CN116344639A - High-transmittance magnesium-doped zinc oxide film and preparation method and application thereof - Google Patents
High-transmittance magnesium-doped zinc oxide film and preparation method and application thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 198
- 239000011787 zinc oxide Substances 0.000 title claims abstract description 99
- 238000002834 transmittance Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000010408 film Substances 0.000 claims abstract description 123
- 239000011777 magnesium Substances 0.000 claims abstract description 88
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 64
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 239000011701 zinc Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000000137 annealing Methods 0.000 claims abstract description 24
- 238000004528 spin coating Methods 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000007789 sealing Methods 0.000 claims abstract description 15
- WILFBXOGIULNAF-UHFFFAOYSA-N copper sulfanylidenetin zinc Chemical compound [Sn]=S.[Zn].[Cu] WILFBXOGIULNAF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000010409 thin film Substances 0.000 claims abstract description 11
- 230000003068 static effect Effects 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 24
- 230000001133 acceleration Effects 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical group OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 claims description 6
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical group O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 claims description 6
- 239000005361 soda-lime glass Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000000395 magnesium oxide Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- PNHVEGMHOXTHMW-UHFFFAOYSA-N magnesium;zinc;oxygen(2-) Chemical compound [O-2].[O-2].[Mg+2].[Zn+2] PNHVEGMHOXTHMW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- UOSXPFXWANTMIZ-UHFFFAOYSA-N cyclopenta-1,3-diene;magnesium Chemical compound [Mg].C1C=CC=C1.C1C=CC=C1 UOSXPFXWANTMIZ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- 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
- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0256—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 characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
- H01L31/02963—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe characterised by the doping material
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Abstract
The invention discloses a high-transmittance magnesium-doped zinc oxide film, the molecular formula of which is Zn 1‑x Mg x O, wherein x is 0.16 to 0.24. The invention also discloses a preparation method of the film, which comprises the following steps: preparing a precursor solution; carrying out constant-temperature reflux stirring; sealing and storing the solution and standing for 48-60 h; cleaning and drying the substrate; adopting a dynamic and static combined spin coating method, and dripping magnesium-doped zinc oxide sol on the substrate obtained in the step four; the redundant organic solvent is eliminated by the preheating treatment; circularly coating to obtain a magnesium-doped zinc oxide film with proper thickness; and (5) annealing. The invention discloses an application of a high-transmittance magnesium-doped zinc oxide film in a copper zinc tin sulfide film solar cell buffer layer. The magnesium doped zinc oxide film obtained by the invention has a single-phase hexagonal wurtzite structure, no secondary phase precipitation and film surfaceThe surface is uniform and compact, and the leakage current can be greatly reduced when the copper zinc tin sulfide thin film solar cell buffer layer is applied.
Description
Technical Field
The invention belongs to the field of semiconductor films, and particularly relates to a high-transmittance magnesium-doped zinc oxide film, and a preparation method and application thereof.
Background
With the increase of energy demand of human beings, the traditional energy sources are not only limited, but also bring great harm to the environment. The solar energy is used as an environment-friendly renewable energy source, has the advantages of wide distribution area, easy exploitation and no environmental pollutionThe advantages of environmental limitation and the like, and has great potential in new energy. Among them, the thin film solar cell has certain advantages in terms of volume, plasticity, raw materials (including a base material), and the like. The film battery component has simple preparation process, the film forming time is reduced to a certain extent compared with that of a silicon-based solar battery, and the film battery component can be integrated with other building materials or functional materials. The copper zinc tin sulfur film solar cell has rich and nontoxic components and has an absorption coefficient higher than 10 4 cm -1 The direct band gap semiconductor has a theoretical conversion efficiency of 32.2%, and has great development potential in future markets. The thin film solar cell is of a layered structure, wherein the buffer layer can not only link the energy band structure of the absorption layer and the window layer in the thin film solar cell, but also reduce lattice defects between the layers. Currently, most of copper zinc tin sulfide thin film solar cells adopt cadmium sulfide as a buffer layer. But cadmium is toxic, and the forbidden bandwidth is 2.4eV, which is unfavorable for the transmission of short wavelength.
