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    Method For Producing Crystalline Nitride Phosphors

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    kinosraj kumaran

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    © All Rights Reserved
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    ca) United States Patent (10) Patent No: US 8,455,273 B2 Cakmak et al. (45) Date of Patent: Jun. 4, 2013 (s8) METHOD FOR PRODUCINGCRYSTALLINE (2). US.CL NITRIDE PHOSPHORS sic $8972; 43829, 251/18: 25779 (75) Taventors: Hasan Cakimak, Stuty Tansen, Leonberg (DE) ut (DE); Martin Mas-Planek-Gesellschaft zur Forderung der Wissenschaften E. Munich (DE) (3) Assignee: (4) Novice: Subject to any disclaimer, the term ofthis, patent is extended or adjusted under 35 USC. 184(b) by 0 days (21) Appl.Nos 10062778 (22) PCT Filed: Sep. 15,2009 (65) PCTNo: — PCTIER2009/061969 $371 60), (2).(4)Date: Mar. 8, 2011 (87) PCT Pub. Nos WOzoLom29186 PCT Pub, Date: Mar 18, 2010 6) Prior Publication Data US 2011/0163344.A1 Jul. 7, 2011 (0) Foreign Application Priority Data Sep. 15,2008 (EP) (08016232 (51) Inch. HOI sV40 (2006.01) 257/98, 257/103; 2S7/E33.03; 257/E33.061 (58) Field of Classitieation Search spc “438/22, 29; 257/13, 79, 98, 103, 2517833.03, F33.061, search history. application file for comple (66) References Cited US. PATENT DOCUMENTS 200200105269 AL POREIGN PATENT DOCUMENTS 2002 llens eal DE 0200601736 2008 DE thnousi7s7 $2008 BP T1096 2001 ‘OTHER PUBLICATIONS. Li.¥.Q etal, "Luminescence popetesof CE" aetiatedaltaline cath ico tide M.S. (M-Ca, Sr, Ba) material", Joural of uminesesnce 2006, 116, 107-16 ‘ie, Ron-Jun al “Silicon based oxynitide an nitidephoephors {ievhie LEDs A Review” Seiene and Technology of Adanead Mattias 2007, 8: 8-600, Primary Examiner — Andy Hoynh (74) Aitornes, Agent, or Firm Swoektoa LLP Kilpatick Townsend & 6) ABSTRACT This invention relates to anew method for the production of. nitride-based phosphors, ia particular, of phosphors contaia- ing rare earth elements. The phosphors can be use, for example, in light soures, especially in Light Emitting Deviees (LEDS) 0c 1s, § Drawing Sheets US. Patent Sun. 4, 2013 Sheet 1 of 5 US 8,455,273 B2 Eu,Si:Ny EvSiN, Intensity (@.u,) 380 400” 450.” st $80 600 65070075080 Wavelength (om) FIG. 2 US. Patent Sun. 4, 2013 Sheet 2 of 5 US 8,455,273 B2 EuSiN, wo mo «oC Wavelenath (om) FIG. 3 caSiNeu 2 350 400 480-500-580 600 680 700750 BOD Wavelength (am) FIG. 4 US. Patent Sun. 4, 2013 Sheet 3 of 5 US 8,455,273 B2 2 200” 210 300 930” 960 30 420” 450 480 Wavelength (am) FIG.5 Sr,SiNjEu 350 400430500 550600650 70075000, Wavelength (nm) FIG.6 US. Patent Sun. 4, 2013 Sheet 4 of 5 US 8,455,273 B2 Sr,Si.NgEu — mo” oD] Wavelength (ne) FIG.7 Sr SiNEu a 350 400 450500550 DO 85D TOD 750800 Wavelength (am) FIG.8 US. Patent Sun. 4, 2013 Sheet 5 of 5 US 8,455,273 B2 = 1 \ i | || A \ INI AN a oak ee FIG. 9 : ao 450500 Wavelength (nm) Fig. 10 US 8,455,273 B2 1 METHOD FOR PRODUCING CRYSTALLINE NITRIDE PHOSPHORS. CROSS REFERENCE TO RELATED "APPLICATIONS ‘This application claims the benefit of International Appl cation No. PCT/EP2000061969, Sep. 15, 2000, which claims priority to EP 08016232.4 fled Sep. 15,2008, which are both incorporated herein by reference in ther entireties Description This invention relates to a new method for the production ‘of nitride-based phosphors, preferably crystalline nitide- based phosphors in particular of phosphors containing rare ‘earth elements. The phosphors can be used, for example, in light sources, espocially in Light Emitting Devices (LEDS). Incomparison withthe conventional lighting technologies, ‘eg. incandescent and fluoresceat lamps, LED-based solid 2 state lighting devices show remarkable improvements in terms of long lifetime, compactness, designability envion- meat friendliness and, most importantly, energy efficiency. Mait-chip light emitting diodes (me-LEDs) and phosphar- ‘sonverted