CN105039926B - A kind of liquid tin heating continuous vulcanization selenizing method prepares method and its CZTSSe films and the application of CZTSSe films - Google Patents
A kind of liquid tin heating continuous vulcanization selenizing method prepares method and its CZTSSe films and the application of CZTSSe films Download PDFInfo
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Abstract
The invention discloses method and its CZTSSe films and the application that a kind of liquid tin heating continuous vulcanization selenizing method prepares CZTSSe films.CuZnSnS alloy firms are prepared on plating molybdenum glass first with sputtering method or CuS/ZnS/Sn multilayers overlap film and are used as presoma, one layer of Se film is deposited on this film, the liquid tin of different temperatures is recycled to be used as heating source, under the nitrogen atmosphere containing element sulphur, vulcanization selenizing is carried out to precursor thin-film, completion CZTSSe solar battery obsorbing layer films are finally prepared.The present invention can not only ensure being rapidly heated for high evenness, the tin that can also suppress in sample is lost in, it ensure that the component of sample is controllable, the quality of sample is improved to improve the efficiency of battery, it is that a kind of energy consumption is low, the uniformity is high, the method for preparing solar battery obsorbing layer CZTSSe films of programming rate soon, there is obvious advantage in terms of material and energy utilization rate and industrialized production.
Description
Technical field
The present invention relates to photoelectric semiconductor material and device arts, heat and connect more particularly, to a kind of liquid tin
Continuous vulcanization selenizing method prepares method and its CZTSSe films and the application of CZTSSe films.
Background technology
In recent years, gradually exhausting with non-renewable resources such as oil and coal limited on the earth, regenerative resource
Utilization seem more and more urgent with exploitation.Wherein, solar energy power generating has become most safe, most ring in regenerative resource
Protect and most potential competitor.The bottleneck of restriction solar energy power generating industry development is that cost is higher and changes effect at present
Rate is relatively low, from material and is manufactured into original, and thin film solar cell is optimal selection.In thin-film solar cells, copper zinc
Tin sulphur selenium（CZTSSe）With the direct band gap matched very much with solar spectrum（1.04-1.67eV）, band gap can be by effective
Regulation sulphur selenium than with the high absorption coefficient to visible ray（105cm-1）, and noble metal and toxic element are not contained, as most
The novel thin film solar cell for having potentiality absorbs layer material.
By the development of nearly more than 30 years, some breakthroughs, Laboratory efficiencies are all achieved in theoretical research and preparation technology
Break through 12%.In the preparation technology of CZTSSe semiconductor thin-film solar cell absorbed layers, presoma and then selenium sulfide are prepared
Change method turns into the main flow of industrialized production, and the sputtering preparation technology of wherein presoma is very ripe, for presoma component ratio
The control of example and the control of distributing homogeneity can meet technological requirement, and the difficult point of sputtering after cure selenizing method technique exists
In, exigent temperature homogeneity in sulfidation, heating rate quickly and strict reaction atmosphere.High temperature is uniform
Property ensures presoma, and the thermal deformation in heating process is consistent with backing material, so that avoid absorbed layer from coming off, fast heating rate
The generation of Binary-phase can be suppressed, suitable reaction atmosphere can suppress the volatilization of metallic element, it is ensured that the composition of absorbed layer into
Divide stable.Vulcanization selenizing fado common at present is radiant heating, and thermal source does not contact presoma, and this heating is difficult to realize big
Area is continuously produced, and energy consumption is very high in vulcanization process.Obviously, the high temperature uniformity of development and the copper zinc of low energy consumption
The vulcanization selenization technology of tin sulphur selenium semiconductor film, the key subjects as the current field face.
The content of the invention
The invention aims to overcome in existing copper zinc tin sulfur selenium method for manufacturing thin film, programming rate is low, temperature is uniform
Property difference and the defect such as energy consumption height there is provided a kind of low energy consumption, high evenness, programming rate soon prepare the copper zinc tin sulfur selenium film sun
The vulcanization selenizing method of energy battery obsorbing layer.
The CZTSSe copper-based compounds semiconductive thin film prepared it is a further object of the present invention to provide the above method is too
Positive energy battery obsorbing layer（That is copper zinc tin sulfur selenium film）.
Another object of the present invention is to provide the solar cell containing above-mentioned CZTSSe absorbed layers.
