CN103343318A - Preparation method of light absorption layer of solar battery - Google Patents
Preparation method of light absorption layer of solar battery Download PDFInfo
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- CN103343318A CN103343318A CN2013102775787A CN201310277578A CN103343318A CN 103343318 A CN103343318 A CN 103343318A CN 2013102775787 A CN2013102775787 A CN 2013102775787A CN 201310277578 A CN201310277578 A CN 201310277578A CN 103343318 A CN103343318 A CN 103343318A
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Abstract
The invention relates to a preparation method of a light absorption layer of a solar battery. The preparation method of the light absorption layer of the solar battery comprises the following steps of: preparing a metal film precursor, wherein the metal film precursor is a copper-zinc-tin-sulfur precursor film or a copper-zinc-tin-selenium precursor film; preparing tin coatings laminated on the metal film precursor, so as to obtain a copper-zinc-tin-sulfur film precursor laminated with the tin coatings or a copper-zinc-tin-selenium film precursor laminated with the tin coatings; annealing the copper-zinc-tin-sulfur film precursor laminated with the tin coatings at high temperature under an anaerobic condition and a hydrogen sulfide atmosphere; or annealing the copper-zinc-tin-selenium film precursor laminated with the tin coatings at high temperature under an anaerobic condition and a selenium atmosphere, so as to obtain the light absorption layer of the solar battery. The tin coatings can prevent SnS2 or SnSe2 in the metal film precursors from being volatilized in the high-temperature annealing; after the annealing, Sn in the tin coatings forms the SnS2 or the SnSe2 and is separated from a crystal, and the Sn loss is inhibited effectively.
Description
Technical field
The present invention relates to the photovoltaic device preparing technical field, particularly relate to a kind of preparation method of light absorbing zone of solar cell.
Background technology
CZTS(copper-zinc-tin-sulfur with custerite structure, Cu
2ZnSnS
4) and the CZTSe(copper-zinc-tin-selenium, Cu
2ZnSnSe
4) energy gap and the best energy gap 1.5eV of semiconductor solar cell approached in ten minutes, its uptake factor can reach 10
4Cm
-1Elemental copper in the copper zinc tin sulfur selenium, zinc, tin, sulphur and selenium reserves on earth are very abundant, low price, and all be the environmental friendliness element, poisonous composition do not contained, become the hot fields of current photovoltaic area research, might 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 is to utilize methods such as magnetron sputtering, coevaporation, galvanic deposit, solution method to prepare the metallic precursor film under cold condition, high temperature annealing then, being about to this metallic film presoma places under the condition of high temperature, make atom generation chemical reaction, resultant of reaction crystallization in the metallic film precursor, obtain CZTS film or the CZTSe film of polycrystalline state, i.e. the light absorbing zone of solar cell.CZTS film after the annealing or CZTSe film are made the Ni-Al electrode through zinc oxide (AZO) film growth, electron beam evaporation that immersion method deposition Cadmium Sulfide (CdS), aluminium mix, are the thin-film solar cells device.
So-called high-temperature annealing process is the metallic film presoma is rapidly heated in a vacuum and keeps temperature after for some time, again the process of lowering the temperature naturally.
Be example with CZTS metallic film presoma, following reaction progressively takes place in CZTS metallic film precursor high-temperature annealing process:
Fs, generate the binary phase:
Cu+S→Cu
2S；
Subordinate phase, the binary phase reaction generates ternary phase:
Cu
2S+SnS
2→Cu
2SnS
3；
Phase III, generate the quaternary phase:
Cu
2SnS
3+ZnS→Cu
2ZnSnS
4。
Recently the binary phase discovered that two kinds of elements of Sn and S begin to form SnS at 300 ℃
2, in the time of 400 ℃, beginning a large amount of volatilizations, this binary no longer exists with solid-state mutually in the time of 460 ℃, and this temperature is far below the needed Tc of CZTS.Change of component to film precursor and crystalline film before and after the annealing of quaternary phase CZTS film presoma shows by the EDS energy spectrum analysis, CZTS film precursor is finished annealing, and the number of dropouts of Sn can be up to 24% afterwards, and the phenomenon of the loss of Sn element does not exist only in film surface, also is present in whole thin film layer inside.Therefore, the CZTS film is before reaching temperature of reaction, and the Sn element can be along with SnS
2Volatilization run off in a large number.The consequence that causes is that the amount of Sn component is wayward in the CZTS film composition, has influenced the quality of CZTS thin film layer.
