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WO2007070880A1 - Traitements post-déposition de pellicules minces à base de cu(in-ga)se2 déposé par voie galvanique - Google Patents

Traitements post-déposition de pellicules minces à base de cu(in-ga)se2 déposé par voie galvanique Download PDF

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WO2007070880A1
WO2007070880A1 PCT/US2006/062189 US2006062189W WO2007070880A1 WO 2007070880 A1 WO2007070880 A1 WO 2007070880A1 US 2006062189 W US2006062189 W US 2006062189W WO 2007070880 A1 WO2007070880 A1 WO 2007070880A1
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films
electrode
substrate
film
creating
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Kevin D. Dobson
Estela M. Calixto
Brian E. Mccandless
Robert W. Birkmire
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University of Delaware
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F10/00—Individual photovoltaic cells, e.g. solar cells
    • H10F10/10—Individual photovoltaic cells, e.g. solar cells having potential barriers
    • H10F10/16—Photovoltaic cells having only PN heterojunction potential barriers
    • H10F10/167—Photovoltaic cells having only PN heterojunction potential barriers comprising Group I-III-VI materials, e.g. CdS/CuInSe2 [CIS] heterojunction photovoltaic cells
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F71/00—Manufacture or treatment of devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F77/00—Constructional details of devices covered by this subclass
    • H10F77/10—Semiconductor bodies
    • H10F77/12—Active materials
    • H10F77/126—Active materials comprising only Group I-III-VI chalcopyrite materials, e.g. CuInSe2, CuGaSe2 or CuInGaSe2 [CIGS]
    • 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
    • Y02E10/541—CuInSe2 material PV cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to improved photovoltaic devices and methods for their manufacture. Specifically, the present invention includes improved photovoltaic solar cells made using single, buffered bath electrodeposition of copper, indium, gallium and selenium.
  • As-deposited films are generally of low crystallinity and a post deposition anneal, often in a selenium-containing atmosphere, is required to drive formation reactions and film recrystallization while maintaining or controlling film chemistry.
  • the present invention provides methods for the electrodeposition of Cu(In 1 Ga)Se 2 films from single buffered aqueous baths and photovoltaic devices derived therefrom.
  • deposition conditions including bath concentrations, deposition potential and the nature of the electrode surface, resulted in production of as-deposited films with smooth morphology and good control of composition.
  • Cu(In 1 Ga)Se 2 films are produced from a vacuum-free, single-step electrodeposition process wherein the buffered bath and careful control of concentrations allowed the growth of films containing up to 8% Ga. Docket No. 51281-00025
  • thin films made accordance with the teachings of the present invention had reduced cracking resulting from growing the thin films Se-poor, while the formation of secondary Cu x Se y phases was attenuated by pretreatment of the Mo electrode by a short deposition process prior to growing the Cu(In, Ga)Se 2 films.
  • the present invention also provides an electrodeposition bath useful for making photovoltaic devices comprising a buffered aqueous solution having from approximately 2.50 imM to approximately 4.00 inM CuCI 2 .2H 2 O, from approximately 2.20 mM to approximately 4.80 mM InCI 3 , from approximately 3.50 mM to approximately 6.00 mM GaCI 3 , from approximately 4.20 mM to approximately 8.0 mM H 2 SeO 3 , and from approximately 0.20M to approximately 0.30 M LiCI; and wherein said electrodeposition bath has a pH from approximately 1.5 to 3.0.
  • an electrodeposition bath useful for making photovoltaic devices comprising a buffered aqueous solution having from approximately 2.56 mM to approximately 3.55 mM CuCI 2 .2H 2 O, from approximately 2.40 mM to approximately 4.55 mM InCI 3 , from approximately 3.73 mM to approximately 5.70 mM GaCI 3 , from approximately 4.47 mM to approximately 7.8 mM H 2 SeO 3 , and approximately 0.24 M LiCI; and wherein said electrodeposition bath has a pH from approximately 1.8 to 2.5.
  • the electrodeposition bath useful for making photovoltaic devices comprises a buffered aqueous solution having approximately 3.55 mM CuCl 2 -2H 2 O, approximately 4.55 mM InCI 3 , approximately 3.73 mM GaCI 3 , approximately 7.8 mM H 2 SeO 3 , and approximately 0.24 M LiCI; and wherein said electrodeposition bath has a pH is approximately 2.5.
  • Still another electrodeposition bath useful for making photovoltaic devices of the present invention comprises a buffered aqueous solution having approximately 2.56 mM CuCI 2 .2H 2 O, approximately 2.40 mM InCI 3 , approximately 5.70 mM GaCI 3 , approximately 4.47 mM H 2 SeO 3 , and approximately 0.24 M LiCI; and wherein said electrodeposition bath has a pH is approximately 2.5.
  • Yet another electrodeposition bath made in accordance with the teachings of the present invention has a H 2 SeO 3 concentration of approximately 5.46 mM.
  • the thin film photovoltaic devices of the present invention have improved film morphology and thus permit processing of devices in accordance the teachings herein resulting in improved overall performance. Docket No. 51281-00025
  • a method for creating an electrodeposited film upon a substrate comprising the steps of: providing a buffered aqueous solution containing Cu, In and Se; providing an electrodeposition set-up in the buffered aqueous solution; placing the substrate in the buffered aqueous solution and performing deposition upon the substrate via the electrode electrodeposition set-up; and performing selenization upon the substrate in H 2 Se/Ar.