Zinc oxide is a II-VI semiconductor, and has the advantages of low cost, abundant and nontoxic raw materials, high light transmittance, good conductivity and the like, and the wide band gap of 3.37eV and the large exciton binding energy of 60meV at room temperature. But the energy band structure between the zinc oxide and the copper zinc tin sulfur absorption layer is a cliff-shaped structure, which is unfavorable for carrier transmission. In order to enable zinc oxide to replace a cadmium sulfide buffer layer, the energy band structure of a zinc oxide film can be effectively changed by doping, the carrier concentration can be changed, and the energy band matching degree between the buffer layer and a copper zinc tin sulfide absorption layer in the film solar cell can be optimized. On the other hand, due to Mg 2+ And Zn 2+ The ionic radius of (2) is only 0.003nm, so that the magnesium atoms can well replace zinc atoms or be dissolved in the zinc oxide crystal structure in a solid manner. But some problems are encountered during actual operation. Wang et al prepared Zn by sol-gel method 1-x Mg x O (x=0 to 0.5) alloy films, it was found that the solid solubility of magnesium in zinc oxide was saturated at a magnesium content of x=0.23. (Wang M, kim E J, kim S, et al optical and Structural Properties ofSol-gel Prepared Mg ZnO Alloy Thin Films [ J)]Thin Solid Films,2008, 516 (6): 1124-1129.) Anhui DadaTeam Wang Weina study found that with Zn 1-x Mg x Increase in x value in O film, mg 2+ Substitution of Zn 2+ The number of (c) is increased, so that the lattice constant is decreased and the crystallinity is deteriorated. In addition, mg is liable to generate MgO in an aerobic environment to inhibit Zn 1- x Mg x And (3) generating an O film. (Wang Weina, fang Qingqing, zhou Jun, etc.. Influence of the preparation Process on the structure and optical Properties of Zn1-xMgxO film [ J ]]Physical journal, 2009, 58 (05): 3461-3467.) C.
The zinc-magnesium oxide film is prepared by adopting an atomic layer deposition method with high cost, diethyl zinc is used as a zinc source, bis (cyclopentadiene) magnesium is used as a magnesium source and nitrogen is used as a carrier gas in a microchemical F-120 reactor, and the zinc-magnesium oxide film is prepared by adopting a ZnO and MgO alternate deposition mode. (PLATZER-BJORKMAN C, TORNDAHL T, HULTQVIST A, et al optimization of ALD- (Zn, mg) O buffer layers and (Zn, mg) O/Cu (In, ga) Se2 interfaces for thin film solar cells [ J ]].Thin Solid Films，2007，515(15)：6024-6027)。
At present, magnesium doped zinc oxide films gradually attract attention of scientific researchers, the film preparation effect is better and better, and the preparation cost is higher and higher. In addition, as the magnesium oxide has a cubic crystal structure, the solid solubility of magnesium element in the zinc oxide film is limited, the magnesium element doping is seriously influenced by the environment and the preparation process, secondary phase precipitation is easy to form, and the conversion efficiency of the film solar cell is reduced.
Disclosure of Invention
The invention aims to: in order to overcome the defects in the prior art, the invention aims to provide a high-transmittance magnesium-doped zinc oxide film with good surface compactness and no secondary phase precipitation, and another aim of the invention is to provide a preparation method of the high-transmittance magnesium-doped zinc oxide film with high film forming efficiency and good film quality.
The technical scheme is as follows: one of the inventionThe molecular formula of the magnesium-doped zinc oxide film with high transmittance is Zn 1-x Mg x O, wherein x is 0.16 to 0.24.
Further, the magnesium doped zinc oxide film has a single-phase hexagonal wurtzite structure.
The invention relates to a preparation method of a high-transmittance magnesium-doped zinc oxide film, which comprises the following steps:
firstly, weighing a zinc source and a magnesium source according to stoichiometric ratio, mixing with a solvent of ethylene glycol methyl ether and a stabilizer of ethanolamine, and preparing a precursor solution with the solution concentration of 0.3-0.4 mol/L;
step two, refluxing at a constant temperature of 65-75 ℃ and continuously stirring;
sealing the solution obtained in the step two, standing and cooling for 48-60 h to obtain magnesium-doped zinc oxide sol;
step four, cleaning the substrate, and drying by an air compressor;
fifthly, adopting a dynamic and static combined spin coating method, and dripping magnesium doped zinc oxide sol on the substrate obtained in the step four;
step six, preheating the product obtained in the step five at the temperature of 100-110 ℃ and the temperature of 230-250 ℃ in sequence, cooling to room temperature, and eliminating redundant organic solvents;
step seven, repeating the step five and the step six, and circularly coating 10-14 layers;
and step eight, annealing at 400-550 ℃ to obtain the magnesium-doped zinc oxide film with high transmittance.