The similar performance of CZTSe and CZTS, two kinds of elements of Se and S 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 is because SnSe
2Volatilization and cause Sn to run off in a large number, cause the deviation of CZTSe film composition, thereby influenced the quality of CZTSe thin film layer.
Summary of the invention
Based on this, be necessary to provide a kind of preparation method that can suppress the light absorbing zone of the solar cell that Sn runs off.
A kind of preparation method of light absorbing zone of solar cell comprises the steps:
Preparation metallic film presoma, described metallic film presoma is copper-zinc-tin-sulfur film presoma or copper-zinc-tin-selenium film presoma;
Preparation is laminated in the tin tectum on the described metallic film presoma, obtain being laminated with the tectal metallic film presoma of tin, the described tectal metallic film presoma of tin that is laminated with is for being laminated with the tectal copper-zinc-tin-sulfur film presoma of tin or being laminated with the tectal copper-zinc-tin-selenium film of tin presoma; And
Under oxygen free condition and in the hydrogen sulfide atmosphere, the described tectal copper-zinc-tin-sulfur film presoma of tin that is laminated with is carried out high temperature annealing; Perhaps under oxygen free condition and in the selenium atmosphere, the described tectal copper-zinc-tin-selenium film of the tin presoma that is laminated with is carried out high temperature annealing, obtain the light absorbing zone of solar cell.
Among embodiment, the step of described preparation metallic film presoma is to adopt cosputtering method or coevaporation method to prepare the metallic film presoma therein.
Among embodiment, the step of described preparation metallic film presoma is to adopt the cosputtering method that copper, zinc sulphide and tin disulfide are sputtered onto on the substrate, forms the copper-zinc-tin-sulfur film presoma that is laminated on the described substrate therein; Or adopt the cosputtering method that copper, zinc selenide and two Tin diselenides are sputtered onto on the substrate, form the copper-zinc-tin-selenium film presoma that is laminated on the described substrate.
Therein among embodiment, the step of described preparation metallic film presoma be adopt coevaporation method with copper, zinc sulphide, tin and sulphur hydatogenesis to substrate, form the copper-zinc-tin-sulfur film presoma that is laminated on the described substrate; Or adopt coevaporation method with copper, zinc selenide, tin and selenium hydatogenesis to substrate, form the copper-zinc-tin-selenium film presoma that is laminated on the described substrate.
Therein among embodiment, described employing cosputtering legal system is equipped with the step that also comprises pre-sputter before the metallic film presoma.
Therein among embodiment, the tectal step of tin that described preparation is laminated on the described metallic film presoma is to adopt magnetron sputtering or thermal evaporation that element tin is deposited on the described metallic film presoma, obtains being laminated with the tectal metallic film presoma of tin.
Among embodiment, the tectal thickness of described tin is 150 nanometers therein.
Among embodiment, the temperature of described high temperature annealing is 550 ℃ therein, and the time is 15 minutes.
Among embodiment, the air pressure of described hydrogen sulfide is 2 * 10 therein
3Pa.
Therein among embodiment, described under oxygen free condition and in the hydrogen sulfide atmosphere, be laminated with the step that the tectal copper-zinc-tin-sulfur film presoma of tin carries out high temperature annealing and be specially described: the described tectal copper-zinc-tin-sulfur film presoma of tin that is laminated with is positioned in the annealing furnace, and feeding hydrogen sulfide to air pressure is 2 * 10
3Pa, feeding nitrogen to air pressure again is 4 * 10
4Pa heats the described tectal copper-zinc-tin-sulfur film of the tin presoma to 550 ℃ of being laminated with then, is incubated naturally cooling after 15 minutes; Described under oxygen free condition and in the selenium atmosphere, be laminated with the step that the tectal copper-zinc-tin-selenium film of tin presoma carries out high temperature annealing and be specially described: the described tectal copper-zinc-tin-selenium film of the tin presoma that is laminated with is positioned in the annealing furnace, and feeding selenium sulfide to air pressure is 2 * 10
3Pa, feeding nitrogen to air pressure again is 4 * 10
4Pa heats the described tectal copper-zinc-tin-selenium film of the tin presoma to 550 ℃ of being laminated with then, is incubated naturally cooling after 15 minutes.