LEDS (pe-LEDs) ae two basic concepts to gener- fate white ight. This evottion in lighting technology is spreading al over the world and improving our everyday ie me-LEDsareobuinedby combiningat east thre, mostften red, green and blue (RGB) LEDs. pe-LEDs use phosphors to ‘convert the radiation of UV or blue LEDs. Although me- LEDs have the advantageous of poteataly higher fficieney and elecioncally control ofthe color, they require more ‘complex design, ea power source for each LED ineteasing the cost dramatically and not applicable forsmall sizes. And ‘even worse, individual lighting character ofeach LED leads to an uneven color mixing and results in insucienillani- nation. Therefore, without dovbt in this revolution, wave length eonverson phosphors play’ crucial ole (C. Ronda Luminescence, WILEY-VCH Verlag Weinheim, 2008). Air the disoovery of elisientbhie-LEDs by Nakamura, the frst white-LEDs by combining a nGaN-bosedblue-LED ‘emiting t 465 nm with a broad-band yellow phosphor, eg. (¥, Gd) Al,,Ga,),0,x:Ce™ (cerium-doped Yttrium Alu- minim Gamet (VAG:Ce) was immediatly commercialized (S. Nakamura: The Blue Laser Dio, Springer-Verlag, Be lin, 1997 and US, Pt. No, 5.998925}. Alhoogh thistype of ‘white LEDs sil has a big share in the market, they have inadequatecolor rendering properties dueto lackof reenand red color elements. Thereore, tremendous efforts have been spent in recent years among te researches to develop new phosphor systems, especially ed ones, Recently, Jansen etal has reported, in DE 10-2006 051757 AA, a novel elass of phosphors base on amorphous SisB,N ‘eramies, which show oustanding thermal, mechanical and ‘chemical stabilities together wit very promising photluni- nescence properics, mainly for general ilumination pur poses. Since these phosphors have an amomphous network, there isan inhomogeneous line broadening in emission spec- tra, Eu" and Ce" doped amorphous SiN, ceramics have very broad emission bands inthe visible region of the specimim, Thus, obtaining. mamower emission bands, espe- ‘ally orange to ed part of the vsile spect, which can be Vital for some specific applications, isnot very probable in these amorphous luminescent Si,B,Ny ceramics. In that respect, ntidesilcate-ype crystalline phosphors. possess superior photoluminescence propeies(e., elatively sharp and very intense orange to red emissions) tether with out- 2 standing thermal, chemical and mechanical stabilities and sauctural diversities compared to other phosphor systems, such as oxides, sulfides and halides. Therefor, an extensive research is going on both in industry and in academia to synthesize new crystalline ntridoslieste-type phosphors and, especialy to find an elegant way for mass-production of these materials. New host latices of ntrdoslicate type, M,Si:N (M-Ca, ‘St, Ba), consist of three dimensional network of crosslinked SIN, tevabeda in which alkaline earth ions Ca, Srand Ba are incorporated. Suc latices were frst synthesized by Schnick snd co-workers and examples are Ca,Si,N, (Schlieper and Schnick, Z. anor. Ally. Chem, 621, (1995), 1087), Sf,SigN, and Ba,ieN Sehlepe, Millan Schnick.Z. anon. ADs Chem. 621, (1995), 1380) and BaSi,Nyo (Huppert and Schnick, Chem, Eur J. 3 (1997), 249). They applied the reaction of stoichimetric amouats of metal M (M-Ca, Sr, Ba) and europium metal (Eu) with sifcon dimide (Si(NH),) in tungsten crucible by vsing a radio frequency famace at extveme temperature and times (eg. for Ba,SigNy Eu, the Weerueible was heated under nitrogen to 800° C, within 30 rin, kept at 800°C. for 1 hour then heated within 2S hours to 1600” C. and maintained at this temperature for 40 hours, further heated to 1650° C. withia 2 hours and finaly «quenched to room temperature within 30 minutes) aecoring 1o flowing reaction (HA. Hoppe, H. Lutz, P. Morys, W. Schnick, A. Seilmeier J. Phys. Chem. Solids 61, (2000), 2001): (0-2MeaBueSSINI MBN NAS ‘The phosphors