CN102891217A - Method for manufacturing diamond/CdTe thin-film solar cell - Google Patents
Method for manufacturing diamond/CdTe thin-film solar cell Download PDFInfo
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Abstract
The invention discloses a method for manufacturing a diamond/CdTe thin-film solar cell. The cell has a silicon substrate/p-type diamond/n-type CdTe three-layer structure. The method comprises the following steps of: performing cleaning pretreatment and surface modification on the silicon substrate/p-type diamond thin-film, depositing an n-type CdTe thin-film on the p-type diamond thin-film to form a heterojunction, performing CdCl2 annealing treatment after CdTe thin-film deposition is finished, etching a silicon substrate in a window layer light absorption area, and performing metal contact deposition to form a thin-film solar cell device. According to the method, the p-type diamond/n-type CdTe thin-film solar cell can be manufactured, the p-type diamond serves as a window layer material, and the n-type CdTe thin-film serves as an absorption layer material, so that the heterojunction solar cell is manufactured, the availability of a wide bandgap p-type semiconductor material in the field of solar cells is realized.
Description
Technical field
The present invention relates to the preparation method of a kind of diamond/CdTe thin-film solar cells, belong to the solar cell fabrication process technical field.
Background technology
The energy and environmental problem are the focus of world attention in recent ten years, and " energy-saving and emission-reduction, sustainable development " has been common recognition and the development trend of the world today.China is " energy-saving and emission-reduction, safety and environmental protection, develop a circular economy, promote low-carbon technology " emphasis direction and the target as using energy source and development during " 12 ".China developed the history that solar cell has more than 50 year till now since 1958, the solar cell of now existing multiple material has entered industrialization, most popular or crystal silicon solar energy battery, but because the raw material use amount of crystal silicon solar energy battery is very large and the production power consumption of polysilicon is high, seriously polluted.Country relatively payes attention to exploitation and the application of thin-film solar cells at present.
The appearance of semiconductive thin film pn heterojunction technology is so that the production of solar cell is more economical, material is more saved, the main material of thin-film solar cells is the semi-conducting material with direct band gap and high absorption coefficient, and this thin-film solar cells mainly contains n-CdS/p-CdTe and n-CdS/p-CuInSe
2Hetero-junction thin-film solar cell.The advantage of thin-film solar cells maximum is to reduce materials'use amount and decrease material cost.
The chemical vapor deposition (CVD) diamond thin has very wide application prospect in modern high-tech field, and the preparation and application of diamond thin also become one of focus of domestic and international material science research already.Diamond has the excellent properties of many uniquenesses: energy gap large (5.5eV) has high resistivity (〉 1013 Ω .cm under the normal temperature); Low dielectric constant (5.7); High electron mobility (1800cm2V-1s-1) and hole mobility (1200cm2V-1s-1); Thermal conductivity is about five times of copper up to 20W/cmK, is the best heat conductor of nature; Superior optical characteristics has very high permeability from the far-infrared band to dark purple outskirt, makes diamond thin become optimal wear-resisting optical window material, mask material and optical coating material; And good chemical stability, frequency stability and temperature stability, make diamond thin can become the ideal material in the fields such as thin-film solar cells, Field Emission Display and field-effect transistor.
CdTe is a kind of compound semiconductor light volt material that has very much application prospect, has good direct band gap (1.45eV) better with the solar spectrum coupling, be best suited for photovoltaic energy conversion, the highest theoretical transformation efficient under air quality AM1.5 condition up to 27%.CdTe easily is deposited as large area film, deposition rate is very high, an amount of doping Cd element can effectively improve the crystalline form of CdTe film, significantly improve the conductance property of film, led by weak p-type electricity and to change the good N-shaped electricity of electric conductivity into and lead, and optical energy gap do not had impact substantially, at present the deposition technique of N-shaped CdTe film is very ripe.Because the CdTe thin-film solar cells contains the heavy metal element cadmium, a lot of people worry CdTe manufacture of solar cells and the impact of using environment.Research according to U.S. Brooker literary composition National Laboratory scientists, in the heavy metals emission amount of the conventional energy resources such as crystal silicon solar energy battery, CdTe solar cell and coal, oil, natural gas and nuclear energy unit's energy output, the cadmium discharge capacity of oil is the highest, reach 44.3g/GWh, and the discharge capacity of solar cell is all less than 1g/GWh, wherein the cadmium discharge capacity of CdTe battery is minimum, is 0.3g/GWh.This shows, the production of CdTe solar cell and use procedure can not produce harm to environment.Because the manufacturing cost of CdTe thin-film solar cells is lower, is preferably novel solar battery of a kind of application prospect, so the development of CdTe thin-film solar cells is subject to extensive concern both domestic and external, become the main object that the states such as U.S., moral, day research and develop.
