EP2171760A1 - Procédé de formation d'un contact arrière non-redresseur dans une cellule solaire cdte/cds à films minces - Google Patents

Procédé de formation d'un contact arrière non-redresseur dans une cellule solaire cdte/cds à films minces

Info

Publication number
EP2171760A1
EP2171760A1 EP07805681A EP07805681A EP2171760A1 EP 2171760 A1 EP2171760 A1 EP 2171760A1 EP 07805681 A EP07805681 A EP 07805681A EP 07805681 A EP07805681 A EP 07805681A EP 2171760 A1 EP2171760 A1 EP 2171760A1
Authority
EP
European Patent Office
Prior art keywords
layer
cdte
deposited
contact
solar cell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07805681A
Other languages
German (de)
English (en)
Inventor
Nicola Romeo
Alessio Bosio
Alessandro Romeo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solar Systems and Equipments SRL
Original Assignee
Solar Systems and Equipments SRL
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Solar Systems and Equipments SRL filed Critical Solar Systems and Equipments SRL
Publication of EP2171760A1 publication Critical patent/EP2171760A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0224—Electrodes
    • H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
    • H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to the field of the solar cells technology and more particularly concerns a process for the large-scale production of CdTe/CdS thin film solar cells.
  • the invention relates to an improvement to this process relating to the formation of a non-rectifying back-contact.
  • CdTe/CdS thin-film solar cells for sake of simplicity, it is to be understood that this term includes all the salt mixtures comprised in the formula
  • a typical configuration of a CdTe/CdS solar cell has a film sequence of the multi-layer arrangement comprising a transparent glass substrate carrying a transparent conductive oxide (TCO) film, a CdS film representing the n-semiconductor, a CdTe film representing the p-semiconductor and a metallic back- contact.
  • TCO transparent conductive oxide
  • the commercial float glass may be used as a transparent substrate, but, in spite of its low cost, special glasses are often preferred to avoid drawbacks of the float glass, in particular Na diffusion into TCO film.
  • the most common TCO is In 2 O 3 containing 10% of Sn (ITO) .
  • ITO Sn
  • This material has a very low resistivity on the order of 3x10 "4 ⁇ cm and high transparency (>85%) in the visible region of the solar spectrum.
  • this material is made by sputtering and the ITO target after several runs forms some nodules which contain an In excess and a discharge between nodules can happen during sputtering which can damage the film.
  • Another material which is commonly used is fluorine doped SnO2 which however exhibits a higher resistivity close to 10 '3 ⁇ cm and as a consequence a 1 ⁇ m thick layer is needed in order for the sheet resistance to be around 10 ⁇ / sguare -
  • a high TCO thickness decreases the transparency and then the photocurrent of the solar cell.
  • Cd 2 SnO 4 has also been proposed by the NREL group (X. Wu et al . , Thin Solid Films, 286 (1996) 274-276) .
  • this material has some drawbacks since the target is made up of a mixture of CdO and SnO 2 and, being CdO highly hygroscopic, the stability of the target may result to be unsatisfactory.
  • WO03/032406 in the name of the same applicant, discloses a process for large-scale production of CdTe/CdS thin-film solar cells in which the deposition of the TCO film is conducted in such a way that a film of very low resistivity can be deposited without formation of any metal nodules on the target and allowing the use of a inexpensive substrate.
  • the TCO layer is formed by sputtering in an inert gas athmosphere containing hydrogen, or an argon-hydrogen mixture, and a gaseous fluoralkyle compound, e.g. CHF 3 . In this way the TCO is doped with fluorine.
  • the CdS film or layer is deposited by sputtering or Close-Spaced Sublimation (CSS) from CdS granulate material.
  • CCS Close-Spaced Sublimation
