CN102214737B - Preparation method of compound thin film for solar battery - Google Patents
Preparation method of compound thin film for solar battery Download PDFInfo
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- CN102214737B CN102214737B CN201110160747XA CN201110160747A CN102214737B CN 102214737 B CN102214737 B CN 102214737B CN 201110160747X A CN201110160747X A CN 201110160747XA CN 201110160747 A CN201110160747 A CN 201110160747A CN 102214737 B CN102214737 B CN 102214737B
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Abstract
The invention discloses a preparation method of a compound thin film for a solar battery. The method comprises the following steps of: firstly, sputtering a copper-indium-gallium-selenium (CIGS) quaternary compound target by using a direct-current pulse power supply, and depositing an amorphous or nano crystalline thin film material with uniform thickness, uniform components and ideal element proportions on a glass substrate at a low temperature; secondly, quickly and thermally treating the thin film in a heat field formed by a resistance heat source and a halogen tungsten lamp tube heat source to restrain the loss of an element Se so as to obtain a CIGS thin film with high crystallinity, large crystallite dimension, high compactness and good chalcopyrite structural phases, and feeding a proper amount of H2Se+Ar or H2S+Ar mixed gas into the heat field for compensation; thirdly, quickly transferring the thin film to an H2S+Ar atmosphere and suddenly cooling the thin film; and finally, performing low-temperature annealing on the CIGS thin film under the atmosphere of H2 and Ar mixed gas so as to eliminate the stress and an inner defect of the thin film and passivate a current carrier compound center.
Description
Technical field
The invention belongs to technical field of new energies, be specifically related to a kind of preparation method of used for solar batteries optoelectronic thin film material.
Technical background
Current traditional fossil fuel worsening shortages or exhaustion, especially human development to the control of greenhouse gas emission with to the advocating of low-carbon economy, so that Renewable Energy Development becomes more urgent.Solar energy has become the important component part of various countries' sustainable development source strategy because cleaning, pollution-free is and inexhaustible.Solar cell as a kind of means of effectively utilizing of solar energy, has vast potential for future development.Present business-like solar cell is mainly crystal silicon solar batteries, and this type of manufacture of solar cells technical maturity, transformation efficiency is high, stability is strong, however this type of battery efficiency almost reach capacity, the cost space is minimum; And high energy consumption, high pollution in the silicon material is purified process with cell piece processing do not meet the category of China's green economy, low-carbon (LC) policy.Thin film solar cell is because cost advantage is subject to the emphasis support of country all the time aspect photovoltaic generation.Recently country about the policy of production capacity surplus and cleaner production also so that the inexorable trend that development is low-cost, the novel thin film solar cell becomes following international photovoltaic industry.The hull cell that has most at present practical prospect mainly contains amorphous silicon film solar battery, cadmium telluride film solar cells and CIGS thin-film solar cell.Wherein commercialization of amorphous silicon film solar battery and cadmium telluride film solar cells, but from the requirement of industrial production and battery applications, problem also obtains far away gratifying solution, still has many work to do.For amorphous silicon, the problem that battery efficiency is low does not also obtain basic solution, and fluctuate recent years always, and the efficient of single junction cell is stuck in about 6.0% always, and has serious photo attenuation.The binode laminated construction is improved the stability of battery, but the raising of efficient is far undesirable, generally is in 6.5% ~ 7.0% scope, and has brought certain fringe cost.Amorphous/crystallite laminated cell has improved stability and the efficient (8.0% ~ 9.5%) of battery really, but the production capacity of corresponding production line significantly descends, and has slackened cost advantage.For the Cadimium telluride thin film battery, the deposition of the three-layer thin-films such as cadmium sulfide, cadmium telluride, composite back contact layer and reprocessing are to obtain high efficiency key technology, and this technology is ripe not enough at present; The problem that the cadmium telluride film solar cells open circuit voltage is excessively low in addition still is not well solved, in addition tellurium scarcity of resources, and