CN102751178A - Method for preparing thin-film solar cell p-n junction - Google Patents
Method for preparing thin-film solar cell p-n junction Download PDFInfo
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- CN102751178A CN102751178A CN2012101281516A CN201210128151A CN102751178A CN 102751178 A CN102751178 A CN 102751178A CN 2012101281516 A CN2012101281516 A CN 2012101281516A CN 201210128151 A CN201210128151 A CN 201210128151A CN 102751178 A CN102751178 A CN 102751178A
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Abstract
The invention discloses a method for preparing a thin-film solar cell p-n junction. The method includes the following steps of cleaning a substrate, drying the substrate by nitrogen, placing the substrate on a substrate table in a cavity of a plasma chemical vapor deposition system, placing a raw material containing tins and a raw material containing sulfurs into two crucibles respectively, placing the two crucibles into a raw material evaporation device of the plasma chemical vapor deposition system, closing the cavity, vacuumpumping, feeding argon to produce an argon plasma, subjecting the cavity of the plasma chemical vapor deposition system and the substrate in the cavity to a cleaning treatment by the argon plasma, heating the substrate, preparing an n type tin sulfur film and a p type tin sulfur film on the substrate surface which is cleaned, subjecting the prepared n type and the p type tin sulfur films to a vacuum annealing in the cavity of the plasma chemical vapor deposition system, and cooling the n type and the p type tin sulfur films subjected to the annealing treatment in an argon environment to the room temperature. The method is simple in preparing process and can meet a requirement of a large area and high speed deposition.
Description
Technical field
The invention belongs to technical field of thin-film solar, more specifically, relate to a kind of method for preparing solar battery p-n junction.
Background technology
Compare traditional fossil energy, solar energy is a kind of regenerative resource of cleaning, therefore is that the solar cell on basis more and more comes into one's own with the photovoltaic effect.And absorbing layer film is technological, occupies considerable status in the research of the solar cell of high-efficiency and low-cost with in producing.Along with research and development, cheap, photoelectric conversion material more and more comes into one's own efficiently to solar cell.Stannous sulfide is a kind of photoelectric material of asepsis environment-protecting; And its optics direct band gap is 1.3eV, and the best energy gap 1.5eV near solar cell material has the very big absorption coefficient of light simultaneously; Theoretical energy conversion efficiency can reach 25%, therefore has broad application prospects.At present, all can prepare all comparatively excellent stannous sulfide thin film of quality through the physics and the method for chemistry.
At present; In the preparation process of solar cell; Normally thin-film materials such as transparent conductive film, light absorbing zone, window material and anti-reflection layer are deposited on respectively on the substrate; Wherein the preparation of p-n junction is the important step in the thin-film solar cells, and it influences the cost of manufacture and the quality of monoblock battery.In the making of solar cell, there is stress problem in the stack of plural layers between the film, influence adhesion of thin film, and then influences the cost of manufacture and the useful life of thin-film solar cells.Simultaneously, the preparation of traditional p-n/p-i-n knot needs to introduce complicated doping process, has increased cost of manufacture, has also prolonged the production cycle.Therefore, a kind of ability satisfies simply, the preparation technology of p-n junction is present problem demanding prompt solution efficiently.
Summary of the invention
Defective to prior art; The object of the present invention is to provide a kind of method for preparing hull cell p-n knot; Its abundant raw material, cheap, environmental friendliness; And preparation technology is simple, can satisfy the requirement of large tracts of land, high-speed deposition, and this method can avoid the use of stress between complicated doping process and the heterogeneous membrane to the influence of hull cell.
