZTA thin film solar cell, including a glass substrate, and a molybdenum metal layer, a CATS light absorbing layer, a cadmium sulfide buffer layer, and an AZO transparent layer sequentially disposed on the glass substrate. Conductive film and silver electrode. The CZTA thin film solar cell can be prepared by the following method:
清洗沉积有金属Mo的钠钙玻璃，清洗方法可参照所述衬底的表面清洁处理的方法，接着连续采用溶胶凝胶技术与高温回火两步法制备CZTS光吸收层，采用化学浴沉积硫化镉缓冲层，200°C回火处理10 min，接着采用所述AZO透明导电薄膜的制备方法继续在样品表面制备AZO透明导电薄膜，使用导电银胶制备顶电极（接线电极），完成CZTS薄膜太阳能电池制备。Cleaning the soda lime glass deposited with metal Mo, the cleaning method can refer to the surface cleaning treatment method of the substrate, and then continuously adopting the sol-gel technique and the high-temperature tempering two-step method to prepare the CZTS light absorbing layer, and chemical bath deposition vulcanization The cadmium buffer layer is tempered at 200 ° C for 10 min, and then the AZO transparent conductive film is prepared on the surface of the sample by using the preparation method of the AZO transparent conductive film, and the top electrode (wiring electrode) is prepared by using the conductive silver paste to complete the CZTS thin film solar energy. Battery preparation.
下面结合具体实施例进行说明。The following description will be made in conjunction with specific embodiments.
实施例1Example 1
一种AZO透明导电薄膜的制备方法，包括以下步骤：A method for preparing an AZO transparent conductive film, comprising the steps of:
S11.提供衬底，对所述衬底进行表面清洁处理；S11. Providing a substrate, and performing surface cleaning treatment on the substrate;
S12.提供氧化锌种子溶液，在所述衬底上旋涂沉积所述氧化锌种子溶液，制备结合在所述衬底表面的氧化锌种子层，其中，所述氧化锌种子溶液的溶液组成为：氧化锌纳米颗粒、高纯水、过量的氨水，其中，氧化锌的浓度为20~50 mmol/L；S12. Providing a zinc oxide seed solution, spin-depositing the zinc oxide seed solution on the substrate to prepare a zinc oxide seed layer bonded to a surface of the substrate, wherein a solution composition of the zinc oxide seed solution is : zinc oxide nanoparticles, high purity water, excess ammonia water, wherein the concentration of zinc oxide is 20~50 Mmmol/L;
S13.提供氧化锌沉积溶液，将沉积好氧化锌种子层的衬底置于所述氧化锌沉积溶液中，使所述氧化锌沉积溶液浸没所述衬底，且所述衬底中沉积有氧化锌种子层的表面不贴壁，在60℃-90℃的条件下，在所述氧化锌沉积溶液中连续引入铝离子并搅拌处理，沉积40 ~80 min，在所述氧化锌种子层表面生长制备AZO预制薄膜，其中，所述氧化锌沉积溶液的pH为 9~12，溶液组成为：氧化锌浓度20~60 mmol/L，柠檬酸铵浓度0~4 mmol/L、硝酸铵浓度0~2 mmol/L、过量氨水；S13. Providing a zinc oxide deposition solution, placing a substrate on which the zinc oxide seed layer is deposited in the zinc oxide deposition solution, immersing the zinc oxide deposition solution in the substrate, and depositing oxidation in the substrate The surface of the zinc seed layer is not attached to the wall, and the aluminum ion is continuously introduced into the zinc oxide deposition solution under stirring at 60 ° C to 90 ° C, and the mixture is stirred and deposited 40 ~80 min, preparing AZO pre-formed film on the surface of the zinc oxide seed layer, wherein the pH of the zinc oxide deposition solution is 9-12, and the solution composition is: zinc oxide concentration 20~60 mmol/L, ammonium citrate Concentration 0~4 mmol/L, ammonium nitrate concentration 0~2 Mmmol/L, excess ammonia water;
S14.对所述AZO预制薄膜进行紫外照射处理，处理条件为：UV灯辐射有效面积100 cm 2，辐射时间1~20 min，制备得到AZO透明导电薄膜。 S14. The AZO pre-formed film is subjected to ultraviolet irradiation treatment under the following conditions: the UV lamp has an effective area of 100 cm 2 and the irradiation time is 1 to 20 min, and an AZO transparent conductive film is prepared.
