CN101609860A - CdTe thin-film solar cells preparation method - Google Patents
CdTe thin-film solar cells preparation method Download PDFInfo
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- CN101609860A CN101609860A CNA200910057602XA CN200910057602A CN101609860A CN 101609860 A CN101609860 A CN 101609860A CN A200910057602X A CNA200910057602X A CN A200910057602XA CN 200910057602 A CN200910057602 A CN 200910057602A CN 101609860 A CN101609860 A CN 101609860A
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Abstract
The invention discloses a kind of CdTe thin-film solar cells preparation method, the CdTe film adopts the near space sublimed method to prepare the CdS/CdTe battery on transparent conducting glass, and the Ni back electrode adopts magnetron sputtering to obtain, and at first carries out the transparent glass substrate preliminary treatment; Preparation In
2O
3: the F transparent conductive film; On the transparent conductive film for preparing, use near space sublimed method growth CdS film; On the CdS film for preparing, use near space sublimed method growth CdTe film, use CdCl
2Film is carried out annealing in process, make the reorganization of CdS/CdTe interface; Use magnetic control sputtering device at CdTe surface sputtering Ni back electrode, annealing at high temperature forms ohmic contact; Obtain efficient CdTe thin-film solar cells; Wherein, described magnetic control sputtering device is connected by gate valve with the near space subliming furnace, and carries out the sample transmission by the magnetic machinery hand, and after above-mentioned steps entered pretreatment chamber from glass substrate, all operation was all finished under vacuum environment automatically.
Description
Technical field:
What the present invention relates to is a kind of manufacture method based on the CdTe thin-film solar cells, belongs to the inorganic compound energy and material and makes the field.
Background technology:
Along with deficient day by day, the environment of the growth of world today's demographic and economic, energy resources go from bad to worse and people increasing to the demand of electric energy, the development and utilization of solar energy has started upsurge in the world.The sustainable development that this is very beneficial for biological environment, the offspring that benefits future generations, so countries in the world investment research exploitation solar cell competitively.Solar energy is a kind of cleaning, pollution-free, inexhaustible natural energy resources, and the natural resources that the mankind depend on for existence almost all is transformed in solar energy, and it is an important technology basis that utilizes solar energy on a large scale that solar energy directly is converted to electric energy.
Solar cell is a kind of device that utilizes photovoltaic effect solar energy to be converted into electric energy.As far back as 1839, the scientists photovoltaic effect that begun one's study, to the mid-40 in 20th century, the development of solar cell has obtained important breakthrough, has found to be referred to as the process of Czochralski in monocrystalline silicon.1954, U.S.'s Bell Laboratory was successfully developed first solar cell in the world according to the process of this Czochralski, and energy conversion efficiency reaches 4%.The appearance of solar cell indicates that solar energy begins directly to be converted to electric energy by artificial device, and this is the once new leap of world energy sources industry.
Solar cell is of a great variety, comprises monocrystaline silicon solar cell, polysilicon solar cell, non-crystal silicon solar cell, compound semiconductor battery and lamination solar cell.
Silicon materials are main flows of present solar cell material (being photovoltaic material), and this is not only because silicon content in the earth's crust is abundant, and the cell conversion efficiency made from it is higher relatively.The under lab the highest conversion efficiency of monocrystaline silicon solar cell is near 25%, and the monocrystaline silicon solar cell of large-scale production, its efficient is 17%.But single product silicon solar cell manufacture craft is loaded down with trivial details, and the monocrystalline silicon cost price is high, and the very difficulty that significantly reduces cost can't realize the extensive universal of solar power generation.Along with continually developing and development of technologies of new material, more and more demonstrate tempting prospect based on the solar cell of other materials.The research of international low-cost mass production techniques at present mainly concentrates on polysilicon, large area film amorphous silicon, cadmium telluride (CdTe), copper indium diselenide (CuInSe
2) solar cell, III-V compound semiconductor high performance solar batteries, aspects such as amorphous silicon and silicon metal hybrid type thin film solar cell.Compare with monocrystaline silicon solar cell, except that polysilicon, GaAs, copper indium diselenide, cadmium telluride etc., the cell photoelectric transformation efficiency of other materials does not generally surpass 15%.However, silicon materials still are not optimal photovoltaic materials, and this mainly is that its optical absorption coefficient is lower, becomes current a kind of trend so study other photovoltaic materials because silicon is the indirect gap semiconductor material.Wherein, CdTe and CuInSe
2Be considered to two kinds of photovoltaic materials that application prospect is arranged very much, obtained at present certain progress, also need to drop into lot of manpower and material resources and research and develop but will contend with their large-scale production and with crystal silicon solar energy battery.
