WO2011096914A1 - Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom - Google Patents
Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom Download PDFInfo
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- WO2011096914A1 WO2011096914A1 PCT/US2010/000311 US2010000311W WO2011096914A1 WO 2011096914 A1 WO2011096914 A1 WO 2011096914A1 US 2010000311 W US2010000311 W US 2010000311W WO 2011096914 A1 WO2011096914 A1 WO 2011096914A1
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- precursor composition
- copper
- primary amine
- thin film
- cuse
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/04—Binary compounds including binary selenium-tellurium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
Definitions
- Patent Cooperation Treaty Publication No. WO/2008/063190 published May 29, 2008 (PCT/US2006/060757 filed November 9, 2006) describes precursor compositions for the formation of copper selenide, indium selenide, copper indium selenide (CIS), and/or copper indium gallium diselenide (CIGS) films.
- Patent Cooperation Treaty Publication No. WO/2008/0571 19 published May 15, 2008 (PCT/US2006/060756 filed November 9, 2006) describes the formation of copper indium selenide and/or copper indium gallium selenide films from indium selenide and copper selenide compositions.
- precursor liquid based material having a copper selenide content defined by the formula Cu x Se y wherein x and y are each in the range of 1 to 2.
- precursor compositions are suitable for forming thin films on a substrate which may be used, for example, in semi-conductor applications such as for the preparation of absorber layers for solar cells.
- the process produces a liquid based material that can be used in deposition techniques that are easier, less expensive, and more efficient to use than solid based deposition techniques such as vacuum deposition.
- the precursor compositions allow for deposition by such techniques as drop coating, dip coating, spin coating, spraying, brushing, air brushing, stamping, printing, including ink jet printing, pouring, wiping, smearing and other methods of applying liquids to the surface of a substrate.
- the present precursor compositions can be used to produce thin . films with additional advantageous properties.
- the films are essentially devoid of oxygen in the form of oxygen-containing compounds.
- oxygen-containing compounds e.g. CuO
- the absorber layer e.g. CIS or CIGS
- an exemplary embodiment is directed to a process of making a precursor composition comprising:
- a precursor composition which comprises: a solution comprising CuSe 2 and a primary amine, substantially devoid of Cu 2 Se.
- a precursor co position which comprises:
- a solution comprising CuSe 2 and hydrazine in which ligands of hydrazine are attached to the CuSe 2 .
- a thin film useful for the production of an absorber layer for a solar cell comprising Cu x Se y having no detectable oxygen containing compounds wherein x and y are each from 1 to 2, and the sum of x+y being in the range of 2-3, preferably where the copper selenide compound is at least substantially CuSe.
- a method of applying the precursor composition to a substrate comprising depositing a precursor composition comprising CuSe 2 and a primary amine, substantially devoid of Cu 2 Se, at a temperature in which the CuSe 2 is converted to a copper selenide having an atomic ratio of selenium of less than about 2:1 , preferably about 1 :1.
- FIG. 1 is a schematic view of a chemical reaction of an embodiment for forming a precursor composition
- FIG. 2 is a trace view of atomic percent of copper and selenium as a function of processing temperature for a given time, representing exemplary embodiments;
- FIG. 3 is a trace view of X-ray diffraction patterns, representing three embodiments in which the percent of copper in the thin film is a function of the process temperature and duration of temperature treatment;
- FIG. 4 is a trace view of Raman spectral data of a precursor composition, representing an exemplary embodiment;
- FIG. 5 is a trace view of X-ray diffraction patterns of precursor compositions heat treated at different temperatures showing changes in copper content
- FIG. 6 is a trace view of a thermogravimetric analysis/differential thermal analysis (TGA-DTA) scan of a precursor composition, representing an exemplary embodiment.
- TGA-DTA thermogravimetric analysis/differential thermal analysis
- a precursor composition (also referred to as a precursor ink) which is suitable for forming a thin film on a substrate and especially for forming a thin film containing a desired chemical species (e.g. CuSe) for use in forming a CIS (copper-indium-selenide) and/or CIGS (copper-indium/gallium-diselenide) absorber layer for solar cells.
- a desired chemical species e.g. CuSe
- CIS copper-indium-selenide
- CIGS copper-indium/gallium-diselenide
- Copper selenide containing thin films are useful in the fabrication of CIS and/or CIGS absorber layers for solar cells.
