CN103343318B - The preparation method of the light absorbing zone of solar cell - Google Patents

The preparation method of the light absorbing zone of solar cell Download PDF

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CN103343318B
CN103343318B CN201310277578.7A CN201310277578A CN103343318B CN 103343318 B CN103343318 B CN 103343318B CN 201310277578 A CN201310277578 A CN 201310277578A CN 103343318 B CN103343318 B CN 103343318B
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tin
zinc
copper
film presoma
laminated
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CN103343318A (en
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杨春雷
鲍浪
程冠铭
冯叶
肖旭东
顾光一
于冰
郭延璐
徐苗苗
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Shenzhen Institute of Advanced Technology of CAS
Chinese University of Hong Kong CUHK
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Shenzhen Institute of Advanced Technology of CAS
Chinese University of Hong Kong CUHK
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Abstract

The present invention relates to a kind of preparation method of light absorbing zone of solar cell, comprise and prepare metallic film presoma, metallic film presoma is copper-zinc-tin-sulfur precursor thin-film or copper-zinc-tin-selenium precursor thin-film; Prepare the tin tectum be laminated on metallic film presoma, obtain being laminated with tin tectal copper-zinc-tin-sulfur film presoma or being laminated with the tectal copper-zinc-tin-selefilm film presoma of tin; And under anaerobic and in hydrogen sulfide atmosphere, the tectal copper-zinc-tin-sulfur film presoma of tin will be laminated with and carry out high temperature annealing; Or under anaerobic and in selenium atmosphere, the tectal copper-zinc-tin-selefilm film presoma of tin will be laminated with and carry out high temperature annealing, obtain the step of the light absorbing zone of solar cell.Tin tectum can to stop in high temperature annealing SnS in metallic film presoma 2or SnSe 2volatilization, after annealing, Sn in tin tectum forms SnS 2or SnSe 2and depart from crystal, effectively suppress the loss of Sn.

Description

The preparation method of the light absorbing zone of solar cell
Technical field
The present invention relates to photovoltaic device preparing technical field, particularly relate to a kind of preparation method of light absorbing zone of solar cell.
Background technology
There is the CZTS(copper-zinc-tin-sulfur of custerite structure, Cu 2znSnS 4) and CZTSe(copper-zinc-tin-selenium, Cu 2znSnSe 4) energy gap and the best energy gap 1.5eV ten points of semiconductor solar cell close, its uptake factor can reach 10 4cm -1.Elemental copper in copper zinc tin sulfur selenium, zinc, tin, sulphur and selenium reserves are on earth very abundant, low price, and be all environmental friendliness element, not containing toxic ingredient, become the hot fields of current photovoltaic art research, likely become the main product of following photovoltaic cell.
The main preparation were established of CZTS thin-film solar cells and CZTSe thin-film solar cells utilizes the method such as magnetron sputtering, coevaporation, galvanic deposit, solution method to prepare metallic precursor film under cryogenic, then high temperature annealing, under being placed in the condition of high temperature by this metallic film presoma, make the atom generation chemical reaction in metallic film precursor, resultant of reaction crystallization, obtain CZTS film or the CZTSe film of polycrystalline state, i.e. the light absorbing zone of solar cell.CZTS film after annealing or CZTSe film deposit Cadmium Sulfide (CdS), zinc oxide (AZO) film growth of aluminium doping, electron beam evaporation making Ni-Al electrode through immersion method, are thin-film solar cells device.
So-called high-temperature annealing process to be rapidly heated in a vacuum by metallic film presoma and after keeping temperature for some time, then the process of Temperature fall.
For CZTS metallic film presoma, progressively there is following reaction in CZTS metallic film precursor high-temperature annealing process:
First stage, generate Binary-phase:
Cu+S→Cu 2S；
Subordinate phase, Binary-phase reaction generates ternary phase:
Cu 2S+SnS 2→Cu 2SnS 3；
Phase III, generate quaternary phase:
Cu 2SnS 3+ZnS→Cu 2ZnSnS 4。
Find the research of Binary-phase recently, Sn and S two kinds of elements start to form SnS at 300 DEG C 2, 400 DEG C time, start a large amount of volatilization, when 460 DEG C, this Binary-phase is no longer with solid-state existence, and this temperature is far below the Tc required for CZTS.The change of component of film precursor and crystalline film before and after the annealing of quaternary phase CZTS thin film precursor is shown by EDS energy spectrum analysis, CZTS film precursor complete annealing after the number of dropouts of Sn can up to 24%, and the phenomenon of the loss of Sn element does not exist only in film surface, be also present in whole thin film layer inner.Therefore, CZTS film is before reaching temperature of reaction, and Sn element can along with SnS 2volatilization run off in a large number.The consequence caused is, in CZTS film composition, the amount of Sn component is wayward, have impact on the quality of CZTS thin film layer.