In recent years, the research direction of solar cell is high conversion efficiency, low cost and high stability.Therefore, the thin film solar cell take the CdTe thin-film solar cells as representative receives much attention.The area of Siemens's exploitation is 3600 cm
2CdTe thin-film solar cells conversion efficiency reach 11.1% level; The area that Solar Cells company has been announced in American National regenerative resource laboratory is 6879 cm
2The test result of CdTe thin-film solar cells, its conversion efficiency reaches 7.7%; The CdTe thin-film solar cells area of Bp Solar is 4540 cm
2, conversion efficiency is 8.4%, area is 706 cm
2, conversion efficiency reaches 10.1%; The CdTe thin-film solar cells of Goldan Photon, area are 3528 cm
2, conversion efficiency is 7.7%.Yet these above solar cells can not be applied in the space owing to a little less than the non-refractory, anti-radiation performance, can only be applied to ground handling.In order to overcome this shortcoming, the present invention is incorporated into solar cell as the Window layer material with diamond high temperature resistant, corrosion-resistant, that radiation resistance is good, and has obtained certain achievement in research.
Summary of the invention
For the defective that prior art exists, the purpose of this invention is to provide the preparation method of a kind of diamond/CdTe thin-film solar cells.Use the p-type diamond to be prepared into heterojunction solar battery as Window layer material and N-shaped CdTe as the absorbed layer material, to solve the p-type simconductor material in the availability of area of solar cell.
For achieving the above object, the present invention adopts following technical scheme:
The preparation method of a kind of diamond/CdTe thin-film solar cells, described hull cell structure is: silicon substrate/p-type diamond thin/N-shaped CdTe film three-decker, the method has following processing step:
A. p-type diamond film surface preliminary treatment: adopt silicon substrate/p-type diamond thin as the p-type Window layer of hull cell, adopt acetone ultrasonic cleaning 5 ~ 15min, to remove the grease of diamond film surface, then deionized water ultrasonic cleaning 10 ~ 20min removes surface impurity.
B. the modification of p-type diamond film surface and modification: the p-type diamond thin film window layer that preliminary treatment is good is put into the UV ozone cleaning machine and is carried out surface modification and modification, change diamond thin band gap and interfacial state at the interface, to reduce contact berrier, improve the adhesion between the heterofilm, ultraviolet wavelength 185nm and 254nm, 50 ~ 150 ℃ of temperature, processing time 1 ~ 5min.
C. deposit N-shaped CdTe film and form heterojunction: use the p-type diamond thin deposition N-shaped CdTe film of near space sublimed method after finishing and modification to form the pn heterojunction, sublimation source is high-purity CdTe powder, and doped source is high-purity Cd.The sublimation source temperature is 550 ~ 650 ℃, 450 ~ 500 ℃ of underlayer temperatures, and sublimation source and substrate distance are 1 ~ 5mm, the distillation time is 1 ~ 2min.Before the deposition N-shaped CdTe film, use mask plate to cover in the edge of p-type diamond thin.
