~lid Sta~ I ~ i ~ 28-30 (1988)529-532

Noah-Holland, Amsterdam

pHASE TRANSITIONS 3NO IONIC CONDUCTIVIIY IN Bi4V=OII

AN OXIDE WITH A L4,YE~D sTRUCTURE

E ABRAHAM, M.F. DEBRELnLLE.GRESSE, (3. MAIRESSE and G. NOWOGROCK1

z e. 108. ~6~2 l'~llen~d~r162 Fran~

Reeelv~Z?July 1987;in~vised vemlon24November1987

The s~cture . f ~i.V~, I ~asist s ~f ~i20~laye~ inler]=v~ with V~O,, h ~ . Dfffr t h ~ a l aa~]~,~ssho~a tn~e
reve~blr pha~ Iran,ilion~at 720. 840 ~nd t 150 ~ The cellsof the lowI~peraturr fo~s derivefromthe highl e m ~ t a~
tetmg~alcell ~ d u m i ~ t y alr theseImnsiti~s and revealt ~ fuaheron~ al 920 and975 K Thecondu~
livilyis in the ~nge 0.0O1-0.01 (~ era)-' forlhea pha~ ~nd0.i-I (~cm)-I forlhe~Ohase~emebi~sp~ie~a~pmbably

1. IntrOduCtion gle eryslals o f Bi4V~O,, w e n obtained by s l ~ cool-

During the study o f the K-Bi-V-O diagram, we
haveisolateda~mpoundK~Bi~(VO,)~i l l ; i n . m e
syntheses, i t w a s a c c o m p a n i e d b y a n e w p h a ~ w h i e h
~vealed itselfto pertain to the Bi2Os-V2Os diagram
l2]. In this system, only the compound BiVO, hay-
ingthe scheeHte st~et u ~ ~ s well cha~etelized [3-
5 ]. R ~ t l y , its electrical conductivitywas int~-
pretedinte~sofionlo~nduetivityduetooxygen
ions vacancies [6]. ~ e p ~ t paper d ~ l s with
some preliminaryresults c o n c ~ i n g the s t m a u m ,
the pha~ transitionsand the elect r i l l properties o f
the ~ t e r i a l we have prepared ~1
2. Expcrim~tal
Samples o f ~mpo~bion 2Bi~O~, xV~O5 ~ p~-
pared by solid slate ~aetion o f the app~prlate
amounts of the oxides BizO~and V~O, at 1120 K i n
a p u ~ goldcontaineri n air at ambientpressure. Sin-
9' During~dactionoft ~ p~per,~e ha~efoundthat ~u~eh~ d
V~evaev5~d~bhshed ~me ~ s ~ ~ Bi,v~o~ [Zh.N~rg.
ing (5 K[h) o f the fused product.
Powder diffractionpatterns ~ r e obtained wilh a
Guinier DeWolf~mematambienttemperatu~and
high-temperature X-my invesllgationswere per-
formed m l n g a Guinier-Lenn~~mera. For this pur-
po~, the sample ~ s deposited ~ a gold grid and
h ~ t e d at 5 K/h. The radiation used was CuK~.
The singlecrystal data we~ ~lleeledwith a Phib
ips PW It00 automated diffra~ometer (MoKa
radiation).
DSCandDTAanMyseswem d o n e v A t h a g l 0 D i f "
f~ential S ~ n i n g Calorimeterand a 1090B Thor-
~ 1 Analyzer (Dn Pont Instruments).
The conduelPAty m e a s u ~ m ~ t s ~ r e ~ n i e d out
by the complex impedance method using an a u t ~
maled Solartmn Frequency Response Anatyser
ModeJ 1174. The sample impedan~ was measured
i n air o v ~ the freqnenee range 1- t 0~ Hz usinga slg-
nal ~ l t a g e o f 1 V. The samples ~ r e obtained by
cold-pressing and slnteringat 1145 K. The relative
density o f the pellets was about 98%.
Oxygen transport meas~ements we~ p e r f o ~ e d
by lhe EMF m ~ h o d using as references gases p ~ e
air i n the 720-1 120
n~-.gen and

( North-Hotl~d Physics PublishingDivision)