The preparation method of the light absorbing zone of above-mentioned solar cell forms the tin tectum on the surface of metallic film presoma, utilizes the tin tectum to stop in high-temperature annealing process SnS in the copper-zinc-tin-sulfur film presoma
2Volatilization or copper-zinc-tin-selenium film presoma in SnSe
2Volatilization, suppress the purpose that the Sn element runs off in the metallic film presoma thereby reach, behind the CZTS crystal or CZTSe crystal of the annealed formation densification of copper-zinc-tin-sulfur film presoma or copper-zinc-tin-selenium film presoma, the Sn in the surperficial tin tectum forms SnS gradually under hydrogen sulfide atmosphere
2And break away from the CZTS plane of crystal, or under selenium sulfide atmosphere, form SnSe
2And breaking away from the CZTSe plane of crystal, this process can not have influence on the component of CZTS crystal or CZTSe crystal, has avoided SnS
2Or SnSe
2Volatilization and cause the loss of Sn, thereby prepare the higher CZTS light absorbing zone of quality or CZTSe light absorbing zone.
Description of drawings
Fig. 1 is preparation method's the schema of light absorbing zone of the solar cell of an embodiment;
Fig. 2 is preparation method's the synoptic diagram of step S110 of the light absorbing zone of solar cell shown in Figure 1.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing the specific embodiment of the present invention is described in detail.A lot of details have been set forth in the following description so that fully understand the present invention.But the present invention can implement much to be different from alternate manner described here, and those skilled in the art can do similar improvement under the situation of intension of the present invention, so the present invention is not subjected to the restriction of following public concrete enforcement.
See also Fig. 1, the preparation method of the light absorbing zone of the solar cell of an embodiment comprises the steps that S110 is to step S130.
Step S110: preparation metallic film presoma.
The metallic film presoma is copper-zinc-tin-sulfur (CZTS) film presoma or copper-zinc-tin-selenium (CZTSe) film presoma.
Please consult Fig. 2 simultaneously, substrate at first is provided.Substrate is glass substrate, substrate is cleaned up and drying after, form the molybdenum dorsum electrode layer that is laminated on the substrate at clean, dry substrate deposition molybdenum, obtain being laminated with the substrate 101 of molybdenum dorsum electrode layer.Preferably, the thickness of molybdenum dorsum electrode layer is 800 nanometers or 150 nanometers.
Be that copper-zinc-tin-sulfur (CZTS) film presoma is example with the metallic film presoma, adopt the cosputtering common sputter copper of method (Cu), zinc sulphide (ZnS) and tin disulfide (SnS
2), copper, zinc sulphide and tin disulfide are sputtered onto on the molybdenum dorsum electrode layer.Preparation process is specific as follows:
The substrate 101 that is laminated with the molybdenum dorsum electrode layer is put on the specimen holder of sputtering chamber of sputtering equipment.Be laminated with the molybdenum dorsum electrode layer of substrate 101 of molybdenum dorsum electrode layer towards substrate baffle plate 102.
Sputtering chamber is vacuumized, and at first being evacuated to the Pirani gauge reading with mechanical pump is 5 * 10
1Pa opens molecular pump then, and to be evacuated to the ionization gauge reading be 2 * 10
-3Pa.Open gas meter, feed 99.999% high-purity argon gas in the sputtering chamber with the flow of 12sccm, the control vacuum system makes the ionization gauge reading maintain 1.1 * 10
-1Pa.Each target (Cu target, ZnS target, SnS are opened in the specimen holder rotation
2Target and Sn target) the radio-frequency sputtering power supply, adjust output power of power supply and reflective power, make the target build-up of luminance.Pre-sputter was opened each target baffle plate (Cu target baffle plate 103, ZnS target baffle plate 104 and SnS after 10 minutes
2Target baffle plate 105), substrate baffle plate 102 and film thickness gauge baffle plate (not shown).Detect sputter rate by film thickness gauge.After the sputter 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 on the molybdenum dorsum electrode layer that is laminated in 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 that the power of 60W, ZnS target is 75W, SnS
2The power of target is 70W.