For realizing above-mentioned purpose, the invention provides a kind of method for preparing the thin-film solar cells p-n junction, comprise the steps:
(1) cleans substrate, and use nitrogen drying;
(2) will clean and dried substrate places on the chip bench in the cavity of plasma chemical vapor deposition system;
(3) raw material with stanniferous and sulphur is put in respectively in two crucibles, and puts into the raw materials evaporate device of plasma chemical vapor deposition system;
(4) close the cavity of plasma chemical vapor deposition system, be evacuated to 5 * 10-3～8 * 10-5Pa;
(5) pressure with 30～150Pa feeds argon gas 20～100sccm, to produce argon plasma;
(6) utilize the cavity and the substrate in the cavity of argon plasma article on plasma body chemical vapor phase growing system to carry out clean, in 10～30 minutes processing times, the power of argon plasma is 10～100W;
(7) open heater on the chip bench, substrate is heated, heating-up temperature is 200～400 ℃;
(8) open the raw materials evaporate device, in plasma chemical vapor deposition system, feed argon gas and hydrogen, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare n type tin sulphur film; Wherein argon flow amount is 10～80sccm; Hydrogen flowing quantity is 5～40sccm, and plasma power is 50～300W, pressure 50～150Pa; 50 ℃～1200 ℃ of raw materials evaporate temperature, sedimentation time 20～150 minutes;
(9) close hydrogen; In plasma chemical vapor deposition system, feed argon gas, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare p type tin sulphur film, wherein argon flow amount 10～80sccm; Plasma power is 50～300W; Plasma pressure 100～150Pa, 50 ℃～1200 ℃ of raw materials evaporate temperature, sedimentation time 20～120 minutes;
(10) close plasma, and stop to feed argon gas;
(11) the heater temperature on the rising chip bench is carried out vacuum annealing, 300～550 ℃ of annealing temperatures, annealing time 30～150 minutes to n type tin sulphur film and the p type tin sulphur film of preparing in the cavity of plasma chemical vapor deposition system;
(12) in the cavity of plasma chemical vapor deposition system, feed argon gas, n type tin sulphur film after the annealing in process and p type tin sulphur film are cooled to room temperature in ar gas environment, to form p-n junction.
The raw material of stanniferous and sulphur comprises nanometer stannous sulfide powder, the compound of simple substance tin, elemental sulfur or stanniferous and element sulphur.
Substrate comprises silicon chip, soda-lime glass, quartz glass, transparent conducting glass.
The quantity of raw materials evaporate device is more than 2 or 2, and the raw materials evaporate device is provided with baffle plate, is used to control raw materials evaporate time and speed.
The raw material of stanniferous and sulphur can be put into the different raw materials vaporising device respectively.
Plasma activated chemical vapour deposition method ionic medium body can be microwave plasma, radio frequency plasma.
Through the above technical scheme that the present invention conceived, compared with prior art, the present invention has following beneficial effect:
1, the preparation method is simple: tin is different with the element sulphur proportioning; Thereby make tin sulphur film by the transformation preparation p-n of p type to the n type; Therefore, this method is utilized tin sulphur thin-film material self characteristics, adopts the reaction of element sulphur in hydrogen and the cavity to obtain hydrogen sulfide and extracts out from cavity through vacuum system; And then the proportioning of two kinds of elements in the change cavity, thereby prepare the p-n junction of solar cell; This preparation method has avoided the preparation of multilayer film in the preparation process of p-n junction and the introducing of complicated doping process, greatly reduces cost of manufacture, has shortened fabrication cycle; Simultaneously, this method can be through the proportioning of the suitable various elements of adjusting, the semi-conducting material that obtains having different energy gaps.
2, abundant raw material, nontoxic: adopt tin and element sulphur in this method, two kinds of elements are environment-friendly material, avoid the pollution to environment; Simultaneously; The tin sulphur compound belongs to IV-VI family semi-conducting material, also is important semi-conducting material, and it comprises multiple compound form.Stannous sulfide is wherein a kind of important semi-conducting material, its asepsis environment-protecting, and abundant raw material, theoretical energy conversion efficiency can reach 25%.
3, the p-n junction constituent is simple: the preparation of p-n junction is formed by tin and sulphur in this method, does not carry out complicated doping process, therefore, has avoided stress between the heterogeneous membrane to the influence of adhesive force, has increased the useful life of film.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The method that the present invention prepares the thin-film solar cells p-n junction comprises the steps:
(1) cleans substrate, and use nitrogen drying;
(2) will clean and dried substrate places on the chip bench in the cavity of plasma chemical vapor deposition system; In this execution mode, substrate comprises silicon chip, soda-lime glass, quartz glass, transparent conducting glass;
(3) raw material with stanniferous and sulphur is put in respectively in two crucibles, and puts into the raw materials evaporate device of plasma chemical vapor deposition system; The raw material of stanniferous and sulphur comprises nanometer stannous sulfide powder, the compound of simple substance tin, elemental sulfur or stanniferous and element sulphur, and can put into the different raw materials vaporising device; The quantity of raw materials evaporate device is more than 2 or 2, and the raw materials evaporate device is provided with baffle plate, is used to control raw materials evaporate time and speed.