D. the annealing in process of p-type diamond/N-shaped CdTe thin-film solar cells: use magnetic control sputtering device that p-type diamond/N-shaped CdTe thin-film solar cells sample is carried out CdCl
2Annealing in process, sputtering target material are high-purity CdCl
2, Ar throughput 5 ~ 20ml/min, reative cell air pressure 500 ~ 1500Pa, sputtering power are 100 ~ 500W, sputtering time is 10 ~ 20min.The logical Ar gas of continuation was made protection gas after sputter was finished, and keeping underlayer temperature is 400 ~ 500 ℃ of annealing 10 ~ 30min.
E. use 1% ~ 20% NaOH solution to etch away the silicon substrate in thin-film solar cells Window layer light absorption district.
F. use vacuum vapour deposition evaporation In on the CdTe film of p-type diamond/N-shaped CdTe thin-film solar cells to use mask plate to cover in the edge of p-type diamond thin as the Metal Contact electrode.
G. use vacuum vapour deposition evaporation Au on the diamond thin of p-type diamond/N-shaped CdTe thin-film solar cells to use mask plate to cover in the In electrode district as the Metal Contact electrode.
H. after the electrode evaporation was finished, p-type diamond/N-shaped CdTe thin-film solar cells was at N
2In 100 ~ 300 ℃ annealing 30 ~ 60min, to obtain good electrode contact.The final p-type diamond/N-shaped CdTe thin-film solar cells that obtains is carried out electric performance test.
Compared with prior art, the present invention has advantages of following giving prominence to:
The present invention is by using the p-type diamond thin to be prepared into hetero-junction thin-film solar cell as Window layer material and N-shaped CdTe film as the absorbed layer material, and this hetero-junction thin-film solar cell structure can change in recent years the p-type simconductor material in the availability of area of solar cell.This battery has high temperature resistant, corrosion-resistant, radiation-resistant advantage, can be applied to field of aerospace.
Description of drawings
Fig. 1 is structural representation figure of the present invention.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
As shown in Figure 1, structure for thin film solar cell, be silicon substrate/p-diamond/n-CdTe structure, 1 is that silicon substrate, 2 is that p-type diamond thin, 3 is that N-shaped CdTe film, 4 is that In contact electrode, 5 is that Au contact electrode, 6 is the Window layer light absorption district that etches away silicon substrate.
A kind of deposition process based on CdTe film on the diamond thin has following processing step:
A. p-type diamond film surface preliminary treatment: adopt p-type diamond thin 2 as the p-type Window layer of hull cell, adopt acetone ultrasonic cleaning 10min, to remove the grease of diamond film surface, then deionized water ultrasonic cleaning 15min removes surface impurity.
B. p-type diamond thin 2 surface modifications and modification: p-type diamond thin 1 Window layer that preliminary treatment is good is put into the UV ozone cleaning machine and is carried out surface modification and modification, change diamond thin band gap and interfacial state at the interface, to reduce contact berrier, improve the adhesion between the heterofilm, ultraviolet wavelength 185nm and 254nm, 120 ℃ of temperature, processing time 3min.
C. the deposition of N-shaped CdTe film 3: use the p-type diamond thin 2 deposition N-shaped CdTe films 3 of near space sublimed method after finishing and modification, sublimation source is high-purity CdTe powder, and doped source is high-purity Cd.Use vacuum pump that subliming furnace is evacuated to below the 5Pa, then with molecular pump subliming furnace is evacuated to 10
-3Below the Pa.Ar throughput 20ml/min, adjustable pressure 1500Pa, the sublimation source temperature is 650 ℃, 450 ℃ of underlayer temperatures, sublimation source and substrate distance are 3mm, the distillation time is 2min.Before N-shaped CdTe film 3 depositions, use mask plate to cover in the edge of p-type diamond thin 2.
D. p-type diamond/N-shaped CdTe thin-film solar cells annealing in process: use magnetic control sputtering device that p-type diamond/N-shaped CdTe thin-film solar cells sample is carried out CdCl
2Annealing in process, sputtering target material are high-purity CdCl
2, with vacuum pump sputtering chamber is evacuated to below the 5Pa first, then with molecular pump reative cell is evacuated to 10
-3Below the Pa.Pass into Ar throughput 20ml/min, reative cell air pressure 1000Pa, sputtering power are 500W, and sputtering time is 15min.The logical Ar gas of continuation was made protection gas after sputter was finished, and keeping underlayer temperature is 450 ℃ of annealing 30min.