produced thereby show orange ta el emis sion and have high quantum efficiency and very low thermal quenching which makes them vey promising red phosphors jn white LEDs to improve the color rendering properties Although these orange-to-ed phosphors shaw the best prop erties ever achieved, the original symesis method was not applicable to industrial scale, First of all the raw powder Si(NH), snot commercially avilable aad has tobe syuthe- sizat separately, Furthermore, itis, together with other reac- ‘aus, very sensitive fo oxygen and moisture and has to be rind in dry-box which makes them dificult in handling, And even worse, pyzolysis is performed ina aio frequency famace in a tungsten crucible at extreme temperature and times whieh makes the cost very high and the yield very low, Therefore, this multistep and complex procedure is not con- sidered as industrial seale production. After this pioneering work, different groups tied to find more reasonable ways to symthesize these compounds, An ‘llerative route has been proposed by the group of Hinzen iY. Q3; vam Stoen, J. EJ. van Krevel J. W. Hl; Bott, G. Delsing A.C. A DiSalvo, PJs de With, Gs Hintzen, HL. ‘FAlloy& Comp. 2006, 417, 279 axl EPI 104799), They kave reacted metal nitride (CasNoy SN, (¥=0.6-0.66), Bab (%+0.6-0.66))and europinm nitride EAN, (x= 94) with iis con nitride (@-Si,N,) ina Mo crucible in's horizontal tube or gripe fumace (the appropriate amounts of starting matri= als were ground in an agate mortar and fred twice with a ‘medium griingin between at 1300-1404? C. foe 12 and 16 hous, respectively) under a nitogen atmosphere acconting to following reaction: C-HM Ne MBANSSSNG=IM, BA SNADSN, [Nitvidation of Eu, Ba and Sr were done separately and grounded together withthe other reactants an agate mortar Ina dry-box, which again makes the handling dificult and tedious. This method is also a multistep and complex proce- US 8,455,273 B2 3 ‘dure whichis less laborious for mass production and, there- fre, its regarded as a method superior to the previous one, Later, Machida and co-workers proposed the carbothenmal reduction and nitridation (CRN) method to produce M,Si,Ny Eu" (M-Ca, Se) ina graphite is crucible in radio frequency furnace using a two-step heating {first o 1200° C, far 2 hours to decompose MCO, to MO and then to 1380? C. for 6 hours) under N, ow based on te following chemical reaction (Piao, X-; Hovikawa, T; Hanzawa, H; Machi, K, Appl. Ph. Lett. 3006, 88, 161908 and Piao, X; Horikawa, Tr; Hanzawa, HL; Machida, K. J. of Blectrockemical Soc: 2006, 183 (12) 1232}. MONS. NEO +CN My Ba SINAC The same authors hive recently synthesized CaS, Eu,SicN, with the same procedure by using CaCN; instead of tripe pmder Pian, X; Machida, Horawa, an fat, 1.1 of Berto Sc 208, 155(1) 317) SOS No OpCAEN CASE SiNACO ‘The big disadvantage of given methods hat itis unavoide able to have residual earbon inthe phosphor, which sini «antl reduces is absorption and emission. Annealing attem- peratures above 600?” C. in air for 2 hours or oxygen atmosphere can be applied in order to remove the resi cabo but Krevel etal. (van Krevel, JW. H. PhD. Thesis, Eindhoven Univesity of Teshnology, 2000) have reported that a heat teatment at 600°C. in ai for 2 hours Kills com pletely theredemissionofr,Si.NeEu"* duet theoxidaton ‘of Fut Bu", Therelore the problem of complete removal ‘of residual earbon in the final phosphor makes tis method unlikely t be used for mass production Same ators in another publication mention thatthe CRN method ean not be applied forthe Ba analog because carbon doesnot work a an effective reducing agent due to having higher affinity to barium ions than to oxygen (Piao, X Machide, K.; Horikawa, 7; Hanzawa, H.; Appl, Phos. Let 2007, 91, 041968), Therefore, they have proposed the so- ‘alled se-propogating high temperature synthesis (SHS) method for BaaSizNa'Eu™, which is widely used in the preparation of ally compounds, borides, and nitrides. The precursor was the nominal Ba, Eu,Sisalley powder syne Sized from Si, Ba, and Eu metal shors. These aw materials ‘were are-melied several times to fom a homogenous alloy ingot that was ground to fine powder, The alloy powder was loaded into a BN crucible nd hate ia a radi frequency faraceundera pure N, flow. ARterthe SHS occured at 1060" C, the temperature was increased. 