  • This last technique allows the preparation of thin films at a substrate temperature much higher than that used in simple vacuum evaporation or sputtering, because substrate and evaporation source are put very close to each other at a distance of 2-6 mm and the deposition is carried out in the presence of an inert gas such as Ar, He or N 2 at a pressure of lO ⁇ -lOO mbar.
  • An important characteristic of the close-spaced sublimation is a very high growth rate up to 10 ⁇ m/min, which is suitable for large-scale production.
  • CdTe film or layer is deposited on top of CdS film by close-spaced sublimation (CSS) at a substrate temperature of 480-520 0 C.
  • CdTe granulate is generally used as a source of CdTe which is evaporated from an open crucible.
  • the electric back contact on the CdTe film is generally obtained by deposition of a film of a highly p- dopant metal for CdTe such as copper, e.g. in graphite contacts, which, upon annealing, can diffuse in the CdTe film.
  • a Sb 2 Te 3 film as a back-contact in a CdTe/CdS solar cell has been disclosed by the same inventors (N. Romeo et al . , A highly efficient and stable CdTe/CdS thin film solar cell, Solar Energy Materials & Solar Cells, 58 (1999), 209-218).
  • the back-contact in the CdTe/Cd thin film solar cells plays a very important role in achieving their efficiency.
  • a rectifying contact i.e. a metal- semiconductor contact which does not follow the Ohm law, that is to say there is no linear relationship between voltage and current, gives rise to a "roll over" (intersection in the first quadrant of the dark condition/lighting condition J-V characteristic curves) in the J-V characteristic, i.e. in the diagram showing the behaviour of the current density as a function of the voltage, which considerably decreases the "Fill factor", and consequently the cell efficiency (D. Bonnet and P.V. Meyers, J. Mater. Res. 13 (1998) 2740-2753)).
  • CdTe has an high electronic affinity ( ⁇ ) and an high prohibited band (1,5 eV) , the majority of the metals forms a Schottky barrier limiting the hole transport in the p-type CdTe.
  • N-P etching a chemical etching is carried out in a phosphoric/nitric acid bath (the so called N-P etching) on CdTe to create a Te-rich surface forming the Cu x Te (1 ⁇ X ⁇ 2) compound with Cu.
  • This compound by interdiffusion, forms a low resistance close contact with CdTe, but its stability is limited to the Cu x Te phase in which 1 ⁇ X ⁇ 1.4, whereas the Cu 2 Te phase is not a stable compound and therefore releases Cu which, being a fast diffusive element, penetrates the CdTe in particular through the grain edges, this possibly resulting in the cell degradation.
  • Cu is a positive ion
  • its diffusion within CdTe depends on the internal electric field of the junction which, in turn, depends on the fact that the cell is undergone to an external bias or illumination. The device degradation is clearly faster when it is heated to a temperature higher than 6O 0 C or is subjected to high lighting (>1 sun) .
  • the solar cells using this type of back-contact for example the solar cells produced by First Solar Inc. (USA), use a Cu thickness of 2 ntn deposited after CdTe is subjected to a chemical etching (C. R. Corwine et al., Sites, Sol. Energy Mat. & Solar Cells 82 (2004) 481-489) .
  • a chemical etching C. R. Corwine et al., Sites, Sol. Energy Mat. & Solar Cells 82 (2004) 481-489.
  • new back- contact materials namely Sb 2 Te 3 and As 2 Te 3
  • WO03/032406 patent application in the name of the same applicant as an alternative to the use of Cu.
  • Sb 2 Te 3 is a material with a low gap (0.3 eV) , is of the p-type and has a resistivity close to 10 "4 ⁇ cm.
  • deposited at a substrate temperature of « 300 0 C it forms a close contact with CdTe and can allow efficiencies close to 16% to be reached.
  • This type of contact has proven very stable even with a device illumination ' of 10- 20 suns and temperatures higher than 100 0 C.
  • the presence of "roll-over" in the J-V characteristic curve has been observed, this being an indication that some rectification, even if not very marked, is present in the back-contact .
  • a particular object of the present invention is to provide a method to form an ohmic back-contact of CdS/CdTe thin film solar cells which allows the stability of the cell to be ensured even under high illumination and temperature conditions and therefore to improve, or at least maintain unchanged, the cell efficiency with respect to the prior art .
