CA2621665A1 - Transparent and/or photovoltaic solar cell and module - Google Patents
Transparent and/or photovoltaic solar cell and module Download PDFInfo
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- CA2621665A1 CA2621665A1 CA002621665A CA2621665A CA2621665A1 CA 2621665 A1 CA2621665 A1 CA 2621665A1 CA 002621665 A CA002621665 A CA 002621665A CA 2621665 A CA2621665 A CA 2621665A CA 2621665 A1 CA2621665 A1 CA 2621665A1
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- 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
- Y02E10/549—Organic PV cells
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- 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
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Abstract
A solar cell has first and second electrically condustive layers and n-type and p-type semiconductor layers. The n-type and p-type semicondutor layers have nanoparticulate semiconductor material and form a junction. At least oneof the electrically conductive layers has pattern forming a three-dimensional relief.
A process for fabricating a solar cell includes providing a first and second electrically conductive layers, patterning either or both of the first and/or second electrically conductive layers with one or more pre-determined patterns forming a three-dimensional relief, providing n-type and p-type semiconductor layers of nanoparticulates semiconductor material on the electrically conductive layers, and forming the solar cell by bringing the n-type semiconductor layer into contact with the p-type conductor layer. Solar modules may be constructed from the solar cells. Such solar cells and modules may simultaneously possess good light transmission and power generation characteristics.
A process for fabricating a solar cell includes providing a first and second electrically conductive layers, patterning either or both of the first and/or second electrically conductive layers with one or more pre-determined patterns forming a three-dimensional relief, providing n-type and p-type semiconductor layers of nanoparticulates semiconductor material on the electrically conductive layers, and forming the solar cell by bringing the n-type semiconductor layer into contact with the p-type conductor layer. Solar modules may be constructed from the solar cells. Such solar cells and modules may simultaneously possess good light transmission and power generation characteristics.
Description
T,ansparent andior P!hotcvoltaic Solar Cell ana hM1odule Fieid of the lnvention The present invention relates to design and tabrication of solar celis and modu!es.
ac ound oi the invention The bulk of today's photovoltaic solar panel sales are integrated to ho.ases ta minirnize system cost, minimize iand use, and also for architectural reasons.
A!thougn in most cases solar paneis are installed on the roof, It is also possible to use the in0;,xiow space ard skylight for this purpose.
Ivlore Lhan 90% of photovoitaic panels (soid and installed) are based on crystalline {mono and polycrystalline) silicon, For aestnetic and for budgeting reasons, crystalline baseC soisr oelis are probably rot the most suitable photovcltaic teehnology. For this reason var9ous thin film based photovoltaic paneis are expec*.sd to overtake crystalline siiicon as the dominant technology in the future For example, thLn film technology uses less than two orders of magnitude less photovoltaic material, and the process of fabrication is simpier.
rhers are two major drawbacks wtien using thin film technclogy to fabricate photovoltac solar panels. First, expensive equipment is required. Indeed uriform and large area coating requires large vacuum sur,tems with muiti-stap slow deposition rates. Second, power efficiency of commercial photovoltaic panels are stil 30-50% lower than their crystalline silicon counterparts.
There are few examples in the Iiterature of using non-vacuurn processes to faoricate solar panels. Sc far the efficiencies achievea are at least 50'/o lo+rjer than cry5ta7ire based saiar oanel.
Nanostructured hybrid materials have beer used in several sclar cell designs. For example, nanoparticles ernhadded in conductive polymer matrix provide power efficiency of about 3% at labora:ory scale. fv?odified Cso molecules can be =nixed with conductlve polymers to form a nanooomposite witfi slightly higher power efficiency.
Althougf? tt=cy,;e rnatc-.nai, are iajaa{ ;r, maximize solar light absorption, excitor caener=G:tirx; ard 1--il separa;iryn, oftc;r charge coll?ctior ray top and i;n*orn electrodes s ve y lirnited, lnrleed the junction does not provide efficient r:h4r7s trenspor towerci ae.t'. I elertredes after e*ctron and hole ere separated. In parFic,u"ar. charge transfer treMEari nercpFrtici<,s or between Gan rr:olc:cuEes ;s ?ne;tcient. To mitigate thai, high nanoparti".1e cr modified Gw oadin,,re is requred.
'"'iere re!^nains a naed #or ;rrsproved solar cell and solar nioduls design.
,S t^ r^an of #I~~ Inventi~!?.
rhere is proviryer5 a sciar celi conrprising a first a'ectrlcali;v conr+uctive iayer, Ir3 a second electricadly corductive iayer, an n-type semiconductor layer and a p-type sarriconauci.or layer, the fZ-t.ype and p-type serr;icnnductor layers forrning a ju^ct;on, the secnicnnducmr ;ayers comprising nanoparticulrate semkonductor rnaterial, end ar ieast one of the eisctr'.c&ly conductive !ayers having a pattern form,;ng a iliree=din9.;~n:,ione.3 ~eiigr.
There is further pr:;videj a solar n?o:luie cornorising a soiar call of the uresent invent!on.
' he,e is yet further p rovidac a process for fabricating a sotar ce!l comprising pE+uviP,;ny a frrst eier,iriually conductive layer, providirg a second eiectri ,a ly condur":ive ayer, pavern!ng eitner cr both of tne first andPrar second elactriaaiiy ca^nduc:~ve 4aa+ers witrr one or m,ore pre-determined pattenis forming a three-d,msnslo^ai rerief, prowidirra arr n-type semiconductor fayer ccrnprising n ancpar:iculate semiconducior materiai ~cn one of the electrically concuJtive layars, prz:vidin~.^i s p4Eyps sen;;conductor layer= cornpri:s9;1g nancparticulate :-amicondu;a:tor material on the otr~er of the eledricaily cr?ndcctive layers, and ferminc fhe solar cell by brincaing the n-tyr.ye semiconductar iayer intu contact with the põtype s9rn's;cnduct-Afa>rer.
The sc;sar ciA nray further ccmpriss ona or more transparent sut-strate.s to pr;.vide protvctiux, for thC a)rprs arld to perrnit easier i`kanul'iny of the cell. A
transparord ~sucr;:trate rrrGiy coa-;prise, for r~xarnfa!o. glass, plastic, etc. Transparent 3 D ~"ubs#.ratas preferab!y r5avc a thickness of 1 iram or crreater, more preferabiy fxrn atnoõ,t "mm to about 70 rr-irn, for exarnple about 3 rrur. Preferably, the solar cail is csonsfructed with two transparerrt sunsirates, other layers being dispcsed cetween the tw substrates.
Or,a or rr,Grs ;:urrant c:ollector kwyers, for ex2rnpip rnEtai strps anTor grids, mray t~~~e inciuc+ed tc a.c: as c.rrrer;t ,crliecto-s. C=urrerrt collector 4oyers are f::referal7hy formed cn the transparent .:ukr.strates between the substrates arrd other layers oT the solar ce!!. Currarrt cailector layers preferably cornprise a high crsnductiv!iy matal for exampRr= si!ver, aluminum, rticiceS, er a mixt;.re thereof.
t:;u; rer,t coiivct.or ia, ar:_a are p^efe^abiy about 1.00 {:rn 'thick.
One or mor-barrier Msiyers may also 45 included to separate a sutrsstrate or substraaas from the other layers of the sclar :el!. A barrier layer preferably ct,rnpriMes silicon dicxfd.a cr poly(;3,4 ethylenedioxythiophene}
no9y(st ~r4~id asuifonate) ;f'Ft~ a?':PSB;. Barrier iayers are pretera'uly thin, pr;fersbly having a thickness :,f from about 0.1 pm to abcut I iam.
5 "1'he; 4lectrical6y corr~;uctiue ab~er s may corr prise, for example, rrratalfic rõrtertsl, transparertt conductive materials, or combinaticns thereof.
tronci.cr:rve 'ayers are creferabl,y tliln Pllms, praferabhy having a thickness of aaout 5 prn or Icss, more preferably about 2 pm or less, ror sxamPle aboui I pn;. A givan condurtiva iayer may comrrise one r,r more thin `iints. Preferably. at feaGt one of i.ne ,;ondl.active lay6rs cornprises a fiin? oF transparQr-!t conductive rraterial.
7rrrsparpnt c.crnrluctive materi;.~fs are Nret'erahiy tr.nsoarent cc,nductlve oxides fcr example indiurn-tin oxide (iT'a"?), Zr~,0, ZnaAl, SnO? and Sn02:d=.
YrFwWf;arent conouctive rr,aterEa;s are preferably chcaer-r to pravde high transparency and imY "`e:'ai,`~i'CEV~iy. .k`atallic matc:riais !noiUde, tDr example, gold.