0 1350-1450 C. and aitained fob for frternitidaton. Quite obviously this method is also not convenient fr mass production, Lastly, Rong-hin and co-workers have proposed direct solid state reaction among metal carbonate (MCO,, where M-Ca, $9), Eu,0,, and SigN, in a gas-pressure sintering funace witha graphite heaters 1600°C. for 2hours under a {0.5 MPaN, according to following rection Xie, RJ Hio- saki, Nz Suehiro, T; Sakuma, K Xu, F-Fs Mitomo, M, Chem, Matter 2006, 18, 578): 28,Ns22-rMOOsox2E0Me ESNet However, the problem ofthis proces is that there isan undesired sie reaction is goingon together withthe proposed reaction given above: 2SiNeANCOAAESLNAMSIO,HCO, ‘Therefore the synthesized phosphor sa complex mixture of M,Si,N:Eu* (64 wt %) and M,SiOJ Eur” 36 wt). ‘The authors claim that the latter does not give emissions 1s 4 under the blue ight excitation, making the complex phosphor resemblea single M,Si.N, Eu phosphor Neverheless, one eannot obtain pare, single pase phosphors with this method, Therefore it was an objet ofthe invention to provide an improved metiod forthe production of nitride-based phos- hors in particular, rare earth element containing nitidesili- «ate phosphors, particularly based on a polymer route Allthese previously described methods ae based on con- ‘eatonal allsolid-state reactions and either requzedcom- plex synthesis techniques with log rection times and adi- tional synthesis steps for the stating materia resulting dificult intermediate handling steps or resulted impure final pndlucts, The novety in the present invention is that the production of the nitride based crystalline phosphors are based onaonessep reaction of commercially available guid state reagents resulting a polymeric intermediate, which can diretly be pyolysed in a common horizontal fame for comparably shor reaction times. Since the mos ofthe stat- ing reagents are liquid, the high purty ean easily be achieved by simpe distillation techniques and any unreacted reagents orintermediate sat products ean be reeyeed easily. ‘The present invention, therefore, provides an alemative method fr the production of nitridosilcate-ype phosphors based on polymer route. The present invention hs fllo- ing advantageous compared to already available allsolid- state-synthesis methods: 1) ll starting reagents are commer- ly available (no additonal synthesis steps forthe stating eompounds, this, mo ational handling and grinding steps ae requre—a real one—pot synthesis) and can easily be Purified either by simple distillation (eq, iguids) or subi- mation (eg, metal-complexes) techniques. Theretore, high purty in the final crystalline compounds can easily be achieved, which is @ major problem in allsolid-statereec- tions 2) This method s hase en a eatin na liguid phase, which llows uch beterhomogeneity inthe nal erystalline compounds 3) Any unreacted or excess reagents and any sub-products ean easily be recycled by simple distillation or sublimation tchnigues, which i envionmentaly and eco- nomically crucial 4) There is polymeric intermediate during production, which may allow various polymer processing techniques to be applied, ex. direct coating on an LED together with pyrolysis via a laser eam, without requiring any additonal resin “According to the invention, this object is achieved by a method forthe production of nitrogen-comaiing phosphors. in particular erystaline nittogencontsining phosphors com- prising the step (reacting a halide with ammonia NH, anda metal source M, i. ammoalyss