本发明实施例1制备的AZO透明导电薄膜的平面图和截面图如图2、3所示，将本发明实施例1制备的AZO透明导电薄膜进行透光性检测，结果如图4所示，透光率大85%-95%。The plan view and the cross-sectional view of the AZO transparent conductive film prepared in the first embodiment of the present invention are as shown in FIG. 2 and FIG. 3, and the AZO transparent conductive film prepared in the first embodiment of the present invention is tested for light transmittance, and the result is shown in FIG. The light rate is 85%-95%.
实施例2Example 2
一种CZTA薄膜太阳能电池的制备方法，包括以下步骤：A method for preparing a CZTA thin film solar cell, comprising the steps of:
清洗沉积有金属Mo的钠钙玻璃，接着连续采用溶胶凝胶技术与高温回火两步法制备CZTS光吸收层，采用化学浴沉积硫化镉缓冲层，200°C回火处理10 min，接着按照实施例1的方法在样品表面制备AZO透明导电薄膜，使用导电银胶制备顶电极（接线电极），完成CZTS薄膜太阳能电池制备。The soda lime glass deposited with metal Mo is cleaned, and then the CZTS light absorbing layer is prepared by a sol gel technique and a high temperature tempering two-step method, and the cadmium sulfide buffer layer is deposited by a chemical bath, tempered at 200 ° C for 10 min, and then The method of Example 1 prepared an AZO transparent conductive film on the surface of the sample, and prepared a top electrode (wiring electrode) using a conductive silver paste to complete the preparation of the CZTS thin film solar cell.
实施例2制备的CZTA薄膜太阳能电池结构如图5所示，CZTA薄膜太阳能电池结构的截面图如图6所示。The structure of the CZTA thin film solar cell prepared in Example 2 is shown in Fig. 5, and a cross-sectional view of the structure of the CZTA thin film solar cell is shown in Fig. 6.
对实施例2制备的CZTA薄膜太阳能电池和高温退火制备的AZO薄膜（采用600 ℃以上的高温长时间退火，随后在550℃的氢气气氛下进行后退火处理，得到电阻率在1.7×10 -3~7.2×10 -3 Ω·cm之间的AZO薄膜，其他层方法相同）得到的CZTS薄膜太阳能电池进行光电性能测试，测试得到的电流电压曲线图如图7所示。因为高温退火制备的AZO薄膜沉积到CZTS薄膜太阳能电池表面，导致pn结界面过量的元素扩散，从而破坏了pn结，因此电池转化效率严重下降。相比于高温退火制备的AZO薄膜得到的CZTS薄膜太阳能电池，实施例2制备的CZTA薄膜太阳能电池光电转化效率明显提高。 The CZTA thin film solar cell prepared in Example 2 and the AZO thin film prepared by high temperature annealing were subjected to long-time annealing at a high temperature of 600 ° C or higher, followed by post-annealing under a hydrogen atmosphere at 550 ° C to obtain a resistivity of 1.7×10 -3 . The CZTS thin film solar cell obtained by the AZO thin film of ~7.2×10 -3 Ω·cm and the other layer method is the same) is subjected to photoelectric performance test, and the current-voltage curve obtained by the test is shown in Fig. 7. Since the AZO thin film prepared by high temperature annealing is deposited on the surface of the CZTS thin film solar cell, an excessive element diffusion at the pn junction interface is caused, thereby destroying the pn junction, and thus the battery conversion efficiency is seriously degraded. The photoelectric conversion efficiency of the CZTA thin film solar cell prepared in Example 2 was significantly improved compared to the CZTS thin film solar cell obtained by the AZO film prepared by high temperature annealing.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims (15)

  1. 一种AZO透明导电薄膜的制备方法，其特征在于，包括以下步骤：A method for preparing an AZO transparent conductive film, comprising the steps of:
    提供衬底，对所述衬底进行表面清洁处理；Providing a substrate, and performing surface cleaning treatment on the substrate;
    提供氧化锌种子溶液，在所述衬底上沉积所述氧化锌种子溶液，制备结合在所述衬底表面的氧化锌种子层；Providing a zinc oxide seed solution, depositing the zinc oxide seed solution on the substrate to prepare a zinc oxide seed layer bonded to the surface of the substrate;
    提供氧化锌沉积溶液，将沉积好氧化锌种子层的衬底置于所述氧化锌沉积溶液中，使所述氧化锌沉积溶液浸没所述衬底，且所述衬底中沉积有氧化锌种子层的表面不贴壁，在加热的条件下，在所述氧化锌沉积溶液中连续引入铝离子并搅拌处理，在所述氧化锌种子层表面生长制备AZO预制薄膜；Providing a zinc oxide deposition solution, placing a substrate on which the zinc oxide seed layer is deposited in the zinc oxide deposition solution, immersing the zinc oxide deposition solution in the substrate, and depositing zinc oxide seeds in the substrate The surface of the layer is not adhered to the wall, and under the heating condition, aluminum ions are continuously introduced into the zinc oxide deposition solution and stirred to form an AZO pre-formed film on the surface of the zinc oxide seed layer;
    对所述AZO预制薄膜进行紫外照射处理，制备得到AZO透明导电薄膜。The AZO pre-formed film is subjected to ultraviolet irradiation treatment to prepare an AZO transparent conductive film.
