A Method for the Clean Syntheses of Sulfides/Selenides II. Ternary Sulfides/Selenides

A Method for the Clean Syntheses of Sulfides/Selenides II. Ternary Sulfides/Selenides
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  A Method for the Clean Syntheses of Sulfides  Õ Selenides II. Ternary Sulfides  Õ Selenides Paul J. Marsh, Dominic A. Davies, *  Jack Silver, * ,z David W. Smith, R. Withnall,and A. Vecht * Centre for Phosphors and Display Materials, University of Greenwich, Woolwich, London SE18 6PF, United Kingdom The syntheses of MGa 2 S 4   where M   Ca, Sr, and Zn  , CuMS 2   where M   In or Cr  , Ba 2 ZnS 3 , and CuInSe 2  by utilizing sulfuror selenium solutions in hydrazine monohydrate are reported. Scanning electron microscope studies of the morphology of theresulting materials prepared by this route are presented. The photoluminescence spectra of the phosphors SrGa 2 S 4 :Eu.SrGa 2 S 4 :Ce, ZnGa 2 S 4 :Mn, CaGa 2 S 4 :Eu, and Ba 2 ZnS 3 :Mn are displayed. The method is more environmentally friendly thantraditional preparations   very little sulfur-based gases are formed  . Additionally, it is a simple and rapid preparation, producing agood yield. The procedure facilitates the formation of ternary metal sulfides or selenides. It is further shown that for optimumperformance of SrGa 2 S 4 :Eu, the phosphor needs to be fired in a reducing atmosphere to convert all of the Eu 3  to Eu 2  .© 2001 The Electrochemical Society.   DOI: 10.1149/1.1373659   All rights reserved.Manuscript submitted January 31, 2000; revised manuscript received January 25, 2001. Available electronically May 31, 2001. We have reported previously the preparation of main groupmetal and transition element binary sulfides and selenides using so-lutions of sulfur or selenium in hydrazine monohydrate, and haveidentified the major species present in a hydrazine monohydrate/ sulfur solution as the tetrasulfide ion (S 42  ). 1-3 The precipitate fromthese reactions has been identified as a mixture of metal sulfide andexcess sulfur   in this method all the excess sulfur is precipitatedfrom solution  . 1 Full details of the mechanism of this reaction havebeen reported elsewhere. 1 This method of preparing binary metalsulfides and selenides has a number of advantages, these include   i  a protocol for the precipitation of a wide range of p and d block metal sulfides,   ii   the reaction is rapid to use and requires onlyminimum safety regulations   sources of ignition and oxidants mustbe avoided  ,   iii   a low sulfurous gas emission during high tempera-ture processing, and   iv   a low potential for other metal contamina-tion because of the nature of the chemicals used.There is current interest in ternary sulfides for a range of appli-cations, especially for their luminescent properties. 4-12 These mate-rials are usually prepared by firing intimate mixtures of the metalcarbonates, oxides or sulfides, and the required activator in a hydro-gen sulfide atmosphere. Specifically, barium zinc sulfide has beensynthesized by firing a mixture of barium oxide and zinc oxideunder a hydrogen sulfide atmosphere. 13 Its luminescent propertieswhen activated by manganese  II   have been reported in theliterature. 14,15 Previously the ternary sulfides containing group I andgroup II metals have been prepared by the reaction of metal carbon-ate with sulfur at elevated temperatures in an inert atmosphere. 16 The sulfides of group I and group II metals are water soluble. Uponaddition of sulfur solutions in hydrazine monohydrate, such metalsdo not completely precipitate as sulfides from aqueous solutions. Inorder to apply the hydrazine monohydrate/sulfur route to multimetalsulfide production involving metals of group I and group II, it isnecessary to precipitate these metals fully from solution when theother components   of the desired ternary sulfide   are precipitated.Therefore, we investigated modification of the hydrazinemonohydrate/sulfur route by the inclusion of carbonate   in the formof ammonium carbonate   as a precipitating anion for group I andgroup II metals. The carbonates can then react   during firing   withthe excess sulfur   inherent in or added to the precipitate   and othermetal sulfides.The versatility of solutions of sulfur or selenium in hydrazinemonohydrate