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CUPROUS OXIDEPHOTOVOLTAIC CELLS FOR SOLAR-ENERGY CONVERSION

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Dan Trivich, P r in c ip a l I n v e s t ig a t o r o s Departme n t f Ch e mi t ry State Univers i ty [.layne Detroi t, Michi gan 48202

a T h l s r e p orti w a sp re p a re d s a n accountof wor k sponsor ed the Un' ited by St a t e s G o ve rn me n t. e i th e r th e United States nor the UnitedStates N of nor any of their Department Energyrror any of their employees, o makes any war r anty, c o n t r a c t o rs' su b co n tra cto rs, r their emp' !oyees, any e x p r e s so r i mp l i e d , o r a ssu mes legal liability or r esponsibility or of f o r t h e a ccu ra cy,co mp l e te n e ss' usefulness any infor m ation, that its use a p p a r a t u s,p ro d u cto r p ro ce ssdisclosedor r epr esents r w o u l dn o t i n fri n g e p ri va te l y o wned ights.

OE OISTRIBUTION THISDOCUME]'{T UNITMITED IS

( i)

ABSTRACT C u p r o u s x l de ca n b e u se dto ma k e photovoltaiccells for solar o inexpensive energyconvers{on but cormercial feasibllity depends increaslng the on co n v e r s l o n ffl cl e n cy fro m ru 1 1to 4- 6%. A newm ethod e using pr oton bombardment prcducecopperon cuprousoxide cells gave improyed to voltage but w i t h s o m e o ss i n cu me n t. L o wbom bar dment l voltagesgayebetter r esults than h i g h v o l t a g e s; A u g e rsu rfa ce a n a lysis showed this wasdue to the ior m atlon o f t h i n n e r co p p e rfi l ms a t th e su r face. Tr anginission electr on m icr oscopy a n d s e l e c t e da re a e l e ctro n d i ffra ction on thin Cur 0single cr ystals subiecte d ion bombardment showed that the Cu formedoriented epitaxial to hydrogen f i l m s o n t h e C u r0 . T h e e ffi ci e n cy of the cells has r eached 1.3%. Som e initia l w o r k u s i n g ato mi ch yd ro g e n p roduce copperon cupr ous to oxide cejls also gave t h i n n e r c o p p e rfi l ms b u t th e fi l ms wer e not unifor m. To im pr ove this condition, in t h e s u r f a c eo f th e ce l l s w e re e xamined detail by a laser scanner appar atu s . 0 t h e r w o r kwa s co n ce rn ew l th fl o at zoner efining of cupr ous d oxide, pur lflcat i o n o f c o p pe rb y zo n ere fi n i n g a nd electr or efining, and ion ir nplantation into ihat a conver sion c u p r o u s x i de . A n a n a l ysi s o f th ese r esults shows o efficiency o f 4 - 6 X l s a re a l i sti c n e a r te rm goal and that et' ficiencies of 10% gr eate r or could be reached eventually.

(tt1

TABLE OF CONTENTS

Page I.
II.

INTRODUCTION PREPAREDHYDROGEN BOMBARDMENT CELLS Cu/Cur0 BY ION A. I n tro d u cti o n

1 2 2 2 2 4 5 5 6 6
6 6

B . Exp e ri me n ta l l . A p p a ra tu s Sampl 2. CrrZO es Procedure 3. Bombardment 4 . E l e ctri ca l Me a su rem ents 5. AugerPleasurements 6 . E l e ctro nMi cro sco py Resul C. Exper'lmental ts C l . Ge n e r,rl h a ra cte r f Results o it . Cument-Vol tage Characteri cs sti b . A n a l ysi s o f C u rrent- Voltage Char acter istlcs 2. E ffe ct o f V a ri a ti o n s in the Pr epar ation Cells of Bombardment by Hydrogen a. Effect of Bombardment Gas b. Effect of Beam Voltage Time c. Effeci of Bombardment Evaporated d. Superimposed Copper Layers e . E ffe ct o f B i a s Voltage f, Effect of SurfaceTreatnents g . H e a tl n go f S a mples h . E ffe ct o f V a ri a tions in Cupr ous Oxide I ) Sourceof Copper of A 2 ) S u cce ssi ve nnealing Cupr ous Oxide 3) Doped Cuprous OxideSamples 4 ) E l e ctro p l a te dCur 0

ls
l9 l9 22 26 26 29 32 40 44 44 44 49 49

t.

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F age 3. P h ysi ca lE xa ml n atlon Copper of Film s a . A u g e rS tu d i e s b. .SurfaceReslstivity Measurements c. Electron l'licroscope Studies Added Coatings a . A n ti re fl e cti o n Coatings b . E n ca p su l a tl o Stability Studies n 53 53 56 6l 68 70 70 74
l'4 74 74 74 80 BO 82 82

4.

