CN113363332B - Transition group element single-doped CZTS film and preparation method thereof - Google Patents
Transition group element single-doped CZTS film and preparation method thereof Download PDFInfo
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- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 14
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- 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
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
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- 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
- H01L31/0216—Coatings
- H01L31/02161—Coatings for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/02167—Coatings for devices characterised by at least one potential jump barrier or surface barrier for solar cells
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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
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
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- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1876—Particular processes or apparatus for batch treatment of the devices
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- 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
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Abstract
The invention relates to a transition group element single-doped CZTS film and a preparation method thereof. The invention can realize the controllability of the band structure and the photoelectric comprehensive performance of the CZTS film by improving the process parameters and regulating and controlling the doping concentration of transition group elements represented by Ni. On the basis of ensuring high density and high uniformity of the film, the CZTS film with controllable energy band structure and controllable performance is prepared at low cost.
Description
Technical Field
The invention relates to the fields of photoelectronic devices, novel thin-film solar cell materials, novel semiconductor heterojunction materials and the like, in particular to a CZTS thin film formed by singly doping transition group elements with low price and high abundance and a preparation process thereof.
Background
With the problems of excessive exploitation of traditional fossil energy and environmental pollution becoming more serious, the call for the vigorous development of clean alternative energy such as solar energy becomes higher, and thin-film solar cells are produced at the same time. Copper zinc tin sulfide (Cu) 2 ZnSnS 4 the/CZTS) film material is distinguished from a plurality of novel film materials by the advantages of rich component element content, no toxicity, low price and the like, and is widely concerned. CZTS is suitable not only for a glass substrate but also for a flexible substrate, a stainless steel substrate, and the like. In addition, compared with other solar cell absorption layers, the CZTS film has the advantages of good light failure resistance, simplicity in preparation and the like, and is remarkable in advantages, so that the CZTS film is very suitable for being used as a P-type semiconductor layer and light absorption layer of a heterojunction solar cell, does not contain toxic substances basically in the production process, and is safe and environment-friendly. Theoretical prediction of CZTS filmThe photoelectric conversion efficiency of the solar cell can reach 32.2%, and the solar cell has immeasurable application prospect as a novel thin-film solar cell material.
The current common preparation methods of the CZTS film are a thermal evaporation method, a magnetron sputtering method, an electrochemical deposition method, a spray pyrolysis method, a sol-gel method and the like. The sol-gel method has the advantages of mild and accessible conditions, easy control of chemical element proportion, easy element doping, simple equipment, low cost and the like.
At present, domestic and foreign researches are focused on utilizing element doping means to cause the change of a CZTS crystal structure and the change of an energy band structure so as to regulate and control physical properties such as photoelectric properties of the CZTS crystal structure, solve the problems that small-sized crystal grains cause more crystal boundary defects in the crystallization process of the CZTS, second phases such as ZnS and the like are generated in the working process of a device, the band gap mismatch of a heterojunction interface, the lattice mismatch, holes in the interface and the like, and finally achieve the purpose of improving the photoelectric conversion efficiency of the device.
Disclosure of Invention
The invention provides a CZTS film singly doped with transition group elements represented by Ni, such as Ni, fe, ti, mn, cr and the like, and a preparation method thereof. The method effectively regulates and controls the energy band structure and the photoelectric property of the CZTS film, and simultaneously ensures the compactness, flatness and uniformity of the CZTS film.
In order to achieve the purpose, the invention adopts the following technical scheme:
the atomic weight of the transition group elements is similar to that of Zn, and the preparation method is easy to realize Zn 2+ Substitutional doping of (c). As the radius of the doping element atoms is different from that of the Zn atoms, the doping element atoms enter the CZTS crystal lattice to occupy the Zn position to cause lattice distortion, and the matching degree of the CZTS and the crystal lattice structure of the buffer layer material is improved. The lattice distortion changes the original periodic potential field of the crystal, and because the electronic structure of the doping element atoms is different from that of Zn atoms, the doping element atoms enter the CZTS lattice and affect the CZTS energy band structure. CZTS belongs to a p-type semiconductor and is doped with a minority electron atom, which traps electrons from the valence band to generate holes, reduces the valence band electron concentration, lowers the fermi level, and bends the energy band downward. First principle pair CZT based on density functional theoryResearch on the S energy band structure finds that the influence of Zn on the forbidden band width of CZTS is small, the optical band gap of the CZTS film of 1.5eV is not greatly changed by substitutional doping of Zn, the band structure can be slightly regulated by controlling the dosage of doping elements, and finally the optical band gap can reach 1.4eV which has the best matching property with the solar spectrum.