E. use 15% NaOH solution to etch away the silicon substrate 1 in thin-film solar cells Window layer light absorption district 6.
F. use vacuum vapour deposition thick In Metal Contact electrode 4 of evaporation 100nm on the CdTe film 3 of p-type diamond/N-shaped CdTe thin-film solar cells, use mask plate to cover in the edge of p-type diamond thin 2.
G. use vacuum vapour deposition thick Au Metal Contact electrode 5 of evaporation 200nm on the p-type diamond thin 2 of p-type diamond/N-shaped CdTe thin-film solar cells, use mask plate to cover in In contact electrode 4.
H. after the electrode evaporation was finished, p-type diamond/N-shaped CdTe thin-film solar cells was at N
2In 150 ℃ annealing 45min, obtain good electrode contact.
I. (1000W/cm under reference condition
2, 25 ℃, Am1.5) use solar simulator that p-type diamond/N-shaped CdTe thin-film solar cells is tested η 〉=8.04%, Jsc 〉=20.55mA/cm
2, Voc 〉=650mV.
Embodiment 2
The present embodiment has following processing step:
A. p-type diamond film surface preliminary treatment: adopt p-type diamond thin 2 as the p-type Window layer of hull cell, adopt acetone ultrasonic cleaning 10min, to remove the grease of diamond film surface, then deionized water ultrasonic cleaning 15min removes surface impurity.
B. p-type diamond thin 2 surface modifications and modification: p-type diamond thin 1 Window layer that preliminary treatment is good is put into the UV ozone cleaning machine and is carried out surface modification and modification, change diamond thin band gap and interfacial state at the interface, to reduce contact berrier, improve the adhesion between the heterofilm, ultraviolet wavelength 185nm and 254nm, temperature 50 C, processing time 5min.
C. the deposition of N-shaped CdTe film 3: use the p-type diamond thin 2 deposition N-shaped CdTe films 3 of near space sublimed method after finishing and modification, sublimation source is high-purity CdTe powder, and doped source is high-purity Cd.Use vacuum pump that subliming furnace is evacuated to below the 5Pa, then with molecular pump subliming furnace is evacuated to 10
-3Below the Pa.Ar throughput 20ml/min, adjustable pressure 1500Pa, the sublimation source temperature is 550 ℃, 500 ℃ of underlayer temperatures, sublimation source and substrate distance are 5mm, the distillation time is 2min.Before N-shaped CdTe film 3 depositions, use mask plate to cover in the edge of p-type diamond thin 2.
D. p-type diamond/N-shaped CdTe thin-film solar cells annealing in process: use magnetic control sputtering device that p-type diamond/N-shaped CdTe thin-film solar cells sample is carried out CdCl
2Annealing in process, sputtering target material are high-purity CdCl
2, with vacuum pump sputtering chamber is evacuated to below the 5Pa first, then with molecular pump reative cell is evacuated to 10
-3Below the Pa.Pass into Ar throughput 5ml/min, reative cell air pressure 1500Pa, sputtering power are 250W, and sputtering time is 10min.The logical Ar gas of continuation was made protection gas after sputter was finished, and keeping underlayer temperature is 500 ℃ of annealing 10min.
E. use 15% NaOH solution to etch away the silicon substrate 1 in thin-film solar cells Window layer light absorption district 6.
F. use vacuum vapour deposition thick In Metal Contact electrode 4 of evaporation 100nm on the CdTe film 3 of p-type diamond/N-shaped CdTe thin-film solar cells, use mask plate to cover in the edge of p-type diamond thin 2.
G. use vacuum vapour deposition thick Au Metal Contact electrode 5 of evaporation 200nm on the p-type diamond thin 2 of p-type diamond/N-shaped CdTe thin-film solar cells, use mask plate to cover in In contact electrode 4.