- the copper selenide layer and the indium/gallium selenide layer are placed into contact under reactive conditions to form a desirable absorber layer.
- An exemplary form of copper selenide is CuSe and it is desirable to form a thin film of copper selenide in which a high degree of selection for CuSe is evident.
- the precursor composition can be applied to a substrate and simultaneously thermally treated in a manner which provides a thin film having a target copper selenide content, preferably predominantly CuSe and most preferably having a substantially 1 :1 copper-selenium atomic ratio.
- An exemplary process as represented by Figure 1 involves first dissolving a copper selenide starting material, e.g., containing CuSe, in a primary amine solvent such as hydrazine to form a preliminary precursor composition. A precipitate of insoluble Cu 2 Se is formed, due to the presence of the primary amine solvent.
- the precipitate can routinely be removed from the solution, such as by filtration and/or centrifugation, leaving a liquid based precursor composition containing copper selenide substantially devoid of the undesirable species Cu 2 Se. Because Cu 2 Se precipitates out of the solution and can be effectively removed, the resulting solution is substantially devoid of Cu 2 Se and therefore can be thermally controlled during deposition to achieve a desirable copper selenide profile.
- the resulting precursor composition is applied to the substrate under elevated temperature conditions sufficient to remove the solvent.
- the selection of a deposition temperature and duration of heating controls the species of copper selenide formed during deposition.
- the thin film can be formed with at least a substantial, preferably all of the copper selenide in the form of CuSe.
- a process for producing a Cu x Se y containing precursor composition wherein x and y are each from 1 to 2, with the sum of x+y being in the range of 2-3, comprising dissolving a copper selenide starting material in a solvent comprised of a primary amine such as hydrazine (N 2 H 4 ) to form a solution (i.e. preliminary precursor composition) containing CuSe 2 and an insoluble precipitate in the form of Cu 2 Se.
- the precipitate is removed in a conventional manner (e.g. filtration and/or centrifugation), leaving a copper selenide containing solution at least substantially free of Cu 2 Se (i.e. precursor composition) for further processing.
- the solution is comprised of a coordination complex of copper, selenium and hydrazine in which ligands of hydrazine are bound to the copper.
- the solution is applied to a substrate such as glass, plastic, ceramic or the like by any of the liquid based deposition techniques previously mentioned (e.g. spraying), for example at a thickness of from about 0.1 to 5.0 pm.
- the precursor composition is heated during or after deposition to remove and recapture the solvent which, in the case of hydrazine, results from the breaking of the ligand bonds between the hydrazine and copper, leaving relatively pure copper selenide.
- the temperature and duration of the heating step has been found to control the atomic ratio of copper to selenium when the precursor composition is deposited on the substrate. Relatively high temperatures favor the formation of the copper rich species (Cu 2 Se). Relatively low temperatures favor the formation of the selenium- rich species (CuSe 2 ). Thus, raising the reaction temperature tends to raise the copper content and lower the selenium content.
- the predominant species is CuSe.
- the copper selenide precursor composition gradually favors the formation of the undesirable Cu 2 Se. Accordingly, by controlling the temperature of the deposition process within the temperature range described above, the content of the copper selenide compounds can be precisely controlled.
- an exemplary method of forming a CIS or CIGS absorption layer is to deposit the copper selenide layer at a temperature of from about 150°C to 225°C, preferably about 200°C.
- the duration of thermal processing is another factor which assists in controlling the atomic ratio of copper to selenium.
- the longer the duration of thermal processing at a given temperature the higher the copper to selenium atomic ratio.
- the longer the duration of thermal processing ten minutes vs. five minutes
- the higher the atomic ratio of copper to selenium i.e. 1 :1 vs. 1 :2.
- the variance of temperature and duration can affect the content of the deposited precursor composition as follows. Assuming the precursor composition is prepared as shown in Figure 1 , then the precursor composition may be deposited under heating at a temperature, for example, of 180°C for five minutes.
- the resulting film may be analyzed by X-ray diffraction (see Figure 3) and/or Raman Spectroscopy (see Figure 4). If the atomic ratio of copper to selenium favors the species CuSe 2 , then the temperature of the deposition step may be raised which favors a higher copper content. In addition or alternatively, the duration of the thermal treatment may be increased (e.g. from five to ten minutes) which likewise favors a higher copper content.
