CN102655187B - Method for preparing tin-sulfur compound laminated solar battery - Google Patents
Method for preparing tin-sulfur compound laminated solar battery Download PDFInfo
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- CN102655187B CN102655187B CN201210125996.XA CN201210125996A CN102655187B CN 102655187 B CN102655187 B CN 102655187B CN 201210125996 A CN201210125996 A CN 201210125996A CN 102655187 B CN102655187 B CN 102655187B
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Abstract
The invention discloses a method for preparing a tin-sulfur compound laminated solar battery. P-type or n-type tin-sulfur films are deposited in the film preparation process by inletting hydrogen and then overlapped to obtain a tin-sulfur laminated film solar battery. By adopting a plasma chemical vapor deposition method, controlling the technological parameters such as the hydrogen flow and inletting time, the quantity or proportion of the added raw materials and the like and adjusting the proportion of the sulfur and tin elements in the cavity in the deposition process to adjust the proportion of the two elements in the obtained film, the thickness and the forbidden bandwidth of each deposited film can be controlled to obtain a relatively ideal tin-sulfur laminated film solar battery. The method disclosed by the invention has a simple technology, can be finished in the same equipment, avoids relatively complicated technology, lowers the production cost, shortens the production period and provides an easier and more efficient method for preparing the laminated film solar battery.
Description
Technical field
The invention belongs to technical field of thin-film solar, more specifically, relate to a kind of method of preparing thiostannate lamination solar cell.
Background technology
Solar energy is a kind of clean regenerative resource, more and more comes into one's own taking photovoltaic effect as basic solar cell.Solar cell development experienced three stages altogether.First stage taking monocrystalline silicon as main, although transformation efficiency is higher, production cost is higher.Second generation solar cell is thin-film solar cells, though its transformation efficiency is not high, production cost has obtained effective reduction.But the raising of the efficiency of unijunction solar cell prepared by homogenous material is restricted, this is because the energy gap of material is fixed value, and the energy range of solar spectrum very wide (0.4～4eV), therefore the photon that in solar spectrum, energy is less than energy gap can not be absorbed by solar cell, though energy is absorbed much larger than the photon of energy gap, but the high energy photo-generated carrier inspiring relaxes towards energy band edge very soon, the part that energy is greater than to energy gap passes to lattice, becomes thermal energy consumption and falls.Address this problem the most effective way and find the solar battery structure that can fully absorb solar spectrum, wherein effective method is employing laminated cell.The principle of laminated cell is using the material with different energy gaps as multiple sub-solar cells, then they leniently stacked up to narrow order by energy gap size, and composition one serial connection more piece solar cell.Each band gap absorbs the photon of the wave band matching with its band gap width, and conversion efficiency is the summation of each batteries conversion efficiency.Therefore stacked solar cell, cascade solar cell absorbs more fully than single battery and changes sunlight, thereby improves the conversion efficiency of solar cell.Laminated cell belongs to third generation solar cell, and has become the important development direction of third generation solar cell.
At present, in the preparation of stacked solar cell, cascade solar cell, there are two important problems, i.e. the selection of raw material and preparation method.The raw material adopting in current preparation mostly is the elements such as gallium, caesium, cadmium, indium, and these elements are all comparatively rare, improved production cost.There is certain harm to environmental protection in some element in addition.Therefore, abundant raw material and nontoxic, is easy to filming, the high condition that becomes the third generation solar cell indispensability of transformation efficiency.Aspect preparation method, the preparation of traditional p-n/p-i-n knot, need to introduce complicated doping process, has increased cost of manufacture, has also extended fabrication cycle.Though some solwution method preparation technologies are simple, the preparation of film needs the preparation time of growing.Therefore, a kind ofly can meet high deposition rate, large area, the preparation method of lamination solar cell becomes problem demanding prompt solution cheaply.
Summary of the invention
For the defect of prior art, the object of the present invention is to provide a kind of method of preparing thiostannate lamination solar cell, it can meet abundant raw material, cheap and eco-friendly requirement, and preparation technology is simple, can meet the requirement of large area, high-speed deposition, and the controllability of the method is strong.