in the preparation of an extensive range of ternarychalcogenides are described. Here, the syntheses of the followingphosphors using this method are reported:  „ 1 …  SrGa 2 S 4 :Eu 2   greenemission  ,  „ 2 …  SrGa 2 S 4 :Ce 3  ,Na   blue emission  ,  „ 3 … CaGa 2 S 4 :Eu 2   yellow emission  ,  „ 4 …  ZnGa 2 S 4 :Mn 2   red emis-sion  , and  „ 5 …  Ba 2 ZnS 3 :Mn 2   red emission  . The adaptable natureof this method is further illustrated by the synthesis of the nonlumi-nescent ternary sulfides:  „ 6 …  copper chromium disulfide,  „ 7 …  copperindium disulfide, which has previously been synthesized as a poten-tial material for use in thin film solar cells, 17-21 and  „ 8 …  copperindium diselenide, which is one of the most promising p-type semi-conductor materials being investigated for thin film solar cells. 22-27 Experimental  Materials .—Ammonium chloride   99.5%  , barium acetate  99%  , calcium chloride hexahydrate   98%  , chromium chloridehexahydrate   AnalaR  , copper chloride dihydrate   AnalaR  , copperacetate monohydrate   AnalaR  , hydrazine monohydrate   99%  , hy-drochloric acid   AnalaR  , manganous acetate   99%  , isopropanol,and zinc acetate dihydrate   98  %   were obtained from BDHChemicals Ltd. Ammonium carbonate   ACS reagent  , cerium chlo-ride heptahydrate   99.99%  , europium acetate hexahydrate  99.99%  , indium sulfate monohydrate   99.99  %  , lithium chloride  99%  , potassium chloride   99  %  , sulfur   99.998%  , selenium  99.99  %  , and strontium chloride hexahydrate   99%   were fromAldrich Chemical Co., and gallium oxide was from Rhone Poulenc.All chemicals were used without further purification. Precipitation methods .—The general synthetic route forthe preparation of unfired M II Ga 2 S 4 :activator   where M II   Sr, Ca, Zn) was as follows.Gallium chloride solution   1 M   was prepared by dissolving gal-lium oxide in the minimum volume of hot concentrated hydrochloricacid, which was then allowed to cool to room temperature and di-luted to the required molarity with distilled water. To this was addedan aqueous solution of the M II metal salt   0.5 M   and the activatormetal salt   transition or rare earth element  .   In the case of strontiumthiogallate doped with cerium, the codopant was added as well.  Separately, sulfur was added very slowly, with stirring, to hydrazinemonohydrate. Once the sulfur had dissolved, the resulting dark red/ brown solution   the color of which is due to the presence of polysul-fide species present in solution  1   5 M   was gravity filtered and thefiltrate added directly dropwise to the stirring aqueous M II  /gallium/ activator solution. Precipitation occurred immediately. After the ad-dition of the sulfur solution, aqueous ammonium carbonate solution  0.5 M   was added to the reaction mixture and stirring was contin-ued for a further 30 min. The precipitate was filtered off, washedthoroughly with isopropanol, and air dried. *  Electrochemical Society Active Member. z E-mail:   Journal of The Electrochemical Society ,  148   7   D89-D93   2001  0013-4651/2001/148  7   /D89/5/$7.00 © The Electrochemical Society, Inc. D89  The synthesis of unfired barium zinc sulfide:manganese was bythe same method except aqueous solutions of barium acetate   1.5 M  and zinc acetate dihydrate   0.75 M   were used. The concentration of aqueous ammonium carbonate solution was 0.75 M.CuCrS 2  was also prepared by the sulfur/hydrazine monohydratemethod from aqueous solutions of copper chloride   0.25 M   andchromium chloride   0.25 M  . There was no addition of ammoniumcarbonate in this precipitation.CuInS 2  and CuInSe 2  were produced in a similar manner toCuCrS 2 . The concentration of sulfur or selenium   as appropriate  dissolved in hydrazine monohydrate was 4 M, and aqueous solutionsof copper acetate   0.25 M   and indium sulfate   0.25 M   were used.There was no addition of ammonium carbonate in these two prepa-rations. Firing methods .—The ternary sulfides were then fired in an ar-gon atmosphere. In the case of the thiogallates, additional powderedsulfur   equal quantity by weight   was added to the unfired materialto prevent and/or deter oxidation. Both strontium thiogallate withcerium as the activator and calcium thiogallate:europium were firedat 800°C for 60 min. Strontium thiogallate:europium, and bariumzinc sulfide:manganese were fired at 850°C for 60 min. Zinc thiogal-late:manganese was fired at 1000°C for 30 min. Copper indiumdisulfide and copper indium diselenide were both fired at 900°C for1 h.  