(4) close the cavity of plasma chemical vapor deposition system, be evacuated to 5 * 10-3～8 * 10-5Pa;
(5) pressure with 30～150Pa feeds argon gas 20～100sccm, to produce argon plasma;
(6) utilize the cavity and the substrate in the cavity of argon plasma article on plasma body chemical vapor phase growing system to carry out clean, in 10～30 minutes processing times, the power of argon plasma is 10～100W;
(7) open heater on the chip bench, substrate is heated, heating-up temperature is 200～400 ℃;
(8) open the raw materials evaporate device, in plasma chemical vapor deposition system, feed argon gas and hydrogen, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare n type tin sulphur film; Wherein argon flow amount is 10～80sccm; Hydrogen flowing quantity is 5～40sccm, and plasma power is 50～300W, pressure 50～150Pa; 50 ℃～1200 ℃ of raw materials evaporate temperature, sedimentation time 20～150 minutes; Plasma activated chemical vapour deposition method ionic medium body can be microwave plasma, radio frequency plasma;
(9) close hydrogen; In plasma chemical vapor deposition system, feed argon gas, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare p type tin sulphur film, wherein argon flow amount 10～80sccm; Plasma power is 50～300W; Plasma pressure 100～150Pa, 50 ℃～1200 ℃ of raw materials evaporate temperature, sedimentation time 20～120 minutes;
(10) close plasma, and stop to feed argon gas;
(11) the heater temperature on the rising chip bench is carried out vacuum annealing, 300～550 ℃ of annealing temperatures, annealing time 30～150 minutes to n type tin sulphur film and the p type tin sulphur film of preparing in the cavity of plasma chemical vapor deposition system;
(12) in the cavity of plasma chemical vapor deposition system, feed argon gas, n type tin sulphur film after the annealing in process and p type tin sulphur film are cooled to room temperature in ar gas environment, to form p-n junction.
Embodiment 1
(1) cleaning is the substrate of transparent conducting glass, and uses nitrogen drying;
(2) will clean and dried substrate places on the chip bench in the cavity of plasma chemical vapor deposition system;
(3) take by weighing stannous chloride and sodium thiosulfate 4.75g and 12.4g respectively, place in two crucibles, and put into the raw materials evaporate device of plasma chemical vapor deposition system;
(4) close the cavity of plasma chemical vapor deposition system, be evacuated to 6 * 10-3Pa;
(5) pressure with 40Pa feeds argon gas 30sccm, to produce argon plasma;
(6) utilize the cavity and the substrate in the cavity of argon plasma article on plasma body chemical vapor phase growing system to carry out clean, in 20 minutes processing times, the power of argon plasma is 30W;
(7) open heater on the chip bench, substrate is heated, heating-up temperature is 300 ℃;
(8) open the raw materials evaporate device, in plasma chemical vapor deposition system, feed argon gas and hydrogen, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare n type tin sulphur film; Wherein argon flow amount is 30sccm; Hydrogen flowing quantity is 30sccm, and plasma power is 150W, pressure 90Pa; 600 ℃ of raw materials evaporate temperature, sedimentation time 40 minutes;
(9) close hydrogen; In plasma chemical vapor deposition system, feed argon gas, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare p type tin sulphur film, wherein argon flow amount 50sccm; Plasma power is 150W; Plasma pressure 80Pa, 600 ℃ of raw materials evaporate temperature, sedimentation time 40 minutes;
(10) close plasma, and stop to feed argon gas;
(11) the heater temperature on the rising chip bench is carried out vacuum annealing, 350 ℃ of annealing temperatures, annealing time 60 minutes to n type tin sulphur film and the p type tin sulphur film of preparing in the cavity of plasma chemical vapor deposition system;
(12) in the cavity of plasma chemical vapor deposition system, feed argon gas, n type tin sulphur film after the annealing in process and p type tin sulphur film are cooled to room temperature in ar gas environment, to form p-n junction.