For achieving the above object, the invention provides a kind of method of preparing thiostannate lamination solar cell, comprise the following steps:
(1) clean deposition has the substrate of nesa coating;
(2) substrate after cleaning is placed on the substrate heating device in the cavity of plasma chemical vapor deposition system;
(3) stanniferous and raw material sulphur is placed in to the raw materials evaporate device in the cavity of plasma chemical vapor deposition system;
(4) pass into argon gas, to produce argon plasma, passing into argon flow amount is 20～70sccm;
(5) utilize argon plasma to process 10～20 minutes the cavity of the substrate after cleaning and plasma chemical vapor deposition system, the power of argon plasma is 10～50W, and pressure when processing is 30～100Pa;
(6) open substrate heating device, substrate is heated, heating-up temperature is 200～350 DEG C;
(7) open raw materials evaporate device, carry out first stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared N-shaped tin sulphur film, and pass into argon gas and hydrogen in plasma chemical vapor deposition system, and wherein argon flow amount is 20～70sccm, hydrogen flowing quantity is 5～50sccm, plasma power is 60～250W, pressure 100～150Pa, 150 DEG C～1000 DEG C of raw materials evaporate temperature, sedimentation time 20～120 minutes;
(8) after first stage deposition finishes, close hydrogen, carry out second stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared p-type tin sulphur film, and pass into argon gas in plasma chemical vapor deposition system, and wherein argon flow amount 20～70sccm, plasma power is 60～250W, plasma pressure 100～150Pa, sedimentation time 20～120 minutes;
(9), after second stage deposition finishes, repeating step (7) and step (8) 1～3 times, to prepare many group p-n junctions;
(10) stop passing into argon gas;
(11) in the cavity of plasma chemical vapor deposition system, many groups p-n junction of preparing is carried out to vacuum annealing, and be cooled to room temperature in ar gas environment, wherein 300～450 DEG C of annealing temperatures, annealing time 30～120 minutes;
(12) utilize the silverskin that magnetron sputtering method is 100～300nm at the many groups p-n junction surface deposition thickness preparing, thereby finally prepare lamination solar cell.
Stanniferous and raw material sulphur comprises that simple substance tin, elemental sulfur, compound or nanometer stanniferous and element sulphur vulcanize sub-tin powder.
Nesa coating is to be made up of ITO, AZO or FTO material.
The quantity of raw materials evaporate device be one or more, and raw materials evaporate device is provided with baffle plate, for controlling raw materials evaporate time and speed.
Plasma activated chemical vapour deposition method applying plasma can be microwave plasma, radio frequency plasma or intermediate frequency plasma.。
The above technical scheme of conceiving by the present invention, compared with prior art, the present invention has following beneficial effect:
1, the selection of raw material is simple: thiostannate belongs to IV-VI family semi-conducting material, it comprises multiple compounds form, stannous sulfide is a kind of important semiconductor wherein, its asepsis environment-protecting, abundant raw material, and its optics direct band gap is 1.3eV, approaches the best energy gap 1.5eV of solar cell material, have the higher absorption coefficient of light, theoretical energy conversion efficiency can reach 25% simultaneously; Meanwhile, the difference of tin and element sulphur proportioning, film can the transformation to N-shaped by p-type.Therefore have broad application prospects;
2, preparation method is simple: plasma activated chemical vapour deposition method is simple, has avoided the introducing of complicated technology and impurity.And the method can complete in same equipment, reduced production cost, due to film in the process of deposition always in vacuum equipment, avoid the impact of extraneous factor on hull cell; Meanwhile, in preparation process, can also directly carry out adulterated al, copper, chlorine etc. to tin sulphur film, thereby improve the conductivity of film, reduce the series resistance of hull cell, increase effective extraction of solar cell photo-generated carrier, improve the fill factor, curve factor of solar cell;
3, p-n junction preparation is simple: pass into the technology of the interior tin of hydrogen adjusting cavity and element sulphur proportioning, make film transformation to N-shaped by p-type.The method is utilized the characteristic of tin sulphur thin-film material self, utilize hydrogen obtain hydrogen sulfide with reacting of element sulphur in cavity and extract out from cavity by vacuum system, and then the proportioning of two kinds of elements in change cavity, thereby can directly prepare as required stacked solar cell, cascade solar cell.The method is simple, easy to control, and by the method, can shorten manufacturing cycle, reduces production costs.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The method that the present invention prepares thiostannate lamination solar cell comprises the following steps:
