CN102891217B - A kind of preparation method of diamond/CdTe thin film solar cell - Google Patents
A kind of preparation method of diamond/CdTe thin film solar cell Download PDFInfo
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Abstract
The present invention discloses the preparation method of a kind of diamond/CdTe thin film solar cell, and battery structure is silicon substrate/p-type diamond/N-shaped CdTe three-decker.The method has following processing step: first, carries out cleaning preliminary treatment and finishing and modification to silicon substrate/p-type diamond thin, p-type diamond thin carries out N-shaped CdTe thin film deposition and forms heterojunction, carry out CdCl after CdTe thin film deposition terminates
2annealing in process, etches away the silicon substrate in Window layer light absorption district, carries out Metal Contact deposition and forms thin-film solar cells device.The preparation of p-type diamond/N-shaped CdTe thin film solar cell can be realized by the method, use p-type diamond to be prepared into heterojunction solar battery as window layer material and N-shaped CdTe as absorbed layer material, solve the availability of p-type simconductor material in area of solar cell.
Description
Technical field
The present invention relates to the preparation method of a kind of diamond/CdTe thin film solar cell, belong to solar cell fabrication process technical field.
Background technology
The energy and environmental problem are the focus of world attention in recent ten years, the common recognition of " energy-saving and emission-reduction, sustainable development " Yi Shi world today and development trend.China using " energy-saving and emission-reduction, safety and environmental protection, develop a circular economy, promote low-carbon technology " as the emphasis direction of " 12 " period using energy source and development and target.China developed the history that solar cell has more than 50 year till now from 1958, the solar cell of existing multiple material enters industrialization now, 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 of polysilicon power consumption is high, seriously polluted.Current country compares the development & application paying attention to thin-film solar cells.
The appearance of semiconductive thin film pn heteroj unction technologies makes 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 maximum advantage of thin-film solar cells can reduce materials'use amount and significantly reduce material cost.
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 normal temperature; Low dielectric constant (5.7); High electron mobility (1800cm2V-1s-1) and hole mobility (1200cm2V-1s-1); Thermal conductivity, up to 20W/cmK, is about five times of copper, is the best heat conductor of nature; Superior optical characteristics, has very high permeability from 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 very with application prospect, there is good direct band gap (1.45eV) mate with solar spectrum better, be best suited for photovoltaic energy conversion, the highest theoretical conversion efficiencies under air quality AM1.5 condition up to 27%.CdTe is easily deposited as large area film, deposition rate is very high, appropriate doping Cd element effectively can improve the crystalline form of CdTe thin film, significantly improve the conductance property of film, be the N-shaped conductance that electric conductivity is good by weak p-type conductance transition, and optical energy gap is not affected substantially, the deposition technique of current N-shaped CdTe thin film is very ripe.Because CdTe thin film solar cell contains heavy metal element cadmium, a lot of people worries CdTe manufacture of solar cells and uses the impact on environment.According to the research of Brooker literary composition National Laboratory of U.S. 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 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.As can be seen here, the production of CdTe solar cell and use procedure can not to environmental danger.Because the manufacturing cost of CdTe thin film solar cell is lower, be the good novel solar battery of a kind of application prospect, therefore the development of CdTe thin film solar cell is subject to extensive concern both domestic and external, has become the main object of U.S., moral, the research and development of Deng state.
In recent years, the research direction of solar cell is high conversion efficiency, low cost and high stability.Therefore, the thin film solar cell being representative with CdTe thin film solar cell receives much attention.The area of Siemens's exploitation is 3600 cm
2cdTe thin film conversion efficiency of solar cell reach 11.1% level; The area that National Renewable Energy laboratory discloses Solar Cells company is 6879 cm
2the test result of CdTe thin film solar cell, its conversion efficiency reaches 7.7%; The CdTe thin film solar-electricity pool area of Bp Solar is 4540 cm
2, conversion efficiency is 8.4%, and area is 706 cm
2, conversion efficiency reaches 10.1%; The CdTe thin film solar cell of Goldan Photon, area is 3528 cm
2, conversion efficiency is 7.7%.But, these above solar cells due to non-refractory, anti-radiation performance weak, can only ground handling be applied to, can not be applied in space.In order to overcome this shortcoming, high temperature resistant, corrosion-resistant, that radiation resistance is good diamond is incorporated into solar cell as window layer material by the present invention, and achieves certain achievement in research.