A preparation method of a transition group element single-doped CZTS film comprises the following steps:
1) Preparing a precursor: taking copper acetate, zinc acetate, stannic chloride and thiourea as raw materials for preparing CZTS, taking acetate of transition elements as a doping source, taking ethylene glycol monomethyl ether as a solvent, mixing all the materials, heating and stirring at 55-60 ℃ for 1-1.5h to prepare a single-doped CZTS precursor, and then aging at room temperature for 3-15 days;
2) Obtaining a supernatant: centrifuging the aged precursor, taking supernatant, and standing the supernatant for later use;
3) Substrate cleaning: ultrasonically cleaning the substrate by using absolute ethyl alcohol, carrying out secondary cleaning after replacing the absolute ethyl alcohol, and drying the substrate by using high-pressure nitrogen for later use after taking out the substrate;
4) Spin coating a film: after fixing the cleaned and dried substrate, dropwise adding the supernatant liquid to the substrate to uniformly distribute the supernatant liquid on the surface of the substrate, and then spin-coating to prepare a film with controllable thickness, uniform structure and uniform surface appearance;
5) And (3) heat treatment: introducing protective gas into the heat treatment equipment with protective atmosphere, and controlling the gas flow to keep 50-60 mL/min -1 When the temperature of the heat treatment equipment with the protective atmosphere rises to 150-155 ℃ and is kept at the temperature for 40-60min, putting the film fully distributed with the supernatant into the heat treatment equipment with the protective atmosphere for heat treatment; and naturally cooling to room temperature after the heat treatment is finished, and closing the protective gas inlet valve to obtain the transition group element single-doped CZTS film.
The preparation method of the transition group element single-doped CZTS film comprises the following steps:
in the step 1), the transition group elements comprise Ni, fe, ti, mn and Cr elements; the dosage of the doping element is Zn in zinc acetate 2+ As a reference, i.e.The content of the ions of the doping element in the precursor is Zn 2+ Calculated in mol percent, in particular Zn 2+ 1-7% of the content; the raw materials comprise copper acetate, zinc acetate, stannic chloride, thiourea = (7-8): (4-5): (3-4): (28-32) in a molar ratio, and the mass volume ratio of the zinc acetate to the ethylene glycol monomethyl ether is 2.75g, (15-17) mL, namely 15-17mL of ethylene glycol monomethyl ether is used for every 2.75g of zinc acetate.
The invention adopts stannic chloride to prevent S with strong reducibility 2- Reducing other metal ions to obtain Sn 2+ . In the step 1), firstly, thiourea and metal ions are subjected to complexation to generate metal-thiourea sulfide, then the metal-thiourea sulfide and ethylene glycol monomethyl ether are subjected to alcoholysis and polycondensation, and finally, decomposition reaction is performed through heat treatment to generate CZTS nano particles. The specific chemical reaction equation is as follows:
M-X+Tu＝[M(Tu) m ]-X
[M(Tu) m ]-X+ROH＝[M(Tu) m ]-OR+H-X
[M(Tu) m ]-X+[M(Tu) m ]-OR＝[M(Tu) m ]-O-[M(Tu) m ]+R-X
[M(Tu) m ]-O-[M(Tu) m ]+R-X＝Cu x S+ZnS+Sn x S+SnO 2 +ZnS+Cu x s + volatile substance
Cu x S+ZnS+Sn x S＝Cu 2 ZnSnS 4
Cu x S+ZnS+SnO 2 +S＝Cu 2 ZnSnS 4
In the above formula, the symbol M represents a metal ion (Cu) 2+ ，Zn 2+ ，Sn 2+ ) X represents an anion (CH) 3 COO - ，Cl - ) And Tu represents an organic molecular chain in thiourea, and R represents an organic molecular chain in ethylene glycol monomethyl ether. The volatile substances represent gases produced by decomposition reactions during the heat treatment, e.g. CO 2 ，CS 2 ，H 2 O，SO 2 And the like.