~.'5 aium,nunn, sihw, rnoiyW srourn. etc. 'vlc:ly'adenum rs rnore suitabie to ba.=it a p-type se:micond::cto- ;ay+s: vahi9a <alurnirn r7 and silver are rnr,re suitapir3 fr,r an n-tyNe sarriicur.ductor layer. +Nhen a oondu=:tive la;yer is a jusi a flrn of rnetaiiic rr7~t~rial, i=re fiir-r prefr+robly has a thicicness cf !e+ss -than about I
Pm, pmferabiy at'out 250-7-,.0 nr,=rr, for example abaut 500 nrn One or more of :ne rxlorluctive layers have a pattern forrning a three-dirr:a,nsional raRie3s. The FYr=: :ern i:,referably covers mnst or all of nne surface af the c-c,nuzic.tive Iayer tr> fr,rr,t e par:erned conductive iayer. Preferably, aq of the cx}nOuc:ive layers have a pattem. The patterned conductive layer prefErabig cX?rriw r! rt3s 8"".fJft pe,t!erried p=Ortlcn ffitl'.i a!JK'tfArned porC;on, the patterned portlo=n bei,ica ?rti con:atYt wi," ; s^4m c,ondu:tor iayer. `I-he catterled por[IQri may be w tqraS with the raon-pat7ernr>d pa tEor; -~;rrning the t! =ree-dimr~nsion re!it f on tt~ie ncn=.,p~~ternar:i p~ji1;iUjy, eDr tr?e patterned ar-itf non-patterned pc;r:icns may be ser.arate'rilros ir, cvtt-aci wiih each oYhÃwr.
In one 4rnboriir",ent, a rznductive layer may romprise an ultrrathin metal,ic f'ilrn and a 1'llni ol- t.rnnsparert conduCi?ve 'naterta9. The uitmathlYi meta9llc fiim prefersbly has a thick.n!?es ot cxbout 10=200 f!rn, for exarnple about 20 nm.
The fili?7 of ~rsnsparent >=~onduotive ma:eri:>:si would be patterned but cont!riuity be;ween pari:ern sPer=i4nts of tre ftlrn wr,uid noi h-a required.
ir. a preterre;l er~rbodÃrnent, one or mcre .f the coriductive iayers is a filrrr of transparent conduUti~,rcA materiafs in which the patternec: portion Is integraf!}r ?S '.;,rmed with the non-naxterned paftian. irr this embodirnent, the patterned portion 10rrnw a:;~rea-ui n~~nsinnaf re;ie4 on t1e non-,.atterned partion and the non-pe tprne~ cor" cen has a thickness that ar`fords'ow she+et a!ectncai resistance ia=;
about ^..2r3 ohrrr!cr-z`,'er r;xampAe about 10 ohrntcrn21 with hig;;
transmission (e.g.
at7,)ut 50-98% fo- exarnpis about 90gfo) }n the v!sl+a:e and nGar i:?ta"ed reglon3 Cf 2 6, the ei?ctrUrT.aqnetlc s"}3eK.'~'=iJri'k.
Patterning of the corductivf: layer or iQyers provides a high aspect ratio ftrr +..~ne or bor'i of these layers arrd +or the one or trnth of the serniconductor layers c::.,ated tharaan. High aspect ratio ~ensds to better photovo!tnic g5nerati;;n wnile !:flirsr.i able to keep ths Ãaye.rs triinrer. Thus, surfa.ce area contact between the 25 ssrtliC:a.+n[1L'cto+" !^oyer or 1aye "s and the t;tlnf"t.tr,tlve layer c,"
layCsrs 's Iricreased v:hile redu,--ir g .he volE~ntv Of rratvriais .r,sed in ;ne layers.
-iartherrn~re. by selecting pat~(Irn perameters !e,.j. distanoe between patterrls, dis~.anrae bet4usen oattern efernenis, shiape of pattern efenierats, dept!1 of the Pa;.tem r~"#c.i it is pc;ssierlt, tn tt:rre a-id or optimize light trgrsmiss"ion through 3i~ the cets, ph<utovoltalc power rF:neration andlor the balance between light transrrriss,orr ar,d photcvoltaic power gene~atfori.
Pattern e,letnents in the patterned part preferably have a sl-,a.pe, siuc; an.-I
s,aiJar=stiorr that optimir_a ovarail cell efficiency. Shapes inr!.jde, `or example, tslar,gr,lar shapes, rec.~tangwar sheapes, pen?agonr3i shapes, uurved shapes (e.y.
+ bmispneres). a rdanrtular shapYd pat:ern e!ements are particulariy praferrec. The size at (he pattern eiornent5 is hrefera:slv aboui 0.1-5 Nm, tnr exarrpte abcui 0.6 p3-t. ,Seoarati*n of ths pattern a9errtar;ts is preferabiy at?cjt ri prn or mere, mom praferabi.; about 2 tr5ir:rons or rr-,are, for example about 2-10 Firn.
T'o c:ust,7rnize or optimize light transrrission through the solar cell, distance and aspect ratio between patterned !ayers in the call may w a.djusted. For euzmpie, to raatimize !ight transmrsion through the cefl, c!istartice betweer=, tuw sur`ace.s of the pa:torned iayars may ha srnaÃ4er thari trye wave!ength of v!sible iiot "'"he semiconductor lay:rs may be very thin, preferably from aboit 1C~ nm to abo-,ft 5 p:-rr t37ick. For the n-type serniconductor layer, the thickness is rrtore 15 I:referablvtrnm abcut 100 nm ts; aboux 1 pm, for example about 500 nm. For the p-tyns sYmicor,duc;'or la}rer, the thickness is more preferably from about 50 nm to a.b~.}:st 1prn, fcr exE mp'e about 200 nm. Coating a-:.emicorductor layer arP, t:ie patterned side of a patterned c-,onauczivo layer irnparts a complemeritary pattern to cne side af tha sernican" +uwtor ieyer 20 "CI-ro ;ae-miconductnr layars con?.pr se nanoparticuiate senii4:onductor rr;atertal. Examples of suitable sernir,*nductor materials are given in comrnon,y ,:vdrred PC7' app!lcatfon PCT/0A2006=11?2 fiiled July 11, 2006. For exGrnpie, semicorductor matrsrials may comprise CdS, GaS, ZnS. CdSe, GeSe. ZnSe CdTE, GaTe, SIC, Si, CIS, GaAs, PbS, PbSe. Culnae2, CUlnv2!, C'utlnGa)(S,Se)2:
25 oha{;opyri!e, pe:iy(3-hexvfth6ochene) (P3H't), poiyi2-methoxy-5-(2'-ethyl-fi 2xyir x,1.1,~-phenylFr~z "Jnyienej SIVrH-r''PV), [6,6]-ishenyl.C-batyric aciu rnethy{
ester (PucN,l), cr a mixture thereof Band gap for the semicorfductors is E;refer,-~jbfy less than about 1.8 eV, fer examale l.ess than about 1.5 eV, for ~..;:rn41e':sss than 1.3 FV. More pr=ferataly the band gap is in a range of about 30 1.1-1.3 eV, for ex.arr~pie abc:ut. 1 1 eV, For r-typ.e serr:iconductors, CdS, GdSe, .ultIS2 arid P;;6N9 are prefer"r:+d. For p-type ssrn!conductors. Gu!ns2, CuInSe2.
Cu(ln6,a);S,Se:k~;, Cd7e, R3ti" and ',=1Eh-PPV are oreferred. Nanoparttci36ate semiccriduc.tor materiai rray ::e enrbz&ed in an organic conductive poiyrner.
The w,. ~c=ess fa fabricating the >,o'arv ceil rvoive's coating layers of Te vel"ioi.lS
Vernen crie or rnare current ccAiectar layers are incluaciia in t.he solar ceil, the currer:t c.oiiecto^ !ayers may "e rJeposi~ad by any suitah!e n2sthoti, tc,r exampie screpn cr;rcting fror=, a prsste, eva:;aration or sputtewing.
Prcviding a{ayer of tre.nsparent ;.onductive m.ateriaiõ such as a transparent conductiv$ oxide. may oe accr3mpi'ished by a variety ot methody. rr or example, a 1it soi-gei solutcn of t-itsi transparent conductive rnaterial may be preparsti and a thin f+,im of soi-Qei scit;tir,n coated c;r a substrate. for example by using spin-coating.
ink-jet prlntinct or dip=-coating. 'The coated soi-gel soiution may then be Datterned using an im.rr.tir;, process (e.g. hat-srribossing) and the sai-ge4 firn s'sn'tereti to fonm, the transparent wnductive layer. Imprinting and sfrstering may be per?ormea se,+arately cr corrcbined'n one step. Ancther exarrwle of a method for preparing the patrerned transparent cond :l;titse layer :crrprises us>rng ,pray deposition to fc+rm an Init".ral ron-patterned structure of t`re'.ransparert conauctive layer fo!lowed by 3pray deposition through a shadov; mask to form a patterned structure Yontiriuous wit^, the :nitial structure. Yet another ex.ampia of a mezhod -or preparing thes paiterned trarsparent r.ont;uct've fayer comprises usi-ig spray depositior to form a no^-patterned structure of the transparent eorquctive follo+rJeci by taxturing t~s non-o;atterned structure using an etching technique. In sti4 yet another exymple, patternirg ttie transuarent w,onductive fayer rnay be accomplist~~,ec by rjepusitirg a non-patterned layer using sol -ge'., pyroiysis cr vacuum capositior techniques foliowed by Iasew atchfng io fabricate the shapes of t~F pattarn ;r, the tra.nsparent conductive layer.
Providing a film of rneia{iic materiai is preferably accomplished by ''_'C or n7agne1ron sputtering of a metal target. Th.e ?`i,m o` rnetaliic rnaterai may be h>atterred tc form a pa:terneui metaliic film structura. Patterring of the firn of 312 rnat.,flic. material is preferably accomplished by iaser sc!iGing or mschan!caf -cribing.
