CN105039926A - Method for preparing CZTSSe film with liquid-tin heating continuous sulfuration and selenization method, CZTSSe film prepared through method and application of CZTSSe film - Google Patents
Method for preparing CZTSSe film with liquid-tin heating continuous sulfuration and selenization method, CZTSSe film prepared through method and application of CZTSSe film Download PDFInfo
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Abstract
The invention discloses a method for preparing a CZTSSe film with a liquid-tin heating continuous sulfuration and selenization method, the CZTSSe film prepared through the method and application of the CZTSSe film. The method includes the steps that a CuZnSnS alloy film or a CuS/ZnS/Sn multi-layer overlapped film is prepared on molybdenum-plating glass with a sputtering method to serve as a precursor; an Se film is evaporated on the CuZnSnS alloy film or the CuS/ZnS/Sn multi-layer overlapped film; liquid tin at different temperatures serves as heating sources, sulfuration and selenization are carried out on the film serving as the precursor under the sulphur-element-containing nitrogen atmosphere; and finally the CZTSSe film for a solar cell absorption layer is prepared. By means of the method, rapid temperature rising with the high evenness can be guaranteed, losses of the tin in a sample can be further suppressed, it is guaranteed that components of the sample are controllable, the quality of the sample is improved, the efficiency of a cell is improved accordingly, and the method for preparing the CZTSSe film for the solar cell absorption layer is low in energy consumption and high in evenness and temperature rising speed, and has the obvious beneficial effects in the aspects of the material and energy use rate and industrial production.
Description
Technical field
The present invention relates to photoelectric semiconductor material and device arts, more specifically, relate to a kind of liquid tin heating endless vulcanization selenizing legal system for the method for CZTSSe film and CZTSSe film thereof and application.
Background technology
In recent years, along with exhausting gradually of the Nonrenewable resources such as oil limited on the earth and coal, the utilization and exploitation of renewable energy source seems more and more urgent.Wherein, solar energy power generating become the safest in renewable energy source, the rival of most environmental protection and most potentiality.The bottleneck of current restriction solar energy power generating industry development is that cost is higher and efficiency of conversion is on the low side, and from material with manufacture originally, thin film solar cell is best selection.In thin-film solar cells, copper zinc tin sulfur selenium (CZTSSe) has the direct band gap (1.04-1.67eV) mated very much with solar spectrum, and band gap can regulate sulphur selenium ratio and the high absorption coefficient (10 to visible ray by effective
5cm
-1), and not containing precious metal and toxic element, become the novel thin film solar cell absorption layer material of most potentiality.
Through the development of nearly more than 30 years, theoretical investigation and preparation technology all achieve some and breaks through, Laboratory efficiencies broke through 12%.In the preparation technology of CZTSSe semiconductor thin-film solar cell absorption layer, prepare the main flow that presoma then sulfuration selenizing method becomes suitability for industrialized production, wherein the Slag coating technique of presoma is very ripe, processing requirement can both be met for the control of presoma component ratio and the control of distributing homogeneity, the difficult point of sputtering postcure selenizing method technique is, exigent temperature homogeneity in sulfidation, very fast temperature rise rate and strict reaction atmosphere.High temperature homogeneity ensures that presoma is consistent with substrate material thermal deformation in heat-processed, thus avoid absorption layer to come off, fast temperature rise rate can suppress the generation of Binary-phase, and suitable reaction atmosphere can suppress the volatilization of metallic element, ensures that the moiety of absorption layer is stablized.Sulfuration selenizing fado common is at present radiation heating, and thermal source does not contact presoma, and this heating method is difficult to realize big area continuous seepage, and in vulcanization process, energy consumption is very high.Obviously, develop the sulfuration selenization technology of the copper zinc tin sulfur selenium semiconductor film of high temperature uniformity and less energy-consumption, become the key subjects of this field face current.