of a halide with a metal source M, ‘The inventors have found that nitride-based phosphors, preferably erystalline nitride-based phosphors, canbe easily produced by using ammonia ina simple reaction, starting out from readily available stating materials such a halides as wll as elemental metals or metal compounis. This makes a very interesting class of substances accessible, namely nitride-based phosphor materials, According tothe invention a metal source M is used. Said metal source M can contain activators (A), charge compen- sators(C) andor sensitizes (B) Activators, particular, arerareeath elements, preferably seleced from the soup Ce, Pr, Na, Sm, En, Ga, T, Dy, Ho, Fr, Tm, Yb, Lu, Se andor. Most preferably the activator is seleced from Fu andiorVb. Themetal source M can comprise the activator inthe form of metals, eg. elemental Es andor elemental Yb, The metal source M, however, eanalso contin the aetvator in the form of activator ions. In a prefered embodiment, the metal source M comprises a complex oon- US 8,455,273 B2 5 taining the aetvator on (RE complex) such a a complex of| Ce, Ma, Pr,Nd, Sm Ea, Gd, Tb, Dy, Ho, Es, Tm, Yb, Lu, Se andlor, However, it was found tat some ofthe rare earth clements ‘sity dissolve in ammonia, so itis often prefrrad t use $ simply rae eath elements such as Fv andr Yb metal dis solved in ammonia asthe metal source M. Eo, Yb alkaline and alkaline earth metals ae soluble in liguid NE and form solvated electrons: M-oM"42e" for Eu, Yb and alkaline earth metals in liguid Ni M->M"46" forall mets in igid NH, ‘Therefore, during the reaction, they are one form. On the other andiany piven metals notsolubein fauid NI, they an be used as molecular complex compounds Inanspecially prefered embodiment, the acta source M ‘only contains ctvatos, however, m0’ sensiizes andor charge compensators. Ina funher embodiment of the invention, the metal souce Mcontains charge compensators. Suitable charge compenst- toesegarealkali metals andor eaahalkalimetals suchas Li, Na, K'Rb, Cs, Ca, Srandor Ba, Preferably the charge com: peso are elected fom Ca, Sandon Ba “The metal source can also contain sensitizers. Suitable sensitizes eg ate Sn, Ma, Zo, $b, Ph andor Bi ‘According othe invention charge compensators ad Sea- sitizes, to, eam be sed in the form of meals or as ios. none embodiment, the metal source only contains activa tors without any sensitizes or charge compensators. In 0 father embodiment, the metal soure only contains charge ‘compensator ions andlor sensitizer ions without any atvator ions In ssid embodiment a nitido-based matrix mata is obtained. Tnfurtherembodimens the meal source Mcontinseither 3s charge compensators o sensitizes, and aetivators, Hereby: a nitdo-bosed late is obtained which s doped with activa toes. The mole pereeat of aetvators with respect to compen- sats of sensitizers, espctvely, is prefebly between 0.1 an 9.9, in partclar, beeen I and 20 Finally the metal source can comprise activators, charge ‘compensators andsesitizers. The mole perent of sensitizers ‘ith spect to activators is preirably between 0.1 and999, in partcla, between 40 ad 60 ‘safer starting mater s halide is used according to the invention. The halide preferably is «binary halide, in pariculr, a halide having the formula DX, wherein D denotes an clement of Group XI, XIV oe XV athe Psigic “Tablet Elements, X denotes halogen and 2-3, 4 oe 8. Disan element which also canbe found inthe phosphor sp foamed. For producing nitidoslicte phospho, terelre the halide used eg. is slicomeoatining compound. Ia particular, D isan clement selected rom B, Al, Gl, T, Si ‘Ge,Sn, Pb, PAS, Sbandor Bi, Preferably Dis selected from an element of Group XIII of XIV ofthe Pedic Table of ss Elements. Especially preferably Dis selected fom Si, Ge,B andr Al ‘X denotes halogen. in articular F.C. Be, and peefereably (CL Asaby-prodt in he eaction ofthe aveation, NX is forme which can be