cadmium element is poisonous, so that this type of hull cell is difficult to become the main product of solar cell of future generation.Copper Indium Gallium Selenide (CIGS) thin film solar cell,, the good characteristics such as cost low, good stability, capability of resistance to radiation strong, life-span long high because of efficient, the attention and the industrialization that are subject to international research mechanism advance always.Small size CIGS thin film solar cell photoelectric conversion efficiency by American National regenerative resource laboratory (NREL) development had reached 19.9% in 2008, was the highest record of all kinds of thin film solar cells at that time.In April, 2010, Germany's solar energy and Hydrogen Energy research institution (ZSW) announced that the electricity conversion of small size Copper Indium Gallium Selenide (CIGS) thin film solar cell that it is developed is 20.1%, refreshed the record that has been kept by NREL 16 years, and create the highest again in August in the same year, reached 20.3% electricity conversion.But, above these high efficiency acquisitions all be derive from vacuum evaporation Copper Indium Gallium Selenide (CIGS) rete [see M.Venkatachalam, M.D.Kannan, N.Muthukumarasamy,
Et al., " Investigations on electron beam evaporated Cu (In
0.85Ga
0.15) Se
2Thin film solar cells "; Solar Energy 83; 1652 – 1655 (2009)] and water-bath prepares CdS or the ZnS rete [is seen Liudmila Larina; Dong Hyeop Shin; Nikolay Tsvetkov; and Byung Tae Ahn, " Growth of ultrathin Zn compound buffer layer by a chemical bath deposition for Cu (In, Ga) Se
2Solar cells ", Journal of The Electrochemical Society, 156 (11), D469-D473 (2009); R. N. Bhattacharya, M. A. Contreras, B. Egaas,
Et al., " High efficiency thin-film CuIn
1 xGa
xSe
2Photovoltaic cells using a Cd
1 xZn
xS buffer layer ", Applied physics letters 89,253503 (2006)].Because the defectives such as complex process, poor repeatability, cycle are long, these technologies are unwell to continuity, high production capacity, suitability for industrialized production cheaply.Some enterprises, for example the Solyndra of the U.S. and Nanosolar adopt the slurry printing technology to realize the large-scale production of CIGS hull cell, owing to production technology and Cost Problems, also are difficult to form competitive advantage on photovoltaic cell market.
Summary of the invention
The purpose of this invention is to provide an a kind of step DC pulse low-temperature and high-speed sputter and multi-source rapid thermal treatment and prepare CuIn
1-x Ga
x Se
2-y S
y The method of film, the method are compatible with the high transformation efficiency of the pure PVD explained hereafter of dry type, the industrialized technology of CIGS thin-film solar cells cheaply.
To achieve these goals, the present invention takes following technical scheme:
The preparation method of used for solar batteries compound film is characterized in that, passes through successively following steps under air-tight state:
The first step, the glass substrate behind the cleaning-drying is loaded onto substrate frame send into sputtering settling chamber, utilize direct current pulse power source sputter CIGS quaternary compound target, sputtering sedimentation thickness is the CuIn of 1.0 ~ 1.5 microns amorphous states or crystalline state nanometer on glass substrate
1-x Ga
x Se
2-y S
y Film, during sputtering sedimentation, the temperature of glass substrate is less than 127 ℃, and sputtering pressure is 0.8 ~ 1.0Pa, and the power density of target is 2.5 ~ 4.0W/cm
2, deposition rate is 25 ~ 60nm/min;
Glass substrate behind second step, the deposit film enters in the thermal field that resistance-type thermal source and halide-tungsten fluorescent lamp thermal source form and carries out annealing in process, H in the thermal field
2S+Ar or H
2The air pressure of Se+Ar mist maintains 20 ~ 60kPa, and the annealing time of film in resistance-type thermal source district is 3 ~ 6min, and the annealing time in halide-tungsten fluorescent lamp thermal source district is 1 ~ 3min, and annealing temperature maintains in 500 ~ 560 ℃ the scope;
The glass substrate that deposits film after the 3rd step, the annealing in process is at H
2Cool off rapidly H under the mist atmosphere of S+Ar
2The air pressure of S+Ar mist maintains 20 ~ 60kPa, and be 3 ~ 5min cooling time rapidly;
The 4th step, the cooled glass substrate of film that deposits is at H rapidly
2+ Ar mist is kept down and is carried out the process annealing processing, and annealing time is 15 ~ 20min, and annealing temperature is 150 ~ 200 ℃, H
2The air pressure of+Ar mist maintains 5 ~ 10kPa, after the process annealing processing finishes, and CuIn
1-x Ga
x Se
2-y S
y Film preparation is finished.
When sputter-deposited thin films, can pass into a little H
2Se or H
2S gas is used for stablizing sputter rate.