The doped transition group metal ion takes part in the reaction, the complexation, alcoholysis and polycondensation are carried out, and the reaction enters the CZTS crystal lattice to carry out Zn 2+ Displacement to generate Cu 2 Zn 1-x N x SnS 4 And the symbol N represents doped transition group elements Ni, fe, ti, mn or Cr, wherein the ion number ratio is Cu (Zn + N), sn: S =2,
i.e. the ratio of the number of doping ions to the number of zinc ions in one CZTS unit cell.
The aging process is the secondary stabilization of the metastable state sol, the sol is slowly polymerized among aged colloidal particles to form a three-dimensional space network structure, and the network is filled with the solvent losing fluidity, so that the sol is converted into gel.
In the step 2), centrifuging the aged precursor at the rotating speed of 4800-5000rpm for 10-20min, and taking supernatant as a coating raw material; the supernatant needs to be kept still for 24-48h at room temperature.
In the step 3), the substrate is made of soda-lime glass and FTO glass; the basic shape is square, and the size is 1.5cm multiplied by 1.5 cm-5 cm multiplied by 5cm; the substrate is cleaned by absolute ethyl alcohol ultrasonic for 3-5min for the first time, and is cleaned for 2-4min for the second time by replacing the absolute ethyl alcohol.
The time interval between the completion of the spin coating in the step 4) and the placement of the film into the tube furnace in the step 5) is not more than 5min; in the spin coating process, specific spin coating parameters are as follows: a doping content of transition group element ions of 1% or more and 5% or less of Zn 2+ The supernatant of CZTS precursor with content is spin-coated at low speed of 500-600rpm for 15-20s and then at high speed of 3000-3300rpm for 30-35s, and the content of transition element ion doping is more than 5% and less than or equal to 7% 2+ The supernatant of the CZTS precursor with the content is spin-coated for 15-20s at low speed of 500-600rpm and then at high speed of 3400-3700rpm for 30-35s.
In the step 5), the protective gas is high-purity nitrogen or high-purity argon; the heat treatment is divided into two continuous stages of low temperature and high temperature, wherein the low temperature is 150-250 ℃, the total low temperature heat preservation time is 150-250min, the high temperature is 300-350 ℃, and the total high temperature heat preservation time is 60-80min.
The invention has the following beneficial effects:
the invention adopts a sol-gel method combined with a spin coating method and adopts transition group elements represented by Ni to carry out single doping on CZTS so as to prepare the high-quality and high-performance transition group element single-doped CZTS film. The crystal grain size of the CZTS film can be increased by doping a small amount of Ni, fe, ti, mn and Cr, the uniformity, the flatness and the compactness of the film are improved, the separation of ZnS impurity phases is inhibited, the defects are reduced, the scattering and the compounding of photo-generated carriers in the migration process are reduced, and the purpose of improving the performance of a device is finally achieved. The controllable preparation of the CZTS film is realized by optimizing parameters such as element doping concentration, water bath temperature, water bath time, rotor rotating speed, aging time, low speed and high speed of spin coating, heat treatment temperature and time, nitrogen flow and the like. The invention can realize the controllability of the band structure and the photoelectric comprehensive performance of the CZTS film by improving the process parameters and regulating and controlling the doping concentration of transition group elements represented by Ni. On the basis of ensuring high density and high uniformity of the film, the CZTS film with controllable energy band structure and controllable performance is prepared at low cost.
Drawings
FIG. 1 XRD diffraction patterns of doped and undoped transition group element CZTS thin films prepared in inventive example 1 to comparative example 3.
