CN111312854A - Magnesium-doped copper-zinc-tin-sulfur thin film solar cell and preparation method thereof - Google Patents

Magnesium-doped copper-zinc-tin-sulfur thin film solar cell and preparation method thereof Download PDF

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CN111312854A
CN111312854A CN202010107305.8A CN202010107305A CN111312854A CN 111312854 A CN111312854 A CN 111312854A CN 202010107305 A CN202010107305 A CN 202010107305A CN 111312854 A CN111312854 A CN 111312854A
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zinc
magnesium
tin
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sulfur
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郝瑞亭
王云鹏
李晓明
郭杰
顾康
李勇
魏国帅
方水柳
刘慧敏
马晓乐
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Yunnan University YNU
Yunnan Normal University
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Abstract

The invention discloses a magnesium-doped copper-zinc-tin-sulfur thin film solar cell and a preparation method thereof, and belongs to the field of solar cells. The preparation method comprises the following steps: preparing a Mo electrode on a glass substrate; coating a magnesium-doped copper-zinc-tin-sulfur precursor solution on the Mo electrode to prepare a precursor film; preparing an absorption layer by vulcanizing the precursor film at high temperature; preparing a buffer layer on the absorption layer; preparing a transparent conductive window layer on the buffer layer; a top electrode is prepared on the window layer. Wherein the absorption layer is a magnesium-doped copper-zinc-tin-sulfur film; the precursor solution is obtained by fully dissolving copper chloride, magnesium acetate, zinc chloride, stannous chloride and thiourea in dimethylformamide and performing centrifugal treatment. The preparation method is safe and simple to operate, the metal source is rich in storage, the method is environment-friendly and low in cost, and the prepared magnesium-doped copper-zinc-tin-sulfur thin film solar cell is good in crystalline grain appearance, few in pores, high in carrier mobility, strong in charge collection capacity and few in defects.

Description

Magnesium-doped copper-zinc-tin-sulfur thin film solar cell and preparation method thereof
Technical Field
The invention relates to the field of solar cells, in particular to a magnesium-doped copper-zinc-tin-sulfur thin film solar cell and a preparation method thereof.
Background
Fossil energy reserves are decreasing day by day, and it is imperative to seek other energy sources as supplements. In view of the situation of high consumption and high pollution of the traditional energy, clean, rich and environment-friendly novel energy becomes a non-choice for energy supplement. The solar energy is a perfect novel clean energy completely conforming to the heart of people, is purely natural, has no pollution and is rich in resources. The development and utilization of solar energy are undoubtedly a viable path for alleviating environmental pollution and energy crisis, and have profound scientific significance and practical effects.
The silicon-based solar cell is used as a traditional photoelectric conversion device, the technical application is mature, the scientific research significance is not great, and the research of novel photoelectric materials becomes the first major of the majority of researchers. Copper Zinc Tin Sulfide (CZTS) is a direct band gap semiconductor material and has a kesterite structure, the forbidden band width is 1.45 eV-1.50 eV, and the light absorption coefficient exceeds 104cm-1Only 1.5-2.5 μm is needed to absorb most of visible light wavelength. Compared with the same type of copper indium gallium selenide, the copper zinc tin sulfide has rich and nontoxic components and lower preparation cost. Compared with a perovskite solar cell, the copper-zinc-tin-sulfur solar cell has better stability. Therefore, the CZTS becomes a novel photoelectric material with the most prospect, low cost and environmental friendliness.
Up to now, the maximum recorded photoelectric conversion efficiency of the CZTS thin film solar cell in the laboratory is 12.62%, which is far from the theoretical limit value. The main reason for the low efficiency is the open circuit voltage (V)oc) The reason for the low open-circuit voltage is as follows: i) higher non-radiative recombination; ii) the diffusion length is lower; iii) severe band-tail effects; iiii) inversion defects are more abundant. In recent years, cationic doping has attracted much attention as a viable solution to suppress these problems. However, common doping metal cations (Ag and Cd) are not ideal due to their scarcity and toxicity. Other transition metals (such as Mn, Fe, Co or Ni) are multivalent and may form harmful deep defects.