The present invention is at preparation CuIn
1-x Ga
x Se
2-y S
y What adopt during film is a continuous multi-chamber equipment and automation control system, realizes under the enclosed state film deposited the critical operations such as preparation, rapid thermal treatment, cooling and passivation anneal.
This beneficial effect of the invention is: the one step DC pulse sputter of (1) high power, process repeatability is strong, deposition rate is high, large tracts of land, homogenizing, with short production cycle, and sputtered atom has high energy under this pattern, density that can enhanced film; (2) low temperature depositing is conducive to reduce the equilibrium vapour pressure of Volatile Elements, suppresses the loss of the Volatile Elements such as Se, In, obtains desirable element proportioning, also helps in addition to adopt cheap glass as backing material, reduces the cost of raw material; (3) adopt different high power thermal source emission different-waveband spectrum to come the amorphous state that deposits or the CuIn of crystalline state nanometer
1-x Ga
x Se
2-y S
y Film carry out rapid thermal treatment can enhanced film to the absorption of spectrum, improve degree of crystallinity, suppress diffusion, segregation and the volatilization of element, make it form fast the CuIn of yellow copper structure
1-x Ga
x Se
2-y S
y Phase, although rapid heat-treatment temperature is very high, because annealing time is short, thereby thermal source can not produce destruction to glass substrate.
By means of testing such as X-ray diffractometer (XRD), scanning electron microscopy (SEM) and X-ray energy spectrometers (EDX) to the analysis of film crystal structure, microscopic appearance and composition as can be known: step DC pulse low-temperature and high-speed sputter of the present invention can be prepared the amorphous state of even thickness, homogeneous chemical composition and element at infinity proportioning or the CuIn of crystalline state nanometer
1-x Ga
x Se
2-y S
y Film through follow-up rapid thermal treatment, rapidly after cooling and the passivation process annealing, just can obtain good crystallinity, crystallite dimension is large, density is high chalcopyrite phase.Simultaneously the present invention adopts PVD technique, the advantage such as have that deposition velocity is fast, large tracts of land, underlayer temperature are low, be compatible with especially the pure PVD explained hereafter of the dry type high efficiency of continuity, high production capacity, high stability, the industrialized technology of CIGS thin-film solar cells cheaply, have good market prospects and commercial value.Be suitable for efficient CIGS hull cell chip and photovoltaic cell integrated package without cadmium of preparation in the industrialization.The method has that film forming speed is fast, even thickness, homogeneous chemical composition, crystal property is good and have concurrently good stability, repeatability by force, the advantage such as cost is low, be a kind of CuIn that has the industrialization practical prospect
1-x Ga
x Se
2-y S
y Method for manufacturing thin film is expected to solve a high efficiency, low cost CIGS hull cell quantity-produced engineering difficult problem.
Description of drawings
Fig. 1 is that the present invention prepares film sample device structure schematic diagram, and wherein 1 ~ 8 is the family of power and influence, and 9,11,14 is transition chamber thereof, and 10 is thin film deposition chamber, and 12 is rtp chambers, and 13 are cooling chamber rapidly, and 15 is the process annealing chamber.
Fig. 2 be step DC pulse sputter prepared (a) amorphous state in the embodiment of the invention 1,2,3, (b) crystalline state nanometer and (c) follow-up rapid thermal treatment, obtain the CuIn of yellow copper structure crystalline phase behind the backend process such as cooling rapidly
1-x Ga
x Se
2-y S
y The XRD collection of illustrative plates of film, wherein abscissa is 2 times of angle of diffraction 2Theta, ordinate is diffracted intensity Intensity.
Fig. 3 is the amorphous Cu In of step DC pulse sputter preparation in the embodiment of the invention (1)
0.74Ga
0.26Se
1.95The surface of film and profile scanning electromicroscopic photograph.
Fig. 4 is the crystalline state nanometer CuIn of step DC pulse sputter preparation in the embodiment of the invention (2)
0.78Ga
0.24Se
1.91S
0.2The surface of film and profile scanning electromicroscopic photograph.
Fig. 5 is that the thin-film material of the crystalline state nanometer of step DC pulse sputter preparation among the embodiment (3) is through rapid thermal treatment, the CuIn behind the backend process such as cooling rapidly
0.74Ga
0.26Se
1.87S
0.2The surface of film and profile scanning electromicroscopic photograph.