D . S u rma ry n d D i scu ssi o n a l . P ri n ci p a i R e su l ts ' 2, Analys.isof Hydrogen Bombardment Method a . F o rn rti o n o f Cu/Cu20 Junction Conditions the Junction b . E ffe ct o f B o mbar dment on 3 . A n a l ys{so f E l e ctrical Pr oper ties a . Ge n e ra l b . R e l a ti o n o f V o. to Bar r ier Height c. A n a l ysi so f S er ies and ShuntReslstances III. PREPAREDREDUCTI0NCurOl,lITH BY 0F CELLS AT0MIC HYDR0GEN A. I n tro d u cti o n l . Ge n e ra l i o 2. P o ssb l e R e d u cti n Methods c Ana 3. Therrnodynami lys i s

86 86 86 B6 B6 87 87 87 87 B9 89 9l 9l 9t 93

B . Exp e ri me nlta on I . Generatl of Atoriic Hydrogen 2 , A p p a ra tu s 3 , P ro ce d u re R l C . Exp e ri me n ta l e suts ons I . GeneralObservati C 2 . T h e Op e n i rcu i t V oltage 3 , T h e S h o rt C l rcu l t Cur r ent Pr Reduction ocess 4 . T h e A to ml cH yd t.o gen i and Dlscusson D. 3unmary

( i v1

Page IV.

LASER SCANNER A. In tro d u ctio n

95 95 95 95 95 97 l 0t

B . A p p a ra tu s C . Op e ra tl o n f L a se r S c anner o l . Ge n e ra l 2. Some Exampl of Use es

V. O T H EA C T IV IT IE S R A. I n tro d u cti n o

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B . F l o a t Z o n eR e fi n i n g o f Cu20 C . Io n Imp l a n ta ti o n D . A n ays i s a n d P u rifi cati on of Cu a n d Cu 2 0 l

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VI

SUMMARY DISCUSSION AND FERENCES RE

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INTRODUCT I ON

Photovoltalc cells for saiar energyconversionhave not yet reachedthe stage of wfde scale cormerclal use because econonlcfactors. of [thile several technltoo expens i v e

c a l l y e x c e l l e n t typ e s o f ce l l s h avebeendeveloped, they ar e still

wlth present energysources. In this context, cuprousoxide (Cur0) to conipete l s o f i n t e re st a s a ma te ri a l fo r photovoltaiccells because is easily obtai ned it a f r c m c o p p er,a n l n e xp e n si ve n d widely available mater ial. Fur ther , Cur 0 is i and has e a s i l y p r o ce sse dn to ce 'l 'l s, p resentsno substantial toxicity pr oblems, devjce use as r ectifier s. s h o w n t a b i l i ty a n d l o n g l i fe i n conm er cial s of o C u p r ou s xi d e l s a su i ta b l e mater ial fcr photovoltaiccells because i ts r b a n dg a p , 2 .0 e V , w h i ch i s w i th i n the acceptab' leangefor so' lar ener gycon v er s i on. efficiency for Cur O > 20?',, of L o f e r s k i ( 5 ) h a s p re d i cte da p otentia' l conver sion w h i c h i s a s g o o da s th a t o f si l i con. a h o l e m o bl l i ty o f n ,1 0 0 .r2 .V -l .s- I. Cur 9is nor mallya p- type semiconduc tori th w Resistlvities as low as 60 Q.cmhavebeen

o b t a l n e db ut l o w e r va l u e s a p p e arto be possible. l'lost of the Cur0 photovoltafc cell work has beendonewith Schottky barriers in a n d h e t e r oJu n cti o n s.T h e w o rk from this labor ator y has beenpr esented IEEE r P r o c e e d l n ga n d l rr p re vi o u sD OE epor ts ( t,Z) . s Most of the wor k has beendo ne

cells preparedby therma'levaporationof Cu onto etched surfaces of wlth CulCur0 C u r 0 . l { l t h su chce l l i ; a n e ffi ci e ncy n of > l% has beenobtained. This follow s FF from the paranctersof Vo. = 0.35 V, Jr. = 7.0 mA/cm2, = 0.45 where ) theor etlcal estlmatefor n . Vo c J s F F /Pa n d P .,(A !,l l= 1 0 0 nb7cn?. A conser vative C l

j and t Vo . = 1 .0 v , J r. 17 nA /c n? F F= 0 . 8 g iv e sn = 1 3 . 6 % .Hig h e r h e o r e t i ca l valuescouldbe Justifled.

lov Because the comparatively attainedefficlency, the mainresearch of effort cells wlth improved ls belngdevoted developing to efficiency. Recently methods new of preparing CulCutO cells by hydrogen bonrbardment succeeded greatly ion have in
i m p r o v i n g he V o . o f th e ce l l s, fr om 0.35 to > 0.7 V. This andsome elated r es ear c h t r arc the subJectsof this report.

II.

CU/CU,O CELLS PREPARED HYDROGEN BOMBARDMENT BY ION

A. I n t ro d u c t i o n

The work on the preparationof Cu/CuZ} cells by subjecting Cur0 to ion bombardment initiated near the end cf the previous contract and preliminary was r e s u l t s t o g e th e rw i th a l i te ra tur e r eviewwer e p!esented ET- 230102d) . T he ( in cells preparedby hydrogen bombardment found to have substantlally higher were o p e nc l r c ul t p o te n ti a l S , u p to 0.7 V and above,as compar ed with the 0.35 V o b t a i n e dwi th p re vi o u sC u l C u r0 e]ls pr epar ed ther m alevapor ation Cu c by of o n t o i t c h e d C u rO. D u rl n gth e p r esentcontr act, the exper imental condltion s for processwere exp'lored the bombardment further and the bombarded surfaces were e x a m i n e d d e ta i l b y A u g e ra n d electr on m icr oscopy in techniques. B. Experimenta'l I. Ap p a ra tu s. The

