CN1851934A - Copper-idium-selenium CuInSe solar cell and preparing method thereof - Google Patents

Copper-idium-selenium CuInSe solar cell and preparing method thereof Download PDF

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Publication number
CN1851934A
CN1851934A CNA2006100269155A CN200610026915A CN1851934A CN 1851934 A CN1851934 A CN 1851934A CN A2006100269155 A CNA2006100269155 A CN A2006100269155A CN 200610026915 A CN200610026915 A CN 200610026915A CN 1851934 A CN1851934 A CN 1851934A
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China
Prior art keywords
cuinse
copper indium
indium diselenide
electrode
solar cell
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CNA2006100269155A
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Chinese (zh)
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CN100449793C (en
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黄素梅
孙卓
黄士勇
朱红兵
李晓冬
陈奕卫
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华东师范大学
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/541CuInSe2 material PV cells
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

This invention discloses a CuInSe2 solar energy battery and its preparation method, in which, said battery is composed of a lower electrode, a P type CuInSe2 absorption layer, a transition layer CdS, a N-type ZnO layer and an upper electrode, the preparation method includes: applying a low frequency vibration vertical Bridgman method or a low vibration pot falling method to prepare type P CuInSe2 monocrystal chips, applying a water-bath method CBD to manufacture a transition layer CdS on one side of the monocrystal chip, utilizing the RF magnetic control spatter to ZnO target doped by Al2O3 on the CdS to prepare type-N ZnO layer, utilizing magnetic control spatter or electronic beam evaporation to deposit Al or Ag film by masks as the upper electrode and deposit the lower electrode at the other side of the monocrystal chip, which applies Cu/Mo alloy to replace Mo to fasten the link between the back electrode and the CuInSe2 absorption layer to improve the preparation technology of CuInSe2.