The character of CZTSe and CZTS is similar, and Se and S two kinds of elements belong to congeners, its Binary-phase SnSe 2and SnS 2character also similar, can with above-mentioned principle analogy, CZTSe metallic film precursor high-temperature annealing process, due to SnSe 2volatilization and cause Sn to run off in a large number, cause the deviation of CZTSe film composition, thus have impact on the quality of CZTSe thin film layer.
Summary of the invention
Based on this, be necessary the preparation method of the light absorbing zone that a kind of solar cell that Sn can be suppressed to run off is provided.
A preparation method for the light absorbing zone of solar cell, comprises the steps:
Prepare metallic film presoma, described metallic film presoma is copper-zinc-tin-sulfur film presoma or copper-zinc-tin-selefilm film presoma;
Prepare the tin tectum be laminated on described metallic film presoma, obtain being laminated with the tectal metallic film presoma of tin, described in be laminated with tin tectal metallic film presoma for being laminated with tin tectal copper-zinc-tin-sulfur film presoma or being laminated with the tectal copper-zinc-tin-selefilm film presoma of tin; And
Under anaerobic and in hydrogen sulfide atmosphere, the described tectal copper-zinc-tin-sulfur film presoma of tin that is laminated with is carried out high temperature annealing; Or under anaerobic and in selenium atmosphere, the described tectal copper-zinc-tin-selefilm film presoma of tin that is laminated with is carried out high temperature annealing, obtains the light absorbing zone of solar cell.
Wherein in an embodiment, the described step preparing metallic film presoma adopts cosputtering method or coevaporation method to prepare metallic film presoma.
Wherein in an embodiment, the described step preparing metallic film presoma adopts cosputtering method to be sputtered onto on substrate by copper, zinc sulphide and tin disulfide, forms the copper-zinc-tin-sulfur film presoma be laminated on described substrate; Or adopt cosputtering method to be sputtered onto on substrate by copper, zinc selenide and two Tin diselenides, form the copper-zinc-tin-selefilm film presoma be laminated on described substrate.
Wherein in an embodiment, the described step preparing metallic film presoma adopts coevaporation method by copper, zinc sulphide, tin and sulphur hydatogenesis on substrate, the copper-zinc-tin-sulfur film presoma that formation is laminated on described substrate; Or adopt coevaporation method by copper, zinc selenide, tin and selenium hydatogenesis on substrate, the copper-zinc-tin-selefilm film presoma that formation is laminated on described substrate.
Wherein in an embodiment, described employing cosputtering legal system is for the step also comprising pre-sputtering before metallic film presoma.
Wherein in an embodiment, the described preparation tectal step of tin be laminated on described metallic film presoma adopts magnetron sputtering or thermal evaporation to be deposited on by element tin on described metallic film presoma, obtains being laminated with the tectal metallic film presoma of tin.
Wherein in an embodiment, the tectal thickness of described tin is 150 nanometers.
Wherein in an embodiment, the temperature of described high temperature annealing is 550 DEG C, and the time is 15 minutes.
Wherein in an embodiment, the air pressure of described hydrogen sulfide is 2 × 10 3pa.
Wherein in an embodiment, in under anaerobic described and hydrogen sulfide atmosphere, be laminated with the step that tin tectal copper-zinc-tin-sulfur film presoma carries out high temperature annealing be specially described: be positioned in annealing furnace by the described tectal copper-zinc-tin-sulfur film presoma of tin that is laminated with, passing into hydrogen sulfide to air pressure is 2 × 10 3pa, then to pass into nitrogen to air pressure be 4 × 10 4pa, is then laminated with tin tectal copper-zinc-tin-sulfur film presoma to 550 DEG C described in heating, is incubated naturally cooling after 15 minutes; In under anaerobic described and selenium atmosphere, be laminated with the step that tin tectal copper-zinc-tin-selefilm film presoma carries out high temperature annealing be specially described: be positioned in annealing furnace by the described tectal copper-zinc-tin-selefilm film presoma of tin that is laminated with, passing into selenium sulfide to air pressure is 2 × 10 3pa, then to pass into nitrogen to air pressure be 4 × 10 4pa, is then laminated with tin tectal copper-zinc-tin-selefilm film presoma to 550 DEG C described in heating, is incubated naturally cooling after 15 minutes.