Summary of the invention
The object of the invention is to overcome that heat-up rate in existing copper zinc tin sulfur selenium method for manufacturing thin film is low, poor temperature uniformity and the defect such as energy consumption is high, a kind of sulfuration selenizing method preparing copper zinc tin sulfur selenium absorbing layer of thin film solar cell that less energy-consumption, high evenness, heat-up rate are fast is provided.
Another object of the present invention is to provide the CZTSSe copper-based compound semiconductor thin-film solar cell absorption layer (i.e. copper zinc tin sulfur selenium film) that aforesaid method prepares.
Another object of the present invention is to provide the solar cell containing above-mentioned CZTSSe absorption layer.
Above-mentioned purpose of the present invention is achieved by the following technical programs:
Liquid tin heating endless vulcanization selenizing legal system, for a method for CZTSSe film, comprises the following steps:
S1. substrate is through cleaning, drying; Utilize DC sputtering on substrate, prepare dorsum electrode layer Mo layer;
S2. on Mo layer, CuZnSnS alloy firm or the overlapping film of CuS/ZnS/Sn multilayer is then prepared as precursor thin-film, then evaporation last layer Se film;
S3. CZTSSe film is obtained through continuous warming sulfuration selenizing again;
Wherein, the concrete grammar of described continuous warming sulfuration selenizing is:
The evaporation obtained by S2 has the precursor thin-film of Se film successively through the liquid tin pool surface that several temperature raise successively, heats, completes sulfuration selenizing, obtain CZTSSe film under containing the nitrogen atmosphere of element sulphur to precursor thin-film; The liquid tin pond that several described temperature raise successively is that (i.e. sulfuration selenizing is completed by the mode of liquid tin laser heating in several temperature liquid tin pond of raising successively from 200 DEG C to 580 DEG C, precursor thin-film can be made to realize being rapidly heated of high evenness, avoid because presoma and substrate material thermal deformation in heat-processed is inconsistent and cause absorption layer to come off, also suppress the generation of Binary-phase simultaneously, thus obtain the stable copper-zinc-tin-sulfur film presoma of moiety).
Preferably, cleaning described in step S1 utilizes organic solvent, dehydrated alcohol, deionized water to soak and ultrasonic cleaning successively, deionized water rinsing; Preferably, organic solvent is acetone.
Preferably, described element sulphur is solid sulfur or hydrogen sulfide.
Preferably, substrate described in step S1 is (as stainless steel) at the bottom of simple glass or other high temperature-resistant liners.
Further preferably, when substrate described in step S1 is stainless steel, need to prepare SiO on first at the bottom of stainless steel lining
2blocking layer (preferred thickness is 0.5 μm), then d.c. sputtering Mo layer.
Preferably, described in step S1, the thickness of dorsum electrode layer Mo layer is 0.8 ~ 1.2 μm.
Can selection scheme as one, Se film described in step S2 utilizes thermal evaporation to carry out evaporation on described alloy firm or the overlapping film of multilayer, and preferably, the thickness of the Se film of evaporation is 15 ~ 25 μm.
Can selection scheme as one, step S2 utilizes CuZnSnS alloys target sputter or utilize CuS target, ZnS target, Sn target co-sputtering to prepare CuZnSnS alloy firm; Utilize CuS target, ZnS target, the overlapping film of Sn target Slag coating CuS/ZnS/Sn multilayer.
Preferably, the thickness of the CuZnSnS alloy firm described in step S2 or the overlapping film of CuS/ZnS/Sn multilayer is 700 ~ 900nm; The ratio of component of described CuZnSnS alloy firm or the overlapping film of CuS/ZnS/Sn multilayer is Cu/(Zn+Sn)=0.8 ~ 0.9, Zn/Sn=1.1 ~ 1.2.
The CZTSSe film utilizing aforesaid method to prepare and described CZTSSe film prepare the application in solar cell all should within protection scope of the present invention.