  • Another object of the present invention is to provide a method to form a back-contact of thin film solar cells of the above mentioned type wherein, even if Cu is used in the formation of the back-contact, the control of the thickness of the deposited Cu film does not affect the cell stability in the same critical way as occurs in the process according to the prior art.
  • a further object of the present invention is to provide a method to form a thin film solar cell back- contact of the above mentioned type wherein a treatment of chemical etching of the CdTe film is not necessary before the back-contact is formed.
  • Still another object of the present invention is to provide a thin film solar cell wherein the back-contact is completely not-rectifying in such a way to ensure an high stability even under high illumination and temperature conditions, and thus improve their efficiency or, at least, maintain it unchanged with respect to the known similar solar cells.
  • a method to form a ohmic contact which maintains the photovoltaic device stable in the time without changing the way the CdTe film is treated with respect to the process disclosed in WO 03/032406 and therefore without using any kind of etching of the CdTe film surface.
  • This new way of contacting the p-type CdTe consists in the sequential deposition of, first, an As 2 Te 3 film and then a Cu film by sputtering, but the true contact is provided neither by As 2 Te 3 nor by Cu, but through the Cu x Te
  • the method according to the invention provides a way to form a non-rectifying ohmic back-contact of the CdTe film consisting in forming a Cu x Te (with l ⁇ x ⁇ 1.4) thereon, which otherwise could not be formable due to the reactivity between Cu and Te.
  • the final result will be, in any case, the separation of several phases, including the Cu 2 Te phase that does not give an ohmic contact and is unstable as it releases Cu atoms .
  • the stable phase between Cu and Te is that with a Cu content comprised between 1 and 1.4, i.e. the phase which, under energetically favorable conditions, is formed by sputtering deposition of a Cu film on a As 2 Te 3 film, which in turn is deposited on the surface of a CdTe film as treated in the usual way.
  • the maximum amount of Cu that it is useful to deposit on the As 2 Te 3 layer must ensure at the same time a good non-rectifying contact and a stable system and therefore must allow the formation of Cu x Te (with l ⁇ x ⁇ 1.4) either without leaving free Cu or avoiding the Cu 2 Te formation, which would cause the atomic Cu diffusion through the CdTe film and as a consequence the p-n function degradation.
  • the Cu x Te (with l ⁇ x ⁇ 1.4) compound can be formed in a native way either directly, by carrying out the Cu film deposition on As 2 Te 3 at a temperature comprised between 15O 0 C and 250° C, or by depositing the As 2 Te 3 at low temperature ( ⁇ 100°C) and then heating the layer assembly at a temperature comprised between 150° and 250° C.
  • a particularly preferred temperature in both cases is at least 18O 0 C. Even if it is not essential to the end of the Cu x Te (with l ⁇ x ⁇ 1.4) compound formation, it can be helpful to maintain the thus formed back-contact at this temperature for at least 1 minute.
  • advantage is taken of the particular interaction between these materials during the sputtering deposition of the Cu film on As 2 Te 3 .
  • the atoms reaching the substrate can have an energy of some tens of eV (with thermal evaporation it can be as high as some tenths of eV) .
  • the As 2 Te 3 film surface starts to become thermally unstable (it starts to reevaporate at 250 0 C) .
  • the Cu atoms have a large energy excess that is partly lost through surface impacts and partly used to break the As 2 Te 3 molecule and take the place of the As to form a more stable compound (that is to say with a higher formation energy) at that temperature, i.e. Cu x Te (with l ⁇ x ⁇ 1.4).
  • figure 1 schematically shows the structure of a CdTe/CdS thin film solar cell with the back-contact according to the present invention