Disclosure of Invention
The invention aims to provide a magnesium-doped copper-zinc-tin-sulfur thin film solar cell and a preparation method thereof, and aims to solve the problems that the material performance of the existing copper-zinc-tin-sulfur thin film cation doping is poor, such as low carrier mobility, poor charge collection capability and more inversion defects, and finally the photoelectric conversion efficiency of the cell is low.
The technical solution for realizing the purpose of the invention is as follows: a magnesium-doped copper-zinc-tin-sulfur thin film solar cell and a preparation method thereof comprise the following specific steps:
(1) preparing a Mo electrode on a glass substrate;
(2) preparing a precursor film on the Mo electrode by using a magnesium-doped copper-zinc-tin-sulfur precursor solution and adopting a spin-coating method;
(3) vulcanizing the precursor film at high temperature to prepare an absorption layer;
(4) preparing a buffer layer on the absorption layer;
(5) preparing a transparent conductive window layer on the buffer layer;
(6) a top electrode is prepared on the window layer.
Preferably, in the step (1), the Mo electrode has a double-layer structure, and includes a high-resistance layer and a low-resistance layer Mo thin film, the thicknesses of the Mo thin film are 250nm and 1250nm, respectively, and the Mo thin film is obtained by a direct current sputtering method.
Preferably, in the step (2), copper chloride, magnesium acetate, zinc chloride and stannous chloride are used as metal sources, thiourea is used as a sulfur source, dimethylformamide is used as a solvent, and a magnesium-doped copper-zinc-tin-sulfur precursor solution is prepared, wherein the concentrations of copper chloride and stannous chloride in the precursor solution are respectively 0.6mol/L and 0.36 mol/L, the total concentration of magnesium acetate and zinc chloride is 0.44mol/L, the atomic molar ratio Mg/(Mg + Zn) = 4-6%, and the concentration of thiourea is 2.8 mol/L.
Specifically, in the step (2), the preparation process of the magnesium-doped copper-zinc-tin-sulfur precursor solution is as follows: dissolving a metal source in a solvent, sealing, and stirring in a water bath at 50 ℃ for 15 minutes; adding thiourea, and continuously sealing the water bath at 50 ℃ and stirring for 50 minutes; and after the reaction is finished, carrying out centrifugal treatment at the centrifugal rotation speed of 8000 rpm for 5 minutes to obtain the magnesium-doped copper-zinc-tin-sulfur precursor solution.
Preferably, in the step (2), the number of spin coating is 10-15.
Specifically, in the step (2), the spin coating process is as follows: uniformly coating the magnesium-doped copper-zinc-tin-sulfur precursor solution on a Mo electrode, starting a spin coater to spin at a low speed of 700 rpm for 5 seconds; and (3) performing high speed of 3000 r/min for 25 seconds, preheating at 300 ℃ for 3min, cooling at room temperature for 3min, and repeating the coating, preheating and cooling at room temperature for 10-15 times.
Preferably, in the step (3), the thickness of the absorption layer is 1 to 1.5 μm; the vulcanizing temperature is 650-655 ℃, the vulcanizing time is 30-40 minutes, and the working gas N2And the gas flow rate is 30 sccm.
Specifically, in the step (3), the high-temperature vulcanization process is as follows: setting the initial temperature of the vulcanization temperature to be 45-55 ℃, the heating rate to be 10 ℃/min, the final temperature to be 650-655 ℃ and the temperature in N2And (3) preserving heat and vulcanizing for 30-40 minutes in the atmosphere, ventilating at a flow rate of 30sccm, and naturally cooling to room temperature after the ventilation is finished.
Preferably, in the step (4), the buffer layer is cadmium sulfide (CdS) with a thickness of 50-60 nm and is obtained by deposition through a chemical water bath method.
Preferably, in the step (5), the transparent conductive window layer is an i-ZnO and ITO double-layer film, the thicknesses of the i-ZnO and ITO double-layer film are 35-55 nm and 400-500 nm in sequence, and the transparent conductive window layer is obtained by a radio frequency sputtering method.