Further, in the first step, the zinc source is zinc acetate dihydrate, the magnesium source is magnesium acetate tetrahydrate, and the mol ratio of ethanolamine to zinc acetate dihydrate is 2-3:1.
Further, in the second step, the stirring is magnetic stirring, the stirring is performed by a constant-temperature magnetic stirrer, the rotating speed is 570-630 rpm, and the stirring time is 1-2 h.
In the fourth step, the substrate is sequentially cleaned by ultrasonic waves of acetone, alcohol and deionized water for 10-20 min, and the substrate is soda lime glass.
In the fifth step, the dynamic and static combined spin coating is to drop magnesium doped zinc oxide sol on the glass substrate, then spin coating is carried out for 15-20 s at the speed of 900-1000 r/min, the acceleration is 350-450 rpm/s, then the rotation speed is increased to 3400-3600 r/min at the acceleration of 580-600 rpm/s, 2-3 drops of magnesium doped zinc oxide sol are added in the second acceleration process, and spin coating is carried out for 30-40 s.
Further, in the step six, preheating is carried out for 2-4 min at the temperature of 100-110 ℃ on a hot table, and then preheating is carried out for 10-12 min at the temperature of 230-250 ℃.
In the eighth step, the annealing time is 3-4 hours, and the annealing atmosphere is air.
The invention relates to an application of a high-transmittance magnesium-doped zinc oxide film in a copper zinc tin sulfide film solar cell buffer layer.
The preparation principle is as follows: according to the invention, the zinc oxide film is doped with magnesium element, so that the forbidden bandwidth and the carrier concentration of the film can be effectively regulated and controlled. This is because doping of the magnesium element introduces additional electrons that occupy the conduction band of zinc oxide, thereby increasing the carrier concentration. On the other hand, since the electronegativity of magnesium element is greater than that of zinc element, doping of magnesium element forms impurity energy levels which are located in the band gap of zinc oxide and affect the forbidden band width of zinc oxide film. In addition, if the forbidden bandwidth of the magnesium doped zinc oxide film is larger than photon energy, the film cannot absorb the part of sunlight, so that the transmittance of the film is greatly increased. In addition, the bandwidth of the magnesium-doped zinc oxide film can be arbitrarily adjusted by changing the doping amount of magnesium element, and if a spike-shaped energy band structure of 0-0.4 eV is formed between the magnesium-doped zinc oxide film buffer layer and the copper zinc tin sulfide absorption layer, the transmission resistance of electrons can be effectively reduced, so that the electrons can be freely transmitted between the two materials. The small spike-shaped energy band structure can improve the open circuit voltage of the copper zinc tin sulfur solar cell. This is because under this structure, the charge forms a built-in electric field between the copper zinc tin sulfide and the buffer layer, so that electrons and holes are separated and are not easily recombined, and the open circuit voltage is further improved. In addition, under the structure, the recombination rate of electrons and holes is lower, thereby reducing the loss of photo-generated carriers and improving the filling of the batteryAnd (5) filling factors. In addition, due to Mg 2+ And Zn 2+ The ionic radius of the magnesium oxide is only 0.003nm, the magnesium oxide with a cubic crystal structure is not separated out under the condition of controlling the preparation process, and magnesium atoms can well replace zinc atoms or be dissolved in the hexagonal wurtzite zinc oxide crystal structure in a solid mode. Therefore, the magnesium-doped zinc oxide film has excellent optical and electrical properties, so that the magnesium-doped zinc oxide film is more suitable for application to photoelectric devices such as solar cells.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable characteristics:
1. the obtained magnesium doped zinc oxide film has a single-phase hexagonal wurtzite structure, no secondary phase is separated out, the surface of the film is uniform and compact, and leakage current can be greatly reduced when the film is applied to a copper zinc tin sulfide film solar cell buffer layer;
2. the difference of forbidden band width is realized according to the difference of magnesium content, the film transmittance is high, and the absorption of the absorption layer to the photoelectric electrons is improved in the film solar cell;
3. the cost of equipment and raw materials used in the preparation process is extremely low, the operability of each equipment is high, the equipment is easy to operate, the film making efficiency is high, the film quality is good, and the feasibility in the future industrialized development is high.