- the temperature of the deposition and/or the duration of the thermal treatment step may be decreased to thereby favor a higher selenium content.
- Primary amines such as hydrazine and liquid alkylamines (e.g. propylamine) are used as the solvent for the starting copper selenide compound to form the preliminary precursor composition.
- the term "preliminary precursor composition” means the mixture of primary amine and starting copper selenide material prior to the removal of the precipitate (Cu 2 Se).
- the amount of primary amine e.g. hydrazine
- a stoichiometric amount e.g., in a large excess (e.g. about 60:1 weight ratio)
- Hydrazine is not a commonly used solvent because there are safety issues concerned with its use. In the present process, hydrazine can be at least substantially recovered during thermal treatment of the precursor composition thereby enabling its use in the present process.
- a secondary amine such as ethylene diamine may be used as a cosolvent, or additional cosolvents such as water, lower alkanols preferably having 1-6 carbon atoms (e.g. methanol) and glycols (e.g. ethylene glycol) may also be used.
- the function of the cosolvent is to enable the reaction to proceed with a reduced amount of the primary amine.
- the amount of the cosolvent may be up to the amount of the primary amine.
- the precursor composition can be deposited in a single step heat treating method without resorting to multiple step processes in which the last heating step is rapid thermal processing (RTP).
- RTP rapid thermal processing
- the solution of the primary amine e.g. hydrazine (with or without the secondary amine e.g. ethylene diamine) and copper selenide may be heated and converted directly to the desirable copper selenide species as the solution is being deposited on the substrate.
- Rapid thermal processing is defined herein as a heating regimen in which the target film is heated to the desired temperature in a short time, e.g., no more than ten minutes. The desired temperature is maintained until the heating process is completed.
- the precursor material is deposited on the substrate to form a thin film. Thereafter, the film is annealed at high temperatures (i.e. 350°C) to yield a copper selenide film containing Cu 2 Se as the predominant species. In the present process, heating may be conducted while the precursor composition is being deposited on the substrate in a single step process.
- the precursor compositions described herein may be initially deposited on a substrate at relatively low temperatures, about 80°C to 100°C and thereafter treated at higher temperatures including rapid thermal processing to convert the initial copper selenide composition to the CuSe in relatively pure form.
- the present process does not produce significant amounts of copper oxides and particularly the precursor compositions and films formed from such compositions contain no detectable oxygen (i.e. less than about 0.1 % of oxygen).
- the CuSe containing precursor composition representing an embodiment makes efficient use of selenium and in an exemplary embodiment obviates the need for multiple heating steps. Because CuSe is produced in relatively pure form, the precursor compositions can be used effectively to facilitate the formatiori of, for example, CulnSe 2 with large crystal grains in a solid state reaction with ln 2 Se 3 .
- a preliminary precursor composition based on copper selenide was prepared by adding 1.42 g of commercial grade CuSe powder to 80 ml of hydrazine under stirring for three days. During this time a precipitate forms comprised of Cu 2 Se.
- a solution having a clear green color and comprised of CuSe 2 in hydrazine was isolated by removing the precipitate by filtration and/or centrifugation to form a precursor composition.
- a representation of the reaction to yield the preliminary precursor composition and the precursor composition is shown in Figure 1.
- Example 1 were heated .to temperatures of up to 350°C for five minutes as shown in Figure 2. Sample 1 was maintained at room temperature and analyzed for copper selenide content. Sample 1 measured about 33% copper and 67% selenium.
- Samples 2 and 3 heated to about 125°C and 150°C, respectively, showed a slight increase in copper content to about 35%.
- the predominant copper selenide species is CuSe 2 .
- Sample 4 was heated to 200°C and analyzed for copper selenide content.
- the amount of copper was approximately 39% and the amount of selenium was approximately 61%, representing a mixture of CuSe2 and CuSe.
- the duration of heating was extended to ten minutes (Sample 4A), the copper content increased and the selenium content decreased.
- Sample 5 was heated to 250°C and determined to contain approximately 60% copper and 40% selenium.
- Sample 6 was heated to 300°C and found to contain about 65% copper and about 35% selenium, while sample 7 was heated to 350°C and found to contain about 67% copper and 33% selenium.
- Samples 6 and 7 contained a predominant amount of Cu 2 Se.