T h e l on b o mb a rd me n t p a ratus shown ap is schem atically Figur e l. in

s y s t e m a d p re vi o u sl yb e e nu se dfor the sputter ing of oxides, and wasmodi fi ed h t o d i r e c t th e b o mb a rd l nb e a m ir ectly onto the Cur Osamples. The appar atus g d t { a s b a s e do n a V a rl a n va cu u m system with a six- inch oil diffusion pum p fitte d w l t h a l l q u l d n l tro g e n tra p . T he basepr essur e was typically 2 x lo- 5 tor r . T h e s a m p le a mb eco n si ste do f an 18 inch cylindr ical glass chamber .The ch r l o n g u n , d 2 .5 cm Io n T e chg u n (Ion Tech, Inc., Ft. Collins, Color ado) , was p b u i l t l n t o a h e a vya l u mi n u m l a te which ser vedas the top cover of the chan ber . T h e i n l e t syste m n si ste do f two contr ollable gas inlets and a ther npcoup l e co g a u g e n t he mi xi n g ch a mb eso that the com position r i and the pr essur e the of g a s m i x t u r e co u l d b e co n tro l l e d . Typically pr essur es z x 1o- 4to g x l0- 4 of torr were used.

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Dlagran of the vacuum aPParatuq used l n the formati on of CulCu^O cells bY hYdrogen lon bornbardment. z

T h e sa mp l e g e w a sfi tte d with heatingand cocling capabilities and sta a l s o c o u l d b e ro ta te d , so a s to allow positionlng nor malto the bom bar dment b e a m n d al so i n a d i re cti o n fa cing the evapor ation a sour ce. S u i t ab l e p o w e rsu p p l i e sw er e pr ovidedfor ionization of the gas and a c c e l e r a t i o no f th e i o n s. T h e ion beam ltage vo' was var iable fr om 0 to l20OV and the ion current from 0 to 35 mA. A tungstenwire neutralizer provided e l e c t r p n s to n e u tra l i ze th e b e am . A shutter allowedcutting off the beam to control the borbardment time. Further experimental details are given in a r e c e n t t h e si s.fro m th i s l a b o ra tor y ( 3 ) . 2. S Cu 2 0 a mp l e s.

The Cur0 samples for the experiments were preparedby nrethods previously d e v e l o p e dn th i s l a b o ra to rya n d descr ibedin ear lier r epor ts ( Za;. The sta r ti ng i m a t e r i a l wa s u su a l l y h i g h p u ri ty Cu ( 99.999+ U I' IARZ adefr om M ater ials gr Cu: R e s e a r c C o rp o ra ti o n , r Ga l l a rd- Schlesinger h o high pur ity Cu) r olled into a l,' w i d e s h e e t o f t0 .0 2 0 'th i ckn e ss and usually 3" long. Thesesam pr ls wer e o x i d i z e d i n a i r a t 1 0 0 0 " C n d w er e sometimes a subjectedto an annealing ocepr d u r e , t y p i ca l l y a t 5 0 0 " C ,b e fo re quenching. The sam ples e usually usedin wer the polycrystalline form with grain sizes of T,2 nnrbut some samples were con( v e r t e d l n t o si n g l e crysta l s b y the gr aln gr owthr nethodq) . A num ber Cur 0 of

samples were preparedfrom Cu containing small arpunts of addedelementsas posslble dopants.. The coding of the samples represented a series I{-X-Y-Z is by w h e r el l i s th e i n i ti a l s o f th e p er sonwhooxidized the sam ple, is the sour c e X and lot of the Cu or the dopantused, Y is the number the lu x 3" section of c u t f r c m a l o n g sh e e t, a n d Z i s the' location of the I cm2sam ple the in secti on.

The Cur0 sheets were cut into I x I cm2samples and then were groundand p o l l s h e da cco rd i n gto p re vi o u s]ydeveloped ocedur es 2 ) . pr ( The r esistivity

of the samples was measured using ohmicaolc contacts. The top surface was t p p o l f s h e da n d e tch e d , typ i ca l l y for l0- 20 s with 8 M HN03, but other etchants w e r e t e s u eda i so . A fte r b e i n g washed water and dr ied, the sam ples e in wer lrmedlately placed in the bombardment system. 3. Bo mb a rd me n t ce d u re . P ro

U s u a l l y si x sa mp l e s e re p l acedin the sample lder ,undera m askthat w ho' e x p o s e d p o rti o n o f th e su rfa ce of eachsample the beam nor malincidenc e. a to at T h e g a s f l o w , u su a l 'l yo f H r, w a s adjusted, the ion beam was star ted, and the n of t h e s h u t t e r w a s o p e n e d a l l o w bombar dment the sam ples to for the desir ed t i r B. at T h e sa mp l e s u l d b e re moved this point, but in some co casesan addi ti onal

c o p p e rl a y e r w a s a p p l i e d b y th e rmalevapor ation. This wasdoneby r otating the s a m p l e o l d e r i n a d i re cti o n to face the evapor ation h sour ce. The evapor ate d co p p e rl a y e r w a s so me ti mea p p l i ed over the entir e sur face, usually then < 60 A s thick, but moreconmonly througha maskto provide fingers for better contact. voltages, beam currents and bombardment A wlde rangeof beam tlmes were tr i e d . T y pi ca l co n d l ti o n sfo r p repar inga goodce]' l wer e 250 V bombar dment

cu v o l t a g e , 1 5 mAi o n b e a m rre n t, and a bombar dment e of 75 s. tim app' licationof a bias voltage to O t h e r r ra ri a ti o n sth a t w e re tr fed inc' luded d t h e s a m p l es u ri n g b o mb a rd me nt' heatingof the sam ples betor e or after bom bar dtt t e n t ,a p p l l ca ti o n o f a n tl re fl e cti on coatings, encapsu' lation the cel ls, etc . of 4, El e ctrl ca l Me a su re me nts.