FIG. 2 SEM surface and cross-sectional views of transition group element-undoped CZTS thin films prepared in example 1 of the present invention.
FIG. 3 SEM surface and cross-sectional views of transition group element-doped CZTS thin films prepared in comparative example 1 of the present invention.
FIG. 4 SEM surface and cross-sectional views of transition group element-doped CZTS thin films prepared in comparative example 2 of the present invention.
FIG. 5 SEM surface and cross-sectional views of transition group element-doped CZTS thin films prepared in comparative example 3 of the present invention.
FIG. 6 is a graph showing heat treatment temperature curves of transition group doped or undoped CZTS thin films prepared in example 1 to comparative example 3 of the present invention.
FIG. 7I-V curves for top-bottom electrode testing of transition group element doped CZTS films prepared in comparative example 2 of the present invention.
FIG. 8I-V curves of top-bottom electrode testing of transition group element doped CZTS films prepared in comparative example 2 of the present invention.
FIG. 9 optical band gap curves of transition group element doped or undoped CZTS thin films prepared in example 1 to comparative example 3 of the present invention; in the figure, a, b, c and d correspond to example 1, comparative example 2 and comparative example 3 respectively.
Detailed Description
Example 1
A preparation method of a CZTS film not doped with transition group elements comprises the following specific operation steps:
1) Preparing a precursor: copper acetate, zinc acetate, tin tetrachloride and thiourea are used as raw materials for preparing CZTS, the molar ratio of the raw materials is that the ratio of the copper acetate to the zinc acetate to the tin tetrachloride to the thiourea is = 8;
2) Obtaining a supernatant: centrifuging the obtained precursor at 4800rpm for 10min, collecting supernatant, and standing at room temperature for 24h;
3) Cleaning a substrate: ultrasonically cleaning the substrate for 3min by using absolute ethyl alcohol, carrying out secondary cleaning for 2min after replacing the absolute ethyl alcohol, and drying the substrate for later use by using high-pressure nitrogen after taking out the substrate; the substrate is soda-lime glass and FTO glass with the thickness of 1mm and 2mm respectively and the size of 1.7cm multiplied by 1.7 cm;
4) Spin coating a film: fixing the cleaned and dried substrate in the center of a sample table of a spin coater, wiping the substrate with alcohol cotton and drying, dripping the supernatant on the surface of the substrate to ensure that the substrate is uniformly distributed on the surface of the substrate, and spin-coating at a low speed of 500rpm for 15s and at a high speed of 3300rpm for 30s to obtain a film;
5) And (3) heat treatment: introducing protective gas into the tube furnace, and controlling the gas flow to be kept at 53 mL/min -1 When the temperature of the tube furnace rises to 150 ℃ and is kept at the temperature for 40min, the film fully covered with the supernatant is put into the tube furnace for heat treatment, and the specific steps are as follows: after the film is put into a tube furnace, the heat is preserved at 150 DEG C40min, heating to 250 deg.C for 100min, maintaining the temperature at 250 deg.C for 30min, heating to 350 deg.C for 50min, and maintaining the temperature at 350 deg.C for 60min. And naturally cooling to room temperature after the heat treatment is finished, and closing the protective gas inlet valve to obtain the non-doped transition group element CZTS film. The SEM surface and the cross section of the prepared CZTS film not doped with transition group elements are shown in FIG. 2, and as can be seen from FIG. 2, the CZTS film prepared by the process of the invention has good uniformity, compactness, flatness and crystallinity.
Comparative example 1
The preparation method of the transition group element single-doped CZTS film comprises the specific operation steps of the same as those of example 1, except that a doping source nickel acetate is added in the step 1) of the comparative example 1, wherein the content of nickel ions is Zn 2+ 1 percent of the above-mentioned material, and then the transition group element single-doped CZTS film is obtained. SEM surface and cross-sectional view of the CZTS film doped with transition group elements prepared in the comparative example are shown in FIG. 3, the prepared CZTS film is uniform and flat, compact in structure and good in crystallization performance, and crystal grain precipitation is effectively reduced by doping Ni element.