3, Re~It~ t ~ n a ~ w e r b ~ e u ~ the ~ l l parameters ~voluti~n
is imperceptible,
A sic~c p h ~ was obtained for 0.86 ~ x ~ 1, For The sequence o f pha~ travsitlons~ n be written
x > 1, i t was accompaniedby BIVO4 and for ~'<0.86 as:
by an unidvvt~fled ~mpcuncL We have limitedour-
selv~ i n the present study to the upper limito f this 720K 8 ~ y ItS0 K y, I i ~ K liquid
~olld ~ / u t i o n which~ n be f ~ l a t ~ l as Bi~V~O~t, ~ , .,
Yhe oxygen ~ n t e n t was ~ n f i ~ e d by a t b ~ o g m - ~ 6~00Ka 7'~K r - - ~- - 7 - - - -
vi,~etn e analysisp e r f o ~ e d under H2 a t m ~ p h ~
which showed ~ductlon b ~ t w ~ 825 ~ d 900 K to The strongest ~flecfionso f the powder pattern at
metal!inbismuthand VzO3; the r o s s I ~ s ( 1 L44%) ambleat temperatu~ ~ n be indexed i n a f a ~ -
was i n good a g r e ~ e n t with the theoretic] one feted o r t h o r h m b t e ~ l l with a=5.533(1),
(11.49%). bffi5.611 ( 1 ) ~ d cffi 15.298(4) ,~ which~[1 be Unfed
Bi~V20. melts congruentlyat 1160 K, Difl'e~n- further as ' ~ e ~ Cell". H e w e r s . some w ~ k I ~ d l ~
tin] s ~ n n i n g ~ l a d m e t r y ( fig. I ) r~eated t ~ ea- tions m in~mpatib]ewith a F ~ I ] and some ~the~
d o t h e ~ i e eff~ts at 720 and 840 K on h ~ t i n g . On s h ~ that the ~ l l volume must be tripled and thus
~ o l i n g , the last effectoceu~ withouthysteresis, but its a O ~ l p a ~ e ~ a ~ a = 16.599(4), b = 5.611 ( 1)
the first one splits i n two t h ~ a l phenomena: a and c = 15.288(4) A (table 1).
change o f calorificcapacity near 720 K a~d a exoth- Several slng]e crystals havebeen checked on a four-
~ i c e f f ~ t at 680 K. Differevflalt h ~ a l analysis circle d i f f n c t~ e l e r , and the peak huntingp r ~
showed a supplemenlaryr~ersi~ale effect at 1150 K d u ~ systemmicanyfound an orthorhomblccell with
just h e r o n ~e]ting. p a r a m e t ~ about a=16.6, b= 16.8 avd c=15.3 ~.
Powder X-~? d~ff~ct~on verses tempcralU~ in- which ~ e s p o n 8 10 file powder cell with b multi-
di~ted only two ~ymmetry changes ~ p o n d i n g plied by 3. However) a d ~ e ~ m i n a t i o no f lhe X-
to the t h ~ a l effems obse~ed by DSC at 72O ~ d
840 K on heatingand 840 and 680 K on cooling. The TableI
other phenomena (sc~nd order effee~at 720 K and P~ x ~ d~t~~ ~B~V~O"~tamb~emtemPC~m~
traasltlon at I 150 K) ~ not detected either be-
~ u ~ the stabilitydomainsorthe phases f o x e d a ~
0
] 9 3.Sl3 3.815
t 3 ~' 3,773 3,7~2 w
J 3 ~' 3,6Sl ~.6~B
I 3 3.]JS 3~W
2 O 2.e04 2.805 ,
0 0 2.YES 2~67 9
2 0 ~' 2~SS 2.~SS ~
2 ~ 2.~33 2~633 w
0 2 2.602 2.~1
0 ~ 2.547 2.~4~
t 9 2.414 2.41~
4 2262 2.26~
0 ~ 224~ 2~241