Drawings
FIG. 1 is a graph of samples of zinc oxide films doped with different magnesium contents according to example 4 of the present invention;
FIG. 2 is an XRD pattern of zinc oxide films doped with different magnesium contents according to example 4 of the present invention;
FIG. 3 is an SEM image of a zinc oxide film doped with different magnesium contents according to example 4 of the present invention;
FIG. 4 is a UV diagram of zinc oxide films doped with different magnesium contents according to example 4 of the present invention;
FIG. 5 is a graph of the (. Alpha.hν) of zinc oxide films doped with different magnesium contents according to example 4 of the invention 2 A relationship with hν;
FIG. 6 is a graph of resistivity of zinc oxide films doped with different magnesium contents according to example 4 of the present invention.
Detailed Description
In the following examples, the starting materials used were analytically pure in each case without further processing, as shown in Table 1 below.
Table 1 list of reagents used in the experiments
Example 1
The preparation method of the high-transmittance magnesium-doped zinc oxide film comprises the following steps:
(1) Preparing Zn 1-x Mg x O precursor solution: weighing zinc acetate dihydrate and magnesium acetate tetrahydrate according to a stoichiometric ratio, mixing ethanolamine serving as a stabilizer with 20mL of solvent ethylene glycol methyl ether in a dry and clean beaker, wherein the mol ratio of the ethanolamine to the zinc acetate dihydrate is 2:1, and preparing a precursor solution with the solution concentration of 0.4 mol/L; the stoichiometric ratio x of the magnesium element is 0.16, 0.18, 0.20, 0.22 and 0.24 respectively;
(2) Constant temperature reflux stirring: placing a stirrer in a beaker filled with a precursor solution, sealing the beaker opening by using a sealing film, placing the beaker on a constant-temperature magnetic stirrer, setting the temperature to be 70 ℃, increasing the rotating speed to be 580rpm, starting timing after no precipitate exists in the beaker from room temperature to 70 ℃, and continuously stirring for 1h;
(3) Taking out the stirrer, resealing the beaker, sealing the solution obtained in the step (2), naturally cooling to room temperature, standing and aging for 48 hours to obtain magnesium-doped zinc oxide sol;
(4) Cleaning a substrate: placing 15X 15mm soda lime glass as a substrate on a sample rack, respectively placing the substrate in glass containers filled with acetone, alcohol and deionized water, respectively ultrasonically cleaning for 10min, taking out the substrate, and drying by an air compressor for later use;
(5) Preparing a film by dynamic and static combination spin coating: setting a spin coater program, dripping magnesium doped zinc oxide sol on a glass substrate, starting the spin coater, spin coating for 15s at a speed of 1000r/min, increasing the rotating speed to 3500r/min at an acceleration of 600rpm/s, and supplementing 2 drops of magnesium doped zinc oxide sol in the second acceleration (low rotating speed to high rotating speed) process to compensate the phenomenon of uneven sol distribution caused by the increase of centrifugal force, and spin coating for 30s;
(6) Preheating: placing the product obtained in the step (5) on a heating table at 100 ℃ for 2min, replacing the product to the heating table at 250 ℃ for 10min, eliminating redundant organic solvents, and naturally cooling to room temperature;
(7) After spin coating film making and preheating treatment, preparing a layer of film in one cycle, repeating the step (5) and the step (6), and circularly coating 12 layers;
(8) Annealing: and (3) placing the sample obtained in the step (7) on a heating table, heating to 400 ℃ from room temperature, preserving heat for 3 hours, and taking the annealing atmosphere as air to obtain the high-transmittance magnesium-doped zinc oxide film.
Example 2
The remaining steps of this example are the same as those of example 1, except that: in step (8), the annealing temperature was set to 450 ℃.
Example 3
The remaining steps of this example are the same as those of example 1, except that: in step (8), the annealing temperature was set to 500 ℃.