Comparative example 2
The preparation method of the transition group element single-doped CZTS film comprises the specific operation steps of the same as those of example 1, except that a doping source nickel acetate is added in the step 1) of the comparative example 2, wherein the content of nickel ions is Zn 2+ And 3 percent of the total amount of the transition group element, and the single-doped CZTS film of the transition group element is prepared. SEM surface and cross-sectional view of the CZTS film doped with transition group elements prepared in the comparative example are shown in FIG. 4, the prepared CZTS film is uniform and flat, compact in structure and good in crystallization performance, and crystal grain precipitation is effectively reduced by doping Ni element. In addition, the I-V curve of the top-top electrode test and the I-V curve of the top-bottom electrode test of the CZTS film doped with transition group elements prepared in the comparative example are shown in fig. 7 and 8, respectively, and it can be seen that the CZTS film itself shows an obvious gold-half contact with the aluminum electrode, the top-bottom electrode test shows an obvious semi-conducting curve, and the degree of coincidence of the curves is higher, indicating that the uniformity and compactness of the film are good.
Comparative example 3
The preparation method of the transition group element single-doped CZTS film comprises the specific operation steps of the same as those of example 1, except that a doping source nickel acetate is added in the step 1) of the comparative example 3, wherein the content of nickel ions is Zn 2+ 5% of the above-mentioned material, and making the transition group element single-doped CZTS film. SEM surface and cross-sectional views of the transition group element-doped CZTS thin film prepared in this comparative example 3 are shown in FIG. 5. As can be seen from the comparison of FIGS. 2 to 5, the CZTS film prepared by the method of the present invention has the advantages of uniformity, flatness, compact structure and good crystallization performance, the precipitation of crystal grains is effectively reduced by the doping of Ni element, and the CZTS film doped with 3% of nickel ions has the best uniformity and compactness.
The XRD diffractogram of the CZTS film doped or undoped with transition group elements prepared in the above 4 preparation examples is shown in fig. 1, and it can be seen from fig. 1 that the Ni element doping effectively changes the grain size of the CZTS film and suppresses the impurity phase precipitation. The heat treatment temperature curve of the CZTS thin film doped or undoped with transition group elements prepared in the above 4 preparation examples is shown in fig. 6, and it can be known from the figure that the prepared thin film has good crystallinity, uniformity, compactness and flatness through reasonable temperature rise rate, heat preservation temperature and heat preservation time. The optical band gap curves of the transition group element-doped or undoped CZTS thin films prepared in the above 4 preparation examples are shown in fig. 9 and table 1. As can be seen from fig. 9 and table 1, the doping of Ni element effectively regulates the optical band gap of CZTS, and the method of the present invention successfully prepares a CZTS thin film with good matching between the optical band gap and the solar spectrum.
TABLE 1 optical band gap values of CZTS thin films doped with nickel ions of different concentrations
Example 2
A preparation method of a transition group element single-doped CZTS film comprises the following specific operation steps:
1) Preparing a precursor: copper acetate, zinc acetate, stannic chloride and thiourea are used as raw materials for preparing CZTS, and the molar ratio of the raw materials is copper acetate, zinc acetate, stannic chloride and sulfurUrea =7, iron acetate is the doping source, and the content of ferrous ions is Z 2+ 1% of the precursor, taking 17mL of ethylene glycol monomethyl ether as a solvent, mixing all materials, magnetically stirring for 1.5h in a water bath at 55 ℃ to prepare a CZTS precursor doped with transition group elements, and then aging for 15 days at room temperature;
2) Obtaining a supernatant: centrifuging the obtained precursor at 4900rpm for 13min, collecting supernatant, and standing at room temperature for 36h;