Embodiment 2
(1) cleaning is the substrate of quartz glass, and uses nitrogen drying;
(2) will clean and dried substrate places on the chip bench in the cavity of plasma chemical vapor deposition system;
(3) take by weighing stannous chloride and elemental sulfur 4.75g and 1.6g respectively, place respectively in two crucibles, and put into the raw materials evaporate device of plasma chemical vapor deposition system;
(4) close the cavity of plasma chemical vapor deposition system, be evacuated to 2 * 10-4Pa;
(5) pressure with 50Pa feeds argon gas 50sccm, to produce argon plasma;
(6) utilize the cavity and the substrate in the cavity of argon plasma article on plasma body chemical vapor phase growing system to carry out clean, in 30 minutes processing times, the power of argon plasma is 50W;
(7) open heater on the chip bench, substrate is heated, heating-up temperature is 350 ℃;
(8) open the raw materials evaporate device, in plasma chemical vapor deposition system, feed argon gas and hydrogen, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare n type tin sulphur film; Wherein argon flow amount is 50sccm; Hydrogen flowing quantity is 20sccm, and plasma power is 150W, pressure 100Pa; 450 ℃ of raw materials evaporate temperature, sedimentation time 40 minutes;
(9) close hydrogen; In plasma chemical vapor deposition system, feed argon gas, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare p type tin sulphur film, wherein argon flow amount 50sccm; Plasma power is 150W; Plasma pressure 100Pa, 450 ℃ of raw materials evaporate temperature, sedimentation time 40 minutes;
(10) close plasma, and stop to feed argon gas;
(11) the heater temperature on the rising chip bench is carried out vacuum annealing, 400 ℃ of annealing temperatures, annealing time 60 minutes to n type tin sulphur film and the p type tin sulphur film of preparing in the cavity of plasma chemical vapor deposition system;
(12) in the cavity of plasma chemical vapor deposition system, feed argon gas, n type tin sulphur film after the annealing in process and p type tin sulphur film are cooled to room temperature in ar gas environment, to form p-n junction.
Embodiment 3
(1) cleaning is the substrate of transparent conducting glass, and uses nitrogen drying;
(2) will clean and dried substrate places on the chip bench in the cavity of plasma chemical vapor deposition system;
(3) will contain butter of tin and sodium thiosulfate and take by weighing 1.3g and 3.75g respectively and place respectively in two crucibles, and put into the raw materials evaporate device of plasma chemical vapor deposition system;
(4) close the cavity of plasma chemical vapor deposition system, be evacuated to 8 * 10-3Pa;
(5) pressure with 50Pa feeds argon gas 40sccm, to produce argon plasma;
(6) utilize the cavity and the substrate in the cavity of argon plasma article on plasma body chemical vapor phase growing system to carry out clean, in 25 minutes processing times, the power of argon plasma is 50W;
(7) open heater on the chip bench, substrate is heated, heating-up temperature is 250 ℃;
(8) open the raw materials evaporate device, in plasma chemical vapor deposition system, feed argon gas and hydrogen, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare n type tin sulphur film; Wherein argon flow amount is 50sccm; Hydrogen flowing quantity is 30sccm, and plasma power is 200W, pressure 100Pa; 550 ℃ of raw materials evaporate temperature, sedimentation time 30 minutes;
(9) close hydrogen; In plasma chemical vapor deposition system, feed argon gas, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare p type tin sulphur film, wherein argon flow amount 50sccm; Plasma power is 200W; Plasma pressure 120Pa, 550 ℃ of raw materials evaporate temperature, sedimentation time 30 minutes;
(10) close plasma, and stop to feed argon gas;
(11) the heater temperature on the rising chip bench is carried out vacuum annealing, 350 ℃ of annealing temperatures, annealing time 90 minutes to n type tin sulphur film and the p type tin sulphur film of preparing in the cavity of plasma chemical vapor deposition system;
(12) in the cavity of plasma chemical vapor deposition system, feed argon gas, n type tin sulphur film after the annealing in process and p type tin sulphur film are cooled to room temperature in ar gas environment, to form p-n junction.