Example 4
The remaining steps of this example are the same as those of example 1, except that: in step (8), the annealing temperature was set to 550 ℃.
Comparative example 1
The remaining steps of this comparative example are the same as in example 1, except that: in the step (1), the stoichiometric ratio of magnesium element is 0.70; in step (8), the annealing temperature is 550 ℃.
Comparative example 2
The remaining steps of this comparative example are the same as in example 1, except that: in the step (1), the stoichiometric ratio of magnesium element is 0.80; in step (8), the annealing temperature is 550 ℃.
Comparative example 3
The remaining steps of this comparative example are the same as in example 1, except that: in the step (1), the stoichiometric ratio of magnesium element is 0.90; in step (8), the annealing temperature is 550 ℃.
Table 1 example 1-example 4The Zn obtained 1-x Mg x Photoelectric properties of O film
TABLE 2 Zn obtained in comparative examples 1 to 3 1-x Mg x Photoelectric properties of O film
| Chemical formula | Transmittance/(%) | Forbidden bandwidth/(eV) | Resistivity/(Ω·cm) | |
| Comparative example 1 | Zn 0.30 Mg 0.70 O | 93 | 5.33 | 7.33×10 3 |
| Comparative example 2 | Zn 0.20 Mg 0.80 O | 94 | 5.82 | 8.58×10 3 |
| Comparative example 3 | Zn 0.10 Mg 0.90 O | 96 | 6.21 | 1.25×10 4 |
As is clear from tables 1 and 2, in this production process, the magnesium doping content has little influence on the transmittance of the zinc oxide film, but as the magnesium doping content increases, the resistivity of the zinc oxide film starts to gradually increase. This is probably due to the fact that as the magnesium doping content increases, defects in the zinc oxide film increase, resulting in a hindered carrier transport. As can be seen from Table 1, the effect of trace magnesium doping on the energy band of zinc oxide is obvious, which shows that the purpose of the energy band structure of zinc oxide film can be achieved by doping magnesium. On the other hand, the resistivity is slightly reduced with the increase of the annealing temperature, and the semiconductor characteristic is reflected.
FIG. 1 is a graph of a sample of a magnesium doped zinc oxide film having an annealing temperature of 550℃in example 4. As can be seen from fig. 1, the film is uniform and transparent on the surface after being prepared using this method.
Fig. 2 is an XRD pattern of the magnesium-doped zinc oxide thin film of example 4. From fig. 2, it can be seen that the zinc oxide film with the doping content of five magnesium elements has no secondary phase precipitation, the crystal structure is a hexagonal wurtzite structure of zinc oxide, and magnesium ions basically exist in a solid solution or alternative zinc ion mode. From the diffraction peaks at different angles in the graph, the thin film grows in a polycrystalline growth mode.
Fig. 3 is an SEM image of the magnesium-doped zinc oxide film of example 4, and (a) to (e) are surface topography images corresponding to stoichiometric ratios of 0.16, 0.18, 0.20, 0.22 and 0.24, respectively, of magnesium element. As can be seen from FIG. 3, the surface morphology of the zinc oxide films doped with different magnesium contents is approximately uniform, all are interwoven together in a woven manner, and the overall morphology is uniform and has no holes. Zn (zinc) 0.84 Mg 0.16 The surface of the O sample also scatters some small precipitated crystal blocks. And gradually disappearing small crystal blocks precipitated on the surface of the film after the magnesium content is increased, so as to form uniform morphology. But magnesium elementWhen the stoichiometric ratio is 0.24, a large number of cracks appear on the surface of the film after annealing for 3 hours at 550 ℃, and when the stoichiometric ratio is 0.20, the surface has slight cracks, which also shows that the uniformity of the surface morphology can be damaged due to excessive doping of magnesium element.
FIG. 4 is a UV diagram of zinc oxide films doped with different magnesium contents of example 4. As can be seen, the transmittance of the zinc oxide thin film at the doping of different magnesium contents is at the level of 90% as a whole. Wherein the minimum transmittance is Zn 0.84 Mg 0.16 The O film may be due to small crystal blocks precipitated on the surface of the film, which cause a part of scattering for light transmission. Zn (zinc) 0.76 Mg 0.24 The O film possesses a high transmittance of 94% probably due to cracks in the film surface.