Summary of the invention
For the defect that prior art exists, the object of this invention is to provide the preparation method of a kind of diamond/CdTe thin film solar cell.P-type diamond is used to be prepared into heterojunction solar battery as window layer material and N-shaped CdTe as absorbed layer material, to solve the availability of p-type simconductor material in area of solar cell.
For achieving the above object, the present invention adopts following technical scheme:
A kind of preparation method of diamond/CdTe thin film solar cell, described thin-film cell structure is: silicon substrate/p-type diamond thin/N-shaped CdTe thin film three-decker, and 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: p-type diamond thin film window layer good for preliminary treatment is put into UV ozone cleaning machine and carries out surface modification and modification, change band gap and the interfacial state of diamond thin interface, to reduce contact berrier, improve the adhesion between heterofilm, ultraviolet wavelength 185nm and 254nm, temperature 50 ~ 150 DEG C, processing time 1 ~ 5min.
C. depositing n-type CdTe thin film forms heterojunction: depositing n-type CdTe thin film is to form pn heterojunction in finishing and modified p-type diamond thin to use close spaced sublimation method, and sublimation source is high-purity CdTe powder, and doped source is high-purity Cd.Sublimation source temperature is 550 ~ 650 DEG C, underlayer temperature 450 ~ 500 DEG C, and sublimation source and substrate distance are 1 ~ 5mm, and sublimation time is 1 ~ 2min.Before depositing n-type CdTe thin film, mask plate is used to cover in the edge of p-type diamond thin.
The annealing in process of d. p-type diamond/N-shaped CdTe thin film solar cell: use magnetic control sputtering device to carry out CdCl to p-type diamond/N-shaped CdTe thin film solar cell sample
2annealing in process, sputtering target material is high-purity CdCl
2, Ar throughput 5 ~ 20ml/min, reative cell air pressure 500 ~ 1500Pa, sputtering power is 100 ~ 500W, and sputtering time is 10 ~ 20min.Sputter rear continuation and led to Ar gas do protection gas, keep underlayer temperature to be 400 ~ 500 DEG C of annealing 10 ~ 30min.
E. the NaOH solution of 1% ~ 20% is used to etch away the silicon substrate in thin-film solar cells Window layer light absorption district.
F. vacuum vapour deposition evaporation In in the CdTe thin film of p-type diamond/N-shaped CdTe thin film solar cell is used as Metal contact electrode, to use mask plate to cover in the edge of p-type diamond thin.
G. vacuum vapour deposition evaporation Au on the diamond thin of p-type diamond/N-shaped CdTe thin film solar cell is used as Metal contact electrode, to use mask plate to cover in In electrode district.
H., after electrode evaporation completes, p-type diamond/N-shaped CdTe thin film solar cell is at N
2in 100 ~ 300 DEG C annealing 30 ~ 60min, to obtain good electrode contact.Final acquisition p-type diamond/N-shaped CdTe thin film solar cell, carries out electric performance test.
Compared with prior art, the present invention has following outstanding advantage:
The present invention is prepared into hetero-junction thin-film solar cell as window layer material and N-shaped CdTe thin film as absorbed layer material by using p-type diamond thin, this hetero-junction thin-film solar cell structure can change in recent years 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.
Accompanying drawing explanation
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, for the structure of thin film solar cell, for silicon substrate/p-diamond/n-CdTe structure, 1 being silicon substrate, 2 being that Au contact electrode, 6 is for etching away the Window layer light absorption district of silicon substrate for p-type diamond thin, 3 be N-shaped CdTe thin film, 4 is In contact electrode, 5.
embodiment 1
Based on a deposition process for CdTe thin film on diamond thin, there is 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, adopts acetone ultrasonic cleaning 10min, and to remove the grease of diamond film surface, then deionized water ultrasonic cleaning 15min removes surface impurity.
B. p-type diamond thin 2 surface modification and modification: p-type diamond thin 1 Window layer good for preliminary treatment is put into UV ozone cleaning machine and carries out surface modification and modification, change band gap and the interfacial state of diamond thin interface, to reduce contact berrier, improve the adhesion between heterofilm, ultraviolet wavelength 185nm and 254nm, temperature 120 DEG C, processing time 3min.