  • figure 2 shows the J-V characteristic curve for two solar cells whose back-contact has been deposited according to the method of the invention, but at two different deposition temperatures (namely: ambient temperature, curve a; 200 0 C, curve b)
  • figure 3 is the X-ray analysis of an As 2 Te 3 film deposited on glass at a substrate of 200 0 C with (curve b) and without (curve a) a layer of 20 ran of Cu deposited thereon at the same temperature
  • figure 4 is the X-ray analysis of an As 2 Te 3 film deposited on glass at a substrate temperature of 200 0 C with (curve b) and without (curve a) a Cu layer of 50 nm deposited thereon at the same temperature.
  • the fore transparent contact by sputtering on the glass comprising two layers: the first layer is ITO (indium-tin oxide) which ensures the condudibility and the second layer is ZnO which operates as a buffer layer or as a barrier against the possible diffusion of impurities in the layers which will be deposited in the next steps. Both layers as a whole must ensure a transparency not lower than 85% in the visible wave length region.
  • the CdS film by reactive sputtering (RF-magnetron) under Ar + %5 CHF3 environment, the CdS being a n-type semiconductor providing the first part of the junction.. d.
  • the CdTe being a p-type semiconductor, provides the second part of the junction and ensure the complete absorption of the visible light.
  • Thermal treatment at 400 0 C of the whole previously prepared assembly the CdTe film surface is exposed in a Ar+Freon atmosphere for not more than 5 minutes and then, keeping the temperature at 400 0 C for other 5 minutes, vacuum conditions are established thus allowing the volatile compounds, which could have been formed during the first part, to reevaporate from the CdTe film surface.
  • said back-contact by sputtering, said back-contact according to the invention comprising two layers: the first one, As 2 Te 3 , and the second one, Cu: on the back-contact formed in this way a Mo film is then deposited to ensure a proper sheet resistance.
  • the schematic structure of the solar cell thus produced is shown in figure 1.
  • the As 2 Te 3 layer is deposited directly on the CdTe surface, without subjecting the latter to any chemical etching, whereas the Cu layer is deposited at a substrate temperature of around 200 0 C , preferably 18O 0 C.
  • As 2 Te 3 is a p-type semiconductor with prohibited energy band of 0.6 eV and with a resistivity of around 10 "3 ⁇ cm.
  • the As 2 Te 3 thickness can vary between 100 and 300 nm, whereas the Cu thickness can vary between 2 and 20 nm.
  • the way of forming a non-rectifying contact on p-type CdTe looks like to that commonly used in which a Te-rich surface is fist created by a chemical etching of CdTe and then Cu is deposited to form Cu x Te.
  • the substantial difference consists in that, in the method of the invention, any CdTe etching is not carried out and that an up to ten times higher amount of Cu can be used. This makes less critical the risk of formation of the rectifying contact thereby allowing a greater stability of the contact .
  • the back-contact has proven to be a good contact for the CdTe/Cds thin solar film solar cell as shown by the J-V characteristic (figure 2, curve b) .
  • the contact is non-rectifying and from the curve inclination and fill factor it can be deduced that there is not any series resistance effect. Therefore, the contact is non -rectifying and is of low resistance.
  • Stability tests were carried out by subjecting the device, in open circuit condition, to "light soaking", i.e. an exposition to an intense illumination, up to 10 suns and temperature up to 100 0 C for 8 hours without noting any significant degradation of the photovoltaic parameters of the device.
  • the preferred deposition technique for both layers of As 2 Te 3 and Cu is by sputtering, they may be also deposited by thermal evaporation, by electronic gun evaporation or electrodeposition.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Electromagnetism (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Photovoltaic Devices (AREA)