Pre-sputter refers to, opens each target (Cu target, ZnS target, SnS
2Target and Sn target) the radio-frequency sputtering power supply, adjust output power of power supply and reflective power, make the target build-up of luminance, but do not open Cu target baffle plate 103, ZnS target baffle plate 104, SnS this moment
2Target baffle plate 105, Sn target baffle plate 106 and substrate baffle plate 102 are to remove the impurity on each target material surface.Preferably, the time of pre-sputter is 10 minutes, opens Cu target baffle plate 103, ZnS target baffle plate 104, SnS again after with assurance the impurity on each target fully being removed
2Target baffle plate 105 and substrate baffle plate 102 carry out the preparation of presoma, and copper, zinc sulphide and tin disulfide are sputtered onto on the molybdenum dorsum electrode layer, and the copper, zinc sulphide and the tin disulfide that are sputtered onto on the molybdenum dorsum electrode layer form pure copper-zinc-tin-sulfur precursor thin-film.
When the metallic film presoma was copper-zinc-tin-selenium film presoma, it was roughly the same to adopt cosputtering to prepare method and the above-mentioned method for preparing the copper-zinc-tin-sulfur film presoma of this copper-zinc-tin-selenium film presoma, and different is that target replaces with Cu target, ZnSe target, SnSe
2Target.Pre-sputter was opened each target baffle plate (Cu target baffle plate, ZnSe target baffle plate, SnSe after 10 minutes
2The target baffle plate), substrate baffle plate and film thickness gauge baffle plate.Detect sputter rate by film thickness gauge.After the sputter 1 hour, close Cu target baffle plate, ZnSe target baffle plate and SnSe
2The target baffle plate forms the copper-zinc-tin-selenium film presoma on the dorsum electrode layer that is laminated in substrate.Preferably, the power of Cu target is that the power of 60W, ZnSe target is 75W, SnSe
2The power of target is 70W.
Preferably, the thickness of copper-zinc-tin-selenium film presoma is 1.3 microns～1.7 microns.
In other embodiments, also can adopt coevaporation to prepare the metallic film presoma.The common hydatogenesis of copper, zinc sulphide and tin disulfide to the molybdenum dorsum electrode layer of substrate, is formed the copper-zinc-tin-sulfur film presoma that is laminated on the molybdenum dorsum electrode layer; Perhaps with the common hydatogenesis of copper, zinc selenide, tin and selenium to the molybdenum dorsum electrode layer of substrate, form the copper-zinc-tin-selenium film presoma be laminated on the molybdenum dorsum electrode layer.
Adopting coevaporation to prepare the metallic film presoma carries out in molecular beam epitaxy system (MBE system).The substrate 101 that is laminated with the molybdenum dorsum electrode layer is put on the sample table of MBE cavity, after Cu source stove, ZnS source stove, Sn source stove, S source stove and sample table be 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 the copper-zinc-tin-sulfur film presoma.
When coevaporation method prepared the 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 was respectively 1210 ℃, 765 ℃, 1140 ℃, 200 ℃ and 200 ℃.
When coevaporation method prepared copper-zinc-tin-selenium film presoma, preferably, the preset temp of Cu source stove, ZnSe source stove, Sn source stove, Se source stove and sample table was respectively 1210 ℃, 765 ℃, 1140 ℃, 210 ℃ and 200 ℃.
Step S120: preparation is laminated in the tin tectum on the metallic film presoma, obtains being laminated with the tectal metallic film presoma of tin.
Be laminated with the tectal metallic film presoma of tin for being laminated with the tectal copper-zinc-tin-sulfur film presoma of tin or being laminated with the tectal copper-zinc-tin-selenium film of tin presoma.
After the molybdenum dorsum electrode layer of substrate forms the copper-zinc-tin-sulfur film presoma, open Sn target baffle plate 106, after the sputter 10 minutes, close Sn target baffle plate 106, close each target power supply, film thickness gauge, sample rotation and gas meter, cool off after 30 minutes, form the tin tectum at the copper-zinc-tin-sulfur film presoma, 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-selenium film presoma, open Sn target baffle plate, after the sputter 10 minutes, close Sn target baffle plate, close each target power supply, film thickness gauge, sample rotation and gas meter, cool off after 30 minutes, form the tin tectum at copper-zinc-tin-selenium film presoma, obtain being laminated with the tectal copper-zinc-tin-selenium film of tin presoma.