Above-mentioned purpose of the present invention is achieved by the following technical programs：
A kind of method that liquid tin heating continuous vulcanization selenizing method prepares CZTSSe films, comprises the following steps：
S1. the cleaned drying of substrate；Mo layers of dorsum electrode layer is prepared on substrate using DC sputtering；
S2. CuZnSnS alloy firms and then on Mo layers are prepared or CuS/ZnS/Sn multilayers overlap film and are used as presoma
Film, then last layer Se films are deposited；
S3. CZTSSe films are obtained by continuous warming vulcanization selenizing again；
Wherein, the specific method of the continuous warming vulcanization selenizing is：
The precursor thin-film that the obtained evaporations of S2 there are Se films is sequentially passed through into several temperature elevated liquid tin pond successively
Surface, is heated under the nitrogen atmosphere containing element sulphur to precursor thin-film, is completed vulcanization selenizing, is obtained CZTSSe thin
Film；Several described temperature successively elevated liquid tin pond be several temperature from 200 DEG C to 580 DEG C elevated liquid successively
Xi Chi（That is vulcanization selenizing is completed by way of liquid tin laser heating, precursor thin-film can be enable to realize high evenness
Be rapidly heated, it is to avoid cause absorbed layer to come off thermal deformation is inconsistent in heating process because of presoma and backing material, together
When also suppress the generation of Binary-phase, so as to obtain the stable copper-zinc-tin-sulfur film presoma of constituent）.
Preferably, cleaning described in step S1 is to utilize organic solvent, absolute ethyl alcohol, deionized water immersion and ultrasonic wave successively
Cleaning, deionized water rinsing；Preferably, organic solvent is acetone.
Preferably, the element sulphur is solid sulfur or hydrogen sulfide gas.
Preferably, substrate described in step S1 is simple glass or other high temperature-resistant liner bottoms（Such as stainless steel）.
It is further preferred that when substrate described in step S1 is stainless steel, it is necessary to first prepare SiO on stainless steel lining bottom2
Barrier layer（Preferred thickness is 0.5 μm）, then Mo layers of d.c. sputtering.
Preferably, dorsum electrode layer Mo layers of thickness is 0.8 ~ 1.2 μm described in step S1.
As a kind of optional scheme, Se films described in step S2 are to be handed over using thermal evaporation in the alloy firm or multilayer
It is deposited on folded film, it is preferable that the thickness of the Se films of evaporation is 15 ~ 25 μm.
As a kind of optional scheme, step S2 is that CuS targets, ZnS targets, Sn are sputtered or utilized using CuZnSnS alloys targets
Target co-sputtering prepares CuZnSnS alloy firms；CuS/ZnS/Sn multilayers, which are prepared, using CuS targets, ZnS targets, the sputtering of Sn targets overlaps film.
Preferably, described in step S2 CuZnSnS alloy firms or CuS/ZnS/Sn multilayers overlap the thickness of film for 700 ~
900nm；The component ratio that the CuZnSnS alloy firms or CuS/ZnS/Sn multilayers overlap film is Cu/（Zn+Sn）=0.8 ~ 0.9,
Zn/Sn=1.1~1.2。
The CZTSSe films and the CZTSSe films prepared using the above method is in solar cell is prepared
Application all should be within protection scope of the present invention.
In addition, being the CZTSSe solar cells that prepare of absorbed layer also in the guarantor of the present invention by above-mentioned CZTSSe films
Within the scope of shield.Specifically, the CZTSSe solar cells are prepared by following methods：
S1. chemical bath deposition method is utilized（CBD methods）CdS cushions are being prepared described in claim 6 on CZTSSe films；
S2. successively sputtering prepares Window layer i-ZnO and transparent electrode layer AZO films on CdS cushions, then above
Evaporating Al electrode, forms complete CZTSSe solar cells.
Preferably, the thickness of CdS cushions described in step S1 is 40 ~ 60nm.
Preferably, the thickness of Window layer i-ZnO described in step S2 is 50 ~ 120nm, the thickness of transparent electrode layer AZO films
For 0.3 ~ 1.0 μm.
The present invention is heated by the use of the liquid tin of different temperatures as heating source to sample, so can both ensure sample temperature
Uniformity can reach again to be rapidly heated, the Se of outer layer selenizing presoma at high temperature.Wholly liquid state tin pond is positioned over one
In individual confined space, nitrogen dilution hydrogen sulfide gas or the appropriate solid sulphur source of evaporation are passed through, while realizing vulcanization.Confined air
In, sulphur and selenium react to form higher artificial gold and stannic selenide vapour pressure with metallic tin, it is suppressed that the tin in sample is lost in, and protects
The component for having demonstrate,proved sample is controllable, improves the quality of sample to improve the efficiency of battery.Liquid tin is not only heating medium, also
It can reduce substrate with large area support substrate and be thermally deformed, so as to use higher selenizing curing temperature and bigger lining
Bottom.The present invention is that the copper-based compound semiconductor thin-film solar cell that a kind of energy consumption is low, the uniformity is high, programming rate is high absorbs
The vulcanization selenizing method and apparatus of layer, has obvious advantage in terms of material and energy utilization rate and industrialized production.