  2. 如权利要求1所述的AZO透明导电薄膜的制备方法，其特征在于，所述氧化锌沉积溶液中含有氧化锌、氨水和去离子水，所述氧化锌沉积溶液的pH值为9-12，且所述加热的温度为60-90℃。The method for preparing an AZO transparent conductive film according to claim 1, wherein the zinc oxide deposition solution contains zinc oxide, ammonia water and deionized water, and the pH of the zinc oxide deposition solution is 9-12. And the heating temperature is 60-90 °C.
  3. 如权利要求2所述的AZO透明导电薄膜的制备方法，其特征在于，所述氧化锌沉积溶液中还含有柠檬酸铵、硝酸铵。The method for producing an AZO transparent conductive film according to claim 2, wherein the zinc oxide deposition solution further contains ammonium citrate or ammonium nitrate.
  4. 如权利要求3所述的AZO透明导电薄膜的制备方法，其特征在于，所述氧化锌沉积溶液中，各组成物质的浓度为：The method for preparing an AZO transparent conductive film according to claim 3, wherein the concentration of each constituent substance in the zinc oxide deposition solution is:
    氧化锌        20~60 mmol/L；Zinc oxide 20~60 mmol/L;
    柠檬酸铵      0.01~4 mmol/L；Ammonium citrate 0.01~4 mmol/L;
    硝酸铵浓度    0.01~2 mmol/L。Ammonium nitrate concentration 0.01~2 mmol/L.
  5. 如权利要求1-4任一项所述的AZO透明导电薄膜的制备方法，其特征在于，采用蠕动泵向所述氧化锌沉积溶液中连续加入九水硝酸铝或浸入铝片的方式，在所述氧化锌沉积溶液中连续引入铝离子。The method for preparing an AZO transparent conductive film according to any one of claims 1 to 4, wherein a peristaltic pump is used to continuously add aluminum nitrate nonahydrate or immersed in an aluminum sheet to the zinc oxide deposition solution. The aluminum ion is continuously introduced into the zinc oxide deposition solution.
  6. 如权利要求5所述的AZO透明导电薄膜的制备方法，其特征在于，采用蠕动泵在所述氧化锌沉积溶液中连续加入九水硝酸铝引入铝离子的步骤中，铝离子的引入条件满足：所述蠕动泵的转速为≥0.1 rpm，所述氧化锌沉积溶液中的九水硝酸铝浓度为10~300 mmol/L；或The method for preparing an AZO transparent conductive film according to claim 5, wherein a step of introducing aluminum ions into the aluminum oxide non-aqueous solution in the zinc oxide deposition solution by using a peristaltic pump is performed, and the introduction condition of the aluminum ions is satisfied: The rotational speed of the peristaltic pump is ≥0.1 rpm, and the concentration of aluminum nitrate nonahydrate in the zinc oxide deposition solution is 10~300 mmol/L; or
    采用蠕动泵在所述氧化锌沉积溶液中连续浸入铝片引入铝离子的步骤中，铝离子的引入条件满足：所述蠕动泵的转速为≥0.1 rpm，所述铝片的浸入面积为1~10 cm 2。 In the step of continuously immersing the aluminum sheet into the aluminum oxide by the peristaltic pump in the zinc oxide deposition solution, the introduction condition of the aluminum ion is satisfied: the rotational speed of the peristaltic pump is ≥0.1 rpm, and the immersion area of the aluminum sheet is 1~ 10 cm 2 .