Preferably, the power of Sn target is 50W.
The vapour pressure of Sn is very little, only is 10 in the time of 1100 ℃
-4Pa almost can think to stablize nonvolatile, and therefore, the tin tectum is very stable, can stop the SnS in the copper-zinc-tin-sulfur precursor thin-film
2SnSe in volatilization or the prevention copper-zinc-tin-selenium precursor thin-film
2Volatilization.
The tectal thickness of tin is 100 nanometers～200 nanometers, is preferably 150 nanometers.It is enough thick in to suppress the inner SnS of metallic film presoma that the selection of tin cover thickness is wanted on the one hand
2Perhaps SnSe
2Volatilization, on the other hand again can not be too thick so that subsequent step can all be removed.When being 150 nanometers, can satisfy the tectal thickness of tin above-mentioned two requirements preferably.
In other embodiments, the method that also can adopt thermal evaporation is deposited on preparation on the metallic film presoma with tin and is laminated in tin tectum on the metallic film presoma.When adopting thermal evaporation to form the tin tectum, the preset temp of Sn source stove is preferably 1150 ℃.
Step S130: under oxygen free condition and in the hydrogen sulfide atmosphere, will be laminated with the tectal copper-zinc-tin-sulfur film presoma of tin and carry out high temperature annealing; Perhaps under oxygen free condition and in the selenium atmosphere, will be laminated with the tectal copper-zinc-tin-selenium film of tin presoma and carry out high temperature annealing, obtain the light absorbing zone of solar cell.
At the copper-zinc-tin-sulfur film presoma:
To be laminated with the tectal copper-zinc-tin-sulfur film presoma of tin and put into annealing furnace, with mechanical pump from 1 * 10
5It is 0Pa that Pa is evacuated to the diaphragm vacuum gauge reading.Continued to take out 5 minutes with the timing register timing, to guarantee the annealing furnace cleaning.
Close the mechanical pump angle valve, in annealing furnace, lead to 99.999% hydrogen sulfide to 2 * 10 earlier
3Pa, logical 99.999% high pure nitrogen to 4 * 10 again
4Pa.Open the heating power supply switch, rise to 530～600 ℃ with the temperature rise rate of 7.6 ℃ of per minutes from room temperature, kept 15～20 minutes down at 530～600 ℃, naturally cool to room temperature then.Monitor underlayer temperature by armouring K type thermocouple in the heat-processed.
Preferably, the temperature of the annealing of high temperature is 550 ℃, and annealing time is 15 minutes.550 ℃ of Tcs that reach copper-zinc-tin-sulfur (CZTS) precursor thin-film were annealed 15 minutes down at 550 ℃, can form fine and close CZTS light and inhale layer, obtained the light absorbing zone of high-quality solar cell.
In high-temperature annealing process, the continuous and H of the Sn in the tin tectum
2S gas reacts and generates SnS
2, SnS
2Volatilization constantly, the tin tectum finally is removed, and does not influence the light absorbing zone that finally obtains solar cell.
After treating that underlayer temperature is cooled to room temperature, open the mechanical pump angle valve, annealing furnace is evacuated to 0Pa, close the mechanical pump angle valve, logical 99.999% high pure nitrogen to 5 * 10
4Pa opens the mechanical pump angle valve again and is evacuated to 0Pa, cleans the annealing furnace gas, prevents that hydrogen sulfide from remaining in the annealing furnace.Close the mechanical pump angle valve, logical 99.999% high pure nitrogen to 1 * 10
5Pa opens the annealing furnace chamber, takes out finished product.
At copper-zinc-tin-selenium film presoma:
Put into the evaporation boat in the annealing furnace, evaporation is placed granules of selenium in the boat, and heating evaporation boat to 200 ℃ feeds 99.999% high pure nitrogen to 4 * 10
4Pa.Open the heating power supply switch, rise to 530～600 ℃ with the temperature rise rate of 7.6 ℃ of per minutes from room temperature, kept 15～20 minutes down at 530～600 ℃, naturally cool to room temperature then.Monitor underlayer temperature by armouring K type thermocouple in the heat-processed.