Embodiment
The present invention is further illustrated in connection with accompanying drawing for following examples.
Embodiment 1:
Preparation thickness is the CuIn of the chalocopyrite structure phase of 1000nm under the sputtering power of 3kW
1-x Ga
x Se
2-y S
y Film.As shown in Figure 1, the present invention is at preparation CuIn
1-x Ga
x Se
2-y S
y What adopt during film is a continuous multi-chamber equipment and automation control system, realizes under the enclosed state film being deposited the operations such as preparation, rapid thermal treatment, cooling and passivation anneal, and concrete steps are as follows:
One, the glass substrate of the glass substrate behind the cleaning-drying or plating Mo is loaded onto substrate frame, in transition chamber thereof 9, pass into balanced gas Ar to atmospheric pressure 1.0 * 10
5Pa opens the family of power and influence 1, and substrate frame enters transition chamber thereof 9 under the effect of drive system, close the family of power and influence 1, and transition chamber thereof 9 is pumped to 1.0 * 10
-5Pass into balanced gas Ar to 0.8Pa behind the Pa,
Two, open the family of power and influence 2, treat that substrate frame enters thin film deposition chamber 10, close the family of power and influence 2, utilize direct current pulse power source sputter CIGS quaternary compound target, the sputter operating pressure is 0.8Pa, substrate frame is 10mm/min in the pace of deposition chamber, and the temperature of glass substrate is less than 127 ℃, and the power density of target is 2.5 ~ 4.0W/cm
2, deposition rate is 25 ~ 60nm/min,
Three, the transition chamber thereof 11 to high vacuum passes into balanced gas Ar gas to 0.8Pa, opens the family of power and influence 3, after substrate frame enters transition chamber thereof 11, closes the family of power and influence 3,
Four, the air pressure for the treatment of transition chamber thereof 11 rises to 40kPa, opens the family of power and influence 4, treats that substrate frame enters rapid thermal processing chamber 12, closes the family of power and influence 4, the H in the rtp chambers 12
2The air pressure of S+Ar mist maintains 40kPa, and substrate frame is 5min in the time in resistance heat source region, and the annealing time in tungsten halide fluorescent tube thermal source district is 2min,
Five, open the family of power and influence 5, allow substrate frame transfer to fast and be connected with H
2The rapidly cooling chamber 13 of the mist of S+Ar closes the family of power and influence 5, and the air pressure of cooling chamber 13 maintains 40kPa rapidly,
Six, the transition chamber thereof 14 to high vacuum passes into balanced gas Ar gas to 40kPa, opens the family of power and influence 6, after substrate frame enters transition chamber thereof 14, closes the family of power and influence 6,
Seven, transition chamber thereof 14 is bled, treat that air pressure is down to 10kPa, open the family of power and influence 7, after substrate frame enters process annealing chamber 15, close the family of power and influence 7, behind 200 ℃ of lower annealing 15min, open the family of power and influence 8, CuIn
1-x Ga
x Se
2-y S
y Film preparation is finished, and takes out substrate or allows substrate enter next process.
Prepare 1000nm chalocopyrite structure phase CuIn
1-x Ga
x Se
2-y S
y The micro-structural of film, surface topography and crystallographic characteristics are as shown in Figure 3.
Embodiment 2:
Preparation thickness is the CuIn of the yellow copper structure phase of 1500nm under the sputtering power of 6kW
1-x Ga
x Se
2-y S
y Film.
Adopt the step identical with embodiment 1, substrate is 15mm/min in the pace of deposition chamber, passes into the H of a little during sputter
2S.Different sputtering powers are to CuIn
1-x Ga
x Se
2-y S
y The micro-structural of film has obvious impact, and surface topography and crystallographic characteristics also change thereupon, as shown in Figure 4.
Embodiment 3:
Preparation thickness is the CuIn of the yellow copper structure phase of 1000nm under the sputtering power of 6kW
1-x Ga
x Se
2-y S
y Film.
Adopt the step identical with embodiment 1, substrate is 20mm/min in the pace of deposition chamber, passes into the H of a little during sputter
2S.Different substrate paces are to CuIn
1-x Ga
x Se
2-y S
y The thickness of film has obvious impact, as shown in Figure 5.
Above-described embodiment only is preferred implementation of the present invention; describe technical conceive of the present invention and essential implementation in detail; be not to be that protection scope of the present invention is limited; all any simple modification that Spirit Essence is done according to the present invention and equivalent structure transformation or modification all should be encompassed within protection scope of the present invention.