  7. 如权利要求1-4任一项所述的AZO透明导电薄膜的制备方法，其特征在于，在加热容器中加入所述氧化锌沉积溶液，将沉积好氧化锌种子层的衬底置于所述氧化锌沉积溶液中，使所述氧化锌沉积溶液浸没所述衬底，且所述衬底中沉积有氧化锌种子层的表面不贴壁；将所述加热容器置于水浴锅中，在加热的条件下，在所述氧化锌沉积溶液中连续引入铝离子并搅拌处理，在所述氧化锌种子层表面生长制备AZO预制薄膜。The method for preparing an AZO transparent conductive film according to any one of claims 1 to 4, wherein the zinc oxide deposition solution is added to the heating container, and the substrate on which the zinc oxide seed layer is deposited is placed in the In the zinc oxide deposition solution, the zinc oxide deposition solution is immersed in the substrate, and a surface of the substrate in which the zinc oxide seed layer is deposited is not attached; the heating container is placed in a water bath and heated Under the condition, aluminum ions are continuously introduced into the zinc oxide deposition solution and stirred, and an AZO pre-formed film is prepared by growing on the surface of the zinc oxide seed layer.
  8. 如权利要求1-4任一项所述的AZO透明导电薄膜的制备方法，其特征在于，所述氧化锌种子溶液为添加有过量氨水的氧化锌水溶液。The method for producing an AZO transparent conductive film according to any one of claims 1 to 4, wherein the zinc oxide seed solution is an aqueous zinc oxide solution to which an excess amount of aqueous ammonia is added.
  9. 如权利要求8所述的AZO透明导电薄膜的制备方法，其特征在于，所述氧化锌种子溶液中氧化锌的浓度为20-50mmol/L。The method for producing an AZO transparent conductive film according to claim 8, wherein the zinc oxide seed solution has a zinc oxide concentration of 20 to 50 mmol/L.
  10. 如权利要求1-4任一项所述的AZO透明导电薄膜的制备方法，其特征在于，所述衬底竖直放置在所述氧化锌沉积溶液中。The method of producing an AZO transparent conductive film according to any one of claims 1 to 4, wherein the substrate is placed vertically in the zinc oxide deposition solution.
  11. 如权利要求10所述的AZO透明导电薄膜的制备方法，其特征在于，将多份衬底同时放置在所述氧化锌沉积溶液中，制备AZO透明导电薄膜。The method of producing an AZO transparent conductive film according to claim 10, wherein a plurality of substrates are simultaneously placed in the zinc oxide deposition solution to prepare an AZO transparent conductive film.
  12. 一种AZO透明导电薄膜，其特征在于，包括氧化锌种子层，以及结合在所述氧化锌种子层表面的阵列状AZO薄膜。An AZO transparent conductive film characterized by comprising a zinc oxide seed layer, and an array of AZO thin films bonded to the surface of the zinc oxide seed layer.
  13. 如权利要求12所述的AZO透明导电薄膜，其特征在于，所述阵列状AZO薄膜的阵列为柱状纳米阵列。The AZO transparent conductive film according to claim 12, wherein the array of the array-shaped AZO thin films is a columnar nano-array.
  14. 一种薄膜太阳能电池，其特征在于，包括如权利要求12-13任一项所述的AZO透明导电薄膜，或如权利要求1-11任一所述方法制备的AZO透明导电薄膜。A thin film solar cell comprising the AZO transparent conductive film according to any one of claims 12 to 13, or the AZO transparent conductive film prepared by the method according to any one of claims 1 to 11.
  15. 如权利要求14所述的薄膜太阳能电池，其特征在于，所述薄膜太阳能电池为CZTA薄膜太阳能电池，包括玻璃衬底，以及依次设置在所述玻璃衬底上的钼金属层、CATS光吸收层、硫化镉缓冲层、AZO透明导电薄膜和银电极。The thin film solar cell according to claim 14, wherein the thin film solar cell is a CZTA thin film solar cell comprising a glass substrate, and a molybdenum metal layer and a CATS light absorbing layer sequentially disposed on the glass substrate. , cadmium sulfide buffer layer, AZO transparent conductive film and silver electrode.
PCT/CN2018/082599 2018-04-11 2018-04-11 Azo transparent conductive thin film, and preparation method therefor and application thereof WO2019196025A1 (en)

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