I sti b The dark characteri cs of the ceJ s wereme a s u re d y re c o rd in g t h e I -V c u r y e so n a n X -Y re co rd e ru si n g an applied bias o f -5 t o + 1 0 V . T h e p h o t o v ol t a i c by i response was then measured exposng the cel l t o Ml i 1l u min a t i o n p ro v i d e d b y

q a n E L H u a rtz-ta l o g e na mpca l i b r ated by a NASA l standar dsi' licon cell. T h eme a su re meo ft th e su rface r esistivity of the thin Cu sur facefi1m s n w a sd o n eo n b o mb a rd e d rfa ce so f Cur O high bulk r esistivity. su of The contac ts

w e r e t w o p a ra l l e l stri p s o f e va por ated go1d" The sur face r esistivity was m e a s u r ea fte r va ri o u s b o n rb a rd m ent es and sometimes d tim this was done,,in situ,,. 5. AugerMeasurements A number rept'esentative of hy cel'ls p;'epareC hydrogen bombardment were e x a m i n e b y A u g e rsu rfa ce a n a 'i ;sis techniques d using a PhysicalElectr onics M o d e l5 4 9 i nstru me n t(O ). S u rfaceanalyses wer einade and depth pr ofi]es wer e

a l s o m a d e si n g sp u tte r-e tch i n gwith a I kV Ar + ion bear n. u 6. Electron Microscop.v

A v a r i ety o f e 'l e ctro nmi cro scqpic techniques wer e usedto exam ine the mo r p h o l o gof th e su rfa ce sp ro d u ced hydr ogen y by (7 bombar dment ) . Thesein-

c l u d e d s c a nn i n g l e ctro n mi cro scopy, ansm ission e tr electr on micr oscopy of p l a t i n u ms h a d o w eca rb o nsu rfa ce r eplicas ( 8 ) anOdir ect tr ansmission d eJect r on m i c r o s c o p of i o n th i n n e d si n g l e c r ystal samples. The last technique oved y pr m o s t u s e f u l.
C. 1. E xpg rime n t a lRe s u t s l

Ge neral Character of the Re s u t s l

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C urre n t-V o l ta g C h a ra cter istics. The gener alchar acter isticsof the e

b c e l l s p r e p are d y h yd to g e n o mb ar dment be examined compar ison b can in with C u / C u r 0 e l ls p re p a re d y th e rmalevapor ation Cu onto an etchedsur faceof b c of C u r 0 . T a b l e I sh o w s se ri e s o f cells pr epar ed the sam e a on sam ples Cur l, of u s u a l l y f i r s t b y e va p o ra ti o n n d then by hydr ogen a bombar dment. is seen It re t h a t t h e h y dro g e n d u ce d l l s showed ce substantially higher opencir cuit p o t e n t i a l s t ha n th e e va p o ra te d lls but somewhat ce lower shor t cir cuit cur r ent s .

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o rn ({

OOOO rn rn tn C \(\IGIN

tn

o rn (\

()o
In sl

rn (\

o oc) rn rn rn
GI N e.l

dA
HO

"o
h
F A

FA

c, oa 3 'o

r,

!EO N r+{ a oq)

oo o v{o HO
tll

A${

oqt (Ju) I
a

ao EE

F{

h t, .rl Oa NE rl Ao . (.) ,,\r .J qt \ri .r{ t+{ \./ o o O d

A r - {O F {B

l.l

o oa
dF{

\o \o
.f

F{

rn

oooo tn rn rn rn
F{ r-{ F{ F{

co

F{

(v), Fl

\o

f\

( \N

\o

f\

r\

F{ F{ F{

r-l C{

f\F

ca (n

oo, r{o
..l Oo!

o0 otr "t
F{

u o u

r{

u I
L.

trl
H

o
F{

F{

I .$ o I H H H I
I F

Fa ea ra Fa
.f flll

-{

F{

r'{

Ff

rr
{r o
I H H H I I

F{

( >o o c ) ttfl
HHHH HHHH HHHH

..$

.$

.f

rn rn oo tl
HH HH

ll

rn o
I H H I d N I E

FA I

rn rn ( >o tf
HH HH lf dd NN

c{ (\l F qF ll

Ff Fq

r! v,

ts |ta

I frr FT

tr

rtll s 4 'o g {A r t r r 9 { ttll

F C I EIEr l

rr

tr{ I

dd NN ll FE

rl

ooo o OA a' [.4 'r., o O >r 'r l E +. | UO

.tr F{

"o O l'a .r{ r J &J qt d d l .l OO

oo

Al

rl

trl

[<

l.l-{

**

Figure 2 shows another comparison between the a*o rrp., of cells.