Preferably, the temperature of high temperature annealing is 550 ℃, and annealing time is 15 minutes.550 ℃ of Tcs that reach copper-zinc-tin-selenium (CZTSe) precursor thin-film were annealed 15 minutes down at 550 ℃, can form fine and close CZTSe light and inhale layer, obtained the light absorbing zone of high-quality solar cell.
In high-temperature annealing process, the continuous and selenium vapor generation reaction generation SnSe of the Sn in the tin tectum
2, SnSe
2Volatilization constantly, the tin tectum finally is removed, and does not influence the light absorbing zone that finally obtains solar cell.
When nitrogen partial pressure is 4 * 10
4Pa, when the temperature of evaporation boat was 200 ℃, the dividing potential drop of selenium steam was 2 * 10
3Pa.When needs are adjusted the selenium vapor partial pressure, can be by adjusting the dividing potential drop of the temperature change selenium steam that evaporates boat.
Light absorbing zone after the annealing is observed the finished surface gray, and is evenly not reflective, do not come off after water dashes.Measure its diagonal angle resistance about 500-700 kilo-ohm with volt ohm-milliammeter, the tectal Sn of tin complete cure volatilization.
In high-temperature annealing process, also feed high pure nitrogen, oxidized to avoid the being laminated with tectal metallic film presoma of tin.Be appreciated that when in the MBE cavity, annealing, because the MBE inside cavity remains high vacuum (＜10
-5Pa), do not have oxidizing gas existence such as oxygen in the environment, the metallic film precursor can be not oxidized, therefore, can directly anneal in high vacuum MBE, need not feed the rare gas element of protectiveness.
When adopting coevaporation to prepare the metallic film presoma, the step of high temperature annealing is also directly carried out in the MBE cavity, and need not annealing furnace is put in the sample taking-up again, and is easy to operate.
Annealing process is directly proceeded in the MBE cavity.The temperature of Se source stove keeps 210 ℃, open Se source fender plate, the sample table temperature at the uniform velocity is warming up to 550 ℃ with the temperature rise rate of 15 ℃ of per minutes from 200 ℃, 23.3 minutes times spent, keeps 10 minutes after arriving 550 ℃, close the sample table heating power supply, make the sample naturally cooling, close Se source fender plate when sample temperature is lower than 250 ℃, annealing finishes, take out sample, namely obtain the CZTSe light absorbing zone of solar cell.
When the tin tectum on finished product surface during the tight cure volatilization, sample whiting, diagonal angle resistance has only hundreds of Europe, but has vulcanized when thoroughly not volatilizing when the tin tectum on finished product surface, and color sample is darker, and diagonal angle resistance is several kilo-ohms.Run into above two kinds of situations, for the preparation of CZTS light absorbing zone, need to adjust the tectal thickness of tin or adjust H
2S concentration or adjustment H
2The annealing time of precursor under the S atmosphere is to guarantee the volatilization fully of Sn in the tin tectum.For the preparation of CZTSe light absorbing zone, need to adjust the temperature that Se evaporates boat or source stove in the annealing furnace, adjust the amount of Se particle in the Se evaporation boat simultaneously.
The preparation method of the light absorbing zone of above-mentioned solar cell forms the tin tectum on the surface of metallic film presoma, utilizes the tin tectum to stop in high-temperature annealing process SnS in the copper-zinc-tin-sulfur film presoma
2Volatilization or copper-zinc-tin-selenium film presoma in SnSe
2Volatilization, suppress the purpose that the Sn element runs off in the metallic film presoma thereby reach, behind the CZTS crystal or CZTSe crystal of the annealed formation densification of copper-zinc-tin-sulfur film presoma or copper-zinc-tin-selenium film presoma, the Sn in the tin tectum forms SnS gradually under hydrogen sulfide atmosphere
2And break away from the CZTS plane of crystal, or under selenium atmosphere, form SnSe
2And breaking away from the CZTSe plane of crystal, this process can not have influence on the component of CZTS crystal or CZTSe crystal, has avoided SnS
2Or SnSe
2Volatilization and cause the loss of Sn, thereby 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 being extensive use of in laboratory study and the suitability for industrialized production.
Below be described further by the preparation method of specific embodiment to the light absorbing zone of above-mentioned solar cell.