CdTe is a kind of compound semiconductor, generally makes absorbed layer in solar cell.Because its direct band gap is 1.45eV, be suitable for most photovoltaic energy conversion, therefore making the CdTe absorbed layer of about 2 micron thickness reach 90% at its optical absorptivity more than band gap becomes possibility, the highest theoretical transformation efficient of permission under air quality AM1.5 condition up to 27%.CdTe is deposited as large-area film easily, and deposition rate is also high.Therefore, the manufacturing cost of CdTe thin-film solar cells is lower, is a kind of preferably novel solar battery of application prospect, has become the main object of state's research and development such as U.S., moral, day, meaning.At present, acquired peak efficiency is 16.5%, and battery module efficient reaches 11%.Yet current people are relatively scattered to the characteristics of CdTe solar cell and preparation method's understanding, the understanding of neither one system.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of CdTe thin-film solar cells can prepare the CdTe thin-film solar cells by this method in a set of equipment, manufacture craft is simple, has reduced middle pollution section, has increased the validity of battery.
Technical scheme of the present invention is as follows: a kind of manufacture method of CdTe thin-film solar cells, described solar battery structure are that glass/TCO/CdS/CdTe/ back electrode constitutes, and CdS/CdTe forms PN junction respectively.This method has following processing step:
A. transparent glass substrate preliminary treatment: adopt 1713 glass as deposition substrate; Adopt acetone ultrasonic cleaning 5～15min, to remove the grease on surface, deionized water ultrasonic cleaning 10～20min removes glass surface impurity then; To put into pretreatment chamber after the glass oven dry at last, use plasma that glass substrate is cleaned.
B. prepare In
2O
3: F transparent conductive film (TCO): clear glass is delivered to by mechanical arm on the sample stage of magnetic control sputtering device, and sputtering target material is high-purity In
2O
3With vacuum pump sputtering chamber is evacuated to below the 5Pa earlier, with molecular pump reative cell is evacuated to 10 then
-2Below the Pa.Feed Ar gas and 5%CHF
3, the adjusting flow is 30～60ml/min; Conditioned reaction air pressure is 0.2～0.5Pa; Sputtering power 100～500W; Sputtering time 0.5～2h.
C. the CdS film of growing: the substrate that will prepare the TCO film is passed on the near space subliming furnace sample stage by mechanical arm, and sublimation source is high-purity CdS powder; With vacuum pump subliming furnace is evacuated to below the 5Pa earlier, with molecular pump subliming furnace is evacuated to 10 then
-2Below the Pa; Feed 50%Ar gas and 50%O
2, the adjusting flow is 5～20ml/min; Adjusting air pressure is 500～2000Pa; Regulating infrared Halogen lamp LED, to make the sublimation source temperature be 550～620 ℃, and underlayer temperature is 500～550 ℃, and sublimation source and substrate distance are 2～8mm; The distillation time is 3～10s.
D. to CdS film annealing in process: close sublimation source after preparing CdS, feed 80%Ar gas and 20%O
2, keep underlayer temperature at 400～450 ℃ of following annealing in process 20～30min.
E. the CdTe film of growing: the substrate after will annealing is passed on the near space subliming furnace sample stage by mechanical arm, and sublimation source is high-purity CdTe powder.With vacuum pump subliming furnace is evacuated to below the 5Pa earlier, with molecular pump subliming furnace is evacuated to 10 then
-2Below the Pa.Feed Ar gas, the adjusting flow is 5～20ml/min; Adjusting air pressure is 500～2000Pa; Regulating infrared Halogen lamp LED, to make the sublimation source temperature be 560～600 ℃; Underlayer temperature is 480～520 ℃, and sublimation source and substrate distance are 1～5mm; The distillation time is 0.5～2min.