The above-mentioned preparation method of the present invention can be realized by one kind vulcanization selenizing device, as shown in Fig. 1 to 5, including base,
Outer cover, liquid tin pond；Base and outer cover connect and compose confined space by sealing ring；Liquid tin pond is located in confined space；Liquid
State tin pond inwall sets heating chamber, and heating chamber sets heating component；Liquid tin pond includes former and later two buffering areas and two
The Xi Chi of several different warm areas in the middle of buffering area（As shown in Figure 6）.
Further, several rollers, roller upper limb and liquid tin pond are each provided with the outside of the two side in liquid tin pond
Concordantly.The two side upper limb in the liquid tin pond is smooth plane.
In addition, thermocouple and heating power supply control system are connected with heater strip and provide thermal source.The heater strip is uniformly arranged
It is distributed in heating chamber.
Moreover, being all provided between the preceding buffering area in liquid tin pond and liquid tin pond, and between liquid tin pond and rear buffering area
There is gate valve.
Further, solid sulphur source is placed between liquid tin pond and outer cover, solid sulphur source is connected with crucible.The earthenware
Crucible is used to heat solid sulphur source.
The step of preparing copper zinc tin sulfur selenium film using above-mentioned vulcanization selenizing device is as follows：
CuZnSnS alloy firms are prepared in the glass substrate of plating molybdenum or CuS/ZnS/Sn multilayers overlap film using sputtering method
One layer of Se film is deposited as precursor thin-film, then in precursor thin-film, the glass substrate of the above-mentioned film of preparation is placed in dress
Before putting above the liquid tin pond of surge chamber, make the face-up of precursor thin-film, entering from preceding buffering area through gate valve has difference
The Xi Chi of warm area（200 DEG C to 580 DEG C raise successively）, substrate is shifted into high-temperature region from low-temperature space using the roller on Xi Chi both sides,
Heated by the use of the liquid tin of different temperatures as heating source to sample, so can not only ensure sample temperature uniformity but also can reach
To being rapidly heated, the Se of outer layer selenizing presoma at high temperature.Meanwhile, wholly liquid state tin pond is positioned over a confined space
In, nitrogen dilution hydrogen sulfide gas or the appropriate solid sulphur source of evaporation are passed through, while realizing vulcanization, is most entered afterwards through gate valve
Surge chamber completes vulcanization selenizing afterwards, obtains CZTSSe films.
In preparation process, liquid tin is not only heating medium, can with large area support glass substrate, reduce substrate by
Thermal deformation, so as to use higher selenizing curing temperature.Liquid tin by the use of different temperatures adds as heating source to sample
Heat, so can not only reach the effect being enough rapidly heated but also can ensure sample temperature uniformity, and wholly liquid state tin pond is placed
In a confined space, sulphur and selenium react to form higher artificial gold and stannic selenide vapour pressure with metallic tin, it is suppressed that sample
In tin be lost in, it is ensured that the component of sample is controllable, improves the quality of sample, so as to improve the efficiency of battery.
In addition, it is necessary to which explanation, the vulcanization selenizing equipment is only to realize one kind of present invention vulcanization selenizing method
Equipment, preparation method of the equipment not to the present invention is limited in any way.
Compared with prior art, the invention has the advantages that：
The invention provides a kind of vulcanization selenizing method of CZTSSe semiconductor thin-film solar cells absorbed layer, first with
Sputtering method prepares CuZnSnS quaternary alloys film or multilayer overlaps film, then the Se films of suitable thickness are deposited on this film, so
Vulcanization selenizing is carried out to precursor thin-film using liquid tin afterwards, completion CZTSSe solar cells are finally prepared.With following bright
Aobvious advantage：
1. vulcanization selenizing is carried out to sample as heating source using the liquid tin of different temperatures, due to thermal source and presoma
Directly contact, so can both realize and be rapidly heated, ensure the high evenness of sample temperature again, it is to avoid because of presoma and substrate
Material thermal deformation in heating process is inconsistent and causes absorbed layer to come off, and fast heating rate also inhibits Binary-phase
Produce, it is ensured that the constituent of sample is stable.