C. the deposition of N-shaped CdTe thin film 3: use close spaced sublimation method depositing n-type CdTe thin film 3 in finishing and modified p-type diamond thin 2, sublimation source is high-purity CdTe powder, and doped source is high-purity Cd.Use vacuum pump that subliming furnace is evacuated to below 5Pa, then with molecular pump, 10 are evacuated to subliming furnace
-3below Pa.Ar throughput 20ml/min, adjustable pressure 1500Pa, sublimation source temperature is 650 DEG C, underlayer temperature 450 DEG C, and sublimation source and substrate distance are 3mm, and sublimation time is 2min.Before N-shaped CdTe thin film 3 deposits, mask plate is used to cover in the edge of p-type diamond thin 2.
D. p-type diamond/N-shaped CdTe thin film solar cell annealing in process: use magnetic control sputtering device to carry out CdCl to p-type diamond/N-shaped CdTe thin film solar cell sample
2annealing in process, sputtering target material is high-purity CdCl
2, first with vacuum pump, below 5Pa is evacuated to sputtering chamber, then with molecular pump, 10 is evacuated to reative cell
-3below Pa.Pass into Ar throughput 20ml/min, reative cell air pressure 1000Pa, sputtering power is 500W, and sputtering time is 15min.Sputter rear continuation and led to Ar gas do protection gas, keep underlayer temperature to be 450 DEG C of annealing 30min.
E. the NaOH solution of 15% is used to etch away the silicon substrate 1 in thin-film solar cells Window layer light absorption district 6.
F. use the vacuum vapour deposition In Metal contact electrode 4 that evaporation 100nm is thick in the CdTe thin film 3 of p-type diamond/N-shaped CdTe thin film solar cell, use mask plate to cover in the edge of p-type diamond thin 2.
G. use the vacuum vapour deposition Au Metal contact electrode 5 that evaporation 200nm is thick on the p-type diamond thin 2 of p-type diamond/N-shaped CdTe thin film solar cell, use mask plate to cover in In contact electrode 4.
H., after electrode evaporation completes, p-type diamond/N-shaped CdTe thin film solar cell is at N
2in 150 DEG C annealing 45min, obtain good electrode contact.
I. (1000W/cm at the standard conditions
2, 25 DEG C, Am1.5) use solar simulator to test p-type diamond/N-shaped CdTe thin film solar cell, 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, adopts acetone ultrasonic cleaning 10min, and to remove the grease of diamond film surface, then deionized water ultrasonic cleaning 15min removes surface impurity.
B. p-type diamond thin 2 surface modification and modification: p-type diamond thin 1 Window layer good for preliminary treatment is put into UV ozone cleaning machine and carries out surface modification and modification, change band gap and the interfacial state of diamond thin interface, to reduce contact berrier, improve the adhesion between heterofilm, ultraviolet wavelength 185nm and 254nm, temperature 50 C, processing time 5min.
C. the deposition of N-shaped CdTe thin film 3: use close spaced sublimation method depositing n-type CdTe thin film 3 in finishing and modified p-type diamond thin 2, sublimation source is high-purity CdTe powder, and doped source is high-purity Cd.Use vacuum pump that subliming furnace is evacuated to below 5Pa, then with molecular pump, 10 are evacuated to subliming furnace
-3below Pa.Ar throughput 20ml/min, adjustable pressure 1500Pa, sublimation source temperature is 550 DEG C, underlayer temperature 500 DEG C, and sublimation source and substrate distance are 5mm, and sublimation time is 2min.Before N-shaped CdTe thin film 3 deposits, mask plate is used to cover in the edge of p-type diamond thin 2.
D. p-type diamond/N-shaped CdTe thin film solar cell annealing in process: use magnetic control sputtering device to carry out CdCl to p-type diamond/N-shaped CdTe thin film solar cell sample
2annealing in process, sputtering target material is high-purity CdCl
2, first with vacuum pump, below 5Pa is evacuated to sputtering chamber, then with molecular pump, 10 is evacuated to reative cell
-3below Pa.Pass into Ar throughput 5ml/min, reative cell air pressure 1500Pa, sputtering power is 250W, and sputtering time is 10min.Sputter rear continuation and led to Ar gas do protection gas, keep underlayer temperature to be 500 DEG C of annealing 10min.