Preferably, in step (6), the top electrode is made of silver alloy and is obtained by electron beam thermal evaporation.
Compared with the prior art, the invention has the following advantages: (1) the invention provides a safe, nontoxic and stable-valence-state preparation method of a cation-doped copper-zinc-tin-sulfur thin film solar cell, which is safe and simple to operate, rich in metal sources, environment-friendly and low in cost, and a saturated, uniform and stable precursor solution is obtained by heating in a water bath, stirring and centrifuging in the preparation process, and can be stored for one month; (2) the prepared magnesium-doped copper-zinc-tin-sulfur thin film solar cell has good crystal grain appearance, few pores, high carrier mobility, strong charge collection capacity and few defects.
Drawings
The drawings are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated in various figures may be represented by a like numeral. For purposes of clarity, not every component may be labeled in every drawing. Embodiments of various aspects of the present invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic structural diagram of a CMZTS thin film solar cell according to the present invention.
FIG. 2 is a schematic flow chart of the preparation method of the present invention.
FIG. 3 is an X-ray diffraction spectrum of a CMZTS film prepared in example 1 of the present invention.
FIG. 4 shows a Raman spectrum of a CMZTS film prepared in example 1 of the present invention.
FIG. 5 is a scanning electron microscope surface image of a CMZTS film prepared in example 1 of the present invention.
FIG. 6 is a scanning electron microscope cross-sectional view of a CMZTS film prepared in example 1 of the present invention.
FIG. 7 is an X-ray diffraction spectrum of a CMZTS film prepared in example 2 of the present invention.
FIG. 8 shows a Raman spectrum of a CMZTS film prepared in example 2 of the present invention.
FIG. 9 is a scanning electron microscope surface image of a CMZTS film prepared in example 2 of the present invention.
FIG. 10 is a scanning electron microscope cross-sectional view of a CMZTS film prepared in example 2 of the present invention.
Detailed Description
In order that the deposition sequence and the like of the present invention may be more clearly understood, the present invention will be described in further detail with reference to specific embodiments thereof, taken in conjunction with the accompanying drawings.
In order to better dope the cations, the invention uses a solution method, has simple preparation, low cost and good uniformity and can better control the doping amount of the cations. By optimizing the optimal doping amount, the problems of more inversion defects, poor carrier transmission performance and the like are solved, and finally the high-performance CZTS photoelectric device is prepared.
The preparation process of the magnesium-doped copper-zinc-tin-sulfur film (CMZTS) absorbing layer comprises the following three steps: first, preparing a precursor solution. And secondly, coating the solution on a Mo glass substrate by adopting a spin-coating method to prepare a precursor film. And thirdly, vulcanizing the precursor in a tubular vulcanizing furnace at high temperature to prepare the magnesium-doped copper-zinc-tin-sulfur (CMZTS) absorbing layer. The method is characterized in that the magnesium doping of the copper, zinc, tin and sulfur is realized by adopting a simple solution spin-coating method, and the method has the advantages of low cost, environmental protection, safety, no toxicity, stable and rich raw materials and the like. In addition, the doping of magnesium has a significant beneficial effect on the morphological and structural defects of the copper zinc tin sulfide thin film.
Referring to fig. 1, the CMZTS thin film solar cell of the present invention has a six-layer structure. The method comprises the following specific steps:
(1) the glass substrate is made of soda-lime glass and is about 2mm thick;
(2) the back electrode is a double-layer Mo film with the thickness of 1 μm;
(3) the CMZTS absorption layer is a magnesium-doped copper-zinc-tin-sulfur film, and the thickness of the film is 1-1.5 mu m;
(4) the buffer layer is a CdS film with the thickness of 50-60 nm;
(5) the transparent conductive window layer is an i-ZnO and ITO film, and the thickness of the transparent conductive window layer is 35-55 nm and 400-500 nm;
(6) the top electrode is an evaporated silver electrode.
The principle of the invention is as follows:
the magnesium-doped copper-zinc-tin-sulfur film not only solves the problem of doping cation Ag in the mainstream+，Cd+The thin film has larger crystal grains and less pores, which is beneficial to the carrier transmission. Magnesium substituted partial zinc reduces CuZnAcceptor defects and the presence of secondary phases is directly reduced due to the solution instability of MgS.