3) Cleaning a substrate: ultrasonically cleaning the substrate for 3min by using absolute ethyl alcohol, carrying out secondary cleaning for 2min after replacing the absolute ethyl alcohol, and drying the substrate for later use by using high-pressure nitrogen after taking out the substrate; the substrate is soda-lime glass and FTO glass with the thickness of 1mm and 2mm respectively and the size of 1.5cm multiplied by 1.5 cm;
4) Spin coating a film: fixing the cleaned and dried substrate in the center of a sample table of a spin coater, wiping the substrate by alcohol cotton and drying, dropwise adding the supernatant onto the surface of the substrate to ensure that the substrate is uniformly distributed on the surface of the substrate, and spin-coating at a low speed of 550rpm for 20s and at a high speed of 3000rpm for 35s to obtain a film;
5) And (3) heat treatment: introducing protective gas into the tube furnace, and controlling the gas flow to keep 50 mL/min -1 When the temperature of the tube furnace rises to 150 ℃ and is kept at the temperature for 40min, the film fully covered with the supernatant is put into the tube furnace for heat treatment, and the heat treatment comprises the following specific steps: after the film is put into a tube furnace, the heat preservation is carried out for 60min at the temperature of 150 ℃, then the temperature is raised to 250 ℃, the time is 120min, the heat preservation is carried out for 30min after the temperature reaches 250 ℃, then the temperature is raised to 350 ℃, the time is 50min, and the heat preservation is continued for 80min after the temperature reaches 350 ℃. And naturally cooling to room temperature after the heat treatment is finished, and closing the protective gas inlet valve to obtain the 1% ferrous ion doped CZTS film.
Example 3
A preparation method of a transition group element single-doped CZTS film comprises the following specific operation steps:
1) Preparing a precursor: copper acetate, zinc acetate, tin tetrachloride and thiourea are used as raw materials for preparing CZTS, the molar ratio of the raw materials is copper acetate to zinc acetate to tin tetrachloride to thiourea =7 2+ 3% of (2), 16mL of ethylene glycol monomethyl ether as a solventMixing all the materials, magnetically stirring for 1.2h in a water bath at 60 ℃ to prepare a CZTS precursor doped with transition group elements, and then aging for 10 days at room temperature;
2) Obtaining a supernatant: centrifuging the obtained precursor at the rotating speed of 5000rpm for 15min, taking supernatant, and standing the supernatant at room temperature for 48h;
3) Cleaning a substrate: ultrasonically cleaning the substrate for 3min by using absolute ethyl alcohol, carrying out secondary cleaning for 2min after replacing the absolute ethyl alcohol, and drying the substrate for later use by using high-pressure nitrogen after taking out the substrate; adopting soda-lime glass and FTO glass with the thickness of 1mm and 2mm and the size of 3cm multiplied by 3cm as substrates;
4) Spin coating of a film: fixing the cleaned and dried substrate in the center of a sample table of a spin coater, wiping the substrate with alcohol cotton and drying, dripping the supernatant on the surface of the substrate to ensure that the substrate is uniformly distributed on the surface of the substrate, and spin-coating at a low speed of 600rpm for 20s and at a high speed of 3100rpm for 35s to obtain a film;
5) And (3) heat treatment: introducing protective gas into the tube furnace, and controlling the gas flow to be kept at 60 mL/min -1 When the temperature of the tube furnace rises to 150 ℃ and is kept at the temperature for 40min, the film fully covered with the supernatant is put into the tube furnace for heat treatment, and the heat treatment comprises the following specific steps: after the film is put into a tube furnace, the temperature is kept for 20min at 150 ℃, then the temperature is raised to 250 ℃ for 90min, the temperature is kept for 40min after reaching 250 ℃, then the temperature is raised to 350 ℃ for 60min, and the temperature is kept for 70min after reaching 350 ℃. And naturally cooling to room temperature after the heat treatment is finished, and closing the protective gas inlet valve to obtain the 3% titanium ion doped CZTS film.