  • the step of performing selenization upon the substrate in H 2 Se/Ar is performed at 450 0 C for 20 minutes in 0.35% H 2 Se/Ar.
  • the method further comprises the step of performing selenization upon the substrate in Se-vapor after selenization of the substrate in H 2 Se/Ar. In another embodiment, the method further comprises the step of performing selenization upon the substrate at 500 0 C for 30 minutes in Se-vapor.
  • a method for creating an electrodeposited film upon a substrate comprising the steps of: providing a buffered aqueous solution containing Cu, In and Se; providing an electrodeposition set-up in the buffered aqueous solution; placing the substrate in the buffered aqueous solution and performing deposition upon the substrate via the electrode electrodeposition set-up; and performing selenization upon the substrate in Se-vapor.
  • the step of performing selenization upon the substrate in Se-vapor is performed at 500°C for 30 minutes in 0.35% H 2 Se/Ar.
  • a method for creating an electrodeposited film upon a substrate comprising the steps of: providing a buffered aqueous solution containing Cu, In and Se; providing an electrodeposition set-up in the buffered aqueous solution; placing the substrate in the buffered aqueous solution and performing deposition upon the substrate via the electrode electrodeposition set-up; and performing sulfurization upon the substrate in H 2 S/Ar.
  • the step of performing sulfurization upon the substrate in H 2 S/Ar is performed at 550 0 C for 30 minutes in H 2 S/Ar.
  • the buffered aqueous solution containing Cu, In and Se comprises CuCI 2 , InCI 3 and H 2 SeO 3 .
  • the buffered aqueous solution containing Cu, In and Se further comprises Ga.
  • the buffered aqueous solution containing Cu, In, Ga and Se comprises CuCI 2 , InCI 3 , GaCI 3 and H 2 SeO 3 .
  • the electrodeposition set-up is a three-electrode electrodeposition set-up comprising a Mo electrode, a Pt mesh counter-electrode and a saturated calomel electrode reference electrode. Docket No. 51281-00025
  • a photovoltaic device produced according to the claimed methods wherein the photovoltaic device has a conversion efficiency of at least 19%.
  • Figure 1 SEM images of powdery Culno.83Gao.33Se2.25 film deposited from buffered bath A onto a non-treated Mo electrode at -0.6 V for 60 minutes, (a) front view and (b) cross-section.
  • Figure 4 Composition of Cu(In 1 Ga)Se 2 films deposited from buffered bath B onto non-treated Mo electrodes at -0.6 V for 70 minutes with varying [In 3+ ]. Lines are included to aid the eye. Dashed line indicates standard bath [In 3+ ].
  • Figure 5 Composition of Cu(In 1 Ga)Se 2 films deposited from buffered bath B onto non-treated Mo electrodes at -0.6 V for 70 minutes with varying [Ga 3+ ]. Lines are included to aid the eye. Dashed line indicates standard bath [Ga 3+ ].
  • Figure 6 Composition of Cu(In 1 Ga)Se 2 films deposited at various potentials from buffered bath B onto non-treated Mo electrodes for 70 minutes. Lines are included to aid the eye.
  • Figure 8 SEM images of Cu(In 1 Ga)Se 2 films from Figure 6.
  • Figure 9 SEM images of Cu(In 1 Ga)Se 2 film deposited from buffered bath B at - 0.5V for 20 minutes followed by -0.6V for 50 minutes onto a Mo electrode pretreated with a 1 minute deposition from the bath at -0.5 V, (a) front view and (b) cross-section.
  • FIG. 10 XRD patterns of an ED Cu(In 1 Ga)Se 2 film deposited from buffered bath B at -0.5V for 20 minutes followed by -0.6V for 50 minutes onto a Mo electrode pretreated with a 1 minute deposition at -0.5 V from the bath (a) as-deposited and (b) after selenization in H 2 Se/Ar at 450°C for 20 min and (c) after selenization in Se vapor at 500°C for 20 minutes. Inset shows the 112 reflections on expanded scale. Docket No. 51281-00025
  • Figure 11 GIXRD patterns of Cu(In 1 Ga)Se 2 film deposited from buffered bath B at -0.5V for 20 minutes followed by -0.6V for 50 minutes onto a Mo electrode pretreated with a 1 minute deposition at -0.5 V from the bath at incidence angles of (a) 5°, (b) 2°, (c) 1°, (d) 0.5°. Inset shows the 112 reflections on expanded scale.
  • Figure 14 SEM image of an ED CuInSe 2 film after selenization in H 2 Se/Ar at 500 0 C for 30 mins.
  • Figure 15 SEM image of an ED Cu(In 5 Ga)Se 2 film, deposited on a pre-treated Mo electrode, after selenization in H 2 Se/Ar at 450°C for 20 mins.
  • Figure 16 Typical XRD patterns of ED CuInSe 2 films (a) as-deposited and (b) after selenization process in H 2 Se/Ar at 500°C for 30 mins.
  • Figures 17 Typical XRD patterns of ED Cu(In 1 Ga)Se 2 films (a) as-deposited and (b) after selenization at 450 0 C for 20 mins.