Experimental spectroscopic techniques .—The Mo¨ssbauer spectrawere recorded at 77 K. The apparatus and methodology have beendescribed previously. 28 Raman spectra were obtained using a La-bram Raman spectrometer equipped with an 18800 g/mm holo-graphic grating, using a holographic supernotch filter and a Peltier-cooled change-coupled device detector. Samples were excited usinga helium-neon laser with an output 8 nW of power at the sample onthe 632.8 nm line. Luminance was observed using infrared excita-tion using a Spex Triplemate Raman spectrometer equipped with anintensified photodiode array detector. The infrared excitation wasprovided by a 3900 nm titanium-sapphire laser   Spectra Physics  pumped by an intracavity frequency doubles Nd:yttrium-aluminum-garnet   YAG   laser   Spectra Physics  ; the laser power varied be-tween 20 and 50 mW at the sample. X-ray powder diffraction pat-terns were recorded using a PW1729 X-ray generator, PW1710diffractometer control, and a PM8203A on-line recorder X-ray pow-der diffraction spectrometer. The data was compared with knownX-ray powder diffraction patterns. 29 Scanning electron microscopy  SEM   studies were carried out using a Cambridge Instruments Ste-reoscan 90 scanning electron microscope. Photoluminescence emis-sion spectra were measured using a Bentham Tel301D detector,DMC3B programmable monochromator control, M300 monochro-mator, and a 228A programmable current amplifier linked to a PC.Excitation was achieved using a 366 nm wavelength light. Results and Discussion In this investigation we have concentrated on photoluminescent  PL   measurements which yield the color purity of the emission,allowing the selection of potentially useful phosphors for furtherstudies. A common problem encountered with sulfide containingphosphors for cathodoluminescent   CL   measurements is that theyslowly degrade under electron beam bombardment to produce off products that corrode the inside of the measuring equipment. Thislimits the characterization which can be carried out on these mate-rials without incurring excessive expenditure.The following five phosphors were prepared utilizing the addi-tion of ammonium carbonate solution to completely precipitate themetal salts present. Sulfur was added to the precipitate for firing todeter oxidation and to react with group I and group II carbonates toform sulfides. CuCrS 2 , CuInS 2 , and CuInSe 2  were prepared withoutusing ammonium carbonate during the precipitation stage, or sulfurbefore the firing stage.  Luminescent materials.—(1) Strontium thiogallate:europium(Sr  0.97  Ga 2 S  4 :Eu 0.03 ) .—The preparation of strontium thiogalla-te:europium was initially carried out without the addition of theaqueous solution of ammonium carbonate. The X-ray diffraction  XRD   powder data of the fired precipitate prepared in this wayshowed the presence of both SrGa 2 S 4   JCPDS no. 25-895  29 andGa 2 S 3   JCPDS no. 16-500  . 29 The luminescence was inferior to thatof fired strontium thiogallate:europium that had ammonium carbon-ate added during the preparation   see below  . When aqueous ammo-nium carbonate solution   0.5 M   was added to the filtrate from theabove reaction mixture after the precipitate had been filtered off, awhite solid precipitated. The XRD powder data showed that this wasSrCO 3   JCPDS no. 5-418  29 confirming that in the absence of am-monium carbonate group I and group II metal sulfide precipitation isincomplete. The white solid was fired at 900°C with additional sul-fur. The body color was white. The XRD powder data of the firedmaterial showed the presence of SrS   JCPDS no. 8-489  29 The firedmaterial displayed patchy red luminescence under 366 nm UV ex-citation, indicating the presence of SrS:Eu 3  . This also indicatesthat if some europium ions remain in solution after the addition of the hydrazine monohydrate/sulfur solution than they are present asEu 3  .The preparation of strontium thiogallate:europium was then ac-complished with the addition of an aqueous solution of ammoniumcarbonate. There was some evidence from the XRD powder data inthe unfired material of the presence of sulfur   JCPDS no. 8-247  , 29 due to the excess of sulfur used during the precipitation reaction.Otherwise, the XRD powder data of the material consisted of abroad peak. It was only upon firing that the XRD powder data indi-cated the presence of crystalline strontium thiogallate in accord withJCPDS no. 25-895. 