Example 4
A preparation method of a transition group element single-doped CZTS film comprises the following specific operation steps:
1) Preparing a precursor: copper acetate, zinc acetate, tin tetrachloride and thiourea are used as raw materials for preparing CZTS, the molar ratio of the raw materials is that copper acetate, zinc acetate, tin tetrachloride and thiourea is 32 2+ 5% of the above, 17mL of ethylene glycol monomethyl ether is used as a solvent, all the materials are mixed, stirred magnetically for 1.2h at 57 ℃ in a water bath to prepare a CZTS precursor doped with transition group elements, and then aged for 7 days at room temperature；
2) Obtaining a supernatant: centrifuging the obtained precursor at the rotating speed of 5000rpm for 15min, taking supernatant, and standing the supernatant at room temperature for 30h;
3) Cleaning a substrate: ultrasonically cleaning the substrate for 3min by using absolute ethyl alcohol, carrying out secondary cleaning for 2min after replacing the absolute ethyl alcohol, and drying the substrate for later use by using high-pressure nitrogen after taking out the substrate; the substrate is soda-lime glass and FTO glass with the thickness of 1mm and 2mm respectively and the size of 5cm multiplied by 5cm;
4) Spin coating a film: fixing the cleaned and dried substrate in the center of a sample table of a spin coater, wiping the substrate with alcohol cotton and drying, dripping the supernatant on the surface of the substrate to ensure that the substrate is uniformly distributed on the surface of the substrate, and spin-coating at a low speed of 600rpm for 17s and at a high speed of 3200rpm for 33s to obtain a film;
5) And (3) heat treatment: introducing protective gas into the tube furnace, and controlling the gas flow to be kept at 55 mL/min -1 When the temperature of the tube furnace rises to 150 ℃ and is kept at the temperature for 40min, the film fully covered with the supernatant is put into the tube furnace for heat treatment, and the heat treatment comprises the following specific steps: and (3) after the film is placed in a tube furnace, preserving heat for 40min at 150 ℃, then heating to 250 ℃, preserving heat for 40min when the temperature is raised to 250 ℃, then heating to 350 ℃, preserving heat for 60min when the temperature is raised to 350 ℃, and then continuing preserving heat for 60min. And naturally cooling to room temperature after the heat treatment is finished, and closing the protective gas inlet valve to obtain the 5% manganese ion doped CZTS film.
Example 5
A preparation method of a transition group element single-doped CZTS film comprises the following specific operation steps:
1) Preparing a precursor: copper acetate, zinc acetate, tin tetrachloride and thiourea are used as raw materials for preparing CZTS, the molar ratio of the raw materials is that copper acetate, zinc acetate, tin tetrachloride and thiourea is 32 2+ And 7% of the total amount of the precursor, 20mL of ethylene glycol monomethyl ether is used as a solvent, all materials are mixed, and are magnetically stirred for 1.5 hours in a water bath at 60 ℃ to prepare a CZTS precursor doped with transition group elements, and then the precursor is aged for 7 days at room temperature;
2) Obtaining a supernatant: centrifuging the obtained precursor at the rotating speed of 5000rpm for 15min, taking supernatant, and standing the supernatant at room temperature for 30h;
3) Cleaning a substrate: ultrasonically cleaning the substrate for 3min by using absolute ethyl alcohol, carrying out secondary cleaning for 2min after replacing the absolute ethyl alcohol, and drying the substrate for later use by using high-pressure nitrogen after taking out the substrate; the substrate is soda-lime glass and FTO glass with the thickness of 1mm and 2mm respectively and the size of 3cm multiplied by 3 cm;
4) Spin coating a film: fixing the cleaned and dried substrate in the center of a sample table of a spin coater, wiping the substrate with alcohol cotton and drying, dropwise adding the supernatant onto the surface of the substrate to ensure that the substrate is uniformly distributed on the surface of the substrate, and spin-coating at a low speed of 600rpm for 20s and at a high speed of 3500rpm for 35s to obtain a film;
5) And (3) heat treatment: introducing protective gas into the tube furnace, and controlling the gas flow to be kept at 55 mL/min -1 When the temperature of the tube furnace rises to 150 ℃ and is kept at the temperature for 40min, the film fully covered with the supernatant is put into the tube furnace for heat treatment, and the heat treatment comprises the following specific steps: and (3) after the film is placed in a tube furnace, preserving heat for 40min at 150 ℃, then heating to 250 ℃, keeping the temperature for 100min, preserving heat for 50min after reaching 250 ℃, then heating to 350 ℃, preserving heat for 80min after reaching 350 ℃. And naturally cooling to room temperature after the heat treatment is finished, and closing the protective gas inlet valve to obtain the 7% chromium ion doped CZTS film.