FIG. 5 is a graph showing the forbidden bandwidths of zinc oxide films doped with different magnesium contents in example 4. As can be seen from FIG. 5, the forbidden band width of the zinc oxide films doped with different magnesium contents fluctuates within the range of 3.33-3.52 eV, zn 0.84 Mg 0.16 The forbidden band width of the O film is 3.33eV, zn 0.76 Mg 0.24 The maximum forbidden bandwidth of the O film is 3.52eV, which directly proves that the doping of magnesium element can enlarge the forbidden bandwidth of the zinc oxide film.
FIG. 6 is a graph of the resistivity of zinc oxide films doped with different magnesium contents of example 4. As can be seen from FIG. 6, zn is removed 1-x Mg x The three magnesium doping contents except x=0.20 and x=0.24 in O have resistivity proportional to the doping amount of magnesium element, and the resistivity is increased to a certain extent with the increase of the magnesium content. It is possible that defects in the crystal structure are increased due to the increase of magnesium element, and carrier movement is hindered. The resistivity of the samples corresponding to x=0.20 and x=0.24 was reduced, possibly due to surface-formed cracks in combination with surface topography analysis.
Example 5
The preparation method of the high-transmittance magnesium-doped zinc oxide film comprises the following steps:
(1) Preparing Zn 0.80 Mg 0.20 O precursor solution: weighing zinc acetate dihydrate, magnesium acetate tetrahydrate and ethanolamine according to stoichiometric ratioMixing a fixing agent and 20mL of solvent ethylene glycol methyl ether in a dry and clean beaker, wherein the mol ratio of ethanolamine to zinc acetate dihydrate is 2:1, and preparing a precursor solution with the solution concentration of 0.3 mol/L;
(2) Constant temperature reflux stirring: placing a stirrer in a beaker filled with a precursor solution, sealing the beaker opening by using a sealing film, placing the beaker on a constant-temperature magnetic stirrer, setting the temperature to be 65 ℃, increasing the rotating speed to be 570rpm, starting timing after no precipitate exists in the beaker from room temperature to 65 ℃, and continuously stirring for 1h;
(3) Taking out the stirrer, resealing the beaker, sealing the solution obtained in the step (2), naturally cooling to room temperature, standing and aging for 48 hours to obtain magnesium-doped zinc oxide sol;
(4) Cleaning a substrate: taking 15X 15mm soda lime glass as a substrate, placing the substrate on a sample rack, respectively placing the sample rack in glass containers filled with acetone, alcohol and deionized water, respectively carrying out ultrasonic cleaning for 15min, taking out the substrate, and drying the substrate by an air compressor for later use;
(5) Preparing a film by dynamic and static combination spin coating: setting a spin coater program, dripping magnesium-doped zinc oxide sol on a glass substrate, starting the spin coater, spin-coating for 15s at a speed of 900r/min, increasing the rotating speed to 3400r/min at an acceleration of 580rpm/s, and supplementing 2 drops of magnesium-doped zinc oxide sol in the second acceleration (low rotating speed to high rotating speed) process to compensate the phenomenon of uneven sol distribution caused by the increase of centrifugal force, and spin-coating for 30s;
(6) Preheating: placing the product obtained in the step (5) on a heating table at 100 ℃ for heat preservation for 2min, replacing the product to the heating table at 230 ℃ for heat preservation for 10min, eliminating redundant organic solvents, and naturally cooling to room temperature;
(7) After spin coating film making and preheating treatment, preparing a layer of film in one cycle, repeating the step (5) and the step (6), and circularly coating 10 layers;
(8) Annealing: and (3) placing the sample obtained in the step (7) on a heating table, heating to 400 ℃ from room temperature, preserving heat for 3 hours, and taking the annealing atmosphere as air to obtain the high-transmittance magnesium-doped zinc oxide film.