'The ;r;rr~iconductor layers ana other layers stYcti as the :^.arier layer n=oay be pr=avid:sd by any suifr:'hre methcci, fiir example, spsn-ccdtinp, inF-ie;
printing or aip--~oatinp.
Brlngirig tae r.-tytse siimicorductcr layer into contact with the p-type ,>ernicnrduct.or layer is prefE~rably acoomplrshed by a method that provides a ;iraese,i structure. i.anTiration is crse s+.a!rh rtietha =.i. The graded structure forrrr&d cxoniar;svs a 3-D heterojurction iayer at an intarface of the n-type and p-type serni{ ranductor Iayers. ieaving part. of thr: n-type and p-type layers rrot engaged in the interttac:e ;unction. The graded structure allom efficient ciiarge transport 1C tovverr; i:o,r, and tiottcrn ePer, r=,odes. Ire combination with the patterning ot the ccinductive layer or layers. the yradecs strucft+re leads to good photuvoft&ic power uenerration wi^ile pwmittinra the use of Ihlnner samiconduotcr iaye*s thereby !res:reasi 1g the krarsparency of the sular ce l.
in the sriar cefi, ar.a or th~u mnductEve layers acts as one electrode and the ? fi other conductive layer ac#a as the other eiectrocte. Canductive elements, tor exar:ple wires, are attachad 2ra ecich electroda and to a load to ccmpiote a cirr,uit..
Conductive elerfnents may be attached to 4ne condt9ctive ?qyers dire:tly, or prrafer,ahiy ccndur=tive e;pnnerts arc attached tc the current collector layers wnen '.}'ee:y >'3"L"- i.2resent irt !k?',i 20 A pluraiiTy of Indvi:tuai snlar .^ells r-4ay be used tcr construct a solar niorluie, for exarnpte vy creating '.ndiv;Jc.a; solar cells separately and consieLting mem trygptõer, or hy forrring thei scfx cails integrally into the solar nrodule.
Solar ,arsnes ~nay be tarrrred s"rcrn a ph,rrafity of in.dlvldt,al solar cells or from one or more soia = m.-cdules.
26 Solar ce!I and monu!e dpsiyn of the present ir,vention farovitles a number of advantzge.sSolar c=eii;> anci r aodules are cost effective to fabricata.. The n=rethod ot fabricatian oarmits better control over pattern:ng of layers and also provides a graded stnr^t..re that a'Iows eM cie,nt cf=.arge transport toward top and nottorn etlectrrees. H!r:h a=spact ratio structure r!n E;ott=, sides of the solar c.;eli contributes 33 tc irrproved and tunable prr,perties of ;he csil. The design rnay provide tunatsie I Oht trsrsrnissi7rj andlor "unatsle electrical power yeneradlon= Good eiectrica!
Nvn,ar ;er)Er2,tion ind li,ht trarr.=nni sion may ba achieved sinrultan:.ously. Thc-, nom,ia,natiun e:f nanopartir;uiate semicon<iuctor materfals, controlled patterning cf i~nv 3YC; eupacaliy fayers of ivanwparent conducting material, ;:nd forrrraton of a 3-C hetem;unr.tiorQ by faminat!>an prravides solar c9iis anty nrr,duies wtth ;mprt,vea :i t+znai~+ifty c~t light transmissicn anc power generation.
i"urrher ;eatc.,res of the invention wili tse described or wili beconte apparenf:
in thr: coursp of the foliowing dataiiec description.
Crie Le>qriptian, of the ~Jra,~vin:rs in eroer that the irvention may be more cieariy uncerstood, embodirrrerts 1? th reoi wifi now bp described in detail by way of examnle. with reference to tns aceor'nuanring drawings, in which:
i=;g. I is a schamatic prccsss diagrari for fabrication o` a singie transparent phctiovoita'c cefi of ttie present inven':or?.
DesorlaVan c" F'referred Ernb~~r> ii nen's 115 Reterring to F'zC. 1, a process for dasign and fabri(.atioe of a single transparNnt photovoit;aic celi is ille.istrated.
r ar.aricat~on oi frr.si eJeof; oaYa !errorreJ:
A 3000 i<rri thick firs~ high9y transparent glass substrate 1 is thorougiriy oic an~ d and drie~i, fr~r axantf,ie by cieaning witf: dist~iled water, rinsing with 20 acs:tor,:e and dryirsg in air. A 100 prn t;)iclc first PJf1Al grid is deaasited on tha su~; tr,-.+.e. by screen :arin:int} to lir=OVitie a firsSt curre"Yt cci;ector layer 2.
First subatrate I is coated with thin film 3a of a 56-Lei solution of 6nC by spin coatinsr so that first current collector ;ayer 2 is betwaan first :serostrate I anct triiri film 3a. Znl.~ ~s a transparent conduotlve oxide. The so?..ge!
solution is 25 ailo,vr:c to dry and thin film 3a is surFa.ce patterned by hot-embossing to `orrrr ?atters-,ec1 transparent concuctive oxide laver 3b haviny rectangular pattern c~ernents. Tie patterner transparent conduwtive layer is sintereo. F'attaaned a ::ar;vparent conductive oxtde layer Sb i, 1000 pm thick. The patterri elements are 0.1 .rm thick and I Wm long, with a separation of 2lim betwe n pattern eiernents.
A 0.5 prr td?ick n-type sr:rr!`cori:tuctor fi!m 4 is then formed ori patterned trznsqaren4 cor.ductive oxide layer 3b by spir-Goating. The n-type semiconductor c-omprises Guina? nanopariides prepareJ by microwave synthesis as aescribed in cornr-nonly owned k't;'t' apodi.ation PC,TXA2005lUCJ11 12 filed July ~1, 2006, the d;sc:'sosrce of wn8cii is her in incorporated by referenr,a. Solid state bandgap of the C;u1n,32 rrancparticfes is about 1,5 elv'. Such Ranoperbcies are soluble tn water ar,d easy to disperse, f o Pabr,f:;aL'oxt cfsecrrnd s!actrcda (catflods.):
A 300r prr thick second higNiy transcarent glass substrate 5 dvith simiiar ci,mensicns to the first glass substrate is cleaned and dried and coated with 0.3 ihi:ic sillwr d;oxide uarrier layer 6.
A 0.5 pn : thick r;ro(y:acenum fiirr 7a is formed on second giass substrate 5 wa;h barrier layer 6 sandvvyched in betweerc. The molybdenum film is formed by magnetrur sputtering of a maiyb*Jenurn target. Wlalybd rum fiirn %a is pattemad k laser scribing tc iarm patternad metallic flim structure lb having rectangular Mrittem elemFrnt.s. Th s pattern caterrants have the same size anG separation as rhe pattern P ernant s on the patter7ied TG0 layar.
A 0 2 pm thick p-nyce se!r,iconductor r11m 8 Is then formed on patterned me,t~.liic film structtare 7h by sw in-coating. The p-type sarniconductor comprises C:c Te nanoparticias prepared tfy mrcro,vave synthesis as described in commor.ly ownec r+CT apofication PC'lCA2006f001 t 12 fiied July 91, 2006. the disclosure of wh& is hrtire9r; incor,pr;ated by reference. Cr;Te is a su4rab!e p4yzin 2: se *~<<~~,rzs9u;.tcr tc fOrm a 3-w i=ietarojunctlnr vrlth GulnB2.
Fa-Pr;cai;car of it-,e phr.fovci!ta(: ae!f.' The two rrodif~ad y;ast substrates are then laminated together at a tercpErature of about 150'0 under vacuum to form graded photcvottaic cell 10 having a 34) heterojunctiork 11 at an interface between n-type 4 and p=type B
S
semiccntluctor filrivs. At ~E 3-0 heteoJunr.t or),, raat:s oX the n-type and p-tYpe semiconduc-or films are noc encfaged in the irtterface. The pattern elernenis of tr?.nsl:.arevt canductive ox.ide layer 3b Gnd pa7:erned metaliic fiim structure 7b are aliw7ed in the ~..eil.
~ Refarer~cr~s:
Shaheer et Eii ,"2. 5 rb Effinient Orryanic P'astic Solar Gells", AppJted Physics Leff6r~, 78:841-843 i20C1 i Huyrth et ai., "Hybrtd Nancrod-Poiyrner sola: C:lls". Scler?ce, 234(5564;:2.426-242" flVlarch 29, 24x:2), Kapur e; al.: "Non-4's,Wuum Pracesslng of CuEn,.%GarSe, Solar Ce61s or. R.ic9d ard F{ex;ble Substrates us:n; Nanopart:cle Ini<s" 7ehin Solid Fiirrrs, 431==432 (2003) 53-i,fS F'z:tent 5,985.691. Basr+l ot al., POetf;cd of IVtslcing Compo!;nd Semicorid,aL.tor Fi4me inn POaking Relateck Eiectronlc Geiices", issued hioNeemoer 16.1999.
Kr;ssaier st aiõ :`Progress in Low Cost irlactroceposition of CG(in,Ga)(S,Se)2: The CISEL Prcaiect". 20th Europsarr Fhr.fo,vifeic Soldr Eriergy Gont+:arence. 6-10 June 2005, Sarcelona Spain.