  • Figure 20 CV plots, showing first two scans, and film composition versus deposition potential of Cu-Se (A), Cu-In-Se (B), Cu-Ga-Se (C) and Cu-In-Ga-Se (D) baths.
  • FIG. 21 CuKa broad scan of a CuInSe 2 film (a) after annealing in ArZO 2 at 550 0 C for 30 min, (b) after annealing in H 2 S at 550 0 C for 15 min, (c) for 30 min and (d) for 45 min, respectively. Inset shows the shift of the 112 peak towards higher angles with substitution of S for Se.
  • the present invention provides methods for the electrodeposition of Cu(In, Ga)Se 2 films from single buffered aqueous baths and photovoltaic devices derived therefrom.
  • deposition conditions including bath concentrations, deposition potential and the nature of the electrode surface, resulted in production of as-deposited films with smooth morphology and good control of composition.
  • the photovoltaic devices produced according to the methods of the present invention have conversion efficiencies of between approximately 8% and more than 20%. In one embodiment the conversion efficiency is approximately 8%. In another embodiment, the Docket No. 51281-00025
  • conversion efficiency is approximately 12%. In another embodiment, the conversion efficiency is approximately 15%. In another embodiment, the conversion efficiency is approximately 19%. In another embodiment, the conversion efficiency is more than 19%.
  • Electrodeposition of Cu(In 1 Ga)Se 2 is carried out using acidic aqueous baths containing CuCI 2 .2H 2 O, InCI 3 , GaCI 3 and H 2 SeO 3 , with LiCI added as the supporting electrolyte.
  • the supplied buffer preservation solutions are not used in the baths.
  • baths should always be prepared by mixing the Cu 2+ , In 3+ , Ga 3+ and H 2 SeO 3 solutions to a LiCI solution, before adding to a solution of dissolved buffer and diluting to a volume of 500 cm 3 .
  • baths With the addition of the buffer species, baths are stable over a time period of weeks, with no precipitation of metal oxides observed during storage.
  • the baths are stable during deposition and around ten Cu(In, Ga)S ⁇ 2 , ⁇ 2 ⁇ m thick, films can be deposited from a 500 cm 3 low concentration bath without significant depletion of bath species.
  • a three-electrode electrodeposition set-up can be used, employing a Pt mesh counter-electrode and a saturated calomel electrode (SCE) reference electrode. All potentials are reported with respect to SCE.
  • the working electrodes are preferably 1" x 1" dc-sputtered 0.7 ⁇ m Mo layers, deposited on soda-lime glass. The Mo films should be washed prior to deposition by sonication in warm water and detergent (Liquinox) for 5 minutes and then well rinsed with Dl water and sonicated for a further 5 minutes. Depositions are preferably carried out using a Princeton Applied Research 263A potentiostat or the like. All depositions can be carried out at room temperature from slowly stirred baths. Purging the baths with Ar(g) prior to deposition is found to have no effect on the deposition and was generally not used. Docket No. 51281-00025
  • Deposition of Cu(In 1 Ga)Se 2 was generally carried out at -0.6 V for 60-90 minutes. Films of improved morphology were obtained when a short electrode pretreatment, of a 1 minute deposition at -0.5V from the bath was carried out prior to deposition of the film. Following pretreatment, the substrate was removed from the bath, rinsed and dried in an Ar(g) stream before returning to the bath and completing deposition with a multi-potential sequence of -0.5V for 20 minutes, followed by -0.6 V for 50 minutes.
  • H 2 Se-selenized films were etched in aqueous 0.5 M KCN solutions for 1 minute at 55 0 C and were completed by sequential deposition of CdS by chemical bath deposition, and sputtered ZnO:AI and Ni/AI grids using a baseline process described by Shafarman et al. (J Appl Phys, 79:7324, 1996).
  • X-ray diffraction was carried out using a Philips/Norelco diffractometer with Bragg-Brentano focusing geometry and Cu Ka radiation at 35kV.
  • Glancing incidence X-ray diffraction (GIXRD) measurements were obtained using a Rigaku D/Max 2500 system with parallel beam optical configuration and CuKa radiation at 4OkV.
  • Scanning electron microscopy (SEM) was carried out using an Amray 1810 T scanning electron microscope at 2OkV attached with an Oxford Instrument Energy 200 energy dispersive x-ray spectroscopy (EDS) analytical system using evaporated Cu(In 1 Ga)Se 2 films as standards.
  • Current Voltage (J-V) curves were measured using an Oriel Xenon solar simulator at AM 1.5 and 25°C.
  • Figure 1 depicts the SEM image of a Cu(In 1 Ga)Se 2 film deposited from bath A at -0.6V without pretreatment of the Mo electrode. Deposition of Cu(In, Ga)Se 2 from bath A, was found to consistently deposit dark and powdery films, containing large porous grains of -1-1.5 pm in size. Formation of bubbles was also observed on the electrode and growing film during deposition from this bath. Despite the appearance of the films, good film stoichiometry was obtained; 22.8% Cu, 18.5% In 1 7.4% Ga, and 51.3% Se 1 giving a stoichiometry of Culn 0 .8 3 Ga 0 .33Se 2 .
  • pH 3 pHydrion buffer, a potassium biphthalate/sulfamic acid mixture, was added to stabilize the solution chemistry and film growth.