2. wholly liquid state Xi Chi is placed in confined space, sulphur and selenium react to form higher artificial gold and selenium with metallic tin
Change tin vapour pressure, it is suppressed that tin in precursor thin-film is lost in, it is ensured that sample component it is controllable, improve the quality of sample,
So as to improve the efficiency of battery, there is obvious advantage in terms of material and energy utilization rate and industrialized production.
3. liquid tin is not only heating medium, glass substrate can be supported with large area, reduce the heated shape of glass substrate
Become, so as to improve the temperature of selenizing vulcanization.
4. the liquid tin heating of the present invention, has the advantages that energy consumption is low, temperature uniformity is high, programming rate is fast, has
Good market application foreground.
Brief description of the drawings
Fig. 1 prepares the vulcanization selenizing device schematic diagram of film for the present invention；Wherein, 121 be base, and 111 be outer cover, 117
It is roller for liquid tin pond, 115,114 be heating chamber, and 118 be heater strip, and 119 be sealing ring, and 120 be thermocouple and heating electricity
Source control system, 122 be gate valve, and 123 be crucible.
Fig. 2 is the A-A profiles of vulcanization selenizing device.
Fig. 3 is gate 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 vulcanization selenizing device.
Fig. 7 is the process chart for preparing CZTSSe solar cells.
Embodiment
Present disclosure is further illustrated with reference to Figure of description and specific embodiment, but be should not be construed as to this
The limitation of invention.Without departing from the spirit and substance of the case in the present invention, that the inventive method, step or condition are made is simple
Modifications or substitutions, belong to the scope of the present invention；Unless otherwise specified, technological means used in embodiment is art technology
Conventional meanses known to personnel.
The present invention of embodiment 1 prepares the liquid tin heating continuous vulcanization selenizing device of CZTSSe films
1st, a kind of liquid tin heating continuous vulcanization selenizing device for preparing CZTSSe films, as shown in Fig. 1 to 5, including bottom
Seat 121, outer cover 111, liquid tin pond 117；Base 121 and outer cover 111 connect and compose confined space by sealing ring 119；Liquid
Tin pond 117 is located in confined space；The inwall of liquid tin pond 117 sets heating chamber 114, and the inside of heating chamber 114 sets heating component
118；Liquid tin pond 117 includes the Xi Chi of several different warm areas in the middle of former and later two buffering areas and two buffering areas（Such as Fig. 6
It is shown）.
Further, be each provided with several rollers 115 on the outside of the two side in liquid tin pond 117, the upper limb of roller 115 with
Liquid tin pond 117 is concordant.The two side upper limb in the liquid tin pond 117 is smooth plane.
In addition, thermocouple and heating power supply control system 120 are connected with heater strip 118 and provide thermal source.The heater strip
118 are uniformly arranged in inside heating chamber 114.
Moreover, between the preceding buffering area in liquid tin pond 117 and liquid tin pond, and between liquid tin pond and rear buffering area
Provided with gate valve 122.
Further, solid sulphur source is placed between liquid tin pond 117 and outer cover 111, solid sulphur source connects with crucible 123
Connect.The crucible 123 is used to heat solid sulphur source.
2nd, the method for preparing CZTSSe films using said apparatus is as follows：
CuZnSnS alloy firms are prepared in the glass substrate 113 of plating molybdenum or CuS/ZnS/Sn multilayers are handed over using sputtering method
One layer of Se film 112 is deposited as precursor thin-film, then in precursor thin-film in folded film, by the glass substrate of the above-mentioned film of preparation
113 are placed in above the liquid tin pond 117 of surge chamber before device, make the face-up of precursor thin-film, from preceding buffering area through gate valve
122 enter the Xi Chi with different warm areas（200℃-580℃）, substrate is moved from low-temperature space using the roller 115 on Xi Chi both sides
To high-temperature region, heated by the use of the liquid tin 116 of different temperatures as heating source to sample, so can both ensure that sample temperature was equal
Even property can reach again to be rapidly heated, the Se of outer layer selenizing presoma at high temperature.Meanwhile, wholly liquid state tin pond is positioned over
In one confined space, nitrogen dilution hydrogen sulfide gas or the appropriate solid sulphur source of evaporation are passed through, while realizing vulcanization；It is closed
In space, sulphur and selenium react to form higher artificial gold and stannic selenide vapour pressure with metallic tin, and vulcanization selenidation process is very high
Carried out in artificial gold atmosphere, it is suppressed that the loss of tin in sample, it is ensured that the component of sample is controllable, improve the quality of sample from
And improve the efficiency of battery；Surge chamber completes vulcanization selenizing after most entering afterwards through gate valve, obtains CZTSSe films.