F.CdTe film annealing in process: the substrate that will prepare the CdTe film is passed to by mechanical arm on the sample stage of magnetic control sputtering device, and sputtering target material is high-purity CdCl
2, with vacuum pump sputtering chamber is evacuated to below the 5Pa earlier, with molecular pump reative cell is evacuated to 10 then
-2Below the Pa.Feed Ar gas, adjusting air pressure is 0.2～0.5Pa; Sputtering power is 100～500W; Sputtering time is 10～20min.Continue to feed Ar gas after sputter is finished and make protection gas, keeping underlayer temperature is 400～450 ℃ of annealing 15～30min.
G. back electrode preparation: at the indoor preparation back electrode of magnetron sputtering, sputtering target material is high-purity N i, with vacuum pump sputtering chamber is evacuated to below the 5Pa earlier, with molecular pump reative cell is evacuated to 10 then
-2Below the Pa.Feed Ar gas, adjusting air pressure is 0.3～0.5Pa; Sputtering power is 200～500W; Sputtering time is 20～40min.At last with hull cell 400 ℃ of annealing in process 1～2h in Ar gas.Make electrode form better ohmic contact.
Wherein, described magnetic control sputtering device is connected by gate valve with the near space subliming furnace, and carries out the sample transmission by the magnetic machinery hand, and after above-mentioned steps entered pretreatment chamber from glass substrate, all operation was all finished under vacuum environment automatically.
The present invention compares with other CdTe thin-film solar cells preparation method, has following innovative point:
(1) the hull cell preparation section is simple, enter pretreatment chamber from glass substrate after all process steps all in a set of equipment, finish, reduced middle pollution section, increased the validity of battery.All process steps is finished in a set of equipment and is meant: this preparation equipment connects magnetic control sputtering device and near space subliming furnace by gate valve, and carry out the sample transmission by the magnetic machinery hand, after entering pretreatment chamber from glass substrate, all operation is all controlled by computer under vacuum environment, continuous productive process is finished automatically.
(2) the present invention has adopted near space sublimed method (CSS) preparation CdS, CdTe, and carries out high annealing under the Ar gas shiled, makes the reorganization of CdS/CdTe interface, and battery efficiency improves.
Description of drawings:
Fig. 1 is a CdTe thin-film solar cell structure schematic diagram;
Fig. 2 is a cell preparation operation schematic diagram;
The drawing reference numeral explanation:
The 1-transparent glass substrate, 2-transparent conductive film, 3-cadmium sulphide membrane, 4-Cadimium telluride thin film, 5-back electrode, 6-pretreatment chamber, 7-near space subliming furnace A, 8-near space subliming furnace B, 9-magnetic control sputtering device, 10-mechanical arm.
Embodiment:
Carry out the preparation of CdTe thin film solar cell according to following preparation technology:
(1) transparent glass substrate 1 preliminary treatment: adopt 1713 glass as deposition substrate 1.Adopt acetone ultrasonic cleaning 10min, to remove the grease on surface, deionized water ultrasonic cleaning 10min removes glass surface impurity then; To put into pretreatment chamber after the glass oven dry at last, use plasma that glass substrate 1 is cleaned.
(2) preparation In
2O
3: F transparent conductive film 2: transparent glass substrate 1 is delivered to by mechanical arm 10 on the sample stage of magnetic control sputtering device 9, and sputtering target material is high-purity In
2O
3Earlier sputtering chamber is evacuated to 3Pa, with molecular pump reative cell is evacuated to 1 * 10 then with vacuum pump
-3Pa.Feed Ar gas and 5%CHF
3, the adjusting flow is 30ml/min; Conditioned reaction air pressure is 0.2Pa; Sputtering power 200W; Sputtering time 0.5h.