~o ~6o ao~ 46o 5Qo ~ o ~e

l• Vis•l • e•]mat• i•t en•ilies.
FI~ I. D~ll?renli~~ n n i ~ ~lodmele~B~.V,Ot,. •l •ff•cdon Im• in•mpatible•lh *'meancell".
 ~ b v a ~ m et aL ~ t m n s i r t ~ ~md ~nr ~ n d u c t ~ z ~ in Bt. ~ 0 , ,

ray diffracted i n t ~ s i t i e srevealed that ~ e h kPs in- x~b~ 3

tens2li~ for h aud k s i m u h a n ~ u s l ydaff~ent from X'=Y~wder ~ at 975 ~
3n ~ e always null;m o ~ e r , the h t , / l ~ t t ~tto for k h k I
or k ~ 3 n varies from one monocryslat to another.
T h e ~ facts suggest lhnt the crys~al~are ver~ ~ro~-
ably twinned and that tile b para~neter found from
powder dala is c ~ e c t 9 164 3.16s
A p ~ l i m ~ r y study by ele~mn/e mi~odtffrae-
fion ~ n f i ~ e ~ i that onlythe a ~ a ~ a e r o f the mean
~11 mu~t be tri~led, M o r a y s , some very spots in-
dieated thai in the true s l m c t u ~ it should be mtO- Z4~0 2.44~
tipli~'d by ~ix!
Because o f ~ r c~cryslalli~tlonabove 700 K, I.~3S 1.93~
the hightemperaturepowd~ X-ray dtffra~ionmea-
s u r ~ e n t s ~ e o f p ~ r a ~ r a c y . ~ae ~ean cell o f the
13f o ~ ~ems tetrago~l, but ~ m e ~ k f a r . i o n s
imphes that a ~ d (or) b p a m m ~ e ~ must be d ~ -