Example 1
The preparation method of the CMZTS thin film solar cell with the structure shown in FIG. 1 is given by the flow chart shown in FIG. 2.
In step T1, a double-layer Mo electrode was prepared on a glass substrate by a dc sputtering method, in which the high resistance layer was 250nm thick and the low resistance layer was 1250nm thick. Firstly, putting a glass substrate into a magnetron sputtering chamber, and vacuumizing to 5 multiplied by 10-4Pa; then 5.1sccm of high-purity argon gas is introduced as working gas, and the rotating speed of the substrate table is set to be 8.0 rpm. The first layer is a high-resistance layer Mo film sputtered with the sputtering power of 200W and the working gas pressure of 1.2Pa for 15 min; the second layer is sputtered with a low resistance layer Mo film, the sputtering power is 250W, the working air pressure is 0.3Pa, and the sputtering time is 100 min.
In the step T2, firstly, according to the concentration of each metal source and sulfur source in the prepared precursor solution, 0.6mol/L of copper chloride, 0.022 mol/L of magnesium acetate, 0.418 mol/L of zinc chloride and 0.36 mol/L of stannous chloride are weighed, dissolved in 20ml of dimethylformamide solvent, and then the mixture is sealed and stirred in water bath at 50 ℃ for 15 minutes; then adding 2.8 mol/L thiourea, and continuing sealing and stirring in water bath at 50 ℃ for 50 minutes; and after the reaction is finished, carrying out centrifugal treatment at the centrifugal rotation speed of 8000 rpm for 5 minutes to obtain a light yellow or almost transparent magnesium-doped copper-zinc-tin-sulfur precursor solution. Then, uniformly coating a proper amount of precursor solution on a Mo electrode of a glass substrate, starting a spin coater for spin coating, and carrying out low-speed rotation at 700 rpm for 5 seconds; high speed 3000 r/min for 25s to obtain wet precursor film; then transferring the wet precursor film to a hot plate for heating, wherein the temperature of the hot plate is 300 ℃, and the heating and cooling time is 3 minutes, thus obtaining a dry precursor film after the end; the processes of coating, preheating and cooling at room temperature are repeated for 10 times (namely the spin coating times are 10 times), and the magnesium-doped copper-zinc-tin-sulfur precursor film with the thickness of 1 mu m can be obtained.
In step T3, the mg-doped znsn precursor film is high-temperature vulcanized to prepare the absorption layer, which comprises the following steps: sublimed sulfur powder is weighed according to 0.23 gram liter of sulfur powder (excessive) of each sample, the sublimed sulfur powder is evenly spread at the bottom of the graphite boat, and then a precursor film sample is taken and placed in the graphite boat. Setting the initial temperature of the vulcanization temperature to be 50 ℃, the heating rate to be 10 ℃/min and the final temperature to be 650 ℃ and keeping the temperature at N2And (3) preserving the heat and vulcanizing for 30 minutes in the atmosphere, ventilating for 30sccm, and pushing the furnace body to naturally cool after the ventilation is finished to obtain the magnesium-doped copper-zinc-tin-sulfur film (CMZTS) absorption layer.
In the step T4, a chemical water bath method is adopted to prepare a cadmium sulfide (CdS) film on the CMZTS absorption layer as a buffer layer, and the thickness is 50-60 nm. Adding 10mL of 0.01mol/L cadmium acetate, 12mL of 1mol/L thiourea, 8mL of 1mol/L ammonium acetate and 15mL of 25-28% ammonia water into 400mL of deionized water, heating to 80-85 ℃, and keeping for 12 min; the sample was then removed and dried in a drying oven.
In the step T5, firstly preparing an i-ZnO film with the thickness of 55nm on the buffer layer by adopting a radio frequency sputtering method; and sputtering a layer of ITO film with the thickness of 450nm to be used as a transparent conductive window layer. Wherein the sputtering power of the i-ZnO film is 70-80W, the working air pressure is 0.5Pa, and the sputtering time is 20 min; the sputtering power of the ITO film is 70-80W, the working air pressure is 0.3Pa, and the sputtering time is 50 min.