Embodiment 2 prepares CZTSSe films
1. substrate selects simple glass, cleaned through organic solvent, absolute ethyl alcohol, deionized water immersion and ultrasonic wave, go from
Sub- water is rinsed, and is then dried stand-by.
2. prepare the Mo layers that thickness is 1.0 μm on a glass substrate using DC sputtering.
3. the substrate for preparing Mo floor is then put into d.c. sputtering room, CuS targets, ZnS targets, Sn target co-sputtering systems are utilized
The CuZnSnS quaternary alloy films that standby thickness is 800nm, control component compares Cu/（Zn+Sn）=0.8, Zn/Sn=1.1.
4. using thermal evaporation in the Se films that alloy firm surface evaporation thickness is 20 μm.
5. in the equipment of embodiment 1, the continuous warming vulcanization of complete paired samples by way of liquid tin laser heating
Selenizing, obtains CZTSSe films.
Embodiment 3 prepares CZTSSe films
1. substrate selects stainless steel lining bottom, clean, go through organic solvent, absolute ethyl alcohol, deionized water immersion and ultrasonic wave
Ionized water is rinsed, and is then dried stand-by.
2. the SiO that thickness is 0.5 μm is prepared on stainless steel lining bottom using radio frequency sputtering method2Barrier layer, then d.c. sputtering
Thickness is 0.8 μm of Mo layers.
3. the substrate for preparing Mo floor is then put into d.c. sputtering room, thickness is prepared using CuZnSnS alloys target sputterings
For 700nm CuZnSnS quaternary alloy films, control component compares Cu/（Zn+Sn）=0.8, Zn/Sn=1.1.
4. using thermal evaporation in the Se films that alloy firm surface evaporation thickness is 15 μm.
5. in the equipment of embodiment 1, the continuous warming vulcanization of complete paired samples by way of liquid tin laser heating
Selenizing, obtains CZTSSe films.
Embodiment 4 prepares CZTSSe films
1. substrate selects simple glass, cleaned through organic solvent, absolute ethyl alcohol, deionized water immersion and ultrasonic wave, go from
Sub- water is rinsed, and is then dried stand-by.
2. prepare the Mo layers that thickness is 1.2 μm on a glass substrate using DC sputtering.
3. the substrate for preparing Mo floor is then put into d.c. sputtering room, CuS targets, ZnS targets, Sn target co-sputtering systems are utilized
Standby thickness overlaps film for 800nm CuS/ZnS/Sn multilayers, and control component compares Cu/（Zn+Sn）=0.9, Zn/Sn=1.2）
4. it is 20 μm in alloy firm surface evaporation thickness to utilize thermal evaporation（15~25）Se films.
5. in the equipment of embodiment 1, the continuous warming vulcanization of complete paired samples by way of liquid tin laser heating
Selenizing, obtains CZTSSe films.
Embodiment 5 prepares CZTSSe films
1. substrate selects simple glass, cleaned through organic solvent, absolute ethyl alcohol, deionized water immersion and ultrasonic wave, go from
Sub- water is rinsed, and is then dried stand-by.
2. prepare the Mo layers that thickness is 1.1 μm on a glass substrate using DC sputtering.
3. the substrate for preparing Mo floor is then put into d.c. sputtering room, CuS targets, ZnS targets, Sn target co-sputtering systems are utilized
The CuZnSnS quaternary alloy films that standby thickness is 800nm, control component compares Cu/（Zn+Sn）=0.8, Zn/Sn=1.1.
4. using thermal evaporation in the Se films that alloy firm surface evaporation thickness is 20 μm.
5. in the equipment of embodiment 1, the continuous warming vulcanization of complete paired samples by way of liquid tin laser heating
Selenizing, obtains CZTSSe films.
Embodiment 6 prepares CZTSSe solar cells
1st, preparation method
（1）Utilize chemical bath deposition method（CBD methods）Thickness is prepared on CZTSSe films prepared by embodiment 1 for 50nm
（40~60nm）CdS cushions；
（2）The film for being prepared for CdS cushions is sent into sputtering chamber, successively sputtering preparation on CdS cushions is about
100nm（50~120）I-ZnO layers and 0.8 μm（0.3~1.0）AZO films.