775 K (table 2 ). A~ for tile ~ - f o ~ , the s~ng~ee ~ t a l

reft~io~s areab~ontfor k ~ d k slmulm~aousIyodd: "UaeceU d l m e n s i o n s ~ mto indicatea laye~d lat-
~hlsfa~ meiealesz~a~~he c r : s ~ remaL~ probably ~ ~ ~Go~" Ia~e~ b ~ of a ~ype ~ e r ~ un-
t~i~n~dand onlyon~p~rame~er basso be doubled, I~ A ~ v ~ u s ~ha~e~ 17], perovsk~te
investigated,
Above 84D K. lhe y-ph~e is l-~e~rago~al wi~h s~mb~ ~re found b e t ~ e n the ~i~Oz~§ lay~m; i n
a:4.004~1 ), r 1~,48B(8) ~ al 975 K Oablr 3). BI~MO~(M = W, Mo) fo~ example, l h e t~ic~ess o f
Thus lhe prototype 7.ee]lis a subcel] o f ihe e and 1he 1he pe~Wkile slab i ; nnity i n t e ~ s o f MO~ ~ta-
J~cells ae~rding lO Ihe me~ric relaliOns: hcdra In Sillenphases [ 81, lhe in~rlaye~~ n s t i | u t c
of halogen or alkali-h~dogan ions. In BI~V2OII, the
a~#3~/2ar. ~ . ~ / 2 a ~ , c~c~, cpanmeterandthe~mposilionp~clude~mplele
p ~ s k ~ t e nabs.
Teble Z A ~ e t ~ r a l approach r~lized al room temp~a-
X.~ydat~or~-a~.vzo. m 77~K l u ~ i n the mean ~11 c ~ n f i ~ s the e x i s t ~ o f
Bi20~z+ la~ers and the l ~ t i o n o f V atoms near the
h ~ I d,,,, d.~. t gositions o~upic~ by M atoms i n Bi~MO~ corn-
0 0 2 7~0 ~3 ~onnd~. The oxygan atoms o f the Bi~O~+ laye= are
2 2 1 ~63 3t~2 ss e a r l y Io~led, but a d i f f e ~ n ~ syat~sls ~wealed that
2 I 3 3599 36~2 m o x y ~ n alOms o f Ihe vanadiumpolyhedm are split-
2 2 3 3150 3 I~0 v~ ted on crys~lloyaphiesites o f high multiplicity.It
4 0 0 2821 2819
~ 0 27~7 273t was not possible with data ~llected from t w i n e d
2 2649 2647 ~ Crystals to ~tab[ish the h a l struetu~ i n the t ~ e cell.
o o 6 2567 ~S7 m At this stage, it ~ m s lhat the compound~ n be for-
2 2 5 2438 ~.4~7 m mulatedas ( B i 2 0 2 ) : + ( V O ~ 2 . ~ )~ .
4 0 4 2276 22r7 m T h ~ resullssuggest a passible mobilityo f some
4 4 0 I99~ [ 997 m
4 2 1931 [ 935 ~ oxygen ions in tile VO3~ sheets. CoudueliYity men-
4 o 6 i,~99 1899 ~ s ~ m ~ t ~ show indeed hlgh~nduetivity~ e n i n tbe
6 2 i 1773 1773 w n pha~. In fig, 2, a ~ ~porled me value o f log ~ v~-
5 4 4[ 1.7~1 I-?so ~ sus recipro~l temperatureon healing(a) ~ d e~[-
6 0 1.690 z 690 in8 (b) after a t i n t t h e ~ a l cycle. The iransitions
6 2 3 1"6~6 16~a m ~ p ~ d ~ u ~ evidenced by a g~at vallaliono f
 ~ v ~ ,~0n
ii " v o ~ , slabs must b~ specific& This ~n prob~bl~ be
EJ ~v
(~)
t,~.~
' ~ple, eitherperpendicular or parallelto the l a y s ,
* (s~
Fi~ 2" ~ n d~i~itY'recipr~ ~m~eraturePlOtsfat a h v ~ , ,
tile ~ n d u c t i v l t y and a vadation o f activation on-
ergy. The transitiont e m ~ r a t u m s ~ very close to
those obtained by DSC and high-temperature dif-
fraaMn exper/meots, in particularthese ~sults ~ n -
firm the t h ~ a l hyseresl$ observed for the a~l~
z ~ n s f o ~ a t i o n , On the other hand, Iwo slight un-
expected iacre~es o f ~nd~ctivlty o ~ a r i n 7 ph~$~
OR heatingn = r 920 a~d 975 K~
The oxygen t tans~ort n~mber was d e t e ~ i n e f lbe-
twecn 720 a~d I 120 IC its valueis near unity,Thus,
the preponderant mobile speei~ am. at least i n the
p and "/domains,O ~- anions.
Bi~V~O. a ~ p ~ n to be a ver~ exciting ~ r i a l ,
ho~r a ~ u m o ~ o f qu~saons remain u ~ n s w c r e d
aud furfl~r r zre needed,
From th~ s%mc~um~ po~a~ o f view, t~e p~ci~ ar-
~ng~mr oflh~ vanadium~ d ox~*ge~aloms i n ths
obtalned by sludy of an um~,A~ncd cryslalinthe t~le
~11 at ambi~t t emperor ore (~ pha~), at i ~ t e ~
diote t c m p e r a l ~ (~ phase) and even at hightem-
pcmture (y phase) Neutron diffractionexperiments
on powder specim~ or, better, on a slngte crustal
could a]~o provide fntlrfi~l inf o ~ a t i o n s .
willgiveabsolute valueso f 1he c~dueiivity.The ~
suits o f t h ~ studies ~ o u l d allow to prop~e mech-
anisms for the a~ion mobifily.
T h e influeecco f t~e nonstoiehlomeu~on the tran-
sition temp~atu ~ a~d electrical p~perlies must be
s y s t ~ a t i ~ l l yinvegtigated.
R ~ n f l y . A c k e ~ a n [9] has s y n t h ~ i ~ d com-
pounds with st~et~res built o f Bi20~ § layers, per-
ovsklte slabs (AudvdJiu$) and halogen sh~ts
(Sillen). We i~tend to e~molete this sede with a
fourth type o f slabs: v o ~ .
Reruns
[I]MF D e b = u i 0 ~ c ~ n d F Ab=~m,/ ~lid~aleChem"
(t9~7), to ~ pobl~h~
12l M F ~ m l l ~ r r (Univ~ayofL~llr
t98~h
[ 31A-W-$~c~#t-H-Y-C~n- a. F ~ t i a n d t ~ - Cox,m~-Res
141W.LF"Dm,~d.a M Olazer,~d A.W Hcwat.p ~ Tmnslt
I t 1979) 155.
[ 5] A Pi.r B wd~/and F.H.Da~l,SohaSlaleComm0~
29 (I 9~9) ~l
1~] T Lu andB'C H"St~]e' SolidStaleI~ 21 ( i 9~6) ~3"
[7 ] B Aufi~0iut.Arkivgemi I ( 1949) 463
[g] L ~iJlg,.~ Ano~ Align.~ 246 ( 1941) ~31.
[9] J.F.Aekem~.n,J SoliaS~lc ~em. 62 (19~6)92.