easily separated fom the desired prod- 60 “The woctonoftheiavetion takes ploein ammonia, NI, “The rection can be performed in pre liguid ammonia, 10 ‘which te alde and the metal source are added It hasbeen Found that the above-described metal soures are excelelly soluble NE, and ths, reaction wih halides in the pres ‘ence of NH. is posible 6 Pure liguid ammonia hereby especially means ammonia having a purity of 98 wi. %, more preferably 298 wt. % However, itis als possible to eary out the reeton in a mixture of ammonia and a solvent. Stable solvent, for example, ae hydocarbon solvents, in partite, Cio more prefembly C-Cyo alkanes. Hexane is especialy re- fered a co-solvent, ‘When the reaction of step (is conc, by-peodes can becasly separated from the desired compound nd recycle. ifdesied. Excess ammonia, or example cane separated in ‘cod ap under ambient conditions and recycled. Any sole ‘eat used such at hexane canbe separated under vacuum ina cod tap. Further, NH,X i formed in thereaeton especially NACI which can bo separated easily hy sublimation. As a rest, «polymeric intermediate is obtained, which can be dizeetly cated on an LED without eesuting any additional resin, Furthermore his polymer ean be processed easily for any deste shape. According to farther prefered embod ment the polymeric intenediatesobainedin ponder form. Ina fier sep Gi, the product obtained then can be subjected heat tvtime, in particular, in order remove ‘esa hydogen and to obi the final compound The heat treatment refzably consists of to sages. Ina first ste, heating 06000 1000. sefTected, preferably to 80010 90°C. forapeiod fl hour to $ hours, especially for 2.5 hours to 4.8 hous. Heat treatment can take place, foe example, a Nene, During said it stage the atrial ispreferbly treated in a NH, fw. ‘Te first beating stage is preferably followed bya second heating tage, Therein, het treatments cari aut at 11000 2500" C. prefesbly at 1200 0 2000? C mor prefebly at 14000 1600 C-Inapaniculaly prefered embodiment, beat treatment inthe second heating tage is peeformed at 11000 1500" C. The second heating stage s preferably card out for 21 10 hour, in particule, for $07 hous, The second heating stage foray takes place in an inert atmosphere suchas helium, nitrogen andlor argo, in particular, ude a N, flo. Fr the het testment standard horizontal s furnaces canbe used Preferably after the polymerization eatin, an tional heat teetment is applied tothe polymer during which fer polycondensation ake place. Upon sing the emperte ‘olaile components, mainly onganiefagment, are removed. Depending oa the nature of poymes inthe fist sep of the het tratmet, 3. upto 900° C, usually low molecular eight organic fragments are released such as hydrogen, ammonis, methylamine, dimethylamine, methane, hydrogen cae, aceon, trinetiyilyl and ete. Ammonia ow ding pyrolysis is very eniil inthe symtesis of pure nities front arbon-consining precursors, since it removes carbon very eliieally and works as an amiizing or ean- saminizing agent, substituting allylamines and eabances crosslinking. Inthe second step ofthe eat extent sully thot 1100-1200° Cres hyogen and small amount ofnitogen are eleased After the all hat treatment, a pure ‘nrganiesolid residuum obined so tat the end prot is inal 2 phosphor material in particular. in powder Form js obtained according to the invention. After the beating step Gi proferblya ceramic material is obtained Jina prefered embodiment, eating is performed in an atmosphere Which contains no oxygen such asin a NH, atanosphere in the fist heating sage an an ier gas tmo™ shore inthe second heating stage. Therefore, no Unwanted ‘xdaton of activator ions takes place “The emission wavelengths ofthe phosphors obtainable according to he iventon are preferably in the red rang, in US 8,455,273 B2 7 poniculr, fom S00 9 800nn. Since the materials furtber ‘ahiit excitation wavelengths inthe blue range, they