Description

A kind of copper indium diselenide CuInSe 2Solar cell and preparation method thereof
Technical field
The present invention relates to a kind of compound semiconductor single crystal solar cell and preparation method thereof, especially a kind of with copper indium diselenide CuInSe 2Structure and preparation method for the solar cell of absorbed layer belong to the photoelectric material technical field of new energies.
Background technology
The world today, increase along with progress of science and technology, expanding economy and population, human increasing to the demand of the energy, yet valuable sources such as oil, natural gas and coal are limited after all, most countries has felt that the memory space of fossil fuel reduces day by day, even face exhausted danger, and the fossil class A fuel A consumes, influence and the destruction that can cause essence to environment.China scientist makes a prediction to climatic influences with regard to energy resource consumption according to different climatic models: climate change will make the Chinese future agricultural face outstanding problem, estimate the year two thousand thirty, and plant husbandry output reduces about 5%-10% because of the global warming meeting.
The development and use of solar cell then are the optimal selections that can solve two problems of above-mentioned energy and environment simultaneously, what occupy critical positions in solar photocell electricity transition material is silicon materials and compound semiconductor, in the new upsurge of photovoltaic technology development, because I-III-VI2 compound semiconductor CuInSe 2(CIS) material has good photoelectric absorption and conversion efficiency (photoelectric conversion efficiency of CIS thin-film solar cells can reach 19.2% in the laboratory), has the standard of bearing proportioning (I, III and VI family components in proportions) ability that changes, has the flexibility that can change in the design that alloying component brings, and its performance long-term stability, capability of resistance to radiation is strong, there is not photic decline in the battery of preparation, caused people's extensive concern and research recent years, thought the best replacer of silicon materials and the candidate of space power system of future generation by consistent.At present, the research to the CIS solar cell mostly is confined to CuInSe 2The research of hull cell is confined to improve the CIS film, and the preparation technology of entire cell, in the hope of improving conversion efficiency, reduces cost; People mainly adopt polynary coevaporation method film-forming process to make CuInSe 2Thin-film solar cells, i.e. second generation solar cell.Though can prepare the CIS battery of high conversion efficiency, the stoicheiometry of element is difficult to accurately control by evaporation, thereby the yields of battery is not high, and the realization of industrialization is difficulty relatively; When adopting evaporation, utilization ratio of raw materials is low equally, and waste is unfavorable for reducing cost greatly for noble metal.
Summary of the invention
Technical problem to be solved by this invention provides and a kind ofly can effectively improve copper indium diselenide CuInSe 2Solar battery lighting efficient is improved the precious metal material utilance, improves the copper indium diselenide CuInSe of the manufacture craft feature of environmental protection 2Solar cell and preparation method thereof, its goal of the invention can be implemented by the following technical programs.
A kind of copper indium diselenide CuInSe 2Solar cell is successively by bottom electrode, P type copper indium diselenide CuInSe 2Absorbed layer, transition zone CdS, N type ZnO layer and top electrode are formed.
Described P type copper indium diselenide CuInSe 2Absorbed layer is CuInSe 2Single-chip, its thickness are 0.2~3mm.
Described bottom electrode adopts Cu/Mo (copper/molybdenum) alloy.
Described transition zone CdS thickness is 40nm~60nm.
Copper indium diselenide CuInSe of the present invention 2The solar cell making process method comprises the steps:
At first make P type copper indium diselenide CuInSe 2Single-chip comprises the steps:
A certain amount of high purity copper (99.999%), indium (99.999%) and selenium (99.999%) particle removed be Cu: In: Se=1 behind the surface oxide layer in molar ratio: carry out abundant mixing at 1: 2, the heavy wall quartz ampoule (crucible) of packing into clean, this quartz ampoule one end seals, and quartz ampoule is evacuated to 10 -6~10 -7Torr also seals the quartz ampoule other end and to be placed on that aluminium oxide draws down in the pipe and fixing, is put into appropriate location in the decline stove, intensification, insulation, inoculation, degrowth.Concrete steps: will place the quartz ampoule of the sealing two ends of decline stove slowly to be warmed up to 300 ℃~350 ℃, allow Se and In that exothermic reaction takes place, after this exothermic reaction is finished, the temperature of stove is raised to 950 ℃~1150 ℃, on this temperature, keep 24hrs~45hrs at least, and by there being adjustable vibrating controller control lowering means to make melt do low-frequency vibration up and down, it is thorough comprehensively to make that each composition of melt evenly reaches CuInSe chemical combination building-up process.Then, quartz ampoule (crucible) is that the gradient zones of 70 ℃/cm~10 ℃/cm arrives the low-temperature space of vertical Bridgman with 5mm/h~10mm/h speed by temperature gradient, and the temperature of low-temperature space is arranged on 700 ℃~500 ℃.At last, the temperature of stove is cooled to normal temperature with the cooldown rate of 30 ℃/h~40 ℃/h.Quartz ampoule (crucible) is taken out in stove, open quartz ampoule and take out P-type CuInSe 2Ingot is with P-type CuInSe 2Ingot machinery or laser method section (0.2mm~3mm is thick) and twin polishing.