29 SEM studies showed that the unfired materialconsisted of agglomerates,   200 nm diam. These smaller particlesthemselves agglomerated to form larger structures   Fig. 1  . The firedmaterial was made up of irregular agglomerates of crystals of vary-ing size   1-5   m  , and also where the firing was performed in thepresence of additional sulfur, there were needle shaped sulfur crys-tals present   Fig. 2  , which were then removed by Soxhlet extractionusing carbon tetrachloride as the solvent. The body color of the firedmaterial was yellow.The fired material displayed green photoluminescence under 366nm UV excitation   Fig. 3a  . CIE coordinates:  x    0.2728,  y   0.6843.   max  534 nm. The PL CIE values of this material arein very good agreement with the CL CIE values of SrGa 2 S 4 :Euprepared firing intimate mixtures of carbonates and oxides underH 2 S gas. 4 The color of the emission shows that, although the mate-rial was prepared from an Eu 3  salt, the resulting phosphor contains Figure 1.  Scanning electron micrograph of unfired SrGa 2 S 4 :Eu.  Journal of The Electrochemical Society ,  148   7   D89-D93   2001  D90  Eu 2  as desired. However, it must be noted that the sulfur/hydrazinemonohydrate did not fully accomplish the reduction of Eu 3  toEu 2  . This is usually achieved by firing under a reducing H 2 Satmosphere. 4,7,11 The presence of the remaining Eu 3  was detectedusing both Mo¨ssbauer spectroscopy and a new diagnostic methodwhich we will describe in full elsewhere. 30,31 This involves the useof a two photon upconversion method utilizing the 632.8 nm line of a He/Ne laser. Characteristic emission around 700 nm   Fig. 4   sig-nifies the presence of Eu 3  , and arises from the  5 D 0  to  7 F 4  transi-tions. This finding of Eu 3  signifies that the phosphor needs to befired in a reducing atmosphere for optimum performance.Thus, in the absence of ammonium carbonate, strontium salt pre-cipitation will be incomplete, giving rise to a deficit of strontiumions in the precipitated precursor. After firing, this resulted in theformation of nonluminescent gallium sulfide in addition to the stron-tium thiogallate phosphor, and thus, the inferior photoluminescenceobserved in the absence of ammonium carbonate precipitation. (2) Strontium thiogallate:cerium, sodium (Sr  0.985 Ga 2 S  4 :Ce 0.015  , Na 0.015 ) .—The XRD powder data of the unfired material indicatedsome evidence of sulfur   JCPDS no. 8-247  29 but otherwise thematerial consisted of a broad peak, possibly indicating some pre-liminary ordering, but indicating that much of the precipitated ma-terial was closer to amorphous than crystalline. After firing, theXRD powder data showed the presence of strontium thiogallate  JCPDS no. 25-895  , 29 but additionally there was evidence of Ga 2 O 3  JCPDS no. 11-370  29 as a minor constituent of the fired material.The morphology of both the unfired and fired particles were verysimilar in appearance to the particles of the europium doped stron-tium thiogallate both before and after firing. Needle shaped crystalsof sulfur were also present, which were removed by Soxhlet extrac-tion using carbon tetrachloride as the solvent. The body color of thefired material was white.The fired material displayed blue luminescence under 366 nmUV excitation   Fig. 3b  . The CIE coordinates are  x    0.2267 and  y    0.1862.   max  445 nm. Comparison of the PL CIE coordi-nates of this phosphor with the CL coordinates of SrGa 2 S 4 :Ce,Na  Ce concentration   0.6%) prepared by solid-state synthesis undera H 2 S gas atmosphere 9 indicate that the emission color of the phos-phor produced in this investigation was greener than that of thephosphor reported in the literature. The difference in CIE coordi-nates may simply be due to the difference in cerium concentrations.Altering the activator concentration has a noticeable effect on thechromaticity of the phosphor. 