（3）Sample is taken out, evaporating Al electrode forms complete CZTSSe solar cells.
2nd, by the CZTSSe solar cells prepared, i.e., tied with glass/Mo/CZTSSe/CdS/i-ZnO/AZO
The thin-film solar cells of structure carries out electrical performance testing, as a result shows, its voltage V=520mV, I=23mA, the conversion ratio of battery
For 6.8%.
The CZTSSe solar cells of the implication CZTSSe films prepared, its structure is multi-layer film structure, from entering light
Face starts, and includes successively：Metal gate layers（Al）, transparent electrode layer (AZO), Window layer (i-ZnO), cushion (CdS), light inhale
Receive layer（CZTSSe）, dorsum electrode layer (Mo) and glass substrate.
Wherein, metal gate layers, transparent electrode layer, Window layer, cushion, dorsum electrode layer and substrate, not by above-mentioned material
Limit, other materials can also be used.
Claims (8)
1. a kind of method that liquid tin heating continuous vulcanization selenizing method prepares CZTSSe films, it is characterised in that including following step
Suddenly：
S1. the cleaned drying of substrate, the cleaning is to utilize organic solvent, absolute ethyl alcohol, deionized water immersion and ultrasound successively
Ripple is cleaned, deionized water rinsing；Mo layers of dorsum electrode layer is prepared on substrate using DC sputtering；
S2. CuZnSnS alloy firms and then on Mo layers are prepared or the overlapping film of CuS/ZnS/Sn multilayers is thin as presoma
Film, then last layer Se films are deposited；
S3. CZTSSe films are obtained by continuous warming vulcanization selenizing again；
Wherein, the specific method of the continuous warming vulcanization selenizing is：
The precursor thin-film that the obtained evaporations of S2 there are Se films is sequentially passed through into several temperature elevated liquid tin pool surface successively,
Precursor thin-film is heated under the nitrogen atmosphere containing element sulphur, vulcanization selenizing is completed, obtains CZTSSe films；It is described
Several temperature successively elevated liquid tin pond be several temperature from 200 DEG C to 580 DEG C elevated liquid tin pond successively；Institute
Element sulphur is stated for solid sulfur or hydrogen sulfide gas.
2. the method that liquid tin heating continuous vulcanization selenizing method prepares CZTSSe films according to claim 1, its feature exists
In substrate described in step S1 is simple glass or stainless steel；Dorsum electrode layer Mo layers of thickness described in step S1 is 0.8 ~ 1.2 μm；
Se films described in step S2 are to overlap to be deposited on film in the alloy firm or multilayer using thermal evaporation, the Se films of evaporation
Thickness is 15 ~ 25 μm.
3. the method for preparing CZTSSe films according to liquid tin heating continuous vulcanization selenizing method described in claim 1, it is characterised in that
Step S2 is to be sputtered using CuZnSnS alloys targets or prepare CuZnSnS alloy firms using CuS targets, ZnS targets, Sn target co-sputterings；
CuS/ZnS/Sn multilayers, which are prepared, using CuS targets, ZnS targets, the sputtering of Sn targets overlaps film.
4. the method that the liquid tin heating continuous vulcanization selenizing method according to profit requires 1 prepares CZTSSe films, it is characterised in that
The thickness that CuZnSnS alloy firms or CuS/ZnS/Sn multilayers described in step S2 overlap film is 700 ~ 900nm；It is described
The component ratio that CuZnSnS alloy firms or CuS/ZnS/Sn multilayers overlap film is Cu/（Zn+Sn）=0.8 ~ 0.9, Zn/Sn=1.1 ~
1.2。
5. the CZTSSe films that any one of Claims 1-4 methods described is prepared.
6. application of the CZTSSe films in solar cell is prepared described in claim 5.
7. a kind of CZTSSe solar cells, it is characterised in that be prepared into using CZTSSe films described in claim 6 as absorbed layer
Arrive, be specifically to be prepared by following methods：
S1. CdS cushions are being prepared described in claim 6 on CZTSSe films using chemical bath deposition method；
S2. successively sputtering prepares Window layer i-ZnO and transparent electrode layer AZO films on CdS cushions, then is deposited above
Al electrodes, form complete CZTSSe solar cells.
8. CZTSSe solar cells according to claim 7, it is characterised in that the thickness of CdS cushions described in step S1
For 40 ~ 60nm；Window layer i-ZnO thickness described in step S2 is 50 ~ 120nm, the thickness of transparent electrode layer AZO films for 0.3 ~
1.0μm。
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