H. after the electrode evaporation was finished, p-type diamond/N-shaped CdTe thin-film solar cells was at N
2In 100 ℃ annealing 60min, obtain good electrode contact.
I. (1000W/cm under reference condition
2, 25 ℃, Am1.5) use solar simulator that p-type diamond/N-shaped CdTe thin-film solar cells is tested η 〉=7.63%, Jsc 〉=19.5mA/cm
2, Voc 〉=630mV.
The present embodiment has following processing step:
A. p-type diamond film surface preliminary treatment: adopt p-type diamond thin 2 as the p-type Window layer of hull cell, adopt acetone ultrasonic cleaning 10min, to remove the grease of diamond film surface, then deionized water ultrasonic cleaning 15min removes surface impurity.
B. p-type diamond thin 2 surface modifications and modification: p-type diamond thin 1 Window layer that preliminary treatment is good is put into the UV ozone cleaning machine and is carried out surface modification and modification, change diamond thin band gap and interfacial state at the interface, to reduce contact berrier, improve the adhesion between the heterofilm, ultraviolet wavelength 185nm and 254nm, 150 ℃ of temperature, processing time 1min.
C. the deposition of N-shaped CdTe film 3: use the p-type diamond thin 2 deposition N-shaped CdTe films 3 of near space sublimed method after finishing and modification, sublimation source is high-purity CdTe powder, and doped source is high-purity Cd.Use vacuum pump that subliming furnace is evacuated to below the 5Pa, then with molecular pump subliming furnace is evacuated to below the 10-3Pa.Ar throughput 20ml/min, adjustable pressure 1500Pa, the sublimation source temperature is 600 ℃, 470 ℃ of underlayer temperatures, sublimation source and substrate distance are 1mm, the distillation time is 1min.Before N-shaped CdTe film 3 depositions, use mask plate to cover in the edge of p-type diamond thin 2.
D. p-type diamond/N-shaped CdTe thin-film solar cells annealing in process: use magnetic control sputtering device that p-type diamond/N-shaped CdTe thin-film solar cells sample is carried out CdCl
2Annealing in process, sputtering target material are high-purity CdCl
2, with vacuum pump sputtering chamber is evacuated to below the 5Pa first, then with molecular pump reative cell is evacuated to 10
-3Below the Pa.Pass into Ar throughput 15ml/min, reative cell air pressure 500Pa, sputtering power are 100W, and sputtering time is 20min.The logical Ar gas of continuation was made protection gas after sputter was finished, and keeping underlayer temperature is 400 ℃ of annealing 20min.
E. use 15% NaOH solution to etch away the silicon substrate 1 in thin-film solar cells Window layer light absorption district 6.
F. use vacuum vapour deposition thick In Metal Contact electrode 4 of evaporation 100nm on the CdTe film 3 of p-type diamond/N-shaped CdTe thin-film solar cells, use mask plate to cover in the edge of p-type diamond thin 2.
G. use vacuum vapour deposition thick Au Metal Contact electrode 5 of evaporation 200nm on the p-type diamond thin 2 of p-type diamond/N-shaped CdTe thin-film solar cells, use mask plate to cover in In contact electrode 4.
H. after the electrode evaporation was finished, p-type diamond/N-shaped CdTe thin-film solar cells was at N
2In 300 ℃ annealing 30min, obtain good electrode contact.
I. (1000W/cm under reference condition
2, 25 ℃, Am1.5) use solar simulator that p-type diamond/N-shaped CdTe thin-film solar cells is tested η 〉=7.56%, Jsc 〉=19.32mA/cm
2, Voc 〉=640mV.