  • Deposition of Cu(In 1 Ga)Se 2 from buffered bath A showed incorporation of 6-10 % Ga and -15 % O.
  • FIG. 1 depicts SEM images of Cu(In 1 Ga)Se 2 films grown from buffered bath B at -0.6 V without electrode pretreatment.
  • the films show columnar grain growth with a film thickness of ⁇ 2 ⁇ m. Films grown from these conditions always exhibited cracking and contained significant secondary phases, resembling cauliflower-like florets -1-2 ⁇ m in size, embedded in the film surface. EDS results tentatively suggest these phases are Cu- and Se-rich. Docket No. 51281-00025
  • This film has similar properties but no cracking is observed due to the lowering of the Se content of the film from 53 % to 50%.
  • Film compositions of -24-25% Cu, 17-19% In, 6-8% Ga and -50% Se, when just considering these species, can be consistently obtained at these conditions.
  • Films deposited from buffered bath B also contain -15% O.
  • Figure 3 depicts plots of composition of films deposited from buffered bath B, without electrode pretreatment, with varying [H 2 SeO 3 ], between 3.8 and 5.5 mM ( Figure 3a), and [Cu 2+ ], between -2 - ⁇ 3mM ( Figure 3b).
  • Increasing [H 2 SeO 3 ] results in a slight increase of deposited Se and a corresponding rise in deposited Ga, while the Cu and In components decrease.
  • [Cu 2+ ] the level of deposited Cu increases, at the expense of Se and Ga, while In levels remain constant.
  • Figure 4 depicts a plot of film composition deposited without electrode pretreatment from buffered bath B with varying [In 3+ ].
  • [In 3+ ] the level of deposited In increases steadily, with a corresponding decrease in deposited Ga, before stabilizing at ⁇ 22% In at [ln 3+ ] ⁇ 3mM, while the Cu and Se compositions remain relatively constant over all concentrations.
  • the sum of deposited In and Ga levels is consistently -24-25%.
  • Figure 5 depicts composition of films deposited from buffered bath B without electrode pretreatment with varying [Ga 3+ ].
  • [Ga 3+ ] With increasing [Ga 3+ ], the level of deposited Ga increases steadily, but stabilizes at -7%, with [Ga 3+ ] ⁇ 6 mM.
  • a steady decrease in Se content and a significant variation in Cu and In levels are observed before all three species stabilize at [Ga 3+ ] ⁇ 3 mM.
  • bath [In 3+ ] can be used to directly tune In and Ga levels in electrodeposited Cu(In 1 Ga)Se 2 .
  • the rate of film growth increased at higher concentrations, which resulted in significant cracking of films deposited from baths of [LiCI] >0.24 M.
  • Figure 6 graphically depicts the composition of Cu(In 1 Ga)Se 2 films deposited at different potentials between -0.1 V to -0.6 V from buffered bath B without electrode Docket No. 51281-00025
  • Figure 7 and Figure 8 depict XRD plots and SEM images, respectively, of these films. From Figure 6, the film deposited at -0.1V contains -50% Cu and -50% Se, suggesting deposition of CuSe, however, XRD ( Figure 7) indicates only the presence of a thin crystalline Cu 3 Se 2 film (JCPDS 47-1745). The discrepancy in film composition may be due to the presence of amorphous elemental Se or other copper selenides (Cu x Se y ). To more negative potentials, the Se profile initially increases for the film deposited at -0.2V, before decreasing to stabilize at 50% at potentials below - 0.35V.
  • Cu levels show a significant decrease at -0.2V and a further decrease for the film grown at -0.4V, dropping to ⁇ 25%. The latter decrease corresponds with a significant increase in In uptake to -18%.
  • Approximately 6% Ga is consistently detected in films deposited at -0.2V and below. Composition remains near constant for films deposited between -0.4V and -0.6V. H 2 bubbling and severe corrosion of the Mo electrode was observed during depositions below -0.6V.
  • the XRD data ( Figure 7) shows a conversion from CUeSe 2 to a CulnSe 2 /Cu(ln,Ga)Se 2 structure for films deposited at -0.1V and -0.4V, with reflections appearing at -27.0° (112), -44.5° (220/204) and -52.6° (312).
  • the broad diffuse appearance of the Cu(In 1 Ga)Se 2 reflections indicates the deposited films are of low crystallinity and small grain size.
  • the structure of films deposited at potentials more negative than -0.4V remains constant.
  • the morphology of the films shows a similar trend, with a dramatic change in morphology between films deposited from -0.1V, consisting of needle-like Cu 3 Se 2 crystals, to those deposited at -0.4V and below, where the films appear smooth and compact, though the cauliflower-like secondary phases are still present.
  • Electrodes of different properties has a significant effect on deposited film morphology.
  • deposition of Cu(ln,Ga)S ⁇ 2 on higher resistance -0.2 ⁇ m thick Mo electrodes reduces the frequency of secondary phases with no effect on film composition.