Figure

dark and light I-V curves for an evaporated 2A shows cell and Figure 28 shows I - V c u r v e sfo r a h yd ro g e n d u ced re cell. In addition to the higher Vo. and factor . Another

l o w e r J u . , th e h yd ro g e n d u ce d re cell exhlbits a better fill

feature to be noted is the very low foruard and reverse currents l:r the dark f o r t h e h y dro g e n d u ce d l l . re ce Illumination causes gr eat change the shape a in

o f t h e I - V c u rve fro m d a rk to l i g ht for the hydr ogeneduced r cell, while the c h a n g es r e l a ti ve l y sma l l fo r the ther mallyevapor ated i cell. ' l , l h l l e th e se g e n e ra lo b se rvations e fair ly r eliab]e, ar the detailed exper l m e n t a lr e s ul ts w e re fo u n d to va ry consider ably that only tentative conclus i ons so var c o u l d b e d r a w nfro m o th e r e xp e ri menta' l iations. The r epr oducibility of the re s u l t s i s il l u stra te d b y T a b l e 2 . The pair ed r esults ar e fr om sam p' les of plate and processed from the same together to makethe cells. Cur0made The Vo.

v a l u e sw e r e fa i rl y re p ro d u ci b l ei n the pair s' the lar gest var iation being 0.0 43 V. The .lr. valrreswere variable, up to 0.5 nA/cm2. Fromone run to another, the v a r l a t l o n s we re su b sta n ti a l l y g re ater so that cor r elations shou' ld m ade y he onl b e t w e e n l o se l y si mi l a r sa mp l e s. c T h e b e st va l u e so f V o ., Jsc and fill factor ar e shown Tab' le3, as obin

Further improvements Jr. were bombardment. tained on cells after hydroEen in finger s and antir eflection coatings, as o b t a i n e db y a p p l i ca ti o n o f co n d u ction cells wlth the best efflciencles for hydr og en s h o w nn T a bl e 4 . T a b l e 5 sh o w s l re d u c e d e l l s. c i fr" b e st i n d i vi d u al ce' ll efficiency shown Table 5 is l.ZlX. in
)

However, one takes the best attained individua'l va'luesof the parameters if of V J r . = 5 . 2 8 m A /cm', o c -- 0 .7 2 V a nd FF = 0.6r or wouldar r ive at an efficiency o f 2 . 3 X . T he o re ti ca le sti ma te so f the efflciency yield valuesof l3X or mor e .

t h Ar&ri

Flgure 2A. CurrenE-voltage curve for a typlcal Cu/Cu2Ocell prepared by ther:ural evaporatl-on of Cu.

-1

-o-_

0 .4

o. 6 V ( v olt s )

a-

1.50

P oi nl A

G|

E t \ ( E
Y

o.75
rF C
lD

o
t

a C)

Dork

-0.1 5

o.f5

0.30

0.45

0.60

o.75
V ol l ogr

(vol fs)

0.9 o

'0.75

'l.5O Flgure 28.

curve CurrenE-voltage lon bornbardrnenE,

for a rypLcal cu/cu2o cell

PrePared by hydrogen

l0
TABTE - Illustratlon
L

of the Reproduclbtltty

of

S i mi l ar

S ampl es of Bombardment

iu/Cu^O Photovoltaic Reslstlvlty of Cu20 (Q'cm) 287 500 1 000 662 ' 526 398 516 340 339 435

Cells Prepared by Hydrogen *

Sanple DLF-mVI-17-Dz
DLF-nVI-l-7-F DLF-mVT-20-A DLF-mVT-20-F DLF-nVII-05-C DLF-mVII-05-D DLF-nVI I-05-G DLF-mVII-05-H DLF-mVII-07-J DLF-nVII-07-K. DLF-mVT-??-D DLF-mVI-22-E DLF-A1-II-04-B DLF-A1-II-04-C AB- Zn-I I-02-Al AB-Zn-II-02-B AB- Zrt-II-05-A AB- Ztr- II-05-82 AB-Pb.III-04-81 AB.Pb.III.O4-D DLF-Sb-II-02-B

Hydrogen ' Bombardment Voltage (VoIts) 250(-275 V Blas) 250(-27 5 V Btas) 100(-60 V Btas) 100 (-50 V Bias ) 250(-230 V Bias) 250(-230 v Bias) 250(-230 V Bias) 250(-230 V Btas) 250 (- 230 V Btas ) 250 (-2 30 V Btas ) 250(-220 V Btas) 250 (-22O V Btas) 250 250 250 250 250 250 250 250 '.

.exP (s) 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75 75

Jsc (*A/cn2) voc (Volt s) ' 1. 61 L.7 4 1. 05 0. g7 1. 55 1. 91 1. 63 1. 30 L.7 2 L. 71 0. 61 0. 41 1. 83 2. 05 2. 49 2.24 2.50 2.7 6 2. 45 2, 65 1. 60 2. 10

rrt
o . 6 74 0. 632 0.637 0. 651 0. 555 0.696 0.685 0. 655 0.640 0 .6 4 1 o .6 2 7 0.587 0 . 62 7 0. 560 0 . 54 3 0 . 64 9 0 . 63 2 0. 670 0. 665 0.653 0.647

59s
964 L64 180 224 148 267 371 ' 150 138 250 274

DLF-Sb-rr-o2-c2

2s0 250

*a^.-r exP

Time of

expogure

to

hydrog,en bombardment .