E. the NaOH solution of 15% is used to etch away the silicon substrate 1 in thin-film solar cells Window layer light absorption district 6.
F. use the vacuum vapour deposition In Metal contact electrode 4 that evaporation 100nm is thick in the CdTe thin film 3 of p-type diamond/N-shaped CdTe thin film solar cell, use mask plate to cover in the edge of p-type diamond thin 2.
G. use the vacuum vapour deposition Au Metal contact electrode 5 that evaporation 200nm is thick on the p-type diamond thin 2 of p-type diamond/N-shaped CdTe thin film solar cell, use mask plate to cover in In contact electrode 4.
H., after electrode evaporation completes, p-type diamond/N-shaped CdTe thin film solar cell is at N
2in 100 DEG C annealing 60min, obtain good electrode contact.
I. (1000W/cm at the standard conditions
2, 25 DEG C, Am1.5) use solar simulator to test p-type diamond/N-shaped CdTe thin film solar cell, η>=7.63%, Jsc>=19.5mA/cm
2, Voc>=630mV.
embodiment 3
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, adopts acetone ultrasonic cleaning 10min, and to remove the grease of diamond film surface, then deionized water ultrasonic cleaning 15min removes surface impurity.
B. p-type diamond thin 2 surface modification and modification: p-type diamond thin 1 Window layer good for preliminary treatment is put into UV ozone cleaning machine and carries out surface modification and modification, change band gap and the interfacial state of diamond thin interface, to reduce contact berrier, improve the adhesion between heterofilm, ultraviolet wavelength 185nm and 254nm, temperature 150 DEG C, processing time 1min.
C. the deposition of N-shaped CdTe thin film 3: use close spaced sublimation method depositing n-type CdTe thin film 3 in finishing and modified p-type diamond thin 2, sublimation source is high-purity CdTe powder, and doped source is high-purity Cd.Use vacuum pump that subliming furnace is evacuated to below 5Pa, then with molecular pump, below 10-3Pa is evacuated to subliming furnace.Ar throughput 20ml/min, adjustable pressure 1500Pa, sublimation source temperature is 600 DEG C, underlayer temperature 470 DEG C, and sublimation source and substrate distance are 1mm, and sublimation time is 1min.Before N-shaped CdTe thin film 3 deposits, mask plate is used to cover in the edge of p-type diamond thin 2.
D. p-type diamond/N-shaped CdTe thin film solar cell annealing in process: use magnetic control sputtering device to carry out CdCl to p-type diamond/N-shaped CdTe thin film solar cell sample
2annealing in process, sputtering target material is high-purity CdCl
2, first with vacuum pump, below 5Pa is evacuated to sputtering chamber, then with molecular pump, 10 is evacuated to reative cell
-3below Pa.Pass into Ar throughput 15ml/min, reative cell air pressure 500Pa, sputtering power is 100W, and sputtering time is 20min.Sputter rear continuation and led to Ar gas do protection gas, keep underlayer temperature to be 400 DEG C of annealing 20min.
E. the NaOH solution of 15% is used to etch away the silicon substrate 1 in thin-film solar cells Window layer light absorption district 6.
F. use the vacuum vapour deposition In Metal contact electrode 4 that evaporation 100nm is thick in the CdTe thin film 3 of p-type diamond/N-shaped CdTe thin film solar cell, use mask plate to cover in the edge of p-type diamond thin 2.
G. use the vacuum vapour deposition Au Metal contact electrode 5 that evaporation 200nm is thick on the p-type diamond thin 2 of p-type diamond/N-shaped CdTe thin film solar cell, use mask plate to cover in In contact electrode 4.
H., after electrode evaporation completes, p-type diamond/N-shaped CdTe thin film solar cell is at N
2in 300 DEG C annealing 30min, obtain good electrode contact.
I. (1000W/cm at the standard conditions
2, 25 DEG C, Am1.5) use solar simulator to test p-type diamond/N-shaped CdTe thin film solar cell, η>=7.56%, Jsc>=19.32mA/cm
2, Voc>=640mV.