(1) clean deposition has the substrate of nesa coating; In the present embodiment, nesa coating is to be made up of ITO, AZO or FTO material;
(2) substrate after cleaning is placed on the substrate heating device in the cavity of plasma chemical vapor deposition system;
(3) stanniferous and raw material sulphur is placed in to the raw materials evaporate device in the cavity of plasma chemical vapor deposition system; In the present embodiment, stanniferous and raw material sulphur comprises that simple substance tin, elemental sulfur, compound or nanometer stanniferous and element sulphur vulcanize sub-tin powder;
(4) pass into argon gas, to produce argon plasma, passing into argon flow amount is 20～70sccm;
(5) utilize argon plasma to process 10～20 minutes the cavity of the substrate after cleaning and plasma chemical vapor deposition system, the power of argon plasma is 10～50W, and pressure when processing is 30～100Pa; The quantity of raw materials evaporate device is one or more, and raw materials evaporate device is provided with baffle plate, for controlling raw materials evaporate time and speed;
(6) open substrate heating device, substrate is heated, heating-up temperature is 200～350 DEG C;
(7) open raw materials evaporate device, carry out first stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared N-shaped tin sulphur film, and pass into argon gas and hydrogen in plasma chemical vapor deposition system, and wherein argon flow amount is 20～70sccm, hydrogen flowing quantity is 5～50sccm, plasma power is 60～250W, pressure 100～150Pa, 150 DEG C～1000 DEG C of raw materials evaporate temperature, sedimentation time 20～120 minutes; Plasma activated chemical vapour deposition method applying plasma can be microwave plasma, radio frequency plasma or intermediate frequency plasma;
(8) after first stage deposition finishes, close hydrogen, carry out second stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared p-type tin sulphur film, and pass into argon gas in plasma chemical vapor deposition system, and wherein argon flow amount 20～70sccm, plasma power is 60～250W, plasma pressure 100～150Pa, sedimentation time 20～120 minutes;
(9), after second stage deposition finishes, repeating step (7) and step (8) 1～3 times, to prepare many group p-n junctions;
(10) stop passing into argon gas;
(11) in the cavity of plasma chemical vapor deposition system, many groups p-n junction of preparing is carried out to vacuum annealing, and be cooled to room temperature in ar gas environment, wherein 300～450 DEG C of annealing temperatures, annealing time 30～120 minutes;
(12) utilize the silverskin that magnetron sputtering method is 100～300nm at the many groups p-n junction surface deposition thickness preparing, thereby finally prepare lamination solar cell.
Embodiment 1
(1) clean deposition has the substrate of FTO nesa coating;
(2) substrate after cleaning is placed on the substrate heating device in the cavity of plasma chemical vapor deposition system;
(3) take respectively stannous chloride and sodium thiosulfate 9.5g and 24.8g, and be placed in the raw materials evaporate device in the cavity of plasma chemical vapor deposition system;
(4) pass into argon gas, to produce argon plasma, passing into argon flow amount is 30sccm;
(5) utilize argon plasma to process 20 minutes the cavity of the substrate after cleaning and plasma chemical vapor deposition system, the power of argon plasma is 30W, and pressure when processing is 50Pa;
(6) open substrate heating device, substrate is heated, heating-up temperature is 300 DEG C;
(7) open raw materials evaporate device, carry out first stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared N-shaped tin sulphur film, and pass into argon gas and hydrogen in plasma chemical vapor deposition system, and wherein argon flow amount is 30sccm, hydrogen flowing quantity is 20sccm, plasma power is 150W, pressure 100Pa, 450 DEG C of raw materials evaporate temperature, sedimentation time 40 minutes;
(8) after first stage deposition finishes, close hydrogen, carry out second stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared p-type tin sulphur film, and pass into argon gas in plasma chemical vapor deposition system, and wherein argon flow amount 30sccm, plasma power is 150W, plasma pressure 80Pa, sedimentation time 30 minutes;
(9) after second stage deposition finishes, repeating step (7) and step (8) 1 times, to prepare two groups of p-n junctions;
(10) stop passing into argon gas;
(11) in the cavity of plasma chemical vapor deposition system, prepare two groups of p-n junctions are carried out to vacuum annealing, and in ar gas environment, be cooled to room temperature, wherein 350 DEG C of annealing temperatures, annealing time 60 minutes;
(12) utilize magnetron sputtering method at two groups of silverskin that p-n junction surface deposition thickness is 200nm that prepare, thereby finally prepare lamination solar cell.