11

Table3

List of the Cu/Cur0 Cells Prepared Hydrogen by Bombardment l'lhichGavethe Best Valuesof Jsc, Vo. and FF
Resistivity Bomba rdment Voltage (trolts )

Sampl e
A.

of CurO (n.c m)

Jr. '.*P (s ) (mA/cmz )

vo. (vot ) ts

Ce lls wlth B est Jr. V alues :

RI-3 l0 B' RI-3 03 C RI-3 l0 C AB-Zn- I I -05- 82 RI GS-I I D F L - m I - 04 -H VI RI-3 II B R I- 3 0 3 E ' AB-Zn- I I -05- Bz AB-Ln-I I-02-B AB-CdF I I -02'C 2I AB - P b -I I -0 4 -D D L F - AI - I II-0 4 -C D L F - m V I-1 4 -A
.'

407 607 298 371 l 2 s7 317 462 263 371 148 290 138 796 539

2s0
250 250 250 2s0 ?50 250 250

7s
75 75 75 75 75 75 75

3.22 3..|3 3.07 3. 04 3. 03 3.00 2.96 2.89 2,76 2 ,66 2.65 2.65 2,61 2,56

0. 585 0. 560 0. 585 0.626 0. 580 0. 630 0. 534 0. 650 0.632 0. 565 0. 390 0.665 0.575 0.6J3

2s0
250 500 250 250 250

7s
75 90

7s
75 60

B. C e l l s w i th B e st V o . V a lu e s: D L F - S i 0 4 -B - VD L F - m V I -1 9 -G I. D L F - Pb I -0 3 .8 D L F - Pb - V-0 4 -C D L F - m VI7-H I D L F - m V I I-0 1 -B DLF-mVI?6-G DLF-mVI -20-D 341 298 160 252 282 313 ?91 536 250 254 250 250 100 750 250 250

7s
75 90 75 75 75 75

I.gg

| ,20
.|.13 0.62 1.65 l.l0 l.59
I .93

a.720 0 .7 1 6
0.710 0. 709 0.7a7 0,7a4 0. 703 0.702

7s

( continued )

12

Ta b le 3

(contlnued ) L l st o f th e C u /C u ZCelI s Prepared Hydrcgen 0 by Bombardment l,lhch Gavethe Bes Values of Jsc, V and FF i t oc

R es l s tl v l t y of C urO
Sampl e

Bomba rdment Voltage (Yolts )

"exp (s)

sc (rnA/cmz )

vo.
( Volts ) F i tl Fffi-r

(n.c m)

c.

: C e lI s w lth B e st F l I 1 F a cto rs 150 250 240 180 90 2.27 2. 38 J.23 0.697 0.690 0.600

I A B - P b -I I . O4 -B I AB . P b - I I I .O4 .A I DLF- I -05- D Zn-

1s1
176

2sa
500

0. 55 0. 55 0. 54

13 T a b l e4
Evaporated l'fetal (Cu, Au Fi nger sand Sl0r ) Ih. Effect of Applylns Antirefl ectl on Coati on the Parametersof Cul ngs ar Cur 0Sol CelI s

:u Source and ;u20Preparatl on*

5-i

Sampl e RI- 3-03- D

Trea tnBnt I ** (n.cm) 300

Cu-f ARC 298 Cu- f ARC

Yo. (v)
0. 640 0.623 0.623 0.523 0. 498 0 .497 0. 548 0.5.| 2 0.500 0.572 0. 500 0.495 0. 550 0. 480 0 .475 0. 505 0 .475 0.477 0.6.|8 0. 593 O.58B

Jsc (rnA/cmz ) 2.620 3. 023 3. 932 3. 050 4..|36 5.284 2.240 3. 909 4. 834 1 .928 2,750 4. 050 2. 300 3.270 4. 090 2.746 3. 489 4.390 2. 580 2,9:2 3 .890

FF 0. 360 0. 496 0,476 0.303 0.393 0.364 0.274 0.40 0 0.38.| 0. 368 0. 360 0. 32 5 0.355 0. 34 .| 0.31 3 c.?87 0. 349 0. 336 0.356 0. 476 0.435

R (%)

0.604 0.935 J .J 67 0.484 0.8.| 0 0.956 0.337 0 .800 0,921 0.406 0.494 0.651 0.449 0. 535 0. 609 0. 398 0.578 0. 704 0. 567 0.825 0.994

5 -c

R I-3 -1 0 -C

5 -c

RI-3 -JJ-C

220
Cu- f ARC

1 -b

RI-2 Ma rzB V I 02c RI-2 Ma rzBVI 04E R I-3 0 2 E

2060 'l378

A u -f ARC A u -f ARC

l-b

5-d

I 6 04
Au- f ARC

5-a

R I-3 0 4 C

280
A u -f ARC

Cel CulCuc0 I : Evaporated

l-d

R I-l Ma rzB II 05c

988

Au-f ARC

0. 326 0. 255 0 .292

2.860 3.270 4. 390

5 0.3.I a ,324 0.3.| 7

0.294 0,270 0,407

S e eT a b l e sl 98 a n d 'l 9 C
**

bombardment 250 V for 75 s at All cells except last preparedby hydrogen

Cu - f r co p p er flngers; A u-f E gold f in g e rs ; A RC= a n t i re f l e c t i o n c o a t i n g o f S iCx a t t u 8 0 0A

l4

Table5

The Parameters the Best Cul Cur0CelI s 0btained by of Ion of Hydrogen Reduction CurO.