In addition, be that the CZTSSe solar cell for preparing of absorption layer is also within protection scope of the present invention by above-mentioned CZTSSe film.Particularly, described CZTSSe solar cell is prepared by following methods:
S1. utilize on chemical bath deposition method (CBD method) CZTSSe film described in claim 6 and prepare CdS buffer layer;
S2. successively Slag coating Window layer i-ZnO and transparent electrode layer AZO film on CdS buffer layer, then at evaporating Al electrode above, form complete CZTSSe solar cell.
Preferably, described in step S1, the thickness of CdS buffer layer is 40 ~ 60nm.
Preferably, the thickness of Window layer i-ZnO described in step S2 is 50 ~ 120nm, and the thickness of transparent electrode layer AZO film is 0.3 ~ 1.0 μm.
The present invention utilizes the liquid tin of differing temps to heat to sample as heating source, so not only can ensure sample temperature homogeneity but also can reach to be rapidly heated, outer field Se at high temperature selenizing presoma.Whole liquid tin pond is positioned in an enclosed space, passes into nitrogen dilution hydrogen sulfide or evaporates appropriate solid sulfur source, realize sulfuration simultaneously.In enclosed space, sulphur and selenium and metallic tin react and form higher tin sulfide and Tin diselenide vapour pressure, inhibit the tin in sample to run off, ensure that the component of sample is controlled, improve the quality of sample thus improve the efficiency of battery.Liquid tin is not only heating medium, all right big area support substrates, reduces substrate by thermal deformation, thus can use higher selenizing curing temperature and larger substrate.The present invention is the sulfuration selenizing method and apparatus of the copper-based compound semiconductor thin-film solar cell absorption layer that a kind of energy consumption is low, uniformity coefficient is high, heat-up rate is high, in material and energy utilization rate and suitability for industrialized production, have obvious advantage.
The above-mentioned preparation method of the present invention can be realized by a kind of selenium sulfide gasifying device, as shown in Fig. 1 to 5, comprises base, outer cover, liquid tin pond; Base and outer cover connect and compose enclosed space by sealing-ring; Liquid tin pond is positioned at enclosed space; Liquid tin pond inwall arranges heating chamber, and heating chamber arranges heating component; Liquid tin pond comprises the Xi Chi (as shown in Figure 6) of several the different warm areas in the middle of former and later two buffer zones and two buffer zones.
Further, the outside of the two side in liquid tin pond is respectively provided with several rollers, and roller upper limb is concordant with liquid tin pond.The two side upper limb in described liquid tin pond is level and smooth plane.
In addition, thermopair and heating power supply Controlling System are connected with heater strip and provide thermal source.Described heater strip is evenly arranged in heating chamber.
And, between the front buffer zone in liquid tin pond and liquid tin pond, and be equipped with sluice valve between liquid tin pond and rear buffer zone.
Further, be placed with solid sulfur source between liquid tin pond and outer cover, solid sulfur source is connected with crucible.Described crucible is used for heat solid sulphur source.
The step using above-mentioned selenium sulfide gasifying device to prepare copper zinc tin sulfur selenium film is as follows:
Sputtering method is utilized in the glass substrate of plating molybdenum, to prepare CuZnSnS alloy firm or the overlapping film of CuS/ZnS/Sn multilayer as precursor thin-film, evaporation one deck Se film in precursor thin-film again, above the liquid tin pond glass substrate of above-mentioned film of preparation being placed in surge chamber before device, make facing up of precursor thin-film, in the past buffer zone enters the Xi Chi (200 DEG C to 580 DEG C raise successively) with different warm area through sluice valve, utilize the roller on Xi Chi both sides that substrate is shifted to high-temperature zone from cold zone, the liquid tin of differing temps is utilized to heat to sample as heating source, so not only can ensure sample temperature homogeneity but also can reach to be rapidly heated, outer field Se at high temperature selenizing presoma.Meanwhile, whole liquid tin pond is positioned in an enclosed space, passes into nitrogen dilution hydrogen sulfide or evaporates appropriate solid sulfur source, realize sulfuration simultaneously, enters rear surge chamber and completes sulfuration selenizing, obtain CZTSSe film finally by sluice valve.