Adopt immersion method CBD to make transition zone CdS then, comprise the steps: P-type CuInSe 2Sheet 2~the 3h that under 350 ℃ and nitrogen atmosphere, anneals, through degreasing, steps such as rinsed with deionized water and sonic oscillation are cleaned, and put into sea water bath, are equipped with the CdS polycrystal film with the CBD legal system, and film forming solution composition mol ratio is CdCl 2: thiocarbamide [(NH 2) 2CS]: NH 4Cl: NH 4OH=2: 20: 20: 200; About 80 ℃ of solution temperatures, pH value 9~10, through 6~9min deposition, film forming is yellow homogeneous film, thickness is 40nm~60nm.
On transition zone CdS, utilize RF magnetron sputtering Al 2O 3The ZnO target that mix (2~2.5%) prepares N type ZnO layer, then with magnetron sputtering or electron beam evaporation by mask deposition of aluminum Al or silver-colored Ag film as top electrode, at last at P-type CuInSe 2The another side of single-chip passes through with magnetron sputtering or electron-beam evaporation bottom electrode Cu/Mo (copper/molybdenum).
Adopt the high efficiency copper indium diselenide CuInSe of above technical scheme 2The present invention of solar cell is to prepare high-quality monocrystalline P type copper indium diselenide CuInSe with vertical bridgman method or Bridgman-Stockbarger method 2Be light absorbing zone, and with Cu/Mo (copper/molybdenum) as bottom electrode, the Cu-Mo alloy or with copper indium diselenide CuInSe 2The sticking tack of single facet is good, and good conductivity, has improved copper indium diselenide CuInSe effectively 2Manufacture craft, improved noble metal copper, indium, the utilance of selenium material and the light conversion efficiency of copper indium diselenide solar cell, and improved the feature of environmental protection of manufacture craft and the rate of finished products of battery.
Description of drawings
Below in conjunction with accompanying drawing the specific embodiment of the present invention being done one describes in detail.
Fig. 1 is copper indium diselenide CuInSe of the present invention 2The structural representation of solar cell;
Fig. 2 is preparation P type copper indium diselenide CuInSe 2The Bridgman-Stockbarger method schematic diagram of single-chip.
Among the figure: 1, bottom electrode 2, P type copper indium diselenide CuInSe 2Absorbed layer 3, transition zone CdS4, N type ZnO layer 5, top electrode
Embodiment
As shown in Figure 1, high efficiency copper indium diselenide CuInSe of the present invention 2Solar cell is by bottom electrode 1, P type copper indium diselenide CuInSe 2Sheet 2, transition zone CdS 3, N type ZnO layer 4 and top electrode 5 are formed.P type copper indium diselenide CuInSe 2Absorbed layer is CuInSe 2Single-chip, bottom electrode adopts Cu/Mo (copper/molybdenum) alloy.
For preparing above-mentioned high efficiency copper indium diselenide CuInSe 2Solar cell, preparation method of the present invention may further comprise the steps:
A certain amount of high purity copper (99.999%), indium (99.999%) and selenium (99.999%) particle removed be Cu: In: Se=1 behind the surface oxide layer in molar ratio: carry out abundant mixing at 1: 2, the heavy wall quartz ampoule (crucible) of packing into clean, this quartz ampoule one end seals.Quartz ampoule is evacuated to 10 -6The quartz ampoule other end also sealed be placed on that aluminium oxide draws down in the pipe and fixing, be put into appropriate location in the decline stove, slowly be warmed up to 300 ℃~350 ℃, allow Se and In that exothermic reaction takes place, after this exothermic reaction is finished, the temperature of stove is raised to 1100 ℃, on this temperature, keep 24hrs, and by there being adjustable vibrating controller control lowering means to make melt do low-frequency vibration up and down, it is thorough comprehensively to make that each composition of melt evenly reaches CuInSe chemical combination building-up process.Then, quartz ampoule (crucible) is the low-temperature space that 70 ℃/cm gradient zones arrives vertical Bridgman with speed 5mm/h by temperature gradient, and the temperature of low-temperature space is arranged on 700 ℃.At last, the temperature of stove is cooled to normal temperature with the cooldown rate of 30 ℃/h.Quartz ampoule (crucible) is taken out in stove, open quartz ampoule and take out P-type CuInSe 2Ingot.With P-type CuInSe 2Ingot machinery section (1mm is thick) and polishing.
Adopt immersion method to make transition zone CdS then, comprise the steps: P-type CuInSe 2The sheet 2h that under 350 ℃ and nitrogen atmosphere, anneals, through degreasing, steps such as rinsed with deionized water and sonic oscillation are cleaned, and put into sea water bath, are equipped with the CdS polycrystal film with the CBD legal system, and film forming solution composition mol ratio is CdCl 2: thiocarbamide [(NH 2) 2CS]: NH 4Cl: NH 4OH=2: 20: 20: 200, solution temperature was 80 ℃, pH value 9, and through the 8min deposition, film forming is yellow homogeneous film, thickness is 50nm.
On transition zone CdS, utilize RF magnetron sputtering Al 2O 3(2%) the ZnO target of Can Zaing prepares N type ZnO layer, then with magnetron sputtering or electron beam evaporation by mask deposition of aluminum Al or silver-colored Ag film as top electrode, at last at P-type CuInSe 2The another side of sheet by mask with magnetron sputtering or electron-beam evaporation bottom electrode Cu/Mo (copper/molybdenum).
Because this high efficiency CIS CuInSe2The invention of solar cell is to prepare high-quality monocrystalline P type CIS CuInSe with vertical bridgman method or Bridgman-Stockbarger method2Be light absorbing zone, and take Cu/Mo (copper/molybdenum) as bottom electrode, this Cu-Mo alloy and CIS CuInSe2The sticking tack of single facet is good, has effectively improved CIS CuInSe2Manufacture craft, improved the utilization rate of noble metal copper, indium, selenium material And the light conversion efficiency of CIS solar cell, and the feature of environmental protection of manufacture craft and becoming of battery have been improved The product rate. Therefore, the present invention have that simple in structure, technology is simple, the conversion efficiency height of light, pollution-free, The advantages such as stability is good.