9 It may also be noted that the   max  of the phosphor prepared in this work matches the CL   max  value re-ported by Peters and Baglio 4 for SrGa 2 S 4 :Ce,Na. They did not, Figure 3.  Photoluminescence spectra   366 nm excitation   of    a  SrGa 2 S 4 :Eu,   b   SrGa 2 S 4 :Ce,Na,   c   ZnGa 2 S 4 :Mn,   d   CaGa 2 S 4 :Eu, and   e  Ba 2 ZnS 3 :Mn. Figure 2.  Scanning electron micrograph of fired SrGa 2 S 4 :Eu.  Journal of The Electrochemical Society ,  148   7   D89-D93   2001   D91  however, report the concentration of cerium used. Sodium, added assodium chloride, was the preferred codopant. Replacement with am-monium chloride, lithium chloride, potassium chloride, or cesiumchloride resulted in inferior luminescence under 366 nm UV excita-tion. The performance of the other codopants were in the orderLi    NH 4    K    Cs  . It would appear that the radius of Na  was a good match to the lattice in size whereas Li  was too smalland NH 4  , K  , and Cs  were all too large. (3) Zinc thiogallate:manganese (Zn 0.98  Ga 2 S  4 :Mn 0.02 ) .—Particles of the thiogallate before and after firing were similar in appearance tothe particles of the europium doped strontium thiogallate. Again,after firing, there were needle shaped crystals of sulfur present. Thebody color of the fired material was white. The fired material dis-played red luminescence under 366 nm UV excitation   Fig. 3c  . TheCIE coordinates are  x    0.6661 and  y    0.3331.   max  653 nm. (4) Calcium thiogallate:europium (Ca 0.8  Ga 2 S  4 :Eu 0.2 ) .—As with thestrontium thiogallate, the XRD spectrum of the unfired material con-sisted of a broad peak. The XRD powder data of the fired materialshowed the presence of calcium thiogallate   JCPDS no. 25-134  . 29 The unfired material consisted of agglomerates similar in appear-ance to the unfired strontium thiogallate, and the fired material ap-peared as irregular agglomerates. The body color of the fired mate-rial was yellow. The fired material displayed yellow luminescenceunder 366 nm UV excitation   Fig. 3d  . The CIE coordinates are  x    0.3908 and  y    0.6031.   max  555 nm. The   max  valuematches that reported by Tagiev  et al.  in PL studies for thisphosphor. 8 (5) Barium zinc sulfide:manganese (Ba 2  Zn 0.985 S  3 :Mn 0.015 ) .—TheXRD powder data of the unfired material showed the presence of BaCO 3   JCPDS no. 5-0378  . 29 The XRD powder data of the firedmaterial indicated the presence of barium zinc sulfide   JCPDS no.33-189  , 29 barium sulfide   JCPDS no. 8-454  , 29 and sulfur   JCPDSno. 8-247  . 29 The unfired barium zinc sulfide also consisted of smallagglomerates, similar to those for the unfired thiogallates describedabove. The fired material consisted of irregular agglomerated crys-tals of varying size   1-5   m  . The body color of the fired materialwas pinkish-white. The optimum mole percentage of manganesewas 1.5% compared to the number of moles of zinc used. The firedmaterial displayed red luminescence under 366 nm UV excitation  Fig. 3e  . CIE coordinates:  x    0.6671,  y    0.3382.   max  637nm.The preparation of barium zinc sulfide:manganese was attemptedwithout the addition of an aqueous solution of ammonium carbon-ate. The XRD powder data of the unfired material indicated thepresence of sulfur   JCPDS no. 8-247  . 29 The XRD spectrum other-wise consisted of a broad band, again indicating possibly some shortrange order. The XRD powder data of the fired material indicatedthe presence of a mixture of the    and    phases of zinc sulfide,JCPDS no. 5-566 and 36-1450, respectively. 29 The fired materialdisplayed orange-yellow luminescence under 366 nm UV excitation,which was indicative of zinc sulfide:manganese. As with the stron-tium thiogallate:europium, an aqueous solution of ammonium car-bonate   0.75 M   was added to the filtrate. A white solid precipitatedfrom the filtrate. The XRD powder data of this precipitate consistedof BaCO 3   JCPDS no. 5-0378  .  Nonluminescent materials.—(6) Copper chromiuum disulfide (CuCrS 2 ).—Ammonium carbonate addition was not required for thecomplete precipitation of the metal ions in the unfired material astransition metal sulfides are insoluble in aqueous solutions. TheXRD powder data of the unfired material indicated the presence of sulfur   JCPDS no. 8-247  . 