In preparation process, liquid tin is not only heating medium, all right big area support glass substrate, reduces substrate by thermal deformation, thus can use higher selenizing curing temperature.The liquid tin of differing temps is utilized to heat to sample as heating source, so not only can reach the effect be enough rapidly heated but also sample temperature homogeneity can be ensured, whole liquid tin pond is placed in an enclosed space, sulphur and selenium and metallic tin react and form higher tin sulfide and Tin diselenide vapour pressure, the tin in sample is inhibit to run off, ensure that the component of sample is controlled, improve the quality of sample, thus improve the efficiency of battery.
In addition, it should be noted that, described sulfuration selenizing equipment is only a kind of equipment realizing sulfuration selenizing method of the present invention, and this equipment is not limited in any way preparation method of the present invention.
Compared with prior art, the present invention has following beneficial effect:
The invention provides a kind of sulfuration selenizing method of CZTSSe semiconductor thin-film solar cell absorption layer, sputtering method is first utilized to prepare CuZnSnS quad alloy film or the overlapping film of multilayer, the Se film of evaporation suitable thickness on this film again, then utilize liquid tin to carry out sulfuration selenizing to precursor thin-film, finally prepare CZTSSe solar cell.There is following obvious advantage:
1. utilize the liquid tin of differing temps to carry out sulfuration selenizing as heating source to sample, because thermal source directly contacts with presoma, so both can realize being rapidly heated, ensure again the high evenness of sample temperature, avoid because presoma and substrate material thermal deformation in heat-processed is inconsistent and cause absorption layer to come off, and fast temperature rise rate also inhibits the generation of Binary-phase, ensure that the moiety of sample is stablized.
2. whole liquid tin pond is placed in enclosed space, sulphur and selenium and metallic tin react and form higher tin sulfide and Tin diselenide vapour pressure, the tin in precursor thin-film is inhibit to run off, ensure that the controlled of sample component, improve the quality of sample, thus improve the efficiency of battery, in material and energy utilization rate and suitability for industrialized production, there is obvious advantage.
3. liquid tin is not only heating medium, all right big area support glass substrate, reduces glass substrate by thermal deformation, thus can improve the temperature of selenizing sulfuration.
4. liquid tin heating method of the present invention, has the advantage that energy consumption is low, temperature uniformity is high, heat-up rate is fast, has good market application foreground.
Accompanying drawing explanation
Fig. 1 is the selenium sulfide gasifying device schematic diagram that the present invention prepares film; Wherein, 121 is base, and 111 is outer cover, and 117 is liquid tin pond, and 115 is roller, and 114 is heating chamber, and 118 is heater strip, and 119 is sealing-ring, and 120 is thermopair and heating power supply Controlling System, and 122 is sluice valve, and 123 is crucible.
Fig. 2 is the A-A sectional view of selenium sulfide gasifying device.
Fig. 3 is sluice valve schematic diagram.
Fig. 4 is sealing-ring schematic diagram.
Fig. 5 is substrate glass and roller schematic diagram.
Fig. 6 is the liquid tin Heating Zone Temperature distribution schematic diagram of selenium sulfide gasifying device.
Fig. 7 is the process flow sheet of preparation CZTSSe solar cell.