US Patent 7,026.256, Taunier ct al., Method for Making 1'hi;'.,.ti::?i SerTiiconductors ESasud or I-IIi-Vit Gompou;t¾ts for Photovoltaic ADplioations issuoci Aadl 11, 4,6+)6.
[3isnt e~ e,"CQmpar!son of Spray Pyroierr-~ad F77, ATO ar!d iTeJ Gcetrngs fcr Flat and Rer,t C:lass S:rbstrat.es", Tfiin Sof,id Fflrrrs, "j6^ (199G) ? 09- s 14, Patant 6,34 0,7&ca, f=atritsaf3 et u~aE., "hAultiE,a~~er t~ttotovo!t,ai~: or Pnotoe~:,nductsve ^vavic.ew`. issuect.january 22, 2002.
?ri US P;:tent 4,611,091, r:huudari at al. "C'u1risSew Tt71n F'ilm Solar Geli with 1'fiin udS iar~d Transparent Window t,.aver" isslaec' Septern5gr 9; 19d6. 10 Anderson et A!õ "EiectrochTornic ,-iX'rYObi'Poiymer laminate,..", Apgdlesy CcUcs, 15 US t'atewit 8,481.482, MitsWairo, ,i amirating Apparatus for tvtanufactiiring Photovoltaic 1<Aodu:e", issi:ed Novernber 19, 2002.
a tJS Patant 6,90.597. Sager et ai., "PhoTovo!taic G+evices Fabrfcs+ted by Growth from Pcous Temp"ate", izss en Septernber 20, 200:.
41, Patent 4,663,495, 9erman at ai., 'Transparent Photovottaic MoJuie`, issued !viay 5. 1987.
Marzolin, et a!., "Fabriraiian of Gias_~~, Wicrostructures= by t.licro-Moltlir g of SoE-Gal Precursors'", .4dvancedMarerlafs, 10 (1998) 571-574, US Patent 7,014.799, Yang et al., Method of Forrn!ng Mesoscop'scatly Structured fvqaterial'. issued N,arch 21. 2408.
US patent -3,285,652, Ku ata o al., "Integrated Thin F(!m 5olar Battery ar,G
i\+lethod of RAanufacturing the Sarne", issued July 24. 2001.
15 tJ.8 patant 4,554.727. [}eckmaw et al., "tf9ethod for Fvsaking fJptica!iy Enhanced Thin Film Photovcltaic Devic Using l,.Ithograjhy Dei'ined Random Surfaces", issuec Novcntber 26, 1 95~..
St.iebig, e. :al., `Silicon Tt,ir==tilm Solar t,eiis with Rectang;_,Ãar-shaped Grating Cr...zware", Ptvg. Phottavol.= R. Apwtõ C2006? -W13-24.
"wJ Other advanT.ages that are inherent to the structure are obvious to ona t;l:i!ledi^t the art= 'ftte a,7?bodiments are deEcrit=ed herein illustratvely and are not rnc,ait ,o iirnÃt the s.:ope of the invention as ciairnea. Variations of tne eoracJoiny arn'e*odirren,+.s will be evident to a person of orc!r!ary s c!!i and are interd c by the inventc,r to be enecmpassad by the fcllovving cla+rns.
(?
ac ound oi the invention The bulk of today's photovoltaic solar panel sales are integrated to ho.ases ta minirnize system cost, minimize iand use, and also for architectural reasons.
A!thougn in most cases solar paneis are installed on the roof, It is also possible to use the in0;,xiow space ard skylight for this purpose.
Ivlore Lhan 90% of photovoitaic panels (soid and installed) are based on crystalline {mono and polycrystalline) silicon, For aestnetic and for budgeting reasons, crystalline baseC soisr oelis are probably rot the most suitable photovcltaic teehnology. For this reason var9ous thin film based photovoltaic paneis are expec*.sd to overtake crystalline siiicon as the dominant technology in the future For example, thLn film technology uses less than two orders of magnitude less photovoltaic material, and the process of fabrication is simpier.
rhers are two major drawbacks wtien using thin film technclogy to fabricate photovoltac solar panels. First, expensive equipment is required. Indeed uriform and large area coating requires large vacuum sur,tems with muiti-stap slow deposition rates. Second, power efficiency of commercial photovoltaic panels are stil 30-50% lower than their crystalline silicon counterparts.
There are few examples in the Iiterature of using non-vacuurn processes to faoricate solar panels. Sc far the efficiencies achievea are at least 50'/o lo+rjer than cry5ta7ire based saiar oanel.
Nanostructured hybrid materials have beer used in several sclar cell designs. For example, nanoparticles ernhadded in conductive polymer matrix provide power efficiency of about 3% at labora:ory scale. fv?odified Cso molecules can be =nixed with conductlve polymers to form a nanooomposite witfi slightly higher power efficiency.
Althougf? tt=cy,;e rnatc-.nai, are iajaa{ ;r, maximize solar light absorption, excitor caener=G:tirx; ard 1--il separa;iryn, oftc;r charge coll?ctior ray top and i;n*orn electrodes s ve y lirnited, lnrleed the junction does not provide efficient r:h4r7s trenspor towerci ae.t'. I elertredes after e*ctron and hole ere separated. In parFic,u"ar. charge transfer treMEari nercpFrtici<,s or between Gan rr:olc:cuEes ;s ?ne;tcient. To mitigate thai, high nanoparti".1e cr modified Gw oadin,,re is requred.
'"'iere re!^nains a naed #or ;rrsproved solar cell and solar nioduls design.
,S t^ r^an of #I~~ Inventi~!?.
rhere is proviryer5 a sciar celi conrprising a first a'ectrlcali;v conr+uctive iayer, Ir3 a second electricadly corductive iayer, an n-type semiconductor layer and a p-type sarriconauci.or layer, the fZ-t.ype and p-type serr;icnnductor layers forrning a ju^ct;on, the secnicnnducmr ;ayers comprising nanoparticulrate semkonductor rnaterial, end ar ieast one of the eisctr'.c&ly conductive !ayers having a pattern form,;ng a iliree=din9.;~n:,ione.3 ~eiigr.
There is further pr:;videj a solar n?o:luie cornorising a soiar call of the uresent invent!on.
' he,e is yet further p rovidac a process for fabricating a sotar ce!l comprising pE+uviP,;ny a frrst eier,iriually conductive layer, providirg a second eiectri ,a ly condur":ive ayer, pavern!ng eitner cr both of tne first andPrar second elactriaaiiy ca^nduc:~ve 4aa+ers witrr one or m,ore pre-determined pattenis forming a three-d,msnslo^ai rerief, prowidirra arr n-type semiconductor fayer ccrnprising n ancpar:iculate semiconducior materiai ~cn one of the electrically concuJtive layars, prz:vidin~.^i s p4Eyps sen;;conductor layer= cornpri:s9;1g nancparticulate :-amicondu;a:tor material on the otr~er of the eledricaily cr?ndcctive layers, and ferminc fhe solar cell by brincaing the n-tyr.ye semiconductar iayer intu contact with the põtype s9rn's;cnduct-Afa>rer.
The sc;sar ciA nray further ccmpriss ona or more transparent sut-strate.s to pr;.vide protvctiux, for thC a)rprs arld to perrnit easier i`kanul'iny of the cell. A
transparord ~sucr;:trate rrrGiy coa-;prise, for r~xarnfa!o. glass, plastic, etc. Transparent 3 D ~"ubs#.ratas preferab!y r5avc a thickness of 1 iram or crreater, more preferabiy fxrn atnoõ,t "mm to about 70 rr-irn, for exarnple about 3 rrur. Preferably, the solar cail is csonsfructed with two transparerrt sunsirates, other layers being dispcsed cetween the tw substrates.
Or,a or rr,Grs ;:urrant c:ollector kwyers, for ex2rnpip rnEtai strps anTor grids, mray t~~~e inciuc+ed tc a.c: as c.rrrer;t ,crliecto-s. C=urrerrt collector 4oyers are f::referal7hy formed cn the transparent .:ukr.strates between the substrates arrd other layers oT the solar ce!!. Currarrt cailector layers preferably cornprise a high crsnductiv!iy matal for exampRr= si!ver, aluminum, rticiceS, er a mixt;.re thereof.
t:;u; rer,t coiivct.or ia, ar:_a are p^efe^abiy about 1.00 {:rn 'thick.
One or mor-barrier Msiyers may also 45 included to separate a sutrsstrate or substraaas from the other layers of the sclar :el!. A barrier layer preferably ct,rnpriMes silicon dicxfd.a cr poly(;3,4 ethylenedioxythiophene}
no9y(st ~r4~id asuifonate) ;f'Ft~ a?':PSB;. Barrier iayers are pretera'uly thin, pr;fersbly having a thickness :,f from about 0.1 pm to abcut I iam.
5 "1'he; 4lectrical6y corr~;uctiue ab~er s may corr prise, for example, rrratalfic rõrtertsl, transparertt conductive materials, or combinaticns thereof.
tronci.cr:rve 'ayers are creferabl,y tliln Pllms, praferabhy having a thickness of aaout 5 prn or Icss, more preferably about 2 pm or less, ror sxamPle aboui I pn;. A givan condurtiva iayer may comrrise one r,r more thin `iints. Preferably. at feaGt one of i.ne ,;ondl.active lay6rs cornprises a fiin? oF transparQr-!t conductive rraterial.