Embodiment 2
(1) clean deposition has the substrate of AZO nesa coating;
(2) substrate after cleaning is placed on the substrate heating device in the cavity of plasma chemical vapor deposition system;
(3) take respectively stannous chloride and elemental sulfur 9.5g and 3.2g, and be placed in the raw materials evaporate device in the cavity of plasma chemical vapor deposition system;
(4) pass into argon gas, to produce argon plasma, passing into argon flow amount is 40sccm;
(5) utilize argon plasma to process 15 minutes the cavity of the substrate after cleaning and plasma chemical vapor deposition system, the power of argon plasma is 30W, and pressure when processing is 50Pa;
(6) open substrate heating device, substrate is heated, heating-up temperature is 250 DEG C;
(7) open raw materials evaporate device, carry out first stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared N-shaped tin sulphur film, and pass into argon gas and hydrogen in plasma chemical vapor deposition system, and wherein argon flow amount is 40sccm, hydrogen flowing quantity is 30sccm, plasma power is 200W, pressure 90Pa, 450 DEG C of raw materials evaporate temperature, sedimentation time 40 minutes;
(8) after first stage deposition finishes, close hydrogen, carry out second stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared p-type tin sulphur film, and pass into argon gas in plasma chemical vapor deposition system, and wherein argon flow amount 40sccm, plasma power is 200W, plasma pressure 70Pa, sedimentation time 40 minutes;
(9) after second stage deposition finishes, repeating step (7) and step (8) 1 times, to prepare two groups of p-n junctions;
(10) stop passing into argon gas;
(11) in the cavity of plasma chemical vapor deposition system, prepare two groups of p-n junctions are carried out to vacuum annealing, and in ar gas environment, be cooled to room temperature, wherein 300 DEG C of annealing temperatures, annealing time 50 minutes;
(12) utilize magnetron sputtering method at two groups of silverskin that p-n junction surface deposition thickness is 150nm that prepare, thereby finally prepare lamination solar cell.
Embodiment 3
(1) clean deposition has the substrate of nesa coating ITO;
(2) substrate after cleaning is placed on the substrate heating device in the cavity of plasma chemical vapor deposition system;
(3) will take respectively 2.6g and 7.5g containing butter of tin and sodium thiosulfate, and be placed in the raw materials evaporate device in the cavity of plasma chemical vapor deposition system;
(4) pass into argon gas, to produce argon plasma, passing into argon flow amount is 50sccm;
(5) utilize argon plasma to process 20 minutes the cavity of the substrate after cleaning and plasma chemical vapor deposition system, the power of argon plasma is 25W, and pressure when processing is 30Pa;
(6) open substrate heating device, substrate is heated, heating-up temperature is 200 DEG C;
(7) open raw materials evaporate device, carry out first stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared N-shaped tin sulphur film, and pass into argon gas and hydrogen in plasma chemical vapor deposition system, and wherein argon flow amount is 30sccm, hydrogen flowing quantity is 30sccm, plasma power is 150W, pressure 120Pa, 350 DEG C of raw materials evaporate temperature, sedimentation time 60 minutes;
(8) after first stage deposition finishes, close hydrogen, carry out second stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared p-type tin sulphur film, and pass into argon gas in plasma chemical vapor deposition system, and wherein argon flow amount 50sccm, plasma power is 150W, plasma pressure 80Pa, sedimentation time 40 minutes;
(9) after second stage deposition finishes, repeating step (7) and step (8) 2 times, to prepare three groups of p-n junctions;
(10) stop passing into argon gas;
(11) in the cavity of plasma chemical vapor deposition system, prepare three groups of p-n junctions are carried out to vacuum annealing, and in ar gas environment, be cooled to room temperature, wherein 300 DEG C of annealing temperatures, annealing time 60 minutes;
(12) utilize magnetron sputtering method at three groups of silverskin that p-n junction surface deposition thickness is 250nm that prepare, thereby finally prepare lamination solar cell.