(3) growth CdS film 3: the transparent glass substrate 1 that will prepare transparent conductive film 2 (TCO) is passed near space subliming furnace A 7 sample stage by mechanical arm 10, and sublimation source is high-purity CdS powder.Earlier subliming furnace is evacuated to 3Pa, with molecular pump subliming furnace is evacuated to 1 * 10 then with vacuum pump
-3Pa; Feed 50%Ar gas and 50%O
2, the adjusting flow is 10ml/min; Adjusting air pressure is 1000Pa; Regulating infrared Halogen lamp LED, to make the sublimation source temperature be 550 ℃, and underlayer temperature is 500 ℃, and source and substrate distance are 4mm; The distillation time is 6s.
(4) CdS film 3 annealing in process: close sublimation source after preparing CdS film 3, feed 80%Ar gas and 20%O
2, keep underlayer temperature at 400 ℃ of following annealing in process 20min.
(5) growth CdTe film 4: the CdS film 3 after will annealing is passed near space subliming furnace B 8 sample stage by mechanical arm 10, and sublimation source is high-purity CdTe powder.Earlier subliming furnace is evacuated to 5Pa, with molecular pump subliming furnace is evacuated to 1 * 10 then with vacuum pump
-3Pa; Feed Ar gas, the adjusting flow is 10ml/min; Adjusting air pressure is 800Pa; Regulating infrared Halogen lamp LED, to make the sublimation source temperature be 600 ℃; Underlayer temperature is 500 ℃, and source and substrate distance are 5mm; The distillation time is 2min.
(6) CdTe film 4 annealing in process: the substrate that will prepare CdTe film 4 is passed to by mechanical arm 10 on the sample stage of magnetic control sputtering device 9, and sputtering target material is high-purity CdCl
2, earlier the sputtering chamber of magnetic control sputtering device 9 is evacuated to 5Pa with vacuum pump, with molecular pump reative cell is evacuated to 1 * 10 then
-3Below the Pa; Feed Ar gas, adjusting air pressure is 0.2Pa; Sputtering power is 150W; Sputtering time is 10min.After sputter is finished, continue to feed Ar gas and make protection gas, keeping underlayer temperature is 450 ℃ of annealing 15min.
(7) back electrode 5 preparations: preparation back electrode 5 in the sputtering chamber of magnetic control magnetic control sputtering device 9, sputtering target material is high-purity N i, with vacuum pump sputtering chamber is evacuated to 3Pa earlier, with molecular pump reative cell is evacuated to 1 * 10 then
-3Below the Pa.Feed Ar gas, adjusting air pressure is 0.3Pa; Sputtering power is 200W; Sputtering time is 20min; At last with hull cell 400 ℃ of annealing in process 1 hour in Ar gas.Make electrode form better ohmic contact.
By to above prepared solar cell, use the solar simulator test after, the result shows that the photoelectric conversion efficiency of thin-film solar cells is excellent, battery efficiency is greater than 15%.By CSS technology epitaxial growth CdTe hull cell on glass substrate, the accurate thickness of the growth of control material and layers of material, thus further improve the efficient of solar cell.
Claims (6)
1. CdTe thin-film solar cells preparation method, described CdTe film adopts the near space sublimed method prepare CdS/CdTe battery on transparent conducting glass, and the Ni back electrode adopts the magnetron sputtering acquisition, it is characterized in that:
A. transparent glass substrate preliminary treatment;
B. prepare In
2O
3: the F transparent conductive film;
C. on the transparent conductive film for preparing, use near space sublimed method growth CdS film;
D. on the CdS film for preparing, use near space sublimed method growth CdTe film, use CdCl
2Film is carried out annealing in process, make the reorganization of CdS/CdTe interface;
E. use magnetic control sputtering device at CdTe surface sputtering Ni back electrode, annealing at high temperature forms ohmic contact;
F. obtain efficient CdTe thin-film solar cells;
Wherein, described magnetic control sputtering device is connected by gate valve with the near space subliming furnace, and carries out the sample transmission by the magnetic machinery hand, and after above-mentioned steps entered pretreatment chamber from glass substrate, all operation was all finished under vacuum environment automatically.