Embodiment
Further illustrate content of the present invention below in conjunction with Figure of description and specific embodiment, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the simple modification do the inventive method, step or condition or replacement, all belong to scope of the present invention; If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art.
embodiment 1 the present invention prepares the liquid tin heating endless vulcanization selenizing device of CZTSSe film
1, prepare a liquid tin heating endless vulcanization selenizing device for CZTSSe film, as shown in Fig. 1 to 5, comprise base 121, outer cover 111, liquid tin pond 117; Base 121 and outer cover 111 connect and compose enclosed space by sealing-ring 119; Liquid tin pond 117 is positioned at enclosed space; Liquid tin pond 117 inwall arranges heating chamber 114, and heating chamber 114 inside arranges heating component 118; Liquid tin pond 117 comprises the Xi Chi (as shown in Figure 6) of several the different warm areas in the middle of former and later two buffer zones and two buffer zones.
Further, the outside of the two side in liquid tin pond 117 is respectively provided with several rollers 115, and roller 115 upper limb is concordant with liquid tin pond 117.The two side upper limb in described liquid tin pond 117 is level and smooth plane.
In addition, thermopair and heating power supply Controlling System 120 are connected with heater strip 118 and provide thermal source.It is inner that described heater strip 118 is evenly arranged in heating chamber 114.
And, between the front buffer zone in liquid tin pond 117 and liquid tin pond, and be equipped with sluice valve 122 between liquid tin pond and rear buffer zone.
Further, be placed with solid sulfur source between liquid tin pond 117 and outer cover 111, solid sulfur source is connected with crucible 123.Described crucible 123 is for heat solid sulphur source.
2, said apparatus is utilized to prepare the method for CZTSSe film as follows:
Sputtering method is utilized in the glass substrate 113 of plating molybdenum, to prepare CuZnSnS alloy firm or the overlapping film of CuS/ZnS/Sn multilayer as precursor thin-film, evaporation one deck Se film 112 in precursor thin-film again, above the liquid tin pond 117 glass substrate 113 of above-mentioned film of preparation being placed in surge chamber before device, make facing up of precursor thin-film, in the past buffer zone enters the Xi Chi (200 DEG C-580 DEG C) with different warm area through sluice valve 122, utilize the roller 115 on Xi Chi both sides that substrate is shifted to high-temperature zone from cold zone, the liquid tin 116 of differing temps is utilized to heat to sample as heating source, so not only can ensure sample temperature homogeneity but also can reach to be rapidly heated, outer field Se at high temperature selenizing presoma.Meanwhile, whole liquid tin pond is positioned in an enclosed space, passes into nitrogen dilution hydrogen sulfide or evaporates appropriate solid sulfur source, realize sulfuration simultaneously; In enclosed space, sulphur and selenium and metallic tin react and form higher tin sulfide and Tin diselenide vapour pressure, and sulfuration selenidation process carries out in very high tin sulfide atmosphere, inhibits the loss of tin in sample, ensure that the component of sample is controlled, improve the quality of sample thus the efficiency of raising battery; Enter rear surge chamber finally by sluice valve and complete sulfuration selenizing, obtain CZTSSe film.
embodiment 2 prepares CZTSSe film
1. substrate selects simple glass, and soak and ultrasonic cleaning through organic solvent, dehydrated alcohol, deionized water, deionized water rinsing, then dries stand-by.
2. utilize DC sputtering to prepare on a glass substrate Mo layer that thickness is 1.0 μm.
3. then the substrate preparing Mo floor is put into d.c. sputtering room, utilize CuS target, ZnS target, Sn target co-sputtering to prepare CuZnSnS quad alloy film that thickness is 800nm, control group proportion by subtraction Cu/(Zn+Sn)=0.8, Zn/Sn=1.1.
4. utilize thermal evaporation to be the Se film of 20 μm at alloy firm surface evaporation thickness.
5., in the equipment of embodiment 1, by the continuous warming sulfuration selenizing of the complete paired samples of the mode of liquid tin laser heating, obtain CZTSSe film.
embodiment 3 prepares CZTSSe film
1. substrate is selected at the bottom of stainless steel lining, and soak and ultrasonic cleaning through organic solvent, dehydrated alcohol, deionized water, deionized water rinsing, then dries stand-by.