Embodiment 1
The light absorbing zone of preparation solar cell
1, coevaporation method prepares copper-zinc-tin-selenium film presoma
The glass substrate that is coated with the molybdenum dorsum electrode layer of 150nm thickness is placed on the MBE sample table, open the sample table turn switch, the temperature of Cu source stove, ZnSe source stove, Sn source stove, Se source stove and sample table is made as 1210 ℃, 765 ℃, 1140 ℃, 210 ℃ and 200 ℃ 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-selenium film presoma, the mol ratio of the element of this copper-zinc-tin-selenium film precursor is Cu:Zn:Sn:Se=1.8:1.1:1.3:3.9;
2, method of evaporation prepares the tin tectum
The temperature of the Sn source stove of MBE was kept 10 minutes at 1140 ℃, treat that the Sn line is stable after, open sample rotary power source, sample table baffle plate and Sn source fender plate in order successively.Evaporation is closed Sn source fender plate, sample table baffle plate and sample rotary power source successively after 3 minutes.Evaporation finishes, and cools off to form the tin tectum that is laminated on the metallic film presoma after 30 minutes, obtains being laminated with the tectal copper-zinc-tin-selenium film of tin presoma, and wherein, the tectal thickness of tin is 150 nanometers;
3, high temperature annealing
Annealing process is directly proceeded in the MBE cavity.The temperature of Se source stove keeps 210 ℃, open Se source fender plate, the sample table temperature at the uniform velocity is warming up to 550 ℃ from 200 ℃, 15 minutes times spent, keeps 10 minutes after arriving 550 ℃, close the sample table heating power supply, make the sample naturally cooling, close Se source fender plate when sample temperature is lower than 250 ℃, annealing finishes, take out sample, namely obtain the CZTSe light absorbing zone of solar cell.
Embodiment 2
The light absorbing zone of preparation solar cell
1, the cosputtering legal system is equipped with the copper-zinc-tin-sulfur film presoma
The glass substrate that is coated with the molybdenum dorsum electrode layer of 150nm thickness is placed on the magnetron sputtering sample table, opens the sample table turn switch, with Cu target, ZnS target and SnS
2The power of target is made as 60w, 75w and 70w respectively, and pre-sputter is opened Cu target baffle plate, ZnS target baffle plate, SnS after 10 minutes simultaneously
2Target baffle plate and substrate baffle plate, cosputtering 1 hour obtains the 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 the tin tectum
The power of Sn target is made as 50w, pre-sputter is after 10 minutes, open Sn target baffle plate, Sn target baffle plate is closed in sputter after 10 minutes, sputter finishes, and cools off to form the tin tectum that is laminated on the metallic film presoma after 30 minutes, 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, puts into annealing furnace, and being evacuated to the diaphragm vacuum gauge reading with mechanical pump is 0Pa.Continued to take out 5 minutes with the timing register timing, to guarantee the annealing furnace cleaning.Then, in annealing furnace, lead to H earlier
2S(purity is 99.999%) gas to 2 * 10
3Pa, logical 99.999% high pure nitrogen to 4 * 10 again
4Pa.Temperature rise rate with 7.6 ℃ of per minutes rises to 550 ℃ from room temperature, keeps 15 minutes at 550 ℃, naturally cools to room temperature then.Monitor underlayer temperature by armouring K type thermocouple in the heat-processed.After treating that underlayer temperature is cooled to room temperature, clean H remaining in the annealing furnace
2S atmosphere is taken out sample, namely obtains the CZTS light absorbing zone of solar cell.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.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 (10)
1. the preparation method of the light absorbing zone of a solar cell comprises the steps:
Preparation metallic film presoma, described metallic film presoma is copper-zinc-tin-sulfur film presoma or copper-zinc-tin-selenium film presoma;
Preparation is laminated in the tin tectum on the described metallic film presoma, obtain being laminated with the tectal metallic film presoma of tin, the described tectal metallic film presoma of tin that is laminated with is for being laminated with the tectal copper-zinc-tin-sulfur film presoma of tin or being laminated with the tectal copper-zinc-tin-selenium film of tin presoma; And
Under oxygen free condition and in the hydrogen sulfide atmosphere, the described tectal copper-zinc-tin-sulfur film presoma of tin that is laminated with is carried out high temperature annealing; Perhaps under oxygen free condition and in the selenium atmosphere, the described tectal copper-zinc-tin-selenium film of the tin presoma that is laminated with is carried out high temperature annealing, obtain the light absorbing zone of solar cell.