Example 6
The preparation method of the high-transmittance magnesium-doped zinc oxide film comprises the following steps:
(1) Preparing Zn 0.82 Mg 0.18 O precursor solution: weighing zinc acetate dihydrate and magnesium acetate tetrahydrate according to a stoichiometric ratio, mixing ethanolamine serving as a stabilizer with 20mL of solvent ethylene glycol methyl ether in a dry and clean beaker, wherein the mol ratio of the ethanolamine to the zinc acetate dihydrate is 3:1, and preparing a precursor solution with the solution concentration of 0.4 mol/L;
(2) Constant temperature reflux stirring: placing a stirrer in a beaker filled with a precursor solution, sealing the beaker opening by using a sealing film, placing the beaker on a constant-temperature magnetic stirrer, setting the temperature to be 75 ℃, increasing the rotating speed to be 630rpm, increasing the temperature from room temperature to 75 ℃, starting timing after no sediment exists in the beaker, and continuously stirring for 2 hours;
(3) Taking out the stirrer, resealing the beaker, sealing the solution obtained in the step (2), naturally cooling to room temperature, standing and aging for 60 hours to obtain magnesium-doped zinc oxide sol;
(4) Cleaning a substrate: placing 15X 15mm soda lime glass as a substrate on a sample rack, respectively placing the substrate in glass containers filled with acetone, alcohol and deionized water, respectively carrying out ultrasonic cleaning for 20min, taking out the substrate, and drying by an air compressor for later use;
(5) Preparing a film by dynamic and static combination spin coating: setting a spin coater program, dripping magnesium doped zinc oxide sol on a glass substrate, starting the spin coater, spin coating for 20s at a speed of 1000r/min, increasing the rotating speed to 3600r/min at an acceleration of 600rpm/s, and supplementing 3 drops of magnesium doped zinc oxide sol in the second acceleration (low rotating speed to high rotating speed) process to compensate for the phenomenon of uneven sol distribution caused by the increase of centrifugal force, and spin coating for 40s;
(6) Preheating: placing the product obtained in the step (5) on a heating table at 110 ℃ for heat preservation for 4min, replacing the product to the heating table at 250 ℃ for heat preservation for 12min, eliminating redundant organic solvents, and naturally cooling to room temperature;
(7) After spin coating film making and preheating treatment, preparing a layer of film in one cycle, repeating the step (5) and the step (6), and circularly coating 12 layers;
(8) Annealing: and (3) placing the sample obtained in the step (7) on a heating table, heating to 550 ℃ from room temperature, preserving heat for 4 hours, and taking the annealing atmosphere as air to obtain the high-transmittance magnesium-doped zinc oxide film.
Example 7
The preparation method of the high-transmittance magnesium-doped zinc oxide film comprises the following steps:
(1) Preparing Zn 0.78 Mg 0.22 O precursor solution: weighing zinc acetate dihydrate and magnesium acetate tetrahydrate according to a stoichiometric ratio, mixing ethanolamine serving as a stabilizer with 20mL of solvent ethylene glycol methyl ether in a dry and clean beaker, wherein the mol ratio of the ethanolamine to the zinc acetate dihydrate is 2:1, and preparing a precursor solution with the solution concentration of 0.35 mol/L;
(2) Constant temperature reflux stirring: placing a stirrer in a beaker filled with a precursor solution, sealing the beaker opening by using a sealing film, placing the beaker on a constant-temperature magnetic stirrer, setting the temperature to 69 ℃, the rotating speed to 590rpm, heating the temperature from room temperature to 68 ℃, starting timing after no sediment exists in the beaker, and continuously stirring for 1.5h;
(3) Taking out the stirrer, resealing the beaker, sealing the solution obtained in the step (2), naturally cooling to room temperature, standing and aging for 54 hours to obtain magnesium-doped zinc oxide sol;
(4) Cleaning a substrate: placing 15X 15mm soda lime glass as a substrate on a sample rack, respectively placing the substrate in glass containers filled with acetone, alcohol and deionized water, respectively carrying out ultrasonic cleaning for 18min, taking out the substrate, and drying by an air compressor for later use;
(5) Preparing a film by dynamic and static combination spin coating: setting a spin coater program, dripping magnesium-doped zinc oxide sol on a glass substrate, starting the spin coater, spin-coating for 18s at a speed of from 920r/min, wherein the acceleration is 390rpm/s, increasing the rotation speed to 3450r/min at an acceleration of 595rpm/s, and supplementing 3 drops of magnesium-doped zinc oxide sol in the second acceleration (low rotation speed to high rotation speed) process to compensate the phenomenon of uneven sol distribution caused by the increase of centrifugal force, and spin-coating for 34s;
(6) Preheating: placing the product obtained in the step (5) on a heating table at 105 ℃ for 3min, replacing the product with the heating table at 235 ℃ for 11min, eliminating redundant organic solvents, and naturally cooling to room temperature;
(7) After spin coating film making and preheating treatment, preparing a layer of film in one cycle, repeating the step (5) and the step (6), and circularly coating a film 14 layers;
(8) Annealing: and (3) placing the sample obtained in the step (7) on a heating table, heating to 520 ℃ from room temperature, preserving heat for 3.5h, and taking the annealing atmosphere as air to obtain the high-transmittance magnesium-doped zinc oxide film.