2. utilize radio frequency sputtering method at the bottom of stainless steel lining on prepare the SiO that thickness is 0.5 μm
2blocking layer, then d.c. sputtering thickness is the Mo layer of 0.8 μm.
3. then the substrate preparing Mo floor is put into d.c. sputtering room, utilizes the CuZnSnS quad alloy film that CuZnSnS alloys target Slag coating thickness is 700nm, control group proportion by subtraction Cu/(Zn+Sn)=0.8, Zn/Sn=1.1.
4. utilize thermal evaporation to be the Se film of 15 μm at alloy firm surface evaporation thickness.
5., in the equipment of embodiment 1, by the continuous warming sulfuration selenizing of the complete paired samples of the mode of liquid tin laser heating, obtain CZTSSe film.
embodiment 4 prepares CZTSSe film
1. substrate selects simple glass, and soak and ultrasonic cleaning through organic solvent, dehydrated alcohol, deionized water, deionized water rinsing, then dries stand-by.
2. utilize DC sputtering to prepare on a glass substrate Mo layer that thickness is 1.2 μm.
3. then the substrate preparing Mo floor is put into d.c. sputtering room, utilize CuS target, ZnS target, Sn target co-sputtering the to prepare overlapping film of CuS/ZnS/Sn multilayer that thickness is 800nm, control group proportion by subtraction Cu/(Zn+Sn)=0.9, Zn/Sn=1.2)
4. utilize thermal evaporation to be the Se film of 20 μm (15 ~ 25) at alloy firm surface evaporation thickness.
5., in the equipment of embodiment 1, by the continuous warming sulfuration selenizing of the complete paired samples of the mode of liquid tin laser heating, obtain CZTSSe film.
embodiment 5 prepares CZTSSe film
1. substrate selects simple glass, and soak and ultrasonic cleaning through organic solvent, dehydrated alcohol, deionized water, deionized water rinsing, then dries stand-by.
2. utilize DC sputtering to prepare on a glass substrate Mo layer that thickness is 1.1 μm.
3. then the substrate preparing Mo floor is put into d.c. sputtering room, utilize CuS target, ZnS target, Sn target co-sputtering to prepare CuZnSnS quad alloy film that thickness is 800nm, control group proportion by subtraction Cu/(Zn+Sn)=0.8, Zn/Sn=1.1.
4. utilize thermal evaporation to be the Se film of 20 μm at alloy firm surface evaporation thickness.
5., in the equipment of embodiment 1, by the continuous warming sulfuration selenizing of the complete paired samples of the mode of liquid tin laser heating, obtain CZTSSe film.
embodiment 6 prepares CZTSSe solar cell
1, preparation method
(1) it is 50nm(40 ~ 60nm that the CZTSSe film utilizing chemical bath deposition method (CBD method) to prepare in embodiment 1 prepares thickness) CdS buffer layer;
(2) film having prepared CdS buffer layer sends into sputtering chamber, and on CdS buffer layer, successively Slag coating is about 100nm(50 ~ 120) i-ZnO layer and the AZO film of 0.8 μm (0.3 ~ 1.0).
(3) take out sample, evaporating Al electrode, forms complete CZTSSe solar cell.
2, the CZTSSe solar cell will prepared, the thin-film solar cells namely with glass/Mo/CZTSSe/CdS/i-ZnO/AZO structure carries out electrical performance testing, and result shows, and its voltage V=520mV, I=23mA, the turnover ratio of battery is 6.8%.
The CZTSSe solar cell of the implication CZTSSe film prepared, its structure is multi-layer film structure, from incidence surface, comprise successively: metal gate layers (Al), transparent electrode layer (AZO), Window layer (i-ZnO), buffer layer (CdS), light absorbing zone (CZTSSe), dorsum electrode layer (Mo) and glass substrate.
Wherein, metal gate layers, transparent electrode layer, Window layer, buffer layer, dorsum electrode layer and substrate, do not limit by above-mentioned materials, also can use other material.