- Samples 1-3 showed a predominant amount of selenium and are associated with the copper selenide species CuSe 2 -
- Samples 6 and 7 showed a predominant amount of copper and are associated with the species Cu 2 Se.
- samples 4 and 5 and the temperature range of from about 180°C to 240°C where the predominant species is CuSe which is an exemplary species for forming CIS and CIGS absorber layers.
- the data shown in the XRD scan of Figure 3 shows films deposited at relatively low temperatures up to about 150°C are structurally amorphous. At these temperatures the solvent is driven off and a composition corresponding to CuSe 2 is observed but no peaks due to crystalline phases are observed by X-ray diffraction (XRD). As the temperature is raised, there is a shift in the copper selenide content favoring increased amounts of copper and decreased amounts of selenium, resulting in a transition from CuSe 2 to CuSe. In the range of about 180°C to about 240°C, the predominant species of copper selenide is CuSe. Above 250°C, the copper content continues to increase until the predominant species is Cu 2 Se.
- heating to a temperature of 180°C to about 240°C favors the exemplary species CuSe.
- the rate of selenium loss can be controlled by controlling not only the temperature but the duration of the heating process. This is of particular interest in the temperature range of 180°C to 210°C as shown in Figure 3.
- Figure 3 shows an X-ray diffraction scan of a sample prepared in accordance with Example 1. The sample precursor composition was deposited at 80°C on a glass substrate and shown to have a relatively low copper to selenium atomic ratio and no peaks due to the presence of crystalline phases in the XRD.
- the duration of heating can be varied to further control the copper selenium content.
- Example 8 Another sample (Sample 8) was prepared in a manner similar to Example 1 , except that the solvent used to dissolve the starting copper selenide material was a 1 :1 weight ratio of hydrazine and ethylene diamine.
- the molecular signature shown in Figure 4 confirms the formation of a complex due to the presence of hydrazine ligands coordinated to copper.
- the precipitate formed during the reaction (Cu 2 Se) was removed by filtration and/or centrifugation to form the precursor composition.
- the resulting precursor composition was deposited on glass substrates at a temperature of 150°C (Sample 9), 175°C (Sample 10), and 200°C (Sample 1 ), respectively, and the temperature for each sample as deposited was maintained for 30 minutes.
- Figure 5 shows X-ray diffraction scans of Samples 9-11 and a CuSe film deposited by physical vapor deposition. As shown in Figure 5, films that are structurally and compositionally CuSe are made by spray deposition of the precursor composition in the temperature range of from about 150°C to 200°C.
- the mixture was then transferred by a stainless steel cannula to two N 2 -purged 50 ml centrifuge tubes and separated by centrifugation at 3000 rpm for fifteen minutes.
- the clear, dark precursor liquid (precursor composition: Sample 12) was decanted via a cannula into a purged flask and stored under N 2 .
- the color of the liquid lightened with time in storage, becoming dark green within two days and then turning to yellow over a period of a few weeks. This is thought to be due to the presence of small amounts of highly colored polyselenides that oxidize over time in these septum- capped storage flasks.
Abstract
Description
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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PCT/US2010/000311 WO2011096914A1 (en) | 2010-02-04 | 2010-02-04 | Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom |
EP10845368A EP2531447A1 (en) | 2010-02-04 | 2010-02-04 | Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom |
SG2011056389A SG173552A1 (en) | 2010-02-04 | 2010-02-04 | Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom |
CA2748438A CA2748438A1 (en) | 2010-02-04 | 2010-02-04 | Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom |
AU2010330718A AU2010330718A1 (en) | 2010-02-04 | 2010-02-04 | Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom |
KR1020117025574A KR20120011859A (en) | 2010-02-04 | 2010-02-04 | Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom |
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PCT/US2010/000311 WO2011096914A1 (en) | 2010-02-04 | 2010-02-04 | Methods of making copper selenium precursor compositions with a targeted copper selenide content and precursor compositions and thin films resulting therefrom |