The preparation method of the light absorbing zone of above-mentioned solar cell, forms tin tectum on the surface of metallic film presoma, utilizes tin tectum to stop in high-temperature annealing process, SnS in copper-zinc-tin-sulfur film presoma 2volatilization or copper-zinc-tin-selefilm film presoma in SnSe 2volatilization, thus reach the object suppressing Sn loss of elements in metallic film presoma, copper-zinc-tin-sulfur film presoma or copper-zinc-tin-selefilm film presoma is annealed form fine and close CZTS crystal or CZTSe crystal after, the Sn in surperficial tin tectum forms SnS gradually under hydrogen sulfide atmosphere 2and depart from CZTS plane of crystal, or form SnSe under selenium sulfide atmosphere 2and departing from CZTSe plane of crystal, this process can not have influence on the component of CZTS crystal or CZTSe crystal, avoids SnS 2or SnSe 2volatilization and cause the loss of Sn, thus prepare the higher CZTS light absorbing zone of quality or CZTSe light absorbing zone.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the light absorbing zone of the solar cell of an embodiment;
Fig. 2 is the schematic diagram of the step S110 of the preparation method of the light absorbing zone of the solar cell shown in Fig. 1.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with accompanying drawing.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public concrete enforcement.
Refer to Fig. 1, the preparation method of the light absorbing zone of the solar cell of an embodiment, comprise the steps that S110 is to step S130.
Step S110: prepare metallic film presoma.
Metallic film presoma is copper-zinc-tin-sulfur (CZTS) thin film precursor or copper-zinc-tin-selenium (CZTSe) thin film precursor.
Please refer to Fig. 2, first provide substrate.Substrate is glass substrate, is cleaned up by substrate and after drying, forms the molybdenum dorsum electrode layer be laminated on substrate, obtain the substrate 101 being laminated with molybdenum dorsum electrode layer at clean, dry deposited on substrates molybdenum.Preferably, the thickness of molybdenum dorsum electrode layer is 800 nanometers or 150 nanometers.
For metallic film presoma for copper-zinc-tin-sulfur (CZTS) thin film precursor, cosputtering method is adopted jointly to sputter copper (Cu), zinc sulphide (ZnS) and tin disulfide (SnS 2), copper, zinc sulphide and tin disulfide are sputtered onto on molybdenum dorsum electrode layer.Preparation process is specific as follows:
The substrate 101 being laminated with molybdenum dorsum electrode layer is put on the specimen holder of the sputtering chamber of sputtering equipment.Be laminated with the molybdenum dorsum electrode layer of the substrate 101 of molybdenum dorsum electrode layer towards substrate baffle plate 102.
Vacuumize sputtering chamber, being first evacuated to Pirani gauge reading with mechanical pump is 5 × 10 1then Pa opens molecular pump, and to be evacuated to ionization gauge reading be 2 × 10 -3pa.Open gas meter, in sputtering chamber, pass into the high-purity argon gas of 99.999% with the flow of 12sccm, control vacuum system and make ionization gauge reading maintain 1.1 × 10 -1pa.Specimen holder rotates, and opens each target (Cu target, ZnS target, SnS 2target and Sn target) radio-frequency sputtering power supply, adjustment output power of power supply and reflective power, makes target build-up of luminance.Pre-sputtering, after 10 minutes, opens each target baffle plate (Cu target baffle plate 103, ZnS target baffle plate 104 and SnS 2target baffle plate 105), substrate baffle plate 102 and film thickness gauge baffle plate (not shown).Sputter rate is detected by film thickness gauge.Sputter after 1 hour, close Cu target baffle plate 103, ZnS target baffle plate 104 and SnS 2target baffle plate 105, forms the copper-zinc-tin-sulfur film presoma be laminated on the molybdenum dorsum electrode layer of substrate.
Preferably, the thickness of copper-zinc-tin-sulfur film presoma is 1.3 microns ~ 1.7 microns.
Preferably, the power of Cu target is the power of 60W, ZnS target is 75W, SnS 2the power of target is 70W.