Claims (10)
1. A high-transmittance magnesium-doped zinc oxide film is characterized in that: its molecular formula is Zn 1-x Mg x O, wherein x is 0.16 to 0.24.
2. The high-transmittance magnesium-doped zinc oxide film according to claim 1, wherein: the magnesium doped zinc oxide film is of a single-phase hexagonal wurtzite structure.
3. The method for preparing the high-transmittance magnesium-doped zinc oxide film according to claim 1 or 2, comprising the following steps:
firstly, weighing a zinc source and a magnesium source according to stoichiometric ratio, mixing with a solvent of ethylene glycol methyl ether and a stabilizer of ethanolamine, and preparing a precursor solution with the solution concentration of 0.3-0.4 mol/L;
step two, refluxing at a constant temperature of 65-75 ℃ and continuously stirring;
sealing the solution obtained in the step two, standing and cooling for 48-60 h to obtain magnesium-doped zinc oxide sol;
step four, cleaning and drying the substrate;
fifthly, adopting a dynamic and static combined spin coating method, and dripping magnesium doped zinc oxide sol on the substrate obtained in the step four;
step six, preheating the product obtained in the step five at the temperature of 100-110 ℃ and the temperature of 230-250 ℃ in sequence, and cooling to room temperature;
step seven, repeating the step five and the step six, and circularly coating 10-14 layers;
and step eight, annealing at 400-550 ℃ to obtain the magnesium-doped zinc oxide film with high transmittance.
4. The method for preparing the high-transmittance magnesium-doped zinc oxide film according to claim 3, wherein the method comprises the following steps: in the first step, the zinc source is zinc acetate dihydrate, the magnesium source is magnesium acetate tetrahydrate, and the mol ratio of the ethanolamine to the zinc acetate dihydrate is 2-3:1.
5. The method for preparing the high-transmittance magnesium-doped zinc oxide film according to claim 3, wherein the method comprises the following steps: in the second step, the stirring is magnetic stirring, the rotating speed is 570-630 rpm, and the stirring time is 1-2 h.
6. The method for preparing the high-transmittance magnesium-doped zinc oxide film according to claim 3, wherein the method comprises the following steps: in the fourth step, the substrate is sequentially cleaned by adopting acetone, alcohol and deionized water in an ultrasonic mode for 10-20 min, and the substrate is soda lime glass.
7. The method for preparing the high-transmittance magnesium-doped zinc oxide film according to claim 3, wherein the method comprises the following steps: in the fifth step, the dynamic and static combined spin coating method is to drop magnesium doped zinc oxide sol on a glass substrate, spin coat the glass substrate for 15-20 s at a speed of 900-1000 r/min, accelerate the glass substrate for 350-450 rpm/s, increase the rotating speed to 3400-3600 r/min at an acceleration of 580-600 rpm/s, supplement 2-3 drops of magnesium doped zinc oxide sol in the second acceleration process, and spin coat the glass substrate for 30-40 s.
8. The method for preparing the high-transmittance magnesium-doped zinc oxide film according to claim 3, wherein the method comprises the following steps: in the step six, preheating is carried out for 2 to 4 minutes at the temperature of between 100 and 110 ℃ and then preheating is carried out for 10 to 12 minutes at the temperature of between 230 and 250 ℃.
9. The method for preparing the high-transmittance magnesium-doped zinc oxide film according to claim 3, wherein the method comprises the following steps: in the step eight, the annealing time is 3-4 hours, and the annealing atmosphere is air.
10. The use of a high transmittance magnesium doped zinc oxide film according to claim 1 in a buffer layer of a copper zinc tin sulfide thin film solar cell.
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