Those skilled in the art will readily understand; the foregoing is only preferred embodiment of the present invention; not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (5)
1. a method of preparing thiostannate lamination solar cell, is characterized in that, comprises the following steps:
(1) clean deposition has the substrate of nesa coating;
(2) substrate after cleaning is placed on the substrate heating device in the cavity of plasma chemical vapor deposition system;
(3) stanniferous and raw material sulphur is placed in to the raw materials evaporate device in the cavity of plasma chemical vapor deposition system;
(4) pass into argon gas, to produce argon plasma, passing into argon flow amount is 20～70sccm;
(5) utilize argon plasma to process 10～20 minutes the cavity of the substrate after cleaning and plasma chemical vapor deposition system, the power of argon plasma is 10～50W, and pressure when processing is 30～100Pa;
(6) open substrate heating device, substrate is heated, heating-up temperature is 200～350 DEG C;
(7) open raw materials evaporate device, carry out first stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared N-shaped tin sulphur film, and pass into argon gas and hydrogen in plasma chemical vapor deposition system, and wherein argon flow amount is 20～70sccm, hydrogen flowing quantity is 5～50sccm, plasma power is 60～250W, pressure 100～150Pa, 150 DEG C～1000 DEG C of raw materials evaporate temperature, sedimentation time 20～120 minutes;
(8) after first stage deposition finishes, close hydrogen, carry out second stage deposition, the substrate surface of the method for utilizing plasma activated chemical vapour deposition after cleaning prepared p-type tin sulphur film, and pass into argon gas in plasma chemical vapor deposition system, and wherein argon flow amount 20～70sccm, plasma power is 60～250W, plasma pressure 100～150Pa, sedimentation time 20～120 minutes;
(9), after second stage deposition finishes, repeating step (7) and step (8) 1～3 times, to prepare many group p-n junctions;
(10) stop passing into argon gas;
(11) in the cavity of plasma chemical vapor deposition system, many groups p-n junction of preparing is carried out to vacuum annealing, and be cooled to room temperature in ar gas environment, wherein 300～450 DEG C of annealing temperatures, annealing time 30～120 minutes;
(12) utilize the silverskin that magnetron sputtering method is 100～300nm at the many groups p-n junction surface deposition thickness preparing, thereby finally prepare lamination solar cell.
2. method according to claim 1, is characterized in that, stanniferous and raw material sulphur comprises the compound of simple substance tin, elemental sulfur or stanniferous and element sulphur.
3. method according to claim 1, is characterized in that, nesa coating is to be made up of ITO, AZO or FTO material.
4. method according to claim 1, is characterized in that, the quantity of raw materials evaporate device is one or more, and raw materials evaporate device is provided with baffle plate, for controlling raw materials evaporate time and speed.
5. method according to claim 1, is characterized in that, plasma activated chemical vapour deposition method applying plasma can be microwave plasma, radio frequency plasma or intermediate frequency plasma.
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| CN103956396A (en) * | 2014-05-19 | 2014-07-30 | 攀枝花学院 | Stannous sulfide laminated thin-film solar cell and manufacturing method thereof |
| KR101869337B1 (en) * | 2016-04-27 | 2018-06-20 | 영남대학교 산학협력단 | Tin sulfide thin film and method of forming the same, thin film solar cell and method of manufacturing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195909A (en) * | 2007-11-30 | 2008-06-11 | 华南师范大学 | Direct current plasma chemical vapor deposition equipment |
| CN101378090A (en) * | 2008-09-26 | 2009-03-04 | 合肥工业大学 | Tin sulfide film solar battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195909A (en) * | 2007-11-30 | 2008-06-11 | 华南师范大学 | Direct current plasma chemical vapor deposition equipment |
| CN101378090A (en) * | 2008-09-26 | 2009-03-04 | 合肥工业大学 | Tin sulfide film solar battery |
Non-Patent Citations (4)
| Title |
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| A. Sánchez-Juárez,et al.Fabrication of SnS2/SnS heterojunction thin film diodes by plasma-enhanced chemical vapor deposition.《Thin Solid Films》.2005,第480-481卷452-456. |
| A. Sanchez-Juarez,et al.Structural Properties of SnxSy Thin Films Prepared by Plasma‐Enhanced Chemical Vapor Deposition.《Journal of The Electrochemical Society》.2000,第147卷(第10期),3708-3717. |
| Fabrication of SnS2/SnS heterojunction thin film diodes by plasma-enhanced chemical vapor deposition;A. Sánchez-Juárez,et al;《Thin Solid Films》;20050305;第480-481卷;452-456 * |
| Structural Properties of SnxSy Thin Films Prepared by Plasma‐Enhanced Chemical Vapor Deposition;A. Sanchez-Juarez,et al;《Journal of The Electrochemical Society》;20001231;第147卷(第10期);3708-3717 * |
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