  • Figure 9 depicts an SEM images of a Cu(In 1 Ga)Se 2 film grown from bath B on a treated Mo electrode. The film is almost completely free of secondary-growths, with no effect on composition (Culn0.74Ga0.27Se2.03, compare Figure 2b). Devices processed with Cu(In 1 Ga)Se 2 films grown on pre-treated electrodes show improved performance, including no shunting effects. Analysis of the initial 1 minute deposited film showed it to be thin, -150 nm, smooth, and rich in Cu and Se with only a small amount of In. No Ga was detected, indicating the film is Cu x Se y -rich.
  • the GIXRD pattern of the 1 minute deposited film is very similar to the as-deposited CuInSe 2 film pattern, suggesting the 1 minute deposited film is likely dominated by Cu 2- ⁇ Se, which has a diffraction pattern very similar to CuInSe 2 .
  • the growth of the secondary phases may be due to the presence of pinholes in the growing film. These highly conductive sites will short to the Mo electrode resulting in formation of Cu x Se y , which has been determined as a pre-cursor phase of electrodeposited CuInSe 2 films (see later discussion). Due to the high conductivity of the pinholes, Cu x Se y will continue to grow at a faster rate than the inclusion of In 3+ and Ga 3+ , resulting in the formation of the floret-like structures, similar to those observed to form at pinholes during electrodeposition of Cu on thin AI 2 O 3 films deposited on conducting electrodes.
  • Figure 10 depicts XRD patterns of Cu(In 1 Ga)Se 2 films, deposited from bath B onto pretreated Mo electrodes, as-deposited, following selenization at 450°C for 20 minutes in 0.35% H 2 Se/Ar and following selenization in Se vapor at 500°C for 20 minutes.
  • H 2 Se-selenization films become light silvery gray in color and remain smooth and compact with columnar growth.
  • the XRD pattern of the H 2 Se-selenized film shows sharp and well defined peaks, indicating recrystallization of the film, and indicates approximately random orientation. The recrystallization begins within the first few minutes of annealing and is generally completed by 20 minutes.
  • Figure 11 depicts GIXRD patterns of the H 2 Se-selenized Cu(In 1 Ga)Se 2 film, deposited from buffered bath B onto pretreated Mo, obtained with varying incident angles to sample to different depths. All patterns are near identical, indicating uniform composition and crystal structure throughout the film thickness. Following selenization in H 2 Se, complete displacement of O from the film and only a minor, ⁇ 1%, loss of Se is observed, making the film slightly Cu-rich. In contrast, preliminary selenization treatments of electrodeposited Cu(In 1 Ga)Se 2 films in Se vapor resulted in incomplete recrystallization and severe cracking of the films.
  • Photovoltaic devices made in accordance with the teachings of the present invention are typically processed from H 2 Se-selenized Cu(In 1 Ga)Se 2 films, receiving a KCN etch, followed by CBD of CdS, and completed with sputtered ZnO:AI and Ni/AI grids.
  • the presence of the Cu x Se y secondary phases leads to shunting of devices processed with Cu(In 1 Ga)Se 2 films prepared on Mo electrodes without pretreatment.
  • Devices processed with Cu(In 1 Ga)Se 2 films grown on pre-treated Mo electrodes show improved PV performance, including absence of shunting effects.
  • Figure 12 depicts the J-V plot of Cu(In 1 Ga)Se 2 device, deposited on a modified Mo electrode from bath B.
  • the low current collection, observed for the Cu(In 1 Ga)Se 2 thin film device can be due to incomplete processing of the absorber layer. Improvements in device performance are expected with optimization of post-deposition processing.
  • composition and morphology of Cu(In 1 Ga)Se 2 films are sensitive toward changes in bath and deposition conditions.
  • [Se 4+ ]/[Cu 2+ ], [In 3+ ] and bath pH must be controlled to ensure successful depositions of Cu(In 1 Ga)Se 2 films.
  • the use of buffer allows growth of films of compositions adequate for device processing. The buffer alleviates pH changes during deposition and stabilizes the Cu 2+ ions by complexation and beneficially slow film growth by blocking diffusion of the metal ions to the electrode.
  • the deposition of CuInSe 2 generally involves an initial deposition of Cu x Se y phases, though the mechanism of Cu x Se 5 , formation is not confirmed.
  • the observations disclosed herein of the Cu 2-x Se-rich 1 minute deposited pretreatment films, and the deposition of Cu 3 Se 2 at -0.1 V 1 confirms the initial stages of film growth are dominated by the formation of copper selenide phases.
  • Both Cu 2-x Se and Cu 3 Se 2 phases have been reported as initial products of CuInSe 2 electrodeposition. Incorporation of In into Cu(In 1 Ga)Se 2 films was observed in this work at -0.4V and below ( Figure 6), similar to that observed for electrodeposited CuInSe 2 . However, the chemistry of the uptake of In is not well understood.
  • the proposed pathway of In 3+ inclusion is via reduction of the Cu x Se y phase, which has been confirmed from CV to occur potentials more negative than -0.4 V,40 to form Cu 0 and dissolved H 2 Se or Se 2" , though H 2 Se(aq) would be the expected majority species of aqueous Se 2" at pH ⁇ 3.
  • the free energy of formation of CuInSe 2 has been shown to be 10-80 kJ more stable than the mixture of the Cu 2 Se + In 2 Se 3 binaries, indicating that In 2 Se 3 will be rapidly assimilated into the growing CuInSe 2 film.