are ‘especially usful 28 materials for wavelength conversion in phosphor-conveted LEDS. “The phosphors pradueed according to te invention pee ‘erably have formula (2) AED, wherein A denotes activators B denotes sensitizers, ‘Cdenotes charge compensators, D denotes an element of Group XIll, XIV or XV of the Period Table of Elements, N denotes nitoge, and wherein and preferably ¢-5, nd 1510 ia particular, 33:59 and preferably p-& Xz andy are selected such ta the meta ons balance the negative charge provided by DN, In an especially peered eibvment,phosphoes ofthe fomula A.B.CSiN, ar fomed, being (oxojnitdosli ‘aes. Also prefered are (oxonitridealamino-sicates. Oxy zgencanbe introduced into the materials, in particu, into the ‘ceramics, adding wate to the reaction medium and perform ing a paral hyeolysis during polymerization, Pelerbly, water is added ina controlled mous ‘The invention relates to a novel sythesis method forthe prdction of nirie-based phosphors. The present invention Provides an easy’ and veratile method forthe production of nitride -ased phosphors. The invented methods based onthe solubility of actinator ons soch as Eu and Yb metas and RE ‘somplenes where RE is atleast oe ofthe rare-earth met ‘hse rom he group of CPx Nd, Sn, Ea, Gb, Dy Ho, Er Tm, Yb, La, Se,¥, Snand mixtures there, sensitizeons like Sn, Ma, Zn, Sb, Pb, Biand mixture thereofandlorcharge ‘compensutorionssuchasLiNa K Rb, Cs, Ca, Srand Baan inxtres thereon pure liquid ammonia or ammonia mixed with solvent and reaction with bioary halides such as SiCl,, GeC, BC, AIC and ists thereof Compared io ‘couvtational solid tte reactions the present invention which is bas ona rection ina solution allows more homogeneous Aistbaton ofthe elements i the final ceramic. Ina prefered embodinent, the present invention reports a novel synthesis route to M,SisNy Eu" bse nitridesiate phosprs based on direct reaetion of SiC, with metals M (9-Ca, SB) andlor adsslvedia quid ammoais which is optionally diluted with solvent such s hexane, The pro pose reaction is Follow Maan SSCUANI NM, Ba SN ‘pnt ‘The same synthesis route canbe applied by using BulNSi (Ci,),);h insoad oF Eu metal according o following wae: ton isu SSICUANTM Besant SS Ina further embodiment, the present invention reports the symtesis of phosphors M',,RMSieN, based on a direct reaction ofSiCl, with metals Mand Mt” (M'=Li, Na, K, Rb, (Cs preferably M!=Li,Na,K and M"=Ca, Sr, Ba)anda metal complex REN(Si(CH sy (R-Ce, T, Pr, Nd Sm, Dy, Ma Er. Ti, Ho, Eu, Ge, Yb,Lu, ScandlorY preferably R-Ce, Pr, 8 Nd, Sm, Tb, Dy. Ho) in liquid ammonia which is optionally diluted with a solvent such as hexane, The proposed reaction js as follow: -2eMM RINISICH) LASSIE Sal SNE Ina further embodiment, the present invention reports the symthesis of new phosphors Ba, ..R.M/Si;Nio based on a directrectionof Sil, with metals M(MLi,Na,K,Rb,Cs, preferably M=Li, Na, K) and a metal complex’ R(N(Si (CHssls (R-Ce Pr, Nd, Sm, Eo, Gd, T, Dy, Ho, Ex, Tm, Yb, Lu, Se, ¥ andor Ma, preferably R-Ce, Pr, Nd, Sm, Tb, Dy, Ho)in guid ammonia which is optionally dilued with a solvent sch a hexane. The proposed reaction sas fallow: (debut ntiNOCH TSC NT Be RESIN DANE C= spe HISACH After the rescton is completed, by-products can be easily recycle such as excess NH, at ambient condition ina cold trap, hexane under vacuum in a cold tap and NHC via sublimation. The remaining powder mixtreisheatetina BN erie t 900°C. for hours with NH flow ina quartz tube snd finaly to 1500” C. for hours with N, flow in an alumina tube A farther aspect ofthe present invention refers to phos- phors, preferably goon phosphors, having formula (1) EF, G, Si, N,, wherein Eis Ca, Bao Srand mis £24 0r2-2a, 0202 ifm-2-2, preferably 02021, (021205 if m-1-2a, preferably 02205, 15qEX in prtcularq-5 or 7, in particular p-8 or 10, Gis Li, Na, K, Rh or Cs, preferably Li, Fis, Pr Nd, Sm, Fu, Gk Tb, Dy, Ho, Es Tm, Yb, La, Se, YY