Pre-sputtering refers to, opens each target (Cu target, ZnS target, SnS 2target and Sn target) radio-frequency sputtering power supply, adjustment output power of power supply and reflective power, makes target build-up of luminance, but does not now open Cu target baffle plate 103, ZnS target baffle plate 104, SnS 2target baffle plate 105, Sn target baffle plate 106 and substrate baffle plate 102, to remove the impurity on each target material surface.Preferably, the time of pre-sputtering is 10 minutes, after ensureing the impurity on each target fully to remove, open Cu target baffle plate 103, ZnS target baffle plate 104, SnS again 2target baffle plate 105 and substrate baffle plate 102 carry out the preparation of presoma, copper, zinc sulphide and tin disulfide are sputtered onto on molybdenum dorsum electrode layer, are sputtered onto the copper on molybdenum dorsum electrode layer, zinc sulphide and tin disulfide and form pure copper-zinc-tin-sulfur precursor thin-film.
When metallic film presoma is copper-zinc-tin-selefilm film presoma, the method adopting cosputtering to prepare this copper-zinc-tin-selefilm film presoma is roughly the same with the above-mentioned method preparing copper-zinc-tin-sulfur film presoma, replaces with Cu target, ZnSe target, SnSe unlike target 2target.Pre-sputtering, after 10 minutes, opens each target baffle plate (Cu target baffle plate, ZnSe target baffle plate, SnSe 2target baffle plate), substrate baffle plate and film thickness gauge baffle plate.Sputter rate is detected by film thickness gauge.Sputter after 1 hour, close Cu target baffle plate, ZnSe target baffle plate and SnSe 2target baffle plate, forms the copper-zinc-tin-selefilm film presoma be laminated on the dorsum electrode layer of substrate.Preferably, the power of Cu target is the power of 60W, ZnSe target is 75W, SnSe 2the power of target is 70W.
Preferably, the thickness of copper-zinc-tin-selefilm film presoma is 1.3 microns ~ 1.7 microns.
In other embodiments, coevaporation also can be adopted to prepare metallic film presoma.By common to copper, zinc sulphide and tin disulfide hydatogenesis on the molybdenum dorsum electrode layer of substrate, form the copper-zinc-tin-sulfur film presoma be laminated on molybdenum dorsum electrode layer; Or by common to copper, zinc selenide, tin and selenium hydatogenesis on the molybdenum dorsum electrode layer of substrate, form the copper-zinc-tin-selefilm film presoma be laminated on molybdenum dorsum electrode layer.
Adopt coevaporation to prepare metallic film presoma to carry out in molecular beam epitaxy system (MBE system).The substrate 101 being laminated with molybdenum dorsum electrode layer is put in the sample table of MBE cavity, after Cu source stove, ZnS source stove, Sn source stove, S source stove and sample table are heated to preset temp respectively, open Cu source fender plate, ZnS source fender plate, Sn source fender plate, S source fender plate and sample table baffle plate simultaneously, carry out evaporation and obtain copper-zinc-tin-sulfur film presoma.
When coevaporation method prepares copper-zinc-tin-sulfur film presoma, preferably, the preset temp of Cu source stove, ZnS source stove, Sn source stove, S source stove and sample table is respectively 1210 DEG C, 765 DEG C, 1140 DEG C, 200 DEG C and 200 DEG C.
When coevaporation method prepares copper-zinc-tin-selefilm film presoma, preferably, the preset temp of Cu source stove, ZnSe source stove, Sn source stove, Se source stove and sample table is respectively 1210 DEG C, 765 DEG C, 1140 DEG C, 210 DEG C and 200 DEG C.
Step S120: prepare the tin tectum be laminated on metallic film presoma, obtain being laminated with the tectal metallic film presoma of tin.
Be laminated with tin tectal metallic film presoma for being laminated with tin tectal copper-zinc-tin-sulfur film presoma or being laminated with the tectal copper-zinc-tin-selefilm film presoma of tin.
After the molybdenum dorsum electrode layer of substrate forms copper-zinc-tin-sulfur film presoma, open Sn target baffle plate 106, sputter after 10 minutes, close Sn target baffle plate 106, close each target power supply, film thickness gauge, rotary sample and gas meter, cool after 30 minutes, copper-zinc-tin-sulfur film presoma is formed tin tectum, obtain being laminated with the tectal copper-zinc-tin-sulfur film presoma of tin.
Or, after the molybdenum dorsum electrode layer of substrate forms copper-zinc-tin-selefilm film presoma, open Sn target baffle plate, sputter after 10 minutes, close Sn target baffle plate, close each target power supply, film thickness gauge, rotary sample and gas meter, cool after 30 minutes, copper-zinc-tin-selefilm film presoma is formed tin tectum, obtains being laminated with the tectal copper-zinc-tin-selefilm film presoma of tin.