In step T6, a silver electrode is prepared as a top electrode on the transparent conductive window layer using an electron beam evaporation method. When the silver film is evaporated, the deposition rate is controlled to be 0.5-0.8 nm/s, the oxygen charging amount is controlled to be 20-25 sccm, the ion beam voltage is 115-145V, the ion beam current is controlled to be 3-7A, and the deposition time is controlled.
FIG. 3 is an X-ray diffraction pattern of the CMZTS absorber film described in example 1, from which it can be seen that a diffraction peak of molybdenum appears at a diffraction angle of 40.46 deg.. Wherein the diffraction peak of the CMZTS is consistent with the standard peak of kesterite (JCPDS: 26-0575), which indicates that the prepared CMZTS film is zincA cassiterite structure. The figure clearly shows that the crystal grains preferentially grow on the (112), (220) and (312) crystal planes, which indicates that the diffraction peak position of CZTS is not greatly changed by a small amount of magnesium doping, and the diffraction peak is higher, the half-height width is narrower, and the crystallinity is good. FIG. 4 is a Raman spectrum of the CMZTS absorbing film of example 1. As can be seen from the figure, at a wavenumber of 251cm-1、287 cm-1、335 cm-1、366 cm-1The appearance of a characteristic scattering peak is approximately consistent with the Raman spectrum characteristic peak of the CZTS film, and no ZnS scattering peak appears, which indicates that the CMZTS film obtained after doping a small amount of magnesium is single-phase. As can be seen from fig. 3 and 4, no peak positions of Mg and MgS appear, indicating that Mg atoms are well incorporated into the lattice of CZTS. FIGS. 5 and 6 are a surface view and a cross-sectional view, respectively, of a field emission scanning electron microscope of the CMZTS film prepared in example 1. The surface plot of fig. 5 and the cross-sectional plot of fig. 6 show that the CMZTS film prepared in example 1 has a dense morphology, no cracks, no pores, less secondary phases, larger grain size, and fewer fine grains, which helps to improve the carrier transport properties.
Example 2
In example 2, the steps T1 and T3-T6 are the same as those in example 1, the main difference is that in example 2, the concentration of magnesium acetate in the T2 step is 0.0264mol/L, the concentration of zinc chloride is 0.4136mol/L, and the rest are the same. The present example is intended to illustrate that, without changing other conditions, a CMZTS thin-film solar cell with a large crystal grain size, few voids, good crystal quality, and a large carrier mobility can be obtained by only appropriately changing the doping concentration of magnesium (here, the atomic molar ratio Mg/(Mg + Zn) = 4-6%). When the doping amount of magnesium is less than the doping range of the embodiment, the doping effect is not ideal, and the performance improvement is not obvious; when the doping amount of magnesium is larger than the doping range of this embodiment, the grain size and the crystalline quality of the absorption layer will gradually deteriorate and the delamination is severe with the increase of the doping amount; when magnesium completely replaces zinc, a kesterite structure cannot be formed; this fully demonstrates that only a modest amount of magnesium doping has a gain effect on the copper zinc tin sulfide thin film solar cell.
Comparing the X-ray diffraction spectra of FIG. 7 and FIG. 3As can be seen, the diffraction peak of CMZTS of example 2 is consistent with the standard peaks of examples 1 and kesterite (JCPDS: 26-0575), and the crystal grains preferentially grow on the (112), (220) and (312) crystal planes, and the diffraction peak is high, the half height width is narrow, indicating that the crystallinity is good. As can be seen from the Raman spectrum of FIG. 8, example 2 is at 284 cm-1、335 cm-1、366 cm-1The diffraction peak was slightly shifted from the Raman spectrum of example 1, and no ZnS scattering peak was observed, and the CMZTS film was a single phase. The surface diagram of fig. 9 and the cross-sectional diagram of fig. 10 show that the CMZTS film prepared in example 2 has substantially uniform surface grains, no cracks, no pores, less secondary phases, denser cross-sectional grains, less fine grains, and more favorable improvement in carrier transport properties than example 1.