Sampl e RI- 3-03- B RI-3-04- B R:-3 -0 3 - D R I -3 -1 0 - C RI-3 -0 4 - C R I -3 -l I - C

So u rce f C u a n d o Preparati * on Cu,,0 (. 5 -a 5 -,a 5 -a 5 -c 5 -a 5 -c

vo.

(n ' c m )
452 380 300 298 280 2 20

(v)
0.6.|6 0. 578 0.623 0 .497 0.588 J. 500

Jra ,, (nil/cmt )

FF

n (s)
I .213 0.908 I .167 0. 956 0.994 0.9?1

4.A7 3.87 3. g3 5.28 3.Bg 4.83

0. 484 0. 406 0.476 0. 364 0. 435 O.3BJ

* Se e Tab le s 19 8 and l9C

15

b . A n a l .vsl s f C u rre n t-V oltage o Char acter istics. Because the lar ge of d l f f e r c n c e s fro m p re vl o u sC u /C ur 0 Schottkybamier photovoltaiccells, it is e v l d e n t t h at a n e wmo d e l s re q ulr ed. The outlines of a possiblemodelwer e g i v e n l n t h e p re vi o u sn e p o rt (2 d) on the hydr ogeneduced r cells. In this

junction m d e l l t l s p o stu l a te dth a t th e J unctlon in these cells is a Cu/Cur 0 r b l n w h l c ht h e C u i s p ro d u ce d y chemical eCuction the Cur O hydr ogen s of bV ion that ther e is a hlgh r esistancelntr i nbe l n t h e b o mb a rd me n ta m. It i s assum ed th s l c l a y e r of C u r0b e tw e e n e C u and the bulk Cur 0, and that thls layer is produced penetration of some hydrogen this depth in amounts to insufficient by is or to causereduction. The effect of the hydrogen to remove compensate t h e a c c e p to rs a t a re n o rma l l ypr esentin p- type Cur O. The intr insic layer th fo i s r e s p o n s i b l e r th e h l g h re si stanceof the cells at low voltagesin the photoconducting the high r esi s and d a r k . U n d e rl l l u ml n a ti o n th e i a yer becom es gr of so ta n c e d i s a p p e a rs, th a t th e sh ape the I- V cur ve changes eatly. Som e fu r t h e r d e t a i l s o n th e mo d e la re given in the pr eviousr epor t ( 2d) but mor e w o r k i s r e q u i re d . mo!' e conventional analy s es of Pe n d i ng rth e r d e ve l o p me nt this model,some fu CulCur0 will be attemptedhere. An energybanddiagramfor a conventiona'l j u n c t i c n i s sh o w nn F i g u re 3 . A pr oposed diagr am r for the hydr ogeneduced i c e l l s i s g i ve n i n F i g u re 4 . i n t h e t w o typ e s o f ce l l s.
Th e I- V characteristics of th e h y d ro g e nre d u c e dc e lls we re e x a min e da t

It i s possible that the bar r ier height is the sam e

in h i g h v o l t a ge sa n d o n e se t o f d a ta is shown Figur e 5. The limiting slope at h l g h v o l t a ge syl e l d s a va l u e fo r the cell ser ies r eslstance' in this case 12.8 A. to The dark current JO can be assumed be given by the diode equation Jd '' Jo [exp( qv/nkr-) l]
(l )

l6

Cu M e to f

Cu ZO Semicond ct or u
Econduction

Serniconduclor

Eg

Bondgop

E orr i e r Heig h t

Qo

ra -

tr r-

- Fermi
V o le n c e

JEnergy band d lagram f or the Cu/Cu20 sys tem.

Flgure 3 .

17

Cu ZO
f

E Ferrni Evo le n ce

No Bi o

E Fernrl Evotence

Low Bios

Hish
E F e rm i E V o le n c e

B i os

Flgure 4.

P a rt l a l e n e rg y band d l agram f or the C u/ C u20 sys E em of the prcrposed l ntrl nsl c w h l c h s h o w s che effect (B ) unul er l ow bi as, (A ) w l thout bl as, Cu20 layer condl gl ons. (C ) u n d e r hl gh btas vol tage and

IB

o.40
J (a /cm"')
o.30

o, 2o

Dork

o.l o

l2 .g _o

R3

|,2.7 -o-

2.5

5.O

7.5

lo.o

V (votts)
Flgure 5i
Of a hydrogen l on reduced curves, C u rre n t-v o l ta g e l n che dark and under l l l urnC u / C u 2 0 c e 1 l , measured for the P urpose o u E to hi gh appl l ed vol tages i n a tl o n o f c a l c u l a c to n of the serLes res i .scance and the barheighc. ri e r

1e

rhere V ls the Junctlon potenilal VJ = .a - IR, obtalned correcting the appl by i ed voltagefor the dropacross the series resistance, is the el ectr oni char ge, q
c

k ls Boltzmann's constant, is the absolute T temperature n is the diod e and

n o n - i d e al i ty fa cto r. A p l o t of ln Jo vs. Vj is given in Figur e 6. The in ter c ept y l e l d s a va l u e fo r Jo . I f Jo l s u se d l n th e R i char dson equation