Preferably, the power of Sn target is 50W.
The vapour pressure of Sn is very little, 1100 DEG C time, be only 10 -4pa, almost can think to stablize nonvolatile, therefore, tin tectum is very stable, can stop the SnS in copper-zinc-tin-sulfur precursor thin-film 2volatilize or stop the SnSe in copper-zinc-tin-selenium precursor thin-film 2volatilization.
The tectal thickness of tin is 100 nanometer ~ 200 nanometers, is preferably 150 nanometers.The selection of tin cover thickness is enough thick in suppress the inner SnS of metallic film presoma on the one hand 2or SnSe 2volatilization, on the other hand again can not be too thick so that subsequent step can all remove.Above-mentioned two requirements can be met preferably when the tectal thickness of tin is 150 nanometer.
In other embodiments, the method for thermal evaporation also can be adopted tin to be deposited on the tin tectum that on metallic film presoma, preparation is laminated on metallic film presoma.When adopting thermal evaporation to form tin tectum, the preset temp of Sn source stove is preferably 1150 DEG C.
Step S130: under anaerobic and in hydrogen sulfide atmosphere, will be laminated with the tectal copper-zinc-tin-sulfur film presoma of tin and carry out high temperature annealing; Or under anaerobic and in selenium atmosphere, the tectal copper-zinc-tin-selefilm film presoma of tin will be laminated with and carry out high temperature annealing, obtain the light absorbing zone of solar cell.
For copper-zinc-tin-sulfur film presoma:
The tectal copper-zinc-tin-sulfur film presoma of tin will be laminated with and put into annealing furnace, with mechanical pump from 1 × 10 5it is 0Pa that Pa is evacuated to diaphragm vacuum gauge reading.Continue to take out 5 minutes with timing register timing, to ensure that annealing furnace cleans.
Close mechanical pump angle valve, first logical 99.999% hydrogen sulfide to 2 × 10 in annealing furnace 3pa, more logical 99.999% high pure nitrogen to 4 × 10 4pa.Open heating power supply switch, rise to 530 ~ 600 DEG C with the temperature rise rate of per minute 7.6 DEG C from room temperature, keep 15 ~ 20 minutes at 530 ~ 600 DEG C, then naturally cool to room temperature.By armoured K thermocouple monitoring underlayer temperature in heat-processed.
Preferably, the temperature of the annealing of high temperature is 550 DEG C, and annealing time is 15 minutes.550 DEG C of Tcs reaching copper-zinc-tin-sulfur (CZTS) precursor thin-film, anneal 15 minutes at 550 DEG C, can form fine and close CZTS light and inhale layer, obtain the light absorbing zone of high-quality solar cell.
In high-temperature annealing process, the Sn in tin tectum constantly and H 2s gas reacts and generates SnS 2, SnS 2constantly volatilize, tin tectum is finally removed, and does not affect the light absorbing zone finally obtaining solar cell.
Be cooled to after room temperature until underlayer temperature, open mechanical pump angle valve, annealing furnace is evacuated to 0Pa, close mechanical pump angle valve, logical 99.999% high pure nitrogen to 5 × 10 4pa, then open mechanical pump angle valve and be evacuated to 0Pa, cleaning annealing furnace gas, prevent hydrogen sulfide residual in the lehr.Close mechanical pump angle valve, logical 99.999% high pure nitrogen to 1 × 10 5pa, opens annealing furnace chamber, takes out finished product.
For copper-zinc-tin-selefilm film presoma:
Put into evaporation boat in annealing furnace, in evaporation boat, place granules of selenium, heating evaporation boat to 200 DEG C, pass into 99.999% high pure nitrogen to 4 × 10 4pa.Open heating power supply switch, rise to 530 ~ 600 DEG C with the temperature rise rate of per minute 7.6 DEG C from room temperature, keep 15 ~ 20 minutes at 530 ~ 600 DEG C, then naturally cool to room temperature.By armoured K thermocouple monitoring underlayer temperature in heat-processed.
Preferably, the temperature of high temperature annealing is 550 DEG C, and annealing time is 15 minutes.550 DEG C of Tcs reaching copper-zinc-tin-selenium (CZTSe) precursor thin-film, anneal 15 minutes at 550 DEG C, can form fine and close CZTSe light and inhale layer, obtain the light absorbing zone of high-quality solar cell.