Those skilled in the art will readily understand; The above is merely preferred embodiment of the present invention; Not in order to restriction the present invention, all any modifications of within spirit of the present invention and principle, being done, be equal to and replace and improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. a method for preparing the thin-film solar cells p-n junction is characterized in that, comprises the steps:
(1) cleans substrate, and use nitrogen drying;
(2) will clean and dried substrate places on the chip bench in the cavity of plasma chemical vapor deposition system;
(3) raw material with stanniferous and sulphur is put in respectively in two crucibles, and puts into the raw materials evaporate device of plasma chemical vapor deposition system;
(4) close the cavity of plasma chemical vapor deposition system, be evacuated to 5 * 10-3～8 * 10-5Pa;
(5) pressure with 30～150Pa feeds argon gas 20～100sccm, to produce argon plasma;
(6) utilize the cavity and the substrate in the cavity of argon plasma article on plasma body chemical vapor phase growing system to carry out clean, in 10～30 minutes processing times, the power of argon plasma is 10～100W;
(7) open heater on the chip bench, substrate is heated, heating-up temperature is 200～400 ℃;
(8) open the raw materials evaporate device, in plasma chemical vapor deposition system, feed argon gas and hydrogen, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare n type tin sulphur film; Wherein argon flow amount is 10～80sccm; Hydrogen flowing quantity is 5～40sccm, and plasma power is 50～300W, pressure 50～150Pa; 50 ℃～1200 ℃ of raw materials evaporate temperature, sedimentation time 20～150 minutes;
(9) close hydrogen; In plasma chemical vapor deposition system, feed argon gas, utilize the substrate surface of method after cleaning of plasma activated chemical vapour deposition to prepare p type tin sulphur film, wherein argon flow amount 10～80sccm; Plasma power is 50～300W; Plasma pressure 100～150Pa, 50 ℃～1200 ℃ of raw materials evaporate temperature, sedimentation time 20～120 minutes;
(10) close plasma, and stop to feed argon gas;
(11) the heater temperature on the rising chip bench is carried out vacuum annealing, 300～550 ℃ of annealing temperatures, annealing time 30～150 minutes to n type tin sulphur film and the p type tin sulphur film of preparing in the cavity of plasma chemical vapor deposition system;
(12) in the cavity of plasma chemical vapor deposition system, feed argon gas, n type tin sulphur film after the annealing in process and p type tin sulphur film are cooled to room temperature in ar gas environment, to form p-n junction.
2. according to the method for claim 1, it is characterized in that the raw material of stanniferous and sulphur comprises nanometer stannous sulfide powder, the compound of simple substance tin, elemental sulfur or stanniferous and element sulphur.
3. according to the method for claim 1, it is characterized in that substrate comprises silicon chip, soda-lime glass, quartz glass, transparent conducting glass.
4. according to the method for claim 1, it is characterized in that the quantity of raw materials evaporate device is more than 2 or 2, and the raw materials evaporate device is provided with baffle plate, is used to control raw materials evaporate time and speed.
5. according to the method for claim 1, it is characterized in that the raw material of stanniferous and sulphur can be put into the different raw materials vaporising device respectively.
6. according to the method for claim 1, it is characterized in that plasma activated chemical vapour deposition method ionic medium body can be microwave plasma, radio frequency plasma.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104167469A (en) * | 2014-08-12 | 2014-11-26 | 华中科技大学 | Method for manufacturing SnS2/SnS heterojunction thin-film solar cell at a time |
| CN105551946A (en) * | 2016-01-07 | 2016-05-04 | 广东工业大学 | Preparation method for stannous sulfide nanosheet and photoelectric detector prepared based on stannous sulfide nanosheet |
| CN111489969A (en) * | 2019-01-29 | 2020-08-04 | 东莞新科技术研究开发有限公司 | Heat treatment method of semiconductor silicon wafer |
| CN113511638A (en) * | 2021-06-30 | 2021-10-19 | 南京邮电大学 | Preparation method of TiN-S composite anode material by plasma chemical vapor codeposition |
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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Patent 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 |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104167469A (en) * | 2014-08-12 | 2014-11-26 | 华中科技大学 | Method for manufacturing SnS2/SnS heterojunction thin-film solar cell at a time |
| CN104167469B (en) * | 2014-08-12 | 2016-04-13 | 华中科技大学 | A kind of SnS 2the one time to produce method of/SnS hetero-junction thin-film solar cell |
| CN105551946A (en) * | 2016-01-07 | 2016-05-04 | 广东工业大学 | Preparation method for stannous sulfide nanosheet and photoelectric detector prepared based on stannous sulfide nanosheet |
| CN111489969A (en) * | 2019-01-29 | 2020-08-04 | 东莞新科技术研究开发有限公司 | Heat treatment method of semiconductor silicon wafer |
| CN113511638A (en) * | 2021-06-30 | 2021-10-19 | 南京邮电大学 | Preparation method of TiN-S composite anode material by plasma chemical vapor codeposition |
| CN113511638B (en) * | 2021-06-30 | 2022-12-06 | 南京邮电大学 | Preparation method of TiN-S composite anode material by plasma chemical vapor codeposition |
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