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EP (1) | EP2531447A1 (en) |
KR (1) | KR20120011859A (en) |
AU (1) | AU2010330718A1 (en) |
CA (1) | CA2748438A1 (en) |
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WO (1) | WO2011096914A1 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9105797B2 (en) | 2012-05-31 | 2015-08-11 | Alliance For Sustainable Energy, Llc | Liquid precursor inks for deposition of In—Se, Ga—Se and In—Ga—Se |
US9130084B2 (en) | 2010-05-21 | 2015-09-08 | Alliance for Substainable Energy, LLC | Liquid precursor for deposition of copper selenide and method of preparing the same |
US9142408B2 (en) | 2010-08-16 | 2015-09-22 | Alliance For Sustainable Energy, Llc | Liquid precursor for deposition of indium selenide and method of preparing the same |
CN113224462A (en) * | 2021-04-24 | 2021-08-06 | 武汉理工大学 | Intercalation material for lithium sulfur battery and preparation method thereof |
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US6379585B1 (en) * | 1997-06-07 | 2002-04-30 | Aron Vecht | Preparation of sulphides and selenides |
US20070264504A1 (en) * | 2006-05-12 | 2007-11-15 | International Business Machines Corporation | Solution-based deposition process for metal chalcogenides |
US20090280624A1 (en) * | 2006-11-09 | 2009-11-12 | Midwest Research Institute | Precursors for Formation of Copper Selenide, Indium Selenide, Copper Indium Diselenide, and/or Copper Indium Gallium Diselenide Films |
-
2010
- 2010-02-04 KR KR1020117025574A patent/KR20120011859A/en not_active Application Discontinuation
- 2010-02-04 WO PCT/US2010/000311 patent/WO2011096914A1/en active Application Filing
- 2010-02-04 AU AU2010330718A patent/AU2010330718A1/en not_active Abandoned
- 2010-02-04 CA CA2748438A patent/CA2748438A1/en not_active Abandoned
- 2010-02-04 SG SG2011056389A patent/SG173552A1/en unknown
- 2010-02-04 EP EP10845368A patent/EP2531447A1/en not_active Withdrawn
Patent Citations (3)
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US6379585B1 (en) * | 1997-06-07 | 2002-04-30 | Aron Vecht | Preparation of sulphides and selenides |
US20070264504A1 (en) * | 2006-05-12 | 2007-11-15 | International Business Machines Corporation | Solution-based deposition process for metal chalcogenides |
US20090280624A1 (en) * | 2006-11-09 | 2009-11-12 | Midwest Research Institute | Precursors for Formation of Copper Selenide, Indium Selenide, Copper Indium Diselenide, and/or Copper Indium Gallium Diselenide Films |
Non-Patent Citations (3)
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DUSASTRE ET AL.: "Convenient, room-temperature, amine-assisted routes to metal sulfides, selenides and tellurides", J. CHEM. SOC. DALTON TRANS., no. 19, 1997, pages 3505 - 3508, XP055112108 * |
MALIK ET AL.: "Atmospheric pressure synthesis of In2Se3, Cu2Se and Cu1nSe2 without external selenization from solution precursors", J. MATER. RES., vol. 24, no. 4, April 2009 (2009-04-01), pages 1376 - 1380, XP055017333 * |
MIRASANO, A.: "The effect of annealing process on CIGS films prepared by chemical bath deposition", 2007, pages 2, XP008169095, Retrieved from the Internet <URL:http://www.unk.edu/uploadedFiles/academics/gradstudies/ssrp/Mirasano.pdf> [retrieved on 20100330] * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9130084B2 (en) | 2010-05-21 | 2015-09-08 | Alliance for Substainable Energy, LLC | Liquid precursor for deposition of copper selenide and method of preparing the same |
US9142408B2 (en) | 2010-08-16 | 2015-09-22 | Alliance For Sustainable Energy, Llc | Liquid precursor for deposition of indium selenide and method of preparing the same |
US9105797B2 (en) | 2012-05-31 | 2015-08-11 | Alliance For Sustainable Energy, Llc | Liquid precursor inks for deposition of In—Se, Ga—Se and In—Ga—Se |
CN113224462A (en) * | 2021-04-24 | 2021-08-06 | 武汉理工大学 | Intercalation material for lithium sulfur battery and preparation method thereof |
CN113224462B (en) * | 2021-04-24 | 2023-06-16 | 武汉理工大学 | Intercalation material for sulfur lithium battery and preparation method thereof |
Also Published As
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EP2531447A1 (en) | 2012-12-12 |
KR20120011859A (en) | 2012-02-08 |
AU2010330718A1 (en) | 2011-08-18 |
CA2748438A1 (en) | 2011-08-04 |
SG173552A1 (en) | 2011-09-29 |
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