In high-temperature annealing process, the Sn in tin tectum constantly and selenium steam generation react and generate SnSe 2, SnSe 2constantly volatilize, tin tectum is finally removed, and does not affect the light absorbing zone finally obtaining solar cell.
When nitrogen partial pressure is 4 × 10 4pa, when the temperature of evaporation boat is 200 DEG C, the dividing potential drop of selenium steam is 2 × 10 3pa.When needs adjustment selenium vapor partial pressure, can by the dividing potential drop of the temperature change selenium steam of adjustment evaporation boat.
Light absorbing zone after annealing, observes finished surface gray, evenly not reflective, does not come off after water punching.Its diagonal angle resistance is measured at about 500-700 kilo-ohm, the tectal Sn of tin complete cure volatilization with volt ohm-milliammeter.
Also high pure nitrogen is passed in high-temperature annealing process, oxidized to avoid being laminated with tin tectal metallic film presoma.Be appreciated that when annealing in MBE cavity, because MBE inside cavity remains high vacuum (< 10 -5pa), the oxidizing gas such as oxygen can not be had in environment to exist, and metallic film precursor can not be oxidized, therefore, can directly anneal in high vacuum MBE, need not pass into the rare gas element of protectiveness.
When adopting coevaporation to prepare metallic film presoma, the step of high temperature annealing is also directly carried out in MBE cavity, and puts into annealing furnace again without the need to being taken out by sample, easy to operate.
Annealing process directly proceeds in MBE cavity.The temperature of Se source stove keeps 210 DEG C, open Se source fender plate, sample table temperature is at the uniform velocity warming up to 550 DEG C with the temperature rise rate of per minute 15 DEG C from 200 DEG C, 23.3 minutes used times, keeps 10 minutes after arriving 550 DEG C, close sample table heating power supply, make sample naturally cooling, when sample temperature closes Se source fender plate lower than when 250 DEG C, annealing terminates, take out sample, namely obtain the CZTSe light absorbing zone of solar cell.
When the non-tight cure of tin tectum of finished surface is volatilized, sample whitens, and diagonal angle resistance only has hundreds of Europe, and when the tin tectum sulfuration of finished surface is not still thoroughly volatilized, color sample is comparatively dark, and diagonal angle resistance is several kilo-ohms.Run into above two kinds of situations, for the preparation of CZTS light absorbing zone, the tectal thickness of tin or adjustment H need be adjusted 2s concentration or adjustment H 2the annealing time of precursor under S atmosphere, to ensure the volatilization completely of Sn in tin tectum.For the preparation of CZTSe light absorbing zone, need the temperature adjusting Se evaporation boat or source stove in annealing furnace, adjust the amount of Se particle in Se evaporation boat simultaneously.
The preparation method of the light absorbing zone of above-mentioned solar cell, forms tin tectum on the surface of metallic film presoma, utilizes tin tectum to stop in high-temperature annealing process, SnS in copper-zinc-tin-sulfur film presoma 2volatilization or copper-zinc-tin-selefilm film presoma in SnSe 2volatilization, thus reach the object suppressing Sn loss of elements in metallic film presoma, copper-zinc-tin-sulfur film presoma or copper-zinc-tin-selefilm film presoma is annealed form fine and close CZTS crystal or CZTSe crystal after, the Sn in tin tectum forms SnS gradually under hydrogen sulfide atmosphere 2and depart from CZTS plane of crystal, or form SnSe under selenium atmosphere 2and departing from CZTSe plane of crystal, this process can not have influence on the component of CZTS crystal or CZTSe crystal, avoids SnS 2or SnSe 2volatilization and cause the loss of Sn, thus prepare the higher CZTS light absorbing zone of quality or CZTSe light absorbing zone.
Preparation method's green non-pollution of the light absorbing zone of above-mentioned solar cell, low for equipment requirements, operation is simple, is adapted at widely using in laboratory study and suitability for industrialized production.
Below by way of specific embodiment, the preparation method to the light absorbing zone of above-mentioned solar cell is described further.