7rrrsparpnt c.crnrluctive materi;.~fs are Nret'erahiy tr.nsoarent cc,nductlve oxides fcr example indiurn-tin oxide (iT'a"?), Zr~,0, ZnaAl, SnO? and Sn02:d=.
YrFwWf;arent conouctive rr,aterEa;s are preferably chcaer-r to pravde high transparency and imY "`e:'ai,`~i'CEV~iy. .k`atallic matc:riais !noiUde, tDr example, gold.
~.'5 aium,nunn, sihw, rnoiyW srourn. etc. 'vlc:ly'adenum rs rnore suitabie to ba.=it a p-type se:micond::cto- ;ay+s: vahi9a <alurnirn r7 and silver are rnr,re suitapir3 fr,r an n-tyNe sarriicur.ductor layer. +Nhen a oondu=:tive la;yer is a jusi a flrn of rnetaiiic rr7~t~rial, i=re fiir-r prefr+robly has a thicicness cf !e+ss -than about I
Pm, pmferabiy at'out 250-7-,.0 nr,=rr, for example abaut 500 nrn One or more of :ne rxlorluctive layers have a pattern forrning a three-dirr:a,nsional raRie3s. The FYr=: :ern i:,referably covers mnst or all of nne surface af the c-c,nuzic.tive Iayer tr> fr,rr,t e par:erned conductive iayer. Preferably, aq of the cx}nOuc:ive layers have a pattem. The patterned conductive layer prefErabig cX?rriw r! rt3s 8"".fJft pe,t!erried p=Ortlcn ffitl'.i a!JK'tfArned porC;on, the patterned portlo=n bei,ica ?rti con:atYt wi," ; s^4m c,ondu:tor iayer. `I-he catterled por[IQri may be w tqraS with the raon-pat7ernr>d pa tEor; -~;rrning the t! =ree-dimr~nsion re!it f on tt~ie ncn=.,p~~ternar:i p~ji1;iUjy, eDr tr?e patterned ar-itf non-patterned pc;r:icns may be ser.arate'rilros ir, cvtt-aci wiih each oYhÃwr.
In one 4rnboriir",ent, a rznductive layer may romprise an ultrrathin metal,ic f'ilrn and a 1'llni ol- t.rnnsparert conduCi?ve 'naterta9. The uitmathlYi meta9llc fiim prefersbly has a thick.n!?es ot cxbout 10=200 f!rn, for exarnple about 20 nm.
The fili?7 of ~rsnsparent >=~onduotive ma:eri:>:si would be patterned but cont!riuity be;ween pari:ern sPer=i4nts of tre ftlrn wr,uid noi h-a required.
ir. a preterre;l er~rbodÃrnent, one or mcre .f the coriductive iayers is a filrrr of transparent conduUti~,rcA materiafs in which the patternec: portion Is integraf!}r ?S '.;,rmed with the non-naxterned paftian. irr this embodirnent, the patterned portion 10rrnw a:;~rea-ui n~~nsinnaf re;ie4 on t1e non-,.atterned partion and the non-pe tprne~ cor" cen has a thickness that ar`fords'ow she+et a!ectncai resistance ia=;
about ^..2r3 ohrrr!cr-z`,'er r;xampAe about 10 ohrntcrn21 with hig;;
transmission (e.g.
at7,)ut 50-98% fo- exarnpis about 90gfo) }n the v!sl+a:e and nGar i:?ta"ed reglon3 Cf 2 6, the ei?ctrUrT.aqnetlc s"}3eK.'~'=iJri'k.
Patterning of the corductivf: layer or iQyers provides a high aspect ratio ftrr +..~ne or bor'i of these layers arrd +or the one or trnth of the serniconductor layers c::.,ated tharaan. High aspect ratio ~ensds to better photovo!tnic g5nerati;;n wnile !:flirsr.i able to keep ths Ãaye.rs triinrer. Thus, surfa.ce area contact between the 25 ssrtliC:a.+n[1L'cto+" !^oyer or 1aye "s and the t;tlnf"t.tr,tlve layer c,"
layCsrs 's Iricreased v:hile redu,--ir g .he volE~ntv Of rratvriais .r,sed in ;ne layers.
-iartherrn~re. by selecting pat~(Irn perameters !e,.j. distanoe between patterrls, dis~.anrae bet4usen oattern efernenis, shiape of pattern efenierats, dept!1 of the Pa;.tem r~"#c.i it is pc;ssierlt, tn tt:rre a-id or optimize light trgrsmiss"ion through 3i~ the cets, ph<utovoltalc power rF:neration andlor the balance between light transrrriss,orr ar,d photcvoltaic power gene~atfori.
Pattern e,letnents in the patterned part preferably have a sl-,a.pe, siuc; an.-I
s,aiJar=stiorr that optimir_a ovarail cell efficiency. Shapes inr!.jde, `or example, tslar,gr,lar shapes, rec.~tangwar sheapes, pen?agonr3i shapes, uurved shapes (e.y.
+ bmispneres). a rdanrtular shapYd pat:ern e!ements are particulariy praferrec. The size at (he pattern eiornent5 is hrefera:slv aboui 0.1-5 Nm, tnr exarrpte abcui 0.6 p3-t. ,Seoarati*n of ths pattern a9errtar;ts is preferabiy at?cjt ri prn or mere, mom praferabi.; about 2 tr5ir:rons or rr-,are, for example about 2-10 Firn.
T'o c:ust,7rnize or optimize light transrrission through the solar cell, distance and aspect ratio between patterned !ayers in the call may w a.djusted. For euzmpie, to raatimize !ight transmrsion through the cefl, c!istartice betweer=, tuw sur`ace.s of the pa:torned iayars may ha srnaÃ4er thari trye wave!ength of v!sible iiot "'"he semiconductor lay:rs may be very thin, preferably from aboit 1C~ nm to abo-,ft 5 p:-rr t37ick. For the n-type serniconductor layer, the thickness is rrtore 15 I:referablvtrnm abcut 100 nm ts; aboux 1 pm, for example about 500 nm. For the p-tyns sYmicor,duc;'or la}rer, the thickness is more preferably from about 50 nm to a.b~.}:st 1prn, fcr exE mp'e about 200 nm. Coating a-:.emicorductor layer arP, t:ie patterned side of a patterned c-,onauczivo layer irnparts a complemeritary pattern to cne side af tha sernican" +uwtor ieyer 20 "CI-ro ;ae-miconductnr layars con?.pr se nanoparticuiate senii4:onductor rr;atertal. Examples of suitable sernir,*nductor materials are given in comrnon,y ,:vdrred PC7' app!lcatfon PCT/0A2006=11?2 fiiled July 11, 2006. For exGrnpie, semicorductor matrsrials may comprise CdS, GaS, ZnS. CdSe, GeSe. ZnSe CdTE, GaTe, SIC, Si, CIS, GaAs, PbS, PbSe. Culnae2, CUlnv2!, C'utlnGa)(S,Se)2:
25 oha{;opyri!e, pe:iy(3-hexvfth6ochene) (P3H't), poiyi2-methoxy-5-(2'-ethyl-fi 2xyir x,1.1,~-phenylFr~z "Jnyienej SIVrH-r''PV), [6,6]-ishenyl.C-batyric aciu rnethy{
ester (PucN,l), cr a mixture thereof Band gap for the semicorfductors is E;refer,-~jbfy less than about 1.8 eV, fer examale l.ess than about 1.5 eV, for ~..;:rn41e':sss than 1.3 FV. More pr=ferataly the band gap is in a range of about 30 1.1-1.3 eV, for ex.arr~pie abc:ut. 1 1 eV, For r-typ.e serr:iconductors, CdS, GdSe, .ultIS2 arid P;;6N9 are prefer"r:+d. For p-type ssrn!conductors. Gu!ns2, CuInSe2.
Cu(ln6,a);S,Se:k~;, Cd7e, R3ti" and ',=1Eh-PPV are oreferred. Nanoparttci36ate semiccriduc.tor materiai rray ::e enrbz&ed in an organic conductive poiyrner.
The w,. ~c=ess fa fabricating the >,o'arv ceil rvoive's coating layers of Te vel"ioi.lS
Vernen crie or rnare current ccAiectar layers are incluaciia in t.he solar ceil, the currer:t c.oiiecto^ !ayers may "e rJeposi~ad by any suitah!e n2sthoti, tc,r exampie screpn cr;rcting fror=, a prsste, eva:;aration or sputtewing.