Claims (1)
1. a preparation method for diamond/CdTe thin film solar cell, is characterized in that, described thin-film cell structure is: silicon substrate/p-type diamond thin/N-shaped CdTe thin 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 diamond film surface impurity;
B. the modification of p-type diamond film surface and modification: p-type diamond thin film window layer good for preliminary treatment is put into UV ozone cleaning machine and carries out surface modification and modification, change band gap and the interfacial state of diamond thin interface, to reduce contact berrier, improve the adhesion between heterofilm, ultraviolet wavelength 185nm and 254nm, temperature 50 ~ 150 DEG C, processing time 1 ~ 5min;
C. depositing n-type CdTe thin film forms heterojunction: depositing n-type CdTe thin film is to form pn heterojunction in finishing and modified p-type diamond thin to use close spaced sublimation method, and sublimation source is high-purity CdTe powder, and doped source is high-purity Cd; Sublimation source temperature is 550 ~ 650 DEG C, underlayer temperature 450 ~ 500 DEG C, and sublimation source and substrate distance are 1 ~ 5mm, and sublimation time is 1 ~ 2min; Before depositing n-type CdTe thin film, mask plate is used to cover in the edge of p-type diamond thin;
The annealing in process of d. p-type diamond/N-shaped CdTe thin film solar cell: use magnetic control sputtering device to carry out CdCl to p-type diamond/N-shaped CdTe thin film solar cell sample
2annealing in process, sputtering target material is high-purity CdCl
2, Ar throughput 5 ~ 20ml/min, reative cell air pressure 500 ~ 1500Pa, sputtering power is 100 ~ 500W, and sputtering time is 10 ~ 20min; Sputter rear continuation and led to Ar gas do protection gas, keep underlayer temperature to be 400 ~ 500 DEG C of annealing 10 ~ 30min;
E. the NaOH solution of 1% ~ 20% is used to etch away the silicon substrate in thin-film solar cells Window layer light absorption district;
F. vacuum vapour deposition evaporation In in the CdTe thin film of p-type diamond/N-shaped CdTe thin film solar cell is used as Metal contact electrode, to use mask plate to cover in the edge of p-type diamond thin;
G. vacuum vapour deposition evaporation Au on the diamond thin of p-type diamond/N-shaped CdTe thin film solar cell is used as Metal contact electrode, to use mask plate to cover in In electrode district;
H., after electrode evaporation completes, p-type diamond/N-shaped CdTe thin film solar cell is at N
2in 100 ~ 300 DEG C annealing 30 ~ 60min, to obtain good electrode contact; Final acquisition p-type diamond/N-shaped CdTe thin film solar cell, carries 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 |
| 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 |
| CN108281510B (en) * | 2018-02-02 | 2019-11-26 | 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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| US4571447A (en) * | 1983-06-24 | 1986-02-18 | Prins Johan F | Photovoltaic cell of semi-conducting diamond |
| CN101009337A (en) * | 2007-01-26 | 2007-08-01 | 哈尔滨工业大学 | An a-Si:H solar battery with the boron mixing non-crystal diamond film as the window layer and its making method |
| US7368658B1 (en) * | 2003-10-31 | 2008-05-06 | The United States Of America As Represented By The United States Department Of Energy | High efficiency diamond solar cells |
| CN101609860A (en) * | 2009-07-16 | 2009-12-23 | 上海联孚新能源科技有限公司 | CdTe thin-film solar cells preparation method |
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|---|---|---|---|---|
| US4571447A (en) * | 1983-06-24 | 1986-02-18 | Prins Johan F | Photovoltaic cell of semi-conducting diamond |
| US7368658B1 (en) * | 2003-10-31 | 2008-05-06 | The United States Of America As Represented By The United States Department Of Energy | High efficiency diamond solar cells |
| CN101009337A (en) * | 2007-01-26 | 2007-08-01 | 哈尔滨工业大学 | An a-Si:H solar battery with the boron mixing non-crystal diamond film as the window layer and its making method |
| CN101609860A (en) * | 2009-07-16 | 2009-12-23 | 上海联孚新能源科技有限公司 | CdTe thin-film solar cells preparation method |
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