andor Mn, preferably Ce or Tb. According oan especially prefered embodiment, m4 isprefenbly 20 | According tthe present invention, elements represent by the variables F and G as defined above are used to dope host matrix Said non oped host matrix is present when -0. Prefered host matrices ofthe presen invention are E,Si.N and E,SiN,. According to the invention, said host matrices are dope with elements represented by the arable F and G 28 defined above. Upon comesponding doping, a compound having te formula FC, SiN, isobtained sa prefered embodiment ofthe present invention or host matrix E,iN: ‘As a futher prefered embodiment of an inventive com pound, «compound having the formula Fy ,F,G,SiNyo is obtained for host matrix E,Si,Ny by coresponding doping. Especially prefered! embodiments relate to phosphors which are seleted fom the group consisting of Sta, Tb,LiSicNs, C2 2, 10,Li SiN BO 2,TP,LISiN}o andlor Ba, 2,Ce,Li SiN, ‘The invention frter eats to alight source comprising a primary light emitng deve, inparicular, be light emit ting device anda material obtained by the process deseribe herein. Seid phosphor material, in particular, serves for wave- length conversion. Prefraly, the rd emitting Iuminescent ‘material obtained aeconling othe method ofthe inventions combined with a green emitting phosphor to obtain a ight source which emits 2 white secondary light. Thus, the phos- hors oblained are preferably used in LEDs. The materials US 8,455,273 B2 9 ‘bined are preferably used as phosphors for coaversion of lip, in particular, for conversion to higher wavelengths, BRIEF DI RIPTION OF THE DRAWING In the text which follows, the invention is explained in more detail with reference to a plurality of exemplary ‘embodiments. In drawings: IG. 1 shows a) experimental b) theoretical powder X-ray ifration of Fu,SigNy FIG. 2showstheemission speerumof Fu,Si.N, at} 40am, ‘excitation FIG. 3 shows the excitation spectrum of Eu,Si,N, at 622 FIG 4 shows the emission spectrum ofCa,Si,Ny Eat 340 rm excitation FIG. § shows the excitation spectrum of Ca,SigNyEu at $91 nm emission FIG. 6 shows the emission spectrum of r,SigNyEust M0 rm excitation FIG. 7 shows the excitation spectrum of Se.Si,NyEu at (604m emission FIG. 8 shows the emission spectrum of S,SigNy:Euat $62 rm excitation IG. 9 shows the emission spectrum of Sr 2,1b,Li,SiNN, 81365 nm excitation FIG. 10 shows the emission Bay 3,C2,Li,Si.N ot 365 nm excitation spectrum of EXAMPLES “The fimetion and advantage ofthese and other embodi= ments of the present invention willbe more fully understood fiom the examples below. The following examples are intended to illustrate the benefits ofthe present iaveation, but ‘donot exemplify’ the fll scape of he invention All eactions were performs in a purified Ar atmosphere using citer standard Schlenck technique or within a glove box. The final ceramics are not oxy or moisture sensitive, Example 1 Bu,SiN, 1.6576 ml (0.0145 mol) SiCl, in 30 ml hexane was reacted slowly with 0.8797 (0.0058 mol) Eu metal dissolved in 100 nl iguid NH, which was dilute with 20 ml hexane a -76" CC Ttwasthen slowly reached o roam temperature and excess NH was removed with argon flow: Hexane was removed uundee vacuum ina cold tap, The remaining solid was sub- Timed at 210°C. und 10° mbar in onder wo remove NH,CI salts. Almost sat ffee polymer was heated to 900° C. and «welled for3 hours under NH, flow ina BN crucible. The ‘was further heated to 1500" Cand dvelled for 6 hours under N, flow. AF the end, orange-red powder of Fu:SigN, was ‘obsinod, Powder X-ray dffvetion of Bu,SigN emission specttum at 340 am excitation and excitation spoctrum at 622 rm emission are shown in FIGS, 13 xample 2 Ca,SiNeEu 2.89 ml (0.0252 mol) SiCL, in 30 ml hexane was reacted slowly with 0.4085 g (0.01 mol) Ca and 0.0302 g, (0.0002 mol) Eu metals dissolved in 100 ml iguid NH, which was

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