  • the generated Cu 0 will likely react with H 2 Se(aq) or deposited Se to generate further Cu x Se y .
  • the ED of CuInSe 2 was carried out using acidic aqueous baths containing 2.6mM CuCI 2 .2H 2 O, 9.6mM InCI 3 and 5.5mM H 2 SeO 3 , with 0.236M LiCI added as the supporting electrolyte.
  • acidic aqueous baths containing 2.6mM CuCI 2 .2H 2 O, 9.6mM InCI 3 and 5.5mM H 2 SeO 3 , with 0.236M LiCI added as the supporting electrolyte.
  • Cu(In 1 Ga)Se 2 deposition baths containing ⁇ 2.5mM CuCI 2 .2H 2 O, 2.4mM InCI 3 , ⁇ 5.8mM GaCI 3 , ⁇ 4.5mM H 2 SeO 3 , and 0.236M LiCI were used.
  • X-ray diffraction (XRD) patterns of the films were obtained using a Phllips/Norelco diffractometer with CuKa radiation.
  • the composition of the CulnSe 2 /Cu(ln, Ga)Se 2 films were measured by energy dispersive x-ray spectroscopy (EDS) in an Arnray 1810 T scanning electron microscope (SEM) equipped with an Oxford Instrument Energy 200 EDS analytical system.
  • FIG. 13 shows an SEM image of an as-deposited CuInSe 2 film, of ⁇ 2 ⁇ m thickness, with a smooth surface and well-defined columnar grains 0.5 - 0.75 ⁇ m in size.
  • the highly conducting pinholes may nucleate and grow Cu 2-x Se at a faster rate than the slower In 3+ and Ga inclusion reactions. This fast growth of Cu 2-x Se at pinholes results in the formation of the floret-like structures.
  • Figures 16 and 17 show XRD patterns of ED CuInSe 2 and Cu(In 1 Ga)Se 2 films, respectively, both as-deposited and following selenization treatment.
  • the as-deposited films exhibit three main peaks; (112), (220, 204), and (312), corresponding to the CulnSe 2 /Cu(ln, Ga)Se 2 structure.
  • the peaks are very broad and weak, indicating the films are of low crystallinity and small grain size.
  • the peak located at 40.5° (110) corresponds to the main Mo peak (JCPDS 42-1120). No secondary phases are observed from the XRD data, except for MoSe 2 , which is formed at the Mo/film interface during selenization at >450°C (see Figure 16, line b).
  • Cu(In 1 Ga)Se 2 films became light silvery-gray in color after selenization.
  • XRD showed the expected shift of the (112) reflection with the addition of Ga (JCPDS 35-1102, see Figure 17, line b). This recrystallization begins within the first few minutes of annealing and is generally completed by 20 mins. No evidence of Ga segregation is observed from the XRD data, indicating uniform composition throughout the film thickness. Because of Se loss during selenization, the films become slightly Cu rich and require an aqueous KCN etch to remove the excess Cu prior to completing devices.
  • Figures 18 and 19 show the corresponding J-V curves for the best ED CuInSe 2 and Cu(In 1 Ga)Se 2 devices, respectively, measured in the dark and under illumination.
  • the devices have not shown improvement with addition of Ga.
  • the low current collection, observed for both types of devices, may be due to incomplete reaction and processing of the absorber layer.
  • the apparent double diode effect observed for the Cu(In 1 Ga)Se 2 device may be due to conductive secondary phases present in the grain boundaries of the film.
  • the device results are very promising, even though the J-V parameters are low compared to PVD processed devices. Improvements in device performance are expected with optimization of the post-deposition processing.
  • ED of CuInSe 2 was carried out using acidic aqueous baths containing 2.6mM CuCI 2 .2H 2 O, 9.6mM InCI 3 and 5.5mM H 2 SeO 3 , with 0.236M LiCI added as the supporting electrolyte to improve bath conductivity.
  • a three-electrode cell was used, employing a Pt mesh counter-electrode and a saturated calomel reference electrode (SCE). All potentials are reported with respect to SCE.
  • the working electrodes were dc-sputtered Mo layers of 0.7 ⁇ m thickness. All depositions at constant potential were carried out using a Princeton Applied Research 263A potentiostat at room temperature from a stirred bath. The best quality Cu(In 5 Ga)Se 2 films were obtained when a short electrode pre-treatment, of a 1 min deposition at -0.5 V from the Cu(In 1 Ga)Se 2 bath, was carried out prior to deposition.
  • the substrate was then removed, rinsed and dried, before completing deposition at -0.5 V for 20 mins, followed by -0.6 V for 50 mins. Following deposition, films were rinsed with distilled water and dried under flowing argon. For device processing, ED films were selenized in 0.35% H 2 Se/Ar(g) at 400 - 550 0 C. Devices were completed by etching selenized films in aqueous 0.5 M KCN solutions for 1 min at 55 0 C, followed by application of chemical bath deposited CdS and sputtered ZnO:AI and Ni/AI grids.
  • X-ray diffraction was carried out using a Philips/Norelco diffractometer with Bragg-Brentano focusing geometry and CuKa radiation at 35kV.
  • GIXRD measurements were obtained using a Rigaku D/Max 2500 system with parallel beam optical configuration.