Prcviding a{ayer of tre.nsparent ;.onductive m.ateriaiõ such as a transparent conductiv$ oxide. may oe accr3mpi'ished by a variety ot methody. rr or example, a 1it soi-gei solutcn of t-itsi transparent conductive rnaterial may be preparsti and a thin f+,im of soi-Qei scit;tir,n coated c;r a substrate. for example by using spin-coating.
ink-jet prlntinct or dip=-coating. 'The coated soi-gel soiution may then be Datterned using an im.rr.tir;, process (e.g. hat-srribossing) and the sai-ge4 firn s'sn'tereti to fonm, the transparent wnductive layer. Imprinting and sfrstering may be per?ormea se,+arately cr corrcbined'n one step. Ancther exarrwle of a method for preparing the patrerned transparent cond :l;titse layer :crrprises us>rng ,pray deposition to fc+rm an Init".ral ron-patterned structure of t`re'.ransparert conauctive layer fo!lowed by 3pray deposition through a shadov; mask to form a patterned structure Yontiriuous wit^, the :nitial structure. Yet another ex.ampia of a mezhod -or preparing thes paiterned trarsparent r.ont;uct've fayer comprises usi-ig spray depositior to form a no^-patterned structure of the transparent eorquctive follo+rJeci by taxturing t~s non-o;atterned structure using an etching technique. In sti4 yet another exymple, patternirg ttie transuarent w,onductive fayer rnay be accomplist~~,ec by rjepusitirg a non-patterned layer using sol -ge'., pyroiysis cr vacuum capositior techniques foliowed by Iasew atchfng io fabricate the shapes of t~F pattarn ;r, the tra.nsparent conductive layer.
Providing a film of rneia{iic materiai is preferably accomplished by ''_'C or n7agne1ron sputtering of a metal target. Th.e ?`i,m o` rnetaliic rnaterai may be h>atterred tc form a pa:terneui metaliic film structura. Patterring of the firn of 312 rnat.,flic. material is preferably accomplished by iaser sc!iGing or mschan!caf -cribing.
'The ;r;rr~iconductor layers ana other layers stYcti as the :^.arier layer n=oay be pr=avid:sd by any suifr:'hre methcci, fiir example, spsn-ccdtinp, inF-ie;
printing or aip--~oatinp.
Brlngirig tae r.-tytse siimicorductcr layer into contact with the p-type ,>ernicnrduct.or layer is prefE~rably acoomplrshed by a method that provides a ;iraese,i structure. i.anTiration is crse s+.a!rh rtietha =.i. The graded structure forrrr&d cxoniar;svs a 3-D heterojurction iayer at an intarface of the n-type and p-type serni{ ranductor Iayers. ieaving part. of thr: n-type and p-type layers rrot engaged in the interttac:e ;unction. The graded structure allom efficient ciiarge transport 1C tovverr; i:o,r, and tiottcrn ePer, r=,odes. Ire combination with the patterning ot the ccinductive layer or layers. the yradecs strucft+re leads to good photuvoft&ic power uenerration wi^ile pwmittinra the use of Ihlnner samiconduotcr iaye*s thereby !res:reasi 1g the krarsparency of the sular ce l.
in the sriar cefi, ar.a or th~u mnductEve layers acts as one electrode and the ? fi other conductive layer ac#a as the other eiectrocte. Canductive elements, tor exar:ple wires, are attachad 2ra ecich electroda and to a load to ccmpiote a cirr,uit..
Conductive elerfnents may be attached to 4ne condt9ctive ?qyers dire:tly, or prrafer,ahiy ccndur=tive e;pnnerts arc attached tc the current collector layers wnen '.}'ee:y >'3"L"- i.2resent irt !k?',i 20 A pluraiiTy of Indvi:tuai snlar .^ells r-4ay be used tcr construct a solar niorluie, for exarnpte vy creating '.ndiv;Jc.a; solar cells separately and consieLting mem trygptõer, or hy forrring thei scfx cails integrally into the solar nrodule.
Solar ,arsnes ~nay be tarrrred s"rcrn a ph,rrafity of in.dlvldt,al solar cells or from one or more soia = m.-cdules.
26 Solar ce!I and monu!e dpsiyn of the present ir,vention farovitles a number of advantzge.sSolar c=eii;> anci r aodules are cost effective to fabricata.. The n=rethod ot fabricatian oarmits better control over pattern:ng of layers and also provides a graded stnr^t..re that a'Iows eM cie,nt cf=.arge transport toward top and nottorn etlectrrees. H!r:h a=spact ratio structure r!n E;ott=, sides of the solar c.;eli contributes 33 tc irrproved and tunable prr,perties of ;he csil. The design rnay provide tunatsie I Oht trsrsrnissi7rj andlor "unatsle electrical power yeneradlon= Good eiectrica!
Nvn,ar ;er)Er2,tion ind li,ht trarr.=nni sion may ba achieved sinrultan:.ously. Thc-, nom,ia,natiun e:f nanopartir;uiate semicon<iuctor materfals, controlled patterning cf i~nv 3YC; eupacaliy fayers of ivanwparent conducting material, ;:nd forrrraton of a 3-C hetem;unr.tiorQ by faminat!>an prravides solar c9iis anty nrr,duies wtth ;mprt,vea :i t+znai~+ifty c~t light transmissicn anc power generation.
i"urrher ;eatc.,res of the invention wili tse described or wili beconte apparenf:
in thr: coursp of the foliowing dataiiec description.
Crie Le>qriptian, of the ~Jra,~vin:rs in eroer that the irvention may be more cieariy uncerstood, embodirrrerts 1? th reoi wifi now bp described in detail by way of examnle. with reference to tns aceor'nuanring drawings, in which:
i=;g. I is a schamatic prccsss diagrari for fabrication o` a singie transparent phctiovoita'c cefi of ttie present inven':or?.
DesorlaVan c" F'referred Ernb~~r> ii nen's 115 Reterring to F'zC. 1, a process for dasign and fabri(.atioe of a single transparNnt photovoit;aic celi is ille.istrated.
r ar.aricat~on oi frr.si eJeof; oaYa !errorreJ:
A 3000 i<rri thick firs~ high9y transparent glass substrate 1 is thorougiriy oic an~ d and drie~i, fr~r axantf,ie by cieaning witf: dist~iled water, rinsing with 20 acs:tor,:e and dryirsg in air. A 100 prn t;)iclc first PJf1Al grid is deaasited on tha su~; tr,-.+.e. by screen :arin:int} to lir=OVitie a firsSt curre"Yt cci;ector layer 2.
First subatrate I is coated with thin film 3a of a 56-Lei solution of 6nC by spin coatinsr so that first current collector ;ayer 2 is betwaan first :serostrate I anct triiri film 3a. Znl.~ ~s a transparent conduotlve oxide. The so?..ge!
solution is 25 ailo,vr:c to dry and thin film 3a is surFa.ce patterned by hot-embossing to `orrrr ?atters-,ec1 transparent concuctive oxide laver 3b haviny rectangular pattern c~ernents. Tie patterner transparent conduwtive layer is sintereo. F'attaaned a ::ar;vparent conductive oxtde layer Sb i, 1000 pm thick. The patterri elements are 0.1 .rm thick and I Wm long, with a separation of 2lim betwe n pattern eiernents.
A 0.5 prr td?ick n-type sr:rr!`cori:tuctor fi!m 4 is then formed ori patterned trznsqaren4 cor.ductive oxide layer 3b by spir-Goating. The n-type semiconductor c-omprises Guina? nanopariides prepareJ by microwave synthesis as aescribed in cornr-nonly owned k't;'t' apodi.ation PC,TXA2005lUCJ11 12 filed July ~1, 2006, the d;sc:'sosrce of wn8cii is her in incorporated by referenr,a. Solid state bandgap of the C;u1n,32 rrancparticfes is about 1,5 elv'. Such Ranoperbcies are soluble tn water ar,d easy to disperse, f o Pabr,f:;aL'oxt cfsecrrnd s!actrcda (catflods.):
A 300r prr thick second higNiy transcarent glass substrate 5 dvith simiiar ci,mensicns to the first glass substrate is cleaned and dried and coated with 0.3 ihi:ic sillwr d;oxide uarrier layer 6.
A 0.5 pn : thick r;ro(y:acenum fiirr 7a is formed on second giass substrate 5 wa;h barrier layer 6 sandvvyched in betweerc. The molybdenum film is formed by magnetrur sputtering of a maiyb*Jenurn target. Wlalybd rum fiirn %a is pattemad k laser scribing tc iarm patternad metallic flim structure lb having rectangular Mrittem elemFrnt.s. Th s pattern caterrants have the same size anG separation as rhe pattern P ernant s on the patter7ied TG0 layar.
A 0 2 pm thick p-nyce se!r,iconductor r11m 8 Is then formed on patterned me,t~.liic film structtare 7h by sw in-coating. The p-type sarniconductor comprises C:c Te nanoparticias prepared tfy mrcro,vave synthesis as described in commor.ly ownec r+CT apofication PC'lCA2006f001 t 12 fiied July 91, 2006. the disclosure of wh& is hrtire9r; incor,pr;ated by reference. Cr;Te is a su4rab!e p4yzin 2: se *~<<~~,rzs9u;.tcr tc fOrm a 3-w i=ietarojunctlnr vrlth GulnB2.
Fa-Pr;cai;car of it-,e phr.fovci!ta(: ae!f.' The two rrodif~ad y;ast substrates are then laminated together at a tercpErature of about 150'0 under vacuum to form graded photcvottaic cell 10 having a 34) heterojunctiork 11 at an interface between n-type 4 and p=type B
S
semiccntluctor filrivs. At ~E 3-0 heteoJunr.t or),, raat:s oX the n-type and p-tYpe semiconduc-or films are noc encfaged in the irtterface. The pattern elernenis of tr?.nsl:.arevt canductive ox.ide layer 3b Gnd pa7:erned metaliic fiim structure 7b are aliw7ed in the ~..eil.