Claims (10)
1. liquid tin heating endless vulcanization selenizing legal system is for a method for CZTSSe film, it is characterized in that, comprises the following steps:
S1. substrate is through cleaning, drying; Utilize DC sputtering on substrate, prepare dorsum electrode layer Mo layer;
S2. on Mo layer, CuZnSnS alloy firm or the overlapping film of CuS/ZnS/Sn multilayer is then prepared as precursor thin-film, then evaporation last layer Se film;
S3. CZTSSe film is obtained through continuous warming sulfuration selenizing again;
Wherein, the concrete grammar of described continuous warming sulfuration selenizing is:
The evaporation obtained by S2 has the precursor thin-film of Se film successively through the liquid tin pool surface that several temperature raise successively, heats, completes sulfuration selenizing, obtain CZTSSe film under containing the nitrogen atmosphere of element sulphur to precursor thin-film; The liquid tin pond that several described temperature raise successively is the liquid tin pond that several temperature raise successively from 200 DEG C to 580 DEG C.
2. liquid tin heating endless vulcanization selenizing legal system, for the method for CZTSSe film, is characterized in that according to claim 1, and described cleaning utilizes organic solvent, dehydrated alcohol, deionized water to soak and ultrasonic cleaning successively, deionized water rinsing; Described element sulphur is solid sulfur or hydrogen sulfide.
3. liquid tin heating endless vulcanization selenizing legal system is for the method for CZTSSe film according to claim 1, and it is characterized in that, substrate described in step S1 is simple glass or stainless steel; Described in step S1, the thickness of dorsum electrode layer Mo layer is 0.8 ~ 1.2 μm; Se film described in step S2 utilizes thermal evaporation to carry out evaporation on described alloy firm or the overlapping film of multilayer, and the thickness of the Se film of evaporation is 15 ~ 25 μm.
4. according to described in claim 1, liquid tin heating endless vulcanization selenizing legal system is for the method for CZTSSe film, and it is characterized in that, step S2 utilizes CuZnSnS alloys target sputter or utilize CuS target, ZnS target, Sn target co-sputtering to prepare CuZnSnS alloy firm; Utilize CuS target, ZnS target, the overlapping film of Sn target Slag coating CuS/ZnS/Sn multilayer.
5. require that described in 1, liquid tin heating endless vulcanization selenizing legal system is for the method for CZTSSe film according to profit, it is characterized in that, the thickness of the CuZnSnS alloy firm described in step S2 or the overlapping film of CuS/ZnS/Sn multilayer is 700 ~ 900nm; The ratio of component of described CuZnSnS alloy firm or the overlapping film of CuS/ZnS/Sn multilayer is Cu/(Zn+Sn)=0.8 ~ 0.9, Zn/Sn=1.1 ~ 1.2.
6. the CZTSSe film for preparing of method described in any one of claim 1 to 5.
7. CZTSSe film described in claim 6 is preparing the application in solar cell.
8. a CZTSSe solar cell, is characterized in that, with CZTSSe film described in claim 6 for absorption layer prepares.
9. CZTSSe solar cell according to claim 8, is characterized in that, specifically prepared by following methods:
S1. utilize on chemical bath deposition method CZTSSe film described in claim 6 and prepare CdS buffer layer;
S2. successively Slag coating Window layer i-ZnO and transparent electrode layer AZO film on CdS buffer layer, then at evaporating Al electrode above, form complete CZTSSe solar cell.
10. CZTSSe solar cell according to 1 claim 9, is characterized in that, described in step S1, the thickness of CdS buffer layer is 40 ~ 60nm;
The thickness of Window layer i-ZnO described in step S2 is 50 ~ 120nm, and the thickness of transparent electrode layer AZO film is 0.3 ~ 1.0 μm.
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| CN105039926B (en) | 2017-09-26 |
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