  • Scanning electron microscopy (SEM) was carried out using an Amray 1810 T scanning electron microscope attached with an Oxford Instrument Energy 200 energy dispersive x-ray spectroscopy (EDS) analytical system.
  • Current Voltage (J-V) curves were measured using an Oriel Xenon solar simulator at AM1.5 and 25°C.
  • a mixture of Mo electrode pretreatment coupled with a multi- potential deposition regime produces the best quality ED Cu(In 1 Ga)Se 2 films. Films thus can be made almost completely free of copper selenide secondary phases, (copper selenide secondary phases often appear as floret-like structures). The growth of these secondary phases is attenuated due to pretreatment of the Mo electrode.
  • These films are typically ⁇ 2 ⁇ m thick with smooth and compact morphology.
  • the deposited films are of composition suitable for PV application without requiring additional vacuum deposition steps to adjust final composition.
  • the as-deposited films show broad weak peaks, indicating films are of low crystallinity and small grain size.
  • JCPDS 35-1102 the incorporation of Ga into the CuInSe 2 structure produces the expected shift of the (112) reflection.
  • JCPDS 35-1102 the Cu(In 1 Ga)Se 2 annealed in Se vapor peak position is not consistent with measured film composition, containing ⁇ 7 % Ga, indicating that the Ga is not being incorporated into the crystal structure (see Figure 10).
  • Successful processing of electrodeposited CulnSe 2 -based devices has been made by annealing the as-deposited samples in H 2 Se, reporting conversion efficiencies of 6.5% for CuInSe 2 and 6.2% for Cu(In, Ga)Se 2 .
  • Figure 21 shows the first and second CV scans for (A) Cu-Se, (B) Cu-In-Se, (C) Cu-Ga-Se and (D) Cu-In-Ga-Se baths, taken consecutively. The appearance of peaks in Docket No. 51281-00025
  • the CV figures indicates a redox reaction as occurring at the electrode, either in solution or on the surface.
  • the CV plots are shown with cathodic current represented in the positive direction; therefore positive-going peaks represent reduction processes.
  • the CV scans for each system are very similar in appearance, consisting of an initial current rise at ⁇ 0 V, with a very sharp and strong peak, peak A, at — 0.15 V for Cu-Se or at — 0.35 V for the other systems. This is followed, except for the Cu-In-Se system, by a large reduction peak, peak B, which begins to grow at —0.4V and reaches maximum at —0.6 —0.65 V. In the Cu-In-Se system only a very weak peak B, centered at —0.75 V, is observed. The sharpness of peaks A and B indicate that these processes are related to the electrode surface.
  • the rise in current at -0.8V in all plots is due to the beginning of the hydrogen evolution reaction.
  • peak A is absent in each system, as has been observed by Oliveira et al.
  • peak B remains similar on the second scan.
  • peak B becomes more intense on the second scan and is shifted to — 0.6 V, though sometimes this peak has been observed at >-0.7 V.
  • New peaks are also observed for the Cu-In-Se bath at -0.12 V and -0.25 V on the subsequent scan.
  • composition plots for each of these systems show similar behavior. All films grown at -0.1 V were dark and powdery and contain Cu and Se at a ratio of ⁇ 45: ⁇ 55.
  • GIXRD confirms that films grown at this potential consist of CUeSe 2 (JCPDS 47-1745), though for the Cu-Se system a mixture of Cu 3 Se 2 and CuSe (JCPDS 26-0556) was observed. The discrepancy in composition and detected phases may be due to the presence of amorphous Se and other amorphous copper selenides in the films.
  • GIXRD indicated a conversion from Cu 3 Se 2 to CuSe. Below -0.4V, coinciding with the start of peak B, gel-like films that did not adhere to the Mo substrate were obtained.
  • the Cu-In-Ga-Se bath shows similar features to the other three, with a change in Cu and Se compositions, to 30 at% Cu and 60 at% Se, and uptake of ⁇ 8at% Ga at -0.2 V.
  • the Ga composition remains near constant at potentials ⁇ -0.3 V.
  • -0.4 V again corresponding to the back edge of peak A, an increase in In, to -20at%, is observed with a corresponding decrease in Cu, to ⁇ 25at%.
  • the composition of the Cu(In, Ga )S ⁇ 2 films remains constant.
  • GIXRD showed conversion of Cu 3 Se 2 to a CulnSe 2 /Cu(ln,Ga)Se 2 structure at -0.3 V.
  • the liberated H 2 Se will react with In 3+ (aq) forming In 2 Se 3 , which, due to a favorable free energy of formation will rapidly assimilate into the growing CuInSe 2 film through reaction with Cu 2-x Se.
  • CV peak B is assigned to the reduction of Cu 2-x Se to Cu and H 2 Se.
  • the H 2 Se again will react with In 3+ (aq) to form In 2 Se 3 and, subsequently, CuInSe 2 through reaction with copper selenide.
  • the Cu will likely generate further copper selenide by reaction with H 2 Se or other Se species. In the Cu-Se system, films could not be deposited below -0.4 V, likely due to this reduction of Cu 2-x Se.
  • peak B is also related to bath [In 3+ ].
  • [In 3+ ] a greater proportion of In 2 Se 3 will be formed at -0.4 V, which in turn will react with a greater proportion of Cu 2-x Se and, therefore, a decrease in the - 0.6 V peak is expected.