Claims (2)
1. A preparation method of a transition group element single-doped CZTS film is characterized by comprising the following steps:
1) Preparing a precursor: copper acetate, zinc acetate, stannic chloride and thiourea are used as preparation raw materials of CZTS, the molar ratio of the raw materials is copper acetate, zinc acetate, stannic chloride, thiourea = (7-8): (4-5): (3-4): (28-32), acetate of transition group elements is used as a doping source, and the transition group elements comprise Ni, fe, ti, mn and Cr elements; the content of the ions of the doping element in the precursor is Zn 2+ Is Zn in percentage by mole 2+ 1-7% of the content, taking ethylene glycol monomethyl ether as a solvent, and mixing all the materials, heating and stirring at 55-60 ℃ for 1-1.5h to prepare a mono-doped CZTS precursor, wherein the mass-volume ratio of zinc acetate to ethylene glycol monomethyl ether is 2.75g (15-17) mL, and then aging at room temperature for 3-15 days;
2) Obtaining a supernatant: centrifuging the aged precursor at 4800-5000rpm for 10-20min, collecting supernatant, and standing at room temperature for 24-48 h;
3) Substrate cleaning: ultrasonically cleaning the substrate by using absolute ethyl alcohol, carrying out secondary cleaning after replacing the absolute ethyl alcohol, and drying the substrate by using high-pressure nitrogen for later use after taking out the substrate;
4) Spin coating a film: after fixing the cleaned and dried substrate, dropwise adding the supernatant liquid to the substrate to uniformly distribute the supernatant liquid on the surface of the substrate, and then spin-coating to prepare a film with controllable thickness, uniform structure and uniform surface appearance; in the spin coating process, specific spin coating parameters are as follows: zn content of transition group element ion of 1% or more and 5% or less 2+ The supernatant of CZTS precursor has spin coating parameters of low speed 500-600rpm for 15-20s, high speed 3000-3300rpm for 30-35s, transition element ion content greater than 5% and less than or equal to 7% 2+ Spin-coating the supernatant of the CZTS precursor with the content for 15-20s at low speed of 500-600rpm, and then spin-coating at high speed of 3400-3700rpm for 30-35s;
5) And (3) heat treatment: introducing protective gas into heat treatment equipment with high-purity nitrogen or high-purity argon, and controlling gas flow to be kept at 50-60 mL/min -1 When the temperature of the heat treatment equipment with the protective atmosphere rises to 150-155 ℃ and is kept at the temperature for 40-60min, the film fully covered with the supernatant is placed into the heat treatment equipment with the protective atmosphere for heat treatment, the time interval between the end of spin coating in the step 4) and the placement of the film into the tube furnace in the step 5) is not more than 5min, the heat treatment is divided into two continuous stages of low temperature and high temperature, the low temperature is 150-250 ℃, the total duration of low temperature heat preservation is 150-250min, the high temperature is 300-350 ℃, and the total duration of high temperature heat preservation is 60-80min; naturally cooling to room temperature after the heat treatment is finished, and closing a protective gas inlet valve to obtain the transition group element single-doped CZTS film;
the chemical composition of the main crystal phase of the film is Cu 2 Zn 1-x N x SnS 4 N represents doping elements Ni, fe, ti, mn or Cr, wherein the ion number ratio is Cu (Zn + N), sn is S =2,
represents the ion number ratio of the doped transition group element to the zinc ion number ratio in a single CZTS unit cell.
2. The method of claim 1, wherein in step 3), the substrate is made of soda-lime glass or FTO glass with a size of 1.5cm x 1.5cm to 5cm x 5cm; the substrate is cleaned by absolute ethyl alcohol ultrasonic for 3-5min for the first time and 2-4min for the second time.
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