Embodiment 1
Prepare the light absorbing zone of solar cell
1, coevaporation method prepares copper-zinc-tin-selefilm film presoma
The glass substrate of the molybdenum dorsum electrode layer being coated with 150nm thickness is placed in MBE sample table, open sample table turn switch, the temperature of Cu source stove, ZnSe source stove, Sn source stove, Se source stove and sample table is set to 1210 DEG C, 765 DEG C, 1140 DEG C, 210 DEG C and 200 DEG C respectively, open Cu source fender plate, ZnSe source fender plate, Sn source fender plate, Se source fender plate and sample table baffle plate simultaneously, evaporation 720 seconds, obtain copper-zinc-tin-selefilm film presoma, the mol ratio of the element of this copper-zinc-tin-selefilm film precursor is Cu:Zn:Sn:Se=1.8:1.1:1.3:3.9;
2, method of evaporation prepares tin tectum
The temperature of the Sn source stove of MBE is kept 10 minutes at 1140 DEG C, after Sn line is stable, opens rotary sample power supply, sample table baffle plate and Sn source fender plate in order successively.Evaporation closes Sn source fender plate, sample table baffle plate and rotary sample power supply successively after 3 minutes.Evaporation terminates, and cools the tin tectum that after 30 minutes, formation is laminated on metallic film presoma, and obtain being laminated with the tectal copper-zinc-tin-selefilm film presoma of tin, wherein, the tectal thickness of tin is 150 nanometers;
3, high temperature annealing
Annealing process directly proceeds in MBE cavity.The temperature of Se source stove keeps 210 DEG C, open Se source fender plate, sample table temperature is at the uniform velocity warming up to 550 DEG C from 200 DEG C, 15 minutes used times, keeps 10 minutes after arriving 550 DEG C, close sample table heating power supply, make sample naturally cooling, when sample temperature closes Se source fender plate lower than when 250 DEG C, annealing terminates, take out sample, namely obtain the CZTSe light absorbing zone of solar cell.
Embodiment 2
Prepare the light absorbing zone of solar cell
1, cosputtering legal system is for copper-zinc-tin-sulfur film presoma
The glass substrate of the molybdenum dorsum electrode layer being coated with 150nm thickness is placed in magnetron sputtering sample table, opens sample table turn switch, by Cu target, ZnS target and SnS 2the power of target is set to 60w, 75w and 70w respectively, and pre-sputtering, after 10 minutes, opens Cu target baffle plate, ZnS target baffle plate, SnS simultaneously 2target baffle plate and substrate baffle plate, cosputtering 1 hour, obtains copper-zinc-tin-sulfur film presoma, and the mol ratio of the component of copper-zinc-tin-sulfur film presoma is Cu:Zn:Sn:Se=1.8:1.1:1.3:3.9;
2, sputtering method prepares tin tectum
The power of Sn target is set to 50w, pre-sputtering is after 10 minutes, open Sn target baffle plate, sputter and close Sn target baffle plate after 10 minutes, sputtering terminates, and cools the tin tectum that after 30 minutes, formation is laminated on metallic film presoma, obtains being laminated with the tectal copper-zinc-tin-sulfur film presoma of tin, wherein, the tectal thickness of tin is 150 nanometers;
3, taking-up is laminated with the tectal copper-zinc-tin-sulfur precursor thin-film of tin, and put into annealing furnace, being evacuated to diaphragm vacuum gauge reading with mechanical pump is 0Pa.Continue to take out 5 minutes with timing register timing, to ensure that annealing furnace cleans.Then, first in annealing furnace, H is led to 2s(purity is 99.999%) gas to 2 × 10 3pa, more logical 99.999% high pure nitrogen to 4 × 10 4pa.Rise to 550 DEG C with the temperature rise rate of per minute 7.6 DEG C from room temperature, keep 15 minutes at 550 DEG C, then naturally cool to room temperature.By armoured K thermocouple monitoring underlayer temperature in heat-processed.Be cooled to after room temperature until underlayer temperature, H remaining in cleaning annealing furnace 2s atmosphere, takes out sample, namely obtains the CZTS light absorbing zone of solar cell.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.

Claims (8)

1. a preparation method for the light absorbing zone of solar cell, comprises the steps:
Prepare metallic film presoma, described metallic film presoma is copper-zinc-tin-sulfur film presoma or copper-zinc-tin-selefilm film presoma;
Prepare the tin tectum be laminated on described metallic film presoma, obtain being laminated with the tectal metallic film presoma of tin, described in be laminated with tin tectal metallic film presoma for being laminated with tin tectal copper-zinc-tin-sulfur film presoma or being laminated with the tectal copper-zinc-tin-selefilm film presoma of tin; And
Under anaerobic and in hydrogen sulfide atmosphere, the described tectal copper-zinc-tin-sulfur film presoma of tin that is laminated with is carried out high temperature annealing; Or under anaerobic and in selenium atmosphere, the described tectal copper-zinc-tin-selefilm film presoma of tin that is laminated with is carried out high temperature annealing, obtains the light absorbing zone of solar cell;
The tectal thickness of described tin is 150 nanometers;
The temperature of described high temperature annealing is 550 DEG C, and the time is 15 minutes;
The mol ratio of the element of copper-zinc-tin-selefilm film presoma is Cu:Zn:Sn:Se=1.8:1.1:1.3:3.9;
The mol ratio of the element of copper-zinc-tin-sulfur film presoma is Cu:Zn:Sn:S=1.8:1.1:1.3:3.9.