  • peak A is no longer observed, likely due to no Cu 3 Se 2 remaining in the film or being deposited due to changes in the properties of the coated electrode.
  • Peak B on the subsequent scan is assigned to the reduction of the growing film, which was confirmed from CV scans of as-deposited CuInSe 2 and Cu(In 1 Ga)Se 2 films in buffered LiCI solutions.
  • Ga into the growing films may occur via a similar mechanism to In uptake, via the formation and assimilation of Ga 2 Se 3 .
  • Ga profiles of the CuGaSe 2 and Cu(In 1 Ga)Se 2 systems show an uptake at -0.2 — 0.3 V, which remains at Docket No. 51281-00025
  • Thin films are deposited using conditions described above onto Mo electrodes from low concentration aqueous baths containing CuCI 2 , InCI 3 , and H 2 SeO 3 for CuInSe 2 .
  • GaCI 3 was added to the bath.
  • Electrodeposited thin films exhibit low crystallinity and for device processing, require recrystallization by annealing at high temperature in Se- or S-containing atmospheres.
  • Selenization in H 2 Se/Ar and sulfurization in H 2 S/Ar of electrodeposited thin films were performed in a laminar flow thermal chemical vapor deposition reactor at atmospheric pressure previously described.
  • Electrodeposited Cu(In 1 Ga)Se 2 films were selenized in 0.35% H 2 Se/Ar at 450 0 C to 550 0 C for 20-30 min. For comparison, some films were selenized for 30 min at 525°C in Se-vapor in a PVD system, with Se source temperature at 250 0 C. Sulfurization of CulnSe 2 -based films was performed in 0.35% H 2 S/Ar at 550°C for 15-45 min. The temperature, time and H 2 Se/ H 2 S concentrations were used to control the treatment of the electrodeposited CulnSe 2 -based films.
  • Figure 10 illustrates typical XRD patterns of ED Cu(In 5 Ga)Se 2 films (a) as-deposited, (b) after selenization in Se vapor and (c) in H 2 Se/Ar at 500 0 C for 30 min.
  • the inset shows clearly the shift of the 112 peak towards higher angles with the incorporation of Ga. Docket No. 51281-00025
  • Figure 10 shows XRD patterns of Cu(In 1 Ga)Se 2 films, as-deposited, following selenization at 450 0 C for 20 minutes in 0.35% H 2 Se/Ar, and following selenization in Se-vapor at 500°C for 20 minutes.
  • the XRD pattern of the H 2 Se-selenized film shows sharp and well defined peaks, indicating recrystallization of the film, with approximately random orientation.
  • the expected shift of the (1 12) reflection, ( Figure 10 inset) with the addition of Ga to the CuInSe 2 structure is observed for the H 2 Se-selenized film and is consistent with a film stoichiometry of Culno.76Gao.
  • Figure 22 shows XRD patterns of Cu-rich CuInSe 2 films, (a) after annealing in ArAD 2 at 550 0 C for 30 min and sulfurization at 550 0 C for (b) 15 min, (c) 30 min and (d) 45 min in 0.35% H 2 S/Ar.
  • the XRD pattern of the CuInSe 2 based films shows sharp and well defined peaks, indicating recrystallization of the film, with approximately random orientation. It also shows the characteristic shift of the peaks towards higher angles due to the substitution of sulfur for selenium.

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Abstract

La présente invention concerne la déposition par voie galvanique à bain unique de pellicules minces polycristallines au Cu(In, Ga)Se2 pour des applications photovoltaïques. Spécifiquement, du Cu(In, Ga)Se2 a été déposé sur des électrodes en Mo à partir de bains aqueux tamponnés (pH 2,5) à faible concentration contenant du CuCI2, du InCI3, du GaCI3 et du H2SeO3. La présente invention concerne de plus des bains aqueux tamponnés dont les rapports de concentration Se4+/Cu2+ ont été contrôlés pour optimiser les niveaux de Se et de Cu, tandis que la concentration en In3+ a été ajustée pour contrôler l'In et le Ga déposés. La présente invention concerne en outre les procédés de traitement pré et post-déposition résultant en des pellicules lisses, compactes et dépourvues de fissures de valeurs presque stœchiométriques. Elle décrit des traitements thermiques post-déposition sur des pellicules à base de CuInSe2 déposées par voie galvanique dans une atmosphère contenant du sélénium et du soufre. L’invention concerne spécifiquement des pellicules à base CuInSe2 déposées à partir d’un seul bain sur des électrodes au Mo depuis des bains aqueux à faible concentration. Elle concerne également un traitement thermique de Cu(In,Ga)Se2 déposé par voie galvanique dans du H2Se permettant de produire une pellicule cristalline dépourvue d’O et la recuisson en vapeur de Se pour produire du CuInSe2 sans perte de Ga ou de O.
PCT/US2006/062189 2005-12-15 2006-12-15 Traitements post-déposition de pellicules minces à base de cu(in-ga)se2 déposé par voie galvanique Ceased WO2007070880A1 (fr)

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PCT/US2006/038867 WO2007041650A1 (fr) 2005-10-03 2006-10-03 Pellicules minces au cu(in,ga)se2 déposées par voie galvanique à un bain utiles comme dispositifs photovoltaïques

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