2. the preparation method of the light absorbing zone of solar cell according to claim 1 is characterized in that, the step of described preparation metallic film presoma is to adopt cosputtering method or coevaporation method to prepare the 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 step of described preparation metallic film presoma is to adopt the cosputtering method that copper, zinc sulphide and tin disulfide are sputtered onto on the substrate, forms the copper-zinc-tin-sulfur film presoma that is laminated on the described substrate; Or adopt the cosputtering method that copper, zinc selenide and two Tin diselenides are sputtered onto on the substrate, form the copper-zinc-tin-selenium film presoma that is laminated on the described substrate.
4. the preparation method of the light absorbing zone of solar cell according to claim 2, it is characterized in that, the step of described preparation metallic film presoma be adopt coevaporation method with copper, zinc sulphide, tin and sulphur hydatogenesis to substrate, form the copper-zinc-tin-sulfur film presoma that is laminated on the described substrate; Or adopt coevaporation method with copper, zinc selenide, tin and selenium hydatogenesis to substrate, form the copper-zinc-tin-selenium film presoma that is laminated on the 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 equipped with the step that the metallic film presoma also comprises pre-sputter before.
6. the preparation method of the light absorbing zone of solar cell according to claim 1, it is characterized in that, the tectal step of tin that described preparation is laminated on the described metallic film presoma is to adopt magnetron sputtering or thermal evaporation that tin is deposited on the 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 tectal thickness of described tin is 150 nanometers.
8. the preparation method of the light absorbing zone of solar cell according to claim 1 is characterized in that, the temperature of described high temperature annealing is 550 ℃, and the time is 15 minutes.
9. 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.
10. the preparation method of the light absorbing zone of solar cell according to claim 1, it is characterized in that, described under oxygen free condition and in the hydrogen sulfide atmosphere, be laminated with the step that the tectal copper-zinc-tin-sulfur film presoma of tin carries out high temperature annealing and be specially described: the described tectal copper-zinc-tin-sulfur film presoma of tin that is laminated with is positioned in the annealing furnace, and feeding hydrogen sulfide to air pressure is 2 * 10
3Pa, feeding nitrogen to air pressure again is 4 * 10
4Pa heats the described tectal copper-zinc-tin-sulfur film of the tin presoma to 550 ℃ of being laminated with then, is incubated naturally cooling after 15 minutes; Described under oxygen free condition and in the selenium atmosphere, be laminated with the step that the tectal copper-zinc-tin-selenium film of tin presoma carries out high temperature annealing and be specially described: be laminated with tin tectal copper-zinc-tin-selenium film presoma and granules of selenium is positioned in the annealing furnace with described, feeding nitrogen to air pressure is 4 * 10
4Pa heats the described tectal copper-zinc-tin-selenium film of the tin presoma to 550 ℃ of being laminated with then, is incubated naturally cooling after 15 minutes.
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| CN103938169A (en) * | 2014-04-09 | 2014-07-23 | 华东师范大学 | Preparation method of copper-ferrum-tin-selenium thin film |
| CN104409568A (en) * | 2014-11-13 | 2015-03-11 | 郑州大学 | Method for improving quality of copper zinc tin sulfide thin film used for solar battery |
| 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 |
| CN104576827A (en) * | 2014-12-18 | 2015-04-29 | 深圳丹邦投资集团有限公司 | Preparing method of Cu-Zn-Sn-S solar cell |
| 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 |
| CN106549082A (en) * | 2015-09-21 | 2017-03-29 | 云南师范大学 | The method that alloys target prepares copper-zinc-tin-sulfur film absorbed layer with sulfide target cosputtering |
| 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 |
| CN105821384B (en) * | 2015-09-24 | 2018-08-28 | 云南师范大学 | The method that polynary target double target co-sputtering prepares copper-zinc-tin-sulfur film |
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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 |
| US10570015B2 (en) | 2016-09-02 | 2020-02-25 | International Business Machines Corporation | Minimizing tin loss during thermal processing of kesterite films |
| CN114899280A (en) * | 2022-05-11 | 2022-08-12 | 中南大学 | Preparation method of cadmium-doped copper-zinc-tin-sulfur-selenium film and application of cadmium-doped copper-zinc-tin-sulfur-selenium film in solar cell |
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