~ Refarer~cr~s:
Shaheer et Eii ,"2. 5 rb Effinient Orryanic P'astic Solar Gells", AppJted Physics Leff6r~, 78:841-843 i20C1 i Huyrth et ai., "Hybrtd Nancrod-Poiyrner sola: C:lls". Scler?ce, 234(5564;:2.426-242" flVlarch 29, 24x:2), Kapur e; al.: "Non-4's,Wuum Pracesslng of CuEn,.%GarSe, Solar Ce61s or. R.ic9d ard F{ex;ble Substrates us:n; Nanopart:cle Ini<s" 7ehin Solid Fiirrrs, 431==432 (2003) 53-i,fS F'z:tent 5,985.691. Basr+l ot al., POetf;cd of IVtslcing Compo!;nd Semicorid,aL.tor Fi4me inn POaking Relateck Eiectronlc Geiices", issued hioNeemoer 16.1999.
Kr;ssaier st aiõ :`Progress in Low Cost irlactroceposition of CG(in,Ga)(S,Se)2: The CISEL Prcaiect". 20th Europsarr Fhr.fo,vifeic Soldr Eriergy Gont+:arence. 6-10 June 2005, Sarcelona Spain.
US Patent 7,026.256, Taunier ct al., Method for Making 1'hi;'.,.ti::?i SerTiiconductors ESasud or I-IIi-Vit Gompou;t¾ts for Photovoltaic ADplioations issuoci Aadl 11, 4,6+)6.
[3isnt e~ e,"CQmpar!son of Spray Pyroierr-~ad F77, ATO ar!d iTeJ Gcetrngs fcr Flat and Rer,t C:lass S:rbstrat.es", Tfiin Sof,id Fflrrrs, "j6^ (199G) ? 09- s 14, Patant 6,34 0,7&ca, f=atritsaf3 et u~aE., "hAultiE,a~~er t~ttotovo!t,ai~: or Pnotoe~:,nductsve ^vavic.ew`. issuect.january 22, 2002.
?ri US P;:tent 4,611,091, r:huudari at al. "C'u1risSew Tt71n F'ilm Solar Geli with 1'fiin udS iar~d Transparent Window t,.aver" isslaec' Septern5gr 9; 19d6. 10 Anderson et A!õ "EiectrochTornic ,-iX'rYObi'Poiymer laminate,..", Apgdlesy CcUcs, 15 US t'atewit 8,481.482, MitsWairo, ,i amirating Apparatus for tvtanufactiiring Photovoltaic 1<Aodu:e", issi:ed Novernber 19, 2002.
a tJS Patant 6,90.597. Sager et ai., "PhoTovo!taic G+evices Fabrfcs+ted by Growth from Pcous Temp"ate", izss en Septernber 20, 200:.
41, Patent 4,663,495, 9erman at ai., 'Transparent Photovottaic MoJuie`, issued !viay 5. 1987.
Marzolin, et a!., "Fabriraiian of Gias_~~, Wicrostructures= by t.licro-Moltlir g of SoE-Gal Precursors'", .4dvancedMarerlafs, 10 (1998) 571-574, US Patent 7,014.799, Yang et al., Method of Forrn!ng Mesoscop'scatly Structured fvqaterial'. issued N,arch 21. 2408.
US patent -3,285,652, Ku ata o al., "Integrated Thin F(!m 5olar Battery ar,G
i\+lethod of RAanufacturing the Sarne", issued July 24. 2001.
15 tJ.8 patant 4,554.727. [}eckmaw et al., "tf9ethod for Fvsaking fJptica!iy Enhanced Thin Film Photovcltaic Devic Using l,.Ithograjhy Dei'ined Random Surfaces", issuec Novcntber 26, 1 95~..
St.iebig, e. :al., `Silicon Tt,ir==tilm Solar t,eiis with Rectang;_,Ãar-shaped Grating Cr...zware", Ptvg. Phottavol.= R. Apwtõ C2006? -W13-24.
"wJ Other advanT.ages that are inherent to the structure are obvious to ona t;l:i!ledi^t the art= 'ftte a,7?bodiments are deEcrit=ed herein illustratvely and are not rnc,ait ,o iirnÃt the s.:ope of the invention as ciairnea. Variations of tne eoracJoiny arn'e*odirren,+.s will be evident to a person of orc!r!ary s c!!i and are interd c by the inventc,r to be enecmpassad by the fcllovving cla+rns.
(?
Claims (4)
1. A solar cell comprising a first electrically conductive layer, a second electrically conductive layer, an n-type semiconductor layer and a p-type semiconductor layer, the n-type and p-type semiconductor layers forming a junction, the semiconductor layers comprising nanoparticulate semiconductor material and at least one of the electrically conductive layers having a pattern forming a three-dimensional relief.
2. The solar cell according to claim 1, wherein the n-type and p-type semiconductor layers are between the first and second electrically conductive layers.
3. The solar cell according to claim 1 or 2, further comprising one or more transparent substrates.
4. The solar cell according to claim 3, wherein the one or more transparent substrates comprise glass.
6. The solar cell according to claim 3 or 4, wherein the one or more transparent substrates is two transparent substrates and the semiconductor layers and electrically conductive layers are between the substrates.
6. The solar cell according to any one of claims 1 to 5, further comprising one or more current collector layers.
7. The solar cell according to claim 6, wherein the one or more current collector layers comprise silver, aluminum, nickel or a combination thereof.
8. The solar cell according to any one of claims 3 to 5, further comprising one or more current collector layers the one or more current collector layers being between the one or mor substrates and the one or more electrically conductive layers.
9. The solar cell according to any one of claims 1 to 8, further comprising one or more barrier layers for separating the substrate from the other layers of the solar cell.
10. The solar cell according to claim 9, wherein the one or more barrier layers comprise silicon dioxide or poly(3,4-ethylenedioxythiophene) poly(etylenesulfonate).
11. The solar call according to any one of claims 1 to 10, wherein the electrically conductive layers comprises a metallic material, a transparent conductive material or a combination thereof.
12. The solar cell according to any one of claims 1 to 11, wherein at least one of the electrically conductive layers comprises a transparent conductive material.
13. The solar cell according to claim 12, wherein the transparent conductive material comprises a transparent conductive oxide.
14. The solar cell according to claim 13, wherein the transparent conductive oxide comprises indium-tin oxide, ZnO, ZnO:Al, SnO2 or SnO2:F.
15. The solar cell according to any one of claims 1 to 14, wherein at least one of the electrically conductive layers comprises a metallic material and the metallic material comprises gold, aluminum, silver or molybdenum.
16. The solar cell according to any one of claims 1 to 15, wherein the pattern forming a three-dimensional relief is in contact with one of the semiconductor layers.
17. The solar cell according to any one of claims 1 to 15, wherein one surface of each of the electrically conductive layers is patterned.
18. The solar cell according to claim 17, wherein the patterned surface of the first electrically conductive layer is in contact with the n-type semiconductor layer and the patterned surface of the second electrically conductive layer is in contact with the p-type semiconductor layer.
19. The solar cell according to any one of claims 1 to 18, wherein one or more of the electrically conductive layers comprises a patterned portion and a non-patterned portion, the patterned portion being in contact with one of the semi-conductor layers, and the patterned portion being integrally formed with the non-patterned portion.
20. The solar cell according to claim 19, wherein the non-patterned portion has a thickness that affords a sheet electrical resistance of from 1-20 ohm/cm2.
21. The solar cell according to claim 19 or 20, wherein the non-patterned portion has a visible and near infrared transmission of from 50-95%.
22 The solar cell according to any ore of claims 1 to 21, wherein the pattern has triangularly-shaped pattern elements.
23. The solar cell according to any one of claims 1 to 21, wherein the pattern has pattern elements having a size of from 1-5 µm.
24. The solar cell according to any one of claims 1 to 21, wherein the pattern has pattern elements separated by 2-10 µm.
25. The solar cell according to any one of claims 1 to 21, wherein the pattern has 1-15 µm sized triangularly-shaped pattern elements separated by 2-10 µm.
26. The solar cell according to any one of claims 1 to 25, wherein the semiconductor materials comprise CdS, GaS, ZnS, CdSe, GaSe, ZnSe, CdTe, GaTe, SiC, Si, ClS, GaAs, PbS, PbSe, CulnSe2, CulnS2, Cu(InGa)(S,Se)2, chaicopyrite, poly(3-hexylthiophene (P3HT), poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV), [6,6]-phenyl-C-butyric acid methyl ester (PCBM), or a mixture thereof.
27. The solar cell according to any one of Claims 1 to 25, wherein the n-type semiconductor material comprises CdS, CdSe, CulnS2 or [6,6]-phenyl-C-butyric and methyl ester.
28. The solar cell according to any one of claims 1 to 25 or 27, wherein the p-type semiconductor material comprises CulnS2, CulnSe2, Cu(InGa)(S,Se)2, CdTe, P3Ht or MEH-PPV.
29. The solar cell according to any one of claims 1 to 28, wherein the semiconductor material is embedded in an organic conductive polymer.