Claims (2)
1. the preparation method of used for solar batteries compound film is characterized in that, passes through successively following steps under air-tight state:
The first step, the glass substrate behind the cleaning-drying is loaded onto substrate frame send into sputtering settling chamber, utilize direct current pulse power source sputter CIGS quaternary compound target, sputtering sedimentation thickness is the CuIn of 1.0～1.5 microns amorphous states or crystalline state nanometer on glass substrate
1-x Ga
x Se
2-y S
y Film, wherein, 0＜x＜1,0≤y＜2, during sputtering sedimentation, the temperature of glass substrate is less than 127 ℃, and sputtering pressure is 0.8～1.0Pa, and the power density of target is 2.5～4.0W/cm
2, deposition rate is 25～60nm/min;
Glass substrate behind second step, the deposit film enters in the thermal field that resistance-type thermal source and halide-tungsten fluorescent lamp thermal source form and carries out annealing in process, H in the thermal field
2S+Ar or H
2The air pressure of Se+Ar mist maintains 20～60kPa, and the annealing time of film in resistance-type thermal source district is 3～6min, and the annealing time in halide-tungsten fluorescent lamp thermal source district is 1～3min, and annealing temperature maintains in 500～560 ℃ the scope;
The glass substrate that deposits film after the 3rd step, the annealing in process is at H
2Cool off rapidly H under the mist atmosphere of S+Ar
2The air pressure of S+Ar mist maintains 20～60kPa, and be 3～5min cooling time rapidly;
The 4th step, the cooled glass substrate of film that deposits is at H rapidly
2Carry out process annealing under the+Ar mist atmosphere and process, annealing time is 15～20min, and annealing temperature is 150～200 ℃, H
2The air pressure of+Ar mist maintains 5～10kPa, after the process annealing processing finishes, and CuIn
1-x Ga
x Se
2-y S
y Film preparation is finished.
2. the preparation method of used for solar batteries compound film according to claim 1 is characterized in that: during sputter-deposited thin films, pass into H
2Se or H
2S gas is used for stablizing sputter rate.
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| WO2013129044A1 (en) * | 2012-02-27 | 2013-09-06 | 株式会社日本マイクロニクス | Method for fabricating alloy for cigs solar cell |
| CN105506549A (en) * | 2015-12-30 | 2016-04-20 | 中国建材国际工程集团有限公司 | Method for preparing niobium pentoxide thin film through pulse direct current sputtering |
| CN107620117A (en) * | 2017-09-04 | 2018-01-23 | 苏州云舒新材料科技有限公司 | A kind of preparation method of anti-corrosion multilayered film material |
| CN110487834A (en) * | 2019-07-24 | 2019-11-22 | 北京科技大学 | It is a kind of for measuring the sample frame and its application method of Surface Segregation volatile quantity |
| CN114005905B (en) * | 2021-10-22 | 2023-10-17 | 成都中建材光电材料有限公司 | Continuous production equipment of cadmium telluride solar cell |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101330110A (en) * | 2008-08-01 | 2008-12-24 | 中南大学 | Light absorption layer material for film solar battery and preparation method thereof |
| CN101771100A (en) * | 2008-12-30 | 2010-07-07 | 中国电子科技集团公司第十八研究所 | Method for preparing light absorption layer for CuInGaSe thin film solar cell |
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| US20020189665A1 (en) * | 2000-04-10 | 2002-12-19 | Davis, Joseph & Negley | Preparation of CIGS-based solar cells using a buffered electrodeposition bath |
| JP2006013028A (en) * | 2004-06-24 | 2006-01-12 | National Institute Of Advanced Industrial & Technology | Compound solar cell and its manufacturing method |
| US20100055826A1 (en) * | 2008-08-26 | 2010-03-04 | General Electric Company | Methods of Fabrication of Solar Cells Using High Power Pulsed Magnetron Sputtering |
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| CN101330110A (en) * | 2008-08-01 | 2008-12-24 | 中南大学 | Light absorption layer material for film solar battery and preparation method thereof |
| CN101771100A (en) * | 2008-12-30 | 2010-07-07 | 中国电子科技集团公司第十八研究所 | Method for preparing light absorption layer for CuInGaSe thin film solar cell |
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