2. CdTe thin-film solar cells preparation method according to claim 1 is characterized in that:
The transparent glass substrate preliminary treatment is meant and adopts clear glass as deposition substrate among the described step a, adopts acetone ultrasonic cleaning 5～15min, and to remove the grease on surface, deionized water ultrasonic cleaning 10～20min removes glass surface impurity then; To put into pretreatment chamber after the glass oven dry at last, use plasma that glass substrate is cleaned.
3. CdTe thin-film solar cells preparation method according to claim 1 is characterized in that:
Prepare In among the described step b
2O
3: the F transparent conductive film is meant that by magnetic control sputtering device sputter one layer thickness on clear glass be the high conductive layer of 200～300nm, adopts high-purity In
2O
3Target, sputtering chamber feeds 95%Ar gas and 5%CHF
3, sputtering pressure remains on 0.3～0.5Pa.
4. CdTe thin-film solar cells preparation method according to claim 1 is characterized in that:
On the transparent conductive film for preparing, use near space sublimed method growth CdS film to be meant among the described step c and in quartz crucible, add high-purity CdS powder, by infrared Halogen lamp LED sublimation source is heated to 520～580 ℃, underlayer temperature is 480～500 ℃, feeds 50%Ar and 50%O
2, source and substrate distance are 2～4mm, growth one layer thickness is the CdS resilient coating of 70～100nm on substrate.
5. CdTe thin-film solar cells preparation method according to claim 1 is characterized in that:
On the CdS film for preparing, use near space sublimed method growth CdTe film to be meant in the described steps d and in quartz crucible, add high-purity CdTe powder, by infrared Halogen lamp LED sublimation source is heated to 560～600 ℃, underlayer temperature is 480～520 ℃, feed Ar, source and substrate distance are 1～5mm, and growth one layer thickness is the CdTe absorbed layer of 2～6 μ m on the glass substrate for preparing the CdS film; After this sputter 300～400nmCdCl on the CdTe film for preparing
2, the following 450 ℃ of annealing 15～20min of Ar gas shiled.
6. CdTe thin-film solar cells preparation method according to claim 1 is characterized in that:
Use magnetic control sputtering device to be meant among the described step e at CdTe surface preparation Ni back electrode: by magnetic control sputtering device sputter Ni electrode on the CdTe film through annealing in process after, and under the Ar gas shiled 400 ℃ annealed 1 hour, make it to form good Ohmic contact.
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| CN101887921A (en) * | 2010-06-29 | 2010-11-17 | 上海大学 | CdMnTe thin film solar cell and preparation method thereof |
| CN102212780A (en) * | 2011-05-04 | 2011-10-12 | 四川大学 | Method for preparing p-type cadmium sulfide film |
| CN102237448A (en) * | 2010-04-30 | 2011-11-09 | 初星太阳能公司 | Devices and methods of protecting a cadmium sulfide layer for further processing |
| CN102286741A (en) * | 2011-09-02 | 2011-12-21 | 南京大学 | Method for preparing cadmium telluride film |
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| CN101794840B (en) * | 2010-02-11 | 2011-07-20 | 上海联孚新能源科技有限公司 | Method for preparing flexible CdTe thin film solar cell |
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| CN102888584B (en) * | 2012-09-17 | 2014-05-14 | 上海大学 | Method for depositing CdTe thin film based on diamond thin film |
| CN102891217B (en) * | 2012-09-17 | 2015-07-29 | 上海大学 | A kind of preparation method of diamond/CdTe thin film solar cell |
| CN103268906B (en) * | 2013-05-22 | 2016-06-01 | 中国科学技术大学 | Cadmium sulphide membrane and there is the preparation method of the solar cell of cadmium sulphide membrane |
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| WO2018119682A1 (en) * | 2016-12-27 | 2018-07-05 | China Triumph International Engineering Co., Ltd. | Method for producing a cdte thin-film solar cell |
| CN108513683A (en) * | 2016-12-27 | 2018-09-07 | 中国建材国际工程集团有限公司 | Method for producing CdTe thin film solar cell |
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