Claims (1)
1. the preparation method of diamond/CdTe thin-film solar cells is characterized in that, described hull cell structure is: silicon substrate/p-type diamond thin/N-shaped CdTe film three-decker, and the method has following steps:
A. p-type diamond film surface preliminary treatment: adopt silicon substrate/p-type diamond thin as the p-type Window layer of hull cell, adopt acetone ultrasonic cleaning 5 ~ 15min, to remove the grease of diamond film surface, then deionized water ultrasonic cleaning 10 ~ 20min removes surface impurity;
B. the modification of p-type diamond film surface and modification: the p-type diamond thin film window layer that preliminary treatment is good is put into the UV ozone cleaning machine and is carried out surface modification and modification, change diamond thin band gap and interfacial state at the interface, to reduce contact berrier, improve the adhesion between the heterofilm, ultraviolet wavelength 185nm and 254nm, 50 ~ 150 ℃ of temperature, processing time 1 ~ 5min;
C. deposit N-shaped CdTe film and form heterojunction: use the p-type diamond thin deposition N-shaped CdTe film of near space sublimed method after finishing and modification to form the pn heterojunction, sublimation source is high-purity CdTe powder, and doped source is high-purity Cd; The sublimation source temperature is 550 ~ 650 ℃, 450 ~ 500 ℃ of underlayer temperatures, and sublimation source and substrate distance are 1 ~ 5mm, the distillation time is 1 ~ 2min; Before the deposition N-shaped CdTe film, use mask plate to cover in the edge of p-type diamond thin;
D. the annealing in process of p-type diamond/N-shaped CdTe thin-film solar cells: use magnetic control sputtering device that p-type diamond/N-shaped CdTe thin-film solar cells sample is carried out CdCl
2Annealing in process, sputtering target material are high-purity CdCl
2, Ar throughput 5 ~ 20ml/min, reative cell air pressure 500 ~ 1500Pa, sputtering power are 100 ~ 500W, sputtering time is 10 ~ 20min; The logical Ar gas of continuation was made protection gas after sputter was finished, and keeping underlayer temperature is 400 ~ 500 ℃ of annealing 10 ~ 30min;
E. use 1% ~ 20% NaOH solution to etch away the silicon substrate in thin-film solar cells Window layer light absorption district;
F. use vacuum vapour deposition evaporation In on the CdTe film of p-type diamond/N-shaped CdTe thin-film solar cells to use mask plate to cover in the edge of p-type diamond thin as the Metal Contact electrode;
G. use vacuum vapour deposition evaporation Au on the diamond thin of p-type diamond/N-shaped CdTe thin-film solar cells to use mask plate to cover in the In electrode district as the Metal Contact electrode;
H. after the electrode evaporation was finished, p-type diamond/N-shaped CdTe thin-film solar cells was at N
2In 100 ~ 300 ℃ annealing 30 ~ 60min, to obtain good electrode contact; The final p-type diamond/N-shaped CdTe thin-film solar cells that obtains is carried out electric performance test.
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| CN105220197A (en) * | 2015-11-12 | 2016-01-06 | 上海联孚新能源科技集团有限公司 | A kind of diamond thin deposits the method for CdTe thin film |
| CN105390552A (en) * | 2015-11-12 | 2016-03-09 | 上海联孚新能源科技集团有限公司 | CdTe thin film solar cell and manufacturing method thereof |
| CN108281510A (en) * | 2018-02-02 | 2018-07-13 | 辽宁太阳能研究应用有限公司 | Silicon based cells plate deposits the preparation method of cadmium telluride-based pellicular cascade solar cell material |
| CN108336153A (en) * | 2017-12-29 | 2018-07-27 | 长沙新材料产业研究院有限公司 | A kind of Diamond window air locking and preparation method thereof |
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| CN105220197A (en) * | 2015-11-12 | 2016-01-06 | 上海联孚新能源科技集团有限公司 | A kind of diamond thin deposits the method for CdTe thin film |
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| CN108336153A (en) * | 2017-12-29 | 2018-07-27 | 长沙新材料产业研究院有限公司 | A kind of Diamond window air locking and preparation method thereof |
| CN108336153B (en) * | 2017-12-29 | 2020-07-17 | 长沙新材料产业研究院有限公司 | Diamond window sealing device and preparation method thereof |
| CN108281510A (en) * | 2018-02-02 | 2018-07-13 | 辽宁太阳能研究应用有限公司 | Silicon based cells plate deposits the preparation method of cadmium telluride-based pellicular cascade solar cell material |
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