Abstract

Procédé de formation d'un contact ohmique non-redresseur sur un film mince en CdTe à semi-conducteurs de type p comprenant les étapes consistant à déposer une couche de As2Te3 sur la couche de CdTe à une température de substrat comprise entre la température ambiante et 200° C; déposer une couche de Cu sur la couche de As2Te3; amener au moins la couche de Cu déposée à une température comprise entre 150° et 250° C. Le procédé est utilisé pour former un contact arrière stable sur des cellules solaires à films minces en CdTe/CdS.
EP07805681A 2007-06-28 2007-06-28 Procédé de formation d'un contact arrière non-redresseur dans une cellule solaire cdte/cds à films minces Withdrawn EP2171760A1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IT2007/000469 WO2009001389A1 (fr) 2007-06-28 2007-06-28 Procédé de formation d'un contact arrière non-redresseur dans une cellule solaire cdte/cds à films minces

Publications (1)

Publication Number Publication Date
EP2171760A1 true EP2171760A1 (fr) 2010-04-07

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EP07805681A Withdrawn EP2171760A1 (fr) 2007-06-28 2007-06-28 Procédé de formation d'un contact arrière non-redresseur dans une cellule solaire cdte/cds à films minces

Country Status (6)

Country Link
EP (1) EP2171760A1 (fr)
JP (1) JP5042363B2 (fr)
CN (1) CN101816073B (fr)
AU (1) AU2007355717A1 (fr)
CA (1) CA2691506A1 (fr)
WO (1) WO2009001389A1 (fr)

Families Citing this family (6)

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Publication number Priority date Publication date Assignee Title
IT1396166B1 (it) * 2009-10-13 2012-11-16 Arendi S P A Metodo di attivazione di film sottili di cdte per applicazioni in celle solari a film sottili del tipo cdte/cds.
DE102010004996B4 (de) * 2010-01-19 2014-03-06 Institut Für Photonische Technologien E.V. Verfahren zur Herstellung einer Cadmiumtellurid-Solarzelle
US20110265874A1 (en) * 2010-04-29 2011-11-03 Primestar Solar, Inc. Cadmium sulfide layers for use in cadmium telluride based thin film photovoltaic devices and methods of their manufacture
WO2011137216A2 (fr) * 2010-04-30 2011-11-03 Dow Global Technologies Llc Procédé de fabrication de cellules photovoltaïques à base de chalcogénure
JP5508966B2 (ja) * 2010-07-07 2014-06-04 株式会社豊田中央研究所 光電変換素子
US9461186B2 (en) * 2010-07-15 2016-10-04 First Solar, Inc. Back contact for a photovoltaic module

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US4650921A (en) * 1985-10-24 1987-03-17 Atlantic Richfield Company Thin film cadmium telluride solar cell
US5557146A (en) * 1993-07-14 1996-09-17 University Of South Florida Ohmic contact using binder paste with semiconductor material dispersed therein
CN1055792C (zh) * 1995-07-20 2000-08-23 四川联合大学 具有过渡层的碲化镉太阳电池
DE19703615A1 (de) * 1997-01-31 1998-08-06 Siemens Ag Optoelektronisches Halbleiterbauelement
CN1214469C (zh) * 2000-04-06 2005-08-10 阿克佐诺贝尔股份有限公司 制造光伏箔的方法
EP1433207B8 (fr) 2001-10-05 2009-10-07 SOLAR SYSTEMS & EQUIOMENTS S.R.L. Procede permettant la production a grande echelle de photopiles en couches minces de cdte/cds
ITLU20050002A1 (it) * 2005-02-08 2006-08-09 Solar Systems & Equipments Srl UN NUOVO PROCESSO PER IL TRATTAMENTO IN AMBIENTE DI CLORO DELLE CELLE SOLARI A FILM SOTTILI DI CdTe/CdS senza l'uso di CdC12.

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Also Published As

Publication number Publication date
AU2007355717A1 (en) 2008-12-31
JP5042363B2 (ja) 2012-10-03
CN101816073B (zh) 2012-02-01
JP2010531547A (ja) 2010-09-24
CA2691506A1 (fr) 2008-12-31
WO2009001389A1 (fr) 2008-12-31
CN101816073A (zh) 2010-08-25

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