30. A solar module comprising a solar cell as as defined in any one of claims 1 to 29.
30. A process for fabricating a solar cell comprising providing a first electrically conductive layer, providing a second electrically conductive layer, patterning either or both of the first and/or second electrically conductive layers with one or more pre-determined patterns forming a three-dimensional relief, providing an n-type semiconductor layer comprising nanoparticulate semiconductor material on one of the electrically conductive layers, providing a p-type semiconductor layer comprising nanoparticulate semiconductor material on the other of the electrically conductive layers and forming the solar cell by bringing the n-type semiconductor layer into contact with the p-type semiconductor layer.
32. The process according to claim 31 wherein the electrically conductive layers comprise a transparent conductive material.
33. The solar process according to claim 32, wherein the transparent conductive material comprises a transparent conductive oxide.
34. The process according to any one of claim 32 to 33, wherein the electrically conductive layer is provided by coating a sol-gel solution of the transparent conductive material on a substrate to form a sol-gel film, patterning the sol-gel film by imprinting and sintering the sol-gel film.
35. The process according to any one of claims 32 to 33, wherein the electrically conductive layer is provided by spray deposition of an initial non-patterned structure of the transparent conductive material followed by spray disposition of the transparent conductive material through a shadow mask to form a patterned structure continuous with the initial structure.
36. The process according to any one of claims 32 to 33, wherein the electrically conductive layer is provided by spray deposition of the transparent conductive material to form a non-patterned structure followed by texturing the non-patterned structure using an etching technique.
37. The process according to claim 31, wherein the electrically conductive layer comprises a metallic material and is provided by DC or magnetron, sputtering of a metal target followed by laser scribing or mechanical scribing to form the pattern.
38. The process according to any one claims 31 to 37, wherein bringing the n-type semiconductor layer into contact with the p-type semiconductor layer is accomplished by a method that provides a graded structure 39. The process according to any one of claims 31 to 37, wherein bringing the n-type semiconductor layer into contact with the p-type semiconductor layer is accomplished by lamination to provide a graded structure.
40. The process according to claim 38 or 39, wherein the graded structure comprises a 3-D heterojunction layer at an interface of the n-type and p-type semiconductor layers, leaving part of the n-type and p-type layers not engaged in the interface junction.
6. The solar cell according to claim 3 or 4, wherein the one or more transparent substrates is two transparent substrates and the semiconductor layers and electrically conductive layers are between the substrates.
6. The solar cell according to any one of claims 1 to 5, further comprising one or more current collector layers.
7. The solar cell according to claim 6, wherein the one or more current collector layers comprise silver, aluminum, nickel or a combination thereof.
8. The solar cell according to any one of claims 3 to 5, further comprising one or more current collector layers the one or more current collector layers being between the one or mor substrates and the one or more electrically conductive layers.
9. The solar cell according to any one of claims 1 to 8, further comprising one or more barrier layers for separating the substrate from the other layers of the solar cell.
10. The solar cell according to claim 9, wherein the one or more barrier layers comprise silicon dioxide or poly(3,4-ethylenedioxythiophene) poly(etylenesulfonate).
11. The solar call according to any one of claims 1 to 10, wherein the electrically conductive layers comprises a metallic material, a transparent conductive material or a combination thereof.
12. The solar cell according to any one of claims 1 to 11, wherein at least one of the electrically conductive layers comprises a transparent conductive material.
13. The solar cell according to claim 12, wherein the transparent conductive material comprises a transparent conductive oxide.
14. The solar cell according to claim 13, wherein the transparent conductive oxide comprises indium-tin oxide, ZnO, ZnO:Al, SnO2 or SnO2:F.
15. The solar cell according to any one of claims 1 to 14, wherein at least one of the electrically conductive layers comprises a metallic material and the metallic material comprises gold, aluminum, silver or molybdenum.
16. The solar cell according to any one of claims 1 to 15, wherein the pattern forming a three-dimensional relief is in contact with one of the semiconductor layers.
17. The solar cell according to any one of claims 1 to 15, wherein one surface of each of the electrically conductive layers is patterned.
18. The solar cell according to claim 17, wherein the patterned surface of the first electrically conductive layer is in contact with the n-type semiconductor layer and the patterned surface of the second electrically conductive layer is in contact with the p-type semiconductor layer.
19. The solar cell according to any one of claims 1 to 18, wherein one or more of the electrically conductive layers comprises a patterned portion and a non-patterned portion, the patterned portion being in contact with one of the semi-conductor layers, and the patterned portion being integrally formed with the non-patterned portion.
20. The solar cell according to claim 19, wherein the non-patterned portion has a thickness that affords a sheet electrical resistance of from 1-20 ohm/cm2.
21. The solar cell according to claim 19 or 20, wherein the non-patterned portion has a visible and near infrared transmission of from 50-95%.
22 The solar cell according to any ore of claims 1 to 21, wherein the pattern has triangularly-shaped pattern elements.
23. The solar cell according to any one of claims 1 to 21, wherein the pattern has pattern elements having a size of from 1-5 µm.
24. The solar cell according to any one of claims 1 to 21, wherein the pattern has pattern elements separated by 2-10 µm.
25. The solar cell according to any one of claims 1 to 21, wherein the pattern has 1-15 µm sized triangularly-shaped pattern elements separated by 2-10 µm.
26. The solar cell according to any one of claims 1 to 25, wherein the semiconductor materials comprise CdS, GaS, ZnS, CdSe, GaSe, ZnSe, CdTe, GaTe, SiC, Si, ClS, GaAs, PbS, PbSe, CulnSe2, CulnS2, Cu(InGa)(S,Se)2, chaicopyrite, poly(3-hexylthiophene (P3HT), poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV), [6,6]-phenyl-C-butyric acid methyl ester (PCBM), or a mixture thereof.
27. The solar cell according to any one of Claims 1 to 25, wherein the n-type semiconductor material comprises CdS, CdSe, CulnS2 or [6,6]-phenyl-C-butyric and methyl ester.
28. The solar cell according to any one of claims 1 to 25 or 27, wherein the p-type semiconductor material comprises CulnS2, CulnSe2, Cu(InGa)(S,Se)2, CdTe, P3Ht or MEH-PPV.
29. The solar cell according to any one of claims 1 to 28, wherein the semiconductor material is embedded in an organic conductive polymer.
30. A solar module comprising a solar cell as as defined in any one of claims 1 to 29.
30. A process for fabricating a solar cell comprising providing a first electrically conductive layer, providing a second electrically conductive layer, patterning either or both of the first and/or second electrically conductive layers with one or more pre-determined patterns forming a three-dimensional relief, providing an n-type semiconductor layer comprising nanoparticulate semiconductor material on one of the electrically conductive layers, providing a p-type semiconductor layer comprising nanoparticulate semiconductor material on the other of the electrically conductive layers and forming the solar cell by bringing the n-type semiconductor layer into contact with the p-type semiconductor layer.
32. The process according to claim 31 wherein the electrically conductive layers comprise a transparent conductive material.
33. The solar process according to claim 32, wherein the transparent conductive material comprises a transparent conductive oxide.
34. The process according to any one of claim 32 to 33, wherein the electrically conductive layer is provided by coating a sol-gel solution of the transparent conductive material on a substrate to form a sol-gel film, patterning the sol-gel film by imprinting and sintering the sol-gel film.
35. The process according to any one of claims 32 to 33, wherein the electrically conductive layer is provided by spray deposition of an initial non-patterned structure of the transparent conductive material followed by spray disposition of the transparent conductive material through a shadow mask to form a patterned structure continuous with the initial structure.
36. The process according to any one of claims 32 to 33, wherein the electrically conductive layer is provided by spray deposition of the transparent conductive material to form a non-patterned structure followed by texturing the non-patterned structure using an etching technique.
37. The process according to claim 31, wherein the electrically conductive layer comprises a metallic material and is provided by DC or magnetron, sputtering of a metal target followed by laser scribing or mechanical scribing to form the pattern.
38. The process according to any one claims 31 to 37, wherein bringing the n-type semiconductor layer into contact with the p-type semiconductor layer is accomplished by a method that provides a graded structure 39. The process according to any one of claims 31 to 37, wherein bringing the n-type semiconductor layer into contact with the p-type semiconductor layer is accomplished by lamination to provide a graded structure.
40. The process according to claim 38 or 39, wherein the graded structure comprises a 3-D heterojunction layer at an interface of the n-type and p-type semiconductor layers, leaving part of the n-type and p-type layers not engaged in the interface junction.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US99652907P | 2007-11-21 | 2007-11-21 | |
| US60/996,529 | 2007-11-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2621665A1 true CA2621665A1 (en) | 2008-05-22 |
Family
ID=39420486
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002621665A Abandoned CA2621665A1 (en) | 2007-11-21 | 2008-02-19 | Transparent and/or photovoltaic solar cell and module |
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| Country | Link |
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| CA (1) | CA2621665A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110061103A (en) * | 2019-02-28 | 2019-07-26 | 华灿光电(苏州）有限公司 | GaN base light emitting epitaxial wafer and preparation method thereof |
-
2008
- 2008-02-19 CA CA002621665A patent/CA2621665A1/en not_active Abandoned
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110061103A (en) * | 2019-02-28 | 2019-07-26 | 华灿光电(苏州）有限公司 | GaN base light emitting epitaxial wafer and preparation method thereof |
| CN110061103B (en) * | 2019-02-28 | 2022-05-20 | 华灿光电(苏州）有限公司 | GaN-based light emitting diode epitaxial wafer and preparation method thereof |
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