Claims (6)

1, a kind of copper indium diselenide CuInSe 2Solar cell is characterized in that: described battery is by bottom electrode, P type copper indium diselenide CuInSe 2Absorbed layer, transition zone CdS, N type ZnO layer and top electrode are formed.
2, according to the described copper indium diselenide CuInSe of claim 1 2Solar cell is characterized in that: described P type copper indium diselenide CuInSe 2Absorbed layer is CuInSe 2Single-chip, its thickness are 0.2~3mm.
3, according to the described copper indium diselenide CuInSe of claim 1 2Solar cell is characterized in that: described bottom electrode adopts Cu/Mo (copper/molybdenum) alloy.
4, according to the described copper indium diselenide CuInSe of claim 1 2Solar cell is characterized in that: described transition zone CdS thickness is 40nm~60nm.
5, the described copper indium diselenide CuInSe of a kind of claim 1 2The preparation method of solar cell is characterized in that:
May further comprise the steps:
1., adopt low-frequency vibration vertical bridgman method or low-frequency vibration Bridgman-Stockbarger method to prepare P type copper indium diselenide CuInSe 2Single-chip: a certain amount of high purity copper, indium and granules of selenium removed be Cu: In: Se=1 behind the surface oxide layer in molar ratio: carry out abundant mixing at 1: 2, the heavy wall quartz ampoule/crucible of packing into clean, this quartz ampoule one end have sealed, and quartz ampoule is evacuated to 10 -5-10 -6Behind the Torr, the quartz ampoule other end is also sealed, place aluminium oxide to draw pipe and fixing down then, place decline stove appropriate location, intensification, insulation, inoculation, degrowth;
2., adopt immersion method CBD at P type copper indium diselenide CuInSe 2Single-chip is simultaneously made transition zone CdS;
3., on transition zone CdS, utilize RF magnetron sputtering Al 2O 3The ZnO target that mix (2~2.5%) prepares N type ZnO layer;
4., with magnetron sputtering or electron beam evaporation by mask deposition of aluminum Al or silver-colored Ag film as top electrode;
5., at P type copper indium diselenide CuInSe 2The another side of single-chip by mask with magnetron sputtering or electron-beam evaporation bottom electrode.
6, according to the described a kind of copper indium diselenide CuInSe of claim 5 2The preparation method of solar cell is characterized in that: at 1. P type copper indium diselenide CuInSe of step 2In the preparation of absorbed layer, described decline stove high-temperature region temperature is 950 ℃~1150 ℃, and the temperature gradient of gradient zones is 70 ℃/cm~10 ℃/cm, and the crucible fall off rate is 5mm/h~10mm/h, and the temperature of low-temperature space is 700 ℃~500 ℃.
CNB2006100269155A 2006-05-26 2006-05-26 Copper-idium-selenium CuInSe solar cell and preparing method thereof CN100449793C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100466305C (en) * 2007-11-22 2009-03-04 北京科技大学 Method for producing copper-indium-selenium thin-film solar cell wealthy-indium optical absorption layer
CN101452969B (en) * 2008-12-29 2010-06-02 上海太阳能电池研究与发展中心 Copper zincium tin sulfur compound semiconductor thin-film solar cell and manufacturing method
CN102011194A (en) * 2010-10-11 2011-04-13 中国科学院青岛生物能源与过程研究所 Photovoltaic semiconductor nanocrystalline and preparation method and application thereof
CN101719419B (en) * 2009-11-13 2011-08-24 北京大学 Back electrode in dye-sensitized battery structure and preparation method thereof
CN101645466B (en) * 2009-07-09 2011-11-30 深圳丹邦投资集团有限公司 CdS buffer layer of film solar battery and preparation method

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4612411A (en) * 1985-06-04 1986-09-16 Atlantic Richfield Company Thin film solar cell with ZnO window layer
US5474939A (en) * 1992-12-30 1995-12-12 Siemens Solar Industries International Method of making thin film heterojunction solar cell
CN101521249B (en) * 2002-09-30 2012-05-23 米亚索尔公司 Manufacturing apparatus and method for large-scale production of thin-film solar cells
CN1312780C (en) * 2003-12-17 2007-04-25 华南理工大学 A thin-film solar cell and method for preparing same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100466305C (en) * 2007-11-22 2009-03-04 北京科技大学 Method for producing copper-indium-selenium thin-film solar cell wealthy-indium optical absorption layer
CN101452969B (en) * 2008-12-29 2010-06-02 上海太阳能电池研究与发展中心 Copper zincium tin sulfur compound semiconductor thin-film solar cell and manufacturing method
CN101645466B (en) * 2009-07-09 2011-11-30 深圳丹邦投资集团有限公司 CdS buffer layer of film solar battery and preparation method
CN101719419B (en) * 2009-11-13 2011-08-24 北京大学 Back electrode in dye-sensitized battery structure and preparation method thereof
CN102011194A (en) * 2010-10-11 2011-04-13 中国科学院青岛生物能源与过程研究所 Photovoltaic semiconductor nanocrystalline and preparation method and application thereof

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