2. the preparation method of the light absorbing zone of solar cell according to claim 1, is characterized in that, the described step preparing metallic film presoma adopts cosputtering method or coevaporation method to prepare metallic film presoma.
3. the preparation method of the light absorbing zone of solar cell according to claim 2, it is characterized in that, the described step preparing metallic film presoma adopts cosputtering method to be sputtered onto on substrate by copper, zinc sulphide and tin disulfide, forms the copper-zinc-tin-sulfur film presoma be laminated on described substrate; Or adopt cosputtering method to be sputtered onto on substrate by copper, zinc selenide and two Tin diselenides, form the copper-zinc-tin-selefilm film presoma be laminated on described substrate.
4. the preparation method of the light absorbing zone of solar cell according to claim 2, it is characterized in that, the described step preparing metallic film presoma adopts coevaporation method by copper, zinc sulphide, tin and sulphur hydatogenesis on substrate, the copper-zinc-tin-sulfur film presoma that formation is laminated on described substrate; Or adopt coevaporation method by copper, zinc selenide, tin and selenium hydatogenesis on substrate, the copper-zinc-tin-selefilm film presoma that formation is laminated on described substrate.
5. the preparation method of the light absorbing zone of solar cell according to claim 2, is characterized in that, described employing cosputtering legal system is for the step also comprising pre-sputtering before metallic film presoma.
6. the preparation method of the light absorbing zone of solar cell according to claim 1, it is characterized in that, the described preparation tectal step of tin be laminated on described metallic film presoma adopts magnetron sputtering or thermal evaporation to be deposited on by tin on described metallic film presoma, obtains being laminated with the tectal metallic film presoma of tin.
7. the preparation method of the light absorbing zone of solar cell according to claim 1, is characterized in that, the air pressure of described hydrogen sulfide is 2 × 10 3pa.
8. the preparation method of the light absorbing zone of solar cell according to claim 1, it is characterized in that, in under anaerobic described and hydrogen sulfide atmosphere, be laminated with the step that tin tectal copper-zinc-tin-sulfur film presoma carries out high temperature annealing be specially described: be positioned in annealing furnace by the described tectal copper-zinc-tin-sulfur film presoma of tin that is laminated with, passing into hydrogen sulfide to air pressure is 2 × 10 3pa, then to pass into nitrogen to air pressure be 4 × 10 4pa, is then laminated with tin tectal copper-zinc-tin-sulfur film presoma to 550 DEG C described in heating, is incubated naturally cooling after 15 minutes; In under anaerobic described and selenium atmosphere, be laminated with the step that tin tectal copper-zinc-tin-selefilm film presoma carries out high temperature annealing be specially described: be laminated with the tectal copper-zinc-tin-selefilm film presoma of tin and granules of selenium is positioned in annealing furnace by described, passing into nitrogen to air pressure is 4 × 10 4pa, is then laminated with tin tectal copper-zinc-tin-selefilm film presoma to 550 DEG C described in heating, is incubated naturally cooling after 15 minutes.
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CN104409568B (en) * 2014-11-13 2016-08-24 郑州大学 A kind of method improving the copper-zinc-tin-sulfur film quality for solar cell
CN105679878A (en) * 2014-11-17 2016-06-15 中国电子科技集团公司第十八研究所 Method for preparing absorption layer of CZTSSe thin film solar cell by co-evaporation
CN104576827B (en) * 2014-12-18 2016-12-07 深圳丹邦投资集团有限公司 The preparation method of copper-zinc-tin-sulfur solaode
CN106549082B (en) * 2015-09-21 2019-07-05 云南师范大学 The method that alloys target and sulfide target cosputtering prepare copper-zinc-tin-sulfur film absorbed layer
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CN105428212A (en) * 2015-11-11 2016-03-23 云南师范大学 Method for preparing copper-zinc-tin-selenide thin film absorber layer by single target sputtering
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