29 The XRD powder data of the firedmaterial were consistent with that of CuCrS 2   JCPDS no. 23-952  . 29 The aim here was to demonstrate that ternary transition metal sul-fides may be readily synthesized by the unmodified hydrazinemonohydrate route when group I and group II metals are notpresent. (7) Copper indium disulfide  (CuInS 2 ).—Addition of ammonium car-bonate was not required to achieve complete precipitation of theunfired material due to the insolubility of the sulfides of copper andindium in aqueous media. Both the precipitated material and thefired material were black solids. The fired material   Fig. 5   consistedof irregular agglomerated crystals of varying size   1-5   m  . TheXRD powder data of the fired material was consistent with that of CuInS 2   JCPDS no. 27-159  . 29 The aim of this synthesis was toillustrate that main group metal sulfides may be readily prepared bythe unmodified hydrazine monohydrate route, and may be a suitablemethod for making the precursor material for thin film deposition. (8) Copper indium diselenide (CuInSe 2 ) .—As with copper chro-mium disulfide and copper indium disulfide, addition of ammoniumcarbonate was not required to achieve complete precipitation of theunfired material. The fired material was a black solid   Fig. 6   con-sisting of agglomerated crystals of varying size   1-5   m  . The XRDpowder data was in good agreement with known values for copperindium diselenide   JCPDS no. 23-209  . 29 The synthesis of CuInSe 2 demonstrates that the unmodified hydrazine monohydrate route issuitable for the preparation of ternary selenides, which can be usedas precursors for thin film deposition. The role of ammonium carbonate in the synthesis of alkali earthternary sulfides .—In the case of group I and group II ternary sul-fides, it has been demonstrated here that ammonium carbonate ad- Figure 4.  Stokes emission arising from the two photon upconversion of the632.8 nm line of He/Ne laser. The emission peaks around 690 to 712 nm arediagnostic of Eu 3  . Figure 5.  Scanning electron micrograph of fired CuInS 2 .  Journal of The Electrochemical Society ,  148   7   D89-D93   2001  D92  dition is necessary to ensure the complete precipitation of all therequired cations, as sulfides of these metals are soluble in water. Inthe study involving the synthesis of SrGa 2 S 4 :Eu without ammoniumcarbonate addition, there was incomplete precipitation of strontiumions, while in the case of the synthesis of Ba 2 ZnS 3 :Mn withoutammonium carbonate addition, there was no evidence for the pres-ence of barium cations in the fired material. The precipitated car-bonates are converted into sulfides during the firing process by thereaction with excess sulfur that is present in the precipitate andadded to the firing mixture.We believe that the method will prove most useful, not only inthe synthesis of cathodoluminescent and electroluminescent binaryand ternary compounds, but also in the synthesis of a large range of semiconductor materials, particularly those used in photovoltaic de-vices. Conclusions It has been shown that an extensive range of ternary chalco-genides may be successfully prepared by the hydrazinemonohydrate/sulfur method. Preparation of transition metal and/ormain group metal chalcogenides may be readily synthesized by thismethod. Ternary chalcogenides containing group I or group II met-als require the use of ammonium carbonate as a precipitating agent.The hydrazine monohydrate/sulfur route for materials prepared pro-vides a clean method that eliminates most sulfurous gas emission.The method is simple to perform and rapid to use. For laboratorypreparations the materials can be prepared in approximately 5 h. Acknowledgments The authors would like to thank DARPA and the EPSRC   ROPAgrant no. GR/M 78847   for part funding this work, Philip Titler forthe Mo¨ssbauer measurements, and David Nicholas for useful discus-sions concerning the XRD powder data. The University of Greenwich assisted in meeting the publication costs of this article. References 1. D. A. Davies, A. Vecht, J. Silver, P. J. Marsh, and J. A. Rose,  J. Electrochem. Soc., 147 , 765   2000  .2. D. A. Davies, A. Vecht, J. A. Rose, P. J. 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