The above embodiments are further described in detail to illustrate the objects, technical solutions and advantages of the present invention, and it should be understood that the above embodiments are only exemplary of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a magnesium-doped copper-zinc-tin-sulfur thin film solar cell is characterized by comprising the following specific steps:
preparing a Mo electrode on a glass substrate;
on the Mo electrode, preparing a magnesium-doped copper-zinc-tin-sulfur precursor film by adopting a precursor solution and adopting a spin-coating method;
vulcanizing the precursor film at high temperature to prepare an absorption layer;
preparing a buffer layer on the absorption layer;
preparing a transparent conductive window layer on the buffer layer;
a top electrode is prepared on the window layer.
2. The method of claim 1, wherein in the step (1), the Mo electrode has a double-layer structure including Mo thin films of a high resistance layer and a low resistance layer, whose thicknesses are 250nm and 1250nm, respectively, obtained by a dc sputtering method.
3. The method of claim 1, wherein in the step (2), copper chloride, magnesium acetate, zinc chloride and stannous chloride are used as metal sources, thiourea is used as a sulfur source, dimethylformamide is used as a solvent, and a magnesium-doped copper-zinc-tin-sulfur precursor solution is prepared, wherein the concentrations of the copper chloride and the stannous chloride in the precursor solution are respectively 0.6mol/L and 0.36 mol/L, the total concentration of the magnesium acetate and the zinc chloride is 0.44mol/L, the atomic molar ratio Mg/(Mg + Zn) = 4-6%, and the concentration of the thiourea is 2.8 mol/L.
4. The method of claim 1, wherein in step (2), the precursor solution is prepared as follows: dissolving a metal source in a solvent, sealing, and stirring in a water bath at 50 ℃ for 15 minutes; adding thiourea, and continuously sealing the water bath at 50 ℃ and stirring for 50 minutes; and after the reaction is finished, carrying out centrifugal treatment at the centrifugal rotation speed of 8000 rpm for 5 minutes to obtain the precursor solution.
5. The method according to claim 1, wherein the number of spin-coating in step (2) is 10 to 15.
6. The method of claim 1, wherein the spin coating process in step (2) is as follows: uniformly coating the magnesium-doped copper-zinc-tin-sulfur precursor solution on a Mo electrode, starting a spin coater to spin at a low speed of 700 rpm for 5 seconds; high speed 3000 r/min for 25s, preheating at 300 deg.C for 3min, and cooling at room temperature for 3 min.
7. The method according to claim 1, wherein in the step (3), the thickness of the absorption layer is 1 to 1.5 μm; the vulcanizing temperature is 650-655 ℃, the vulcanizing time is 30-40 minutes, and the working gas N2And the gas flow rate is 30 sccm.
8. The method of claim 1The method is characterized in that in the step (3), the high-temperature vulcanization process is as follows: setting the initial temperature of the vulcanization temperature to be 45-55 ℃, the heating rate to be 10 ℃/min, the final temperature to be 650-655 ℃ and the temperature in N2And (3) preserving heat and vulcanizing for 30-40 minutes in the atmosphere, ventilating at a flow rate of 30sccm, and naturally cooling to room temperature after the ventilation is finished.
9. The method of claim 1, wherein in the step (4), the buffer layer is cadmium sulfide with a thickness of 50-60 nm and is obtained by chemical water bath deposition.
10. The method of claim 1, wherein in the step (5), the transparent conductive window layer is a double-layer film of i-ZnO and ITO having a thickness of 35 to 55nm and a thickness of 400 to 500nm in this order, and is obtained by a radio frequency sputtering method.
CN202010107305.8A 2020-02-21 2020-02-21 Magnesium-doped copper-zinc-tin-sulfur thin film solar cell and preparation method thereof Pending CN111312854A (en)

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CN103078010A (en) * 2013-02-03 2013-05-01 电子科技大学 Full-non-vacuum process preparation method of copper-zinc-tin-sulfur thin film solar cell
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Application publication date: 20200619