Jo = A**T2exp(q6o/rr)

e)

w h e r eA** l s 1 2 0A /cn ? .f2 , th " bar r ier height 0g can be evaluated. Bar r ler h e l g h t s of 0 .5 8- 7 0 e V w e reo b tainedby this m ethod. T h e no n -l d e a l l ty fa cto r i s given by n = (q /kT )dvj/cId) ( 3)

a n d c a n b e e va l u a te dfro m th e s lope. Valuesof 12- 59 wer e obtainedwhichar e q u i t e u n usu a l mp a rew i th va luesof I - 2 for near ly idea' l diodes. co d An o th e ra p p ro a ch a t w a s tr ied was that of light biassing. Figur e 7 s how s th a p l o t o f l n Jr. vs. V o . fo r var ious lisht intensities. Sir nllar analyses f o t h l s t y p e o f d a ta g a vea b a rri e r height of 0.60 eV and an n- value of 4.6. The b a r r l e r h e l g h ts p re vi o u sl yme a sur ed Cu/Cur 0 on cells pr epar eci evapor ate d by C u t o p l a ye rs h a d va l u e so f 0 .6 5- 0.70 eV ( la,Za) , whjchar e similar to

those npasured for the cells formedby hydrogen bombardment discussedabove. as However, the present treatment is clearly inadequate and a moreextended treatnent wlll be necessary.
2, E ffect of V arlations in t h e P re p a ra t io n o f Ce lls b v H d ro g e n Bomba rdmen t

A nunber of the conditi ons of the p re p a ra t io n o f t h e c e l Js were v a ri e d t o

determl the opti mum ne cond ti ons. i e. Effe ct o f B o mb a rd me nt The effect of hydr ogen Gas. bombar dment cur O, of

20

-2

#
c J

I.O

2.O

4.O

vj

5.O ( volts)

6.O

7.O

Flgure 6..

Plot of the natural log of the dark current (ln J6) versus the corrected voltage (V5, where Vl = Vmeasured-IR Series) made from the current-volEage curv6 of. a Cu/Cu20 cell formed by hydrogen ion bornbardment, such as shown in Flgure 7, and used to determlne Jo and the barrier height.

*,
Et'

*
i.'

h:r $i.' t.,

.

li', ' t; g.

)1 '

21

"i o E
C'

o.l

o,2 vo.

o.3
( volts)

0.4

Flgure ,7.

currenl: Plot of the natural log of the short-clrcult (ln J"g) versua the open-clrcul.t voltage (Vo") measured under-varlous light lntensitl.es from a Cu/Cu20 ce11 formed by hydrogen ion'bombardrnent and used to deterheight mlne Jo and the barrlei

22

as already implied, was to reducethe top surface of the CurOto Cu. This was v e r i f i e d b y l ) vi su a l o b se rva ti on Cu film s pr oduced of with sufficient tr eatrr : n t t i m e , 2 ) fo rma ti o no f re cti fying junctions, 3) Augeranalysis, and 4 ) a n a l y s i s b y e l e ctro n d i ffra cti on. Pr evious wor k ( lO) naa establishedthat

CurOcould be reducedby atomlc hydrogen. The rgaction should be expectedto be evenmorefavorable with lonized hydrogen. Fromthermodynamics can one + + c a l c u l a t e t h a t fo r th e re a cti o n Cur O( s) ZH+ ( g) Ze- = 2Cu( s)+ HZ0( 9) , A G "( 2 9 8 ) = -7 4 4 .'l kca l .mo ]-], So that one can conclude K that the r eaction w is h i g h l y f a vo ra b l e . P re vi o u s or k ( tt) naa also establishedthat Cur 0could w b e b o m b a r d e di th A rg o ni o n s w i th out leaving Cu on the sur face, and this was fo u s e dt o s p u tte r-e tchC u rO r A u geranalysis. th I t w a s co n ce i va b l e a t mi xtur esof H, and Ar might r esult in par tial C with s p u t t e r i n g w h i l e l e a vi n g so me u on the sur face. Bom bar dment Ar + alone any r ectifying or photovoltaicjunctions . a t 5 0 0 V a n d a t 1 0 0 0V d i d n o t p roduce j in M l x t u r e o f H, a n d A r p ro d u ce du n ctions as shown Table 6. Howeverthe ,

Ar re s u l t s t e n d e dto b e p o o re r fo r mixtur eswith 80- 90% . Ther edid not appear gas. to to be any advantage the use of Ar in the bombardment ,b. Effect of Beam ion bombardment Voltaqe. The voltage of the hydrogen in b e a m a s v a r i e d u p to 1 0 0 0V . A s shown Tab' le7, this had ver y little w o n t h e Vo . of th e ce l l s. effec t

with H o w e verit was foundthat the Jr . decr eased , It wasconcluded that the

in vo h i g h e r b o m ba rd me n tl ta g e sa s shown Figur e 8.

wor b e s t v o l t a g e w a s 2 5 0 V a n d th i s w as usedmost often in subsequent k. Lower v o l t a g e sg a v ep o o re rre su l ts. voltage on Jr . is fo A p l a u s i b l e e xp l a n a ti o n r the effect of bombar dment that the higher voltage allowed deeperpenetration of the hydrogen,thus producing the llght tr ansm ission lnto the t h l c k e r C u f il ms w h i ch i n tu rn w oulddecr ease C u r o ,y i e l d i ng a l o w e r Jr.. is A n o therpossibleexplanation that the continui ty

23

TAEIE 6'

Cu/CurO Celle SputterLng

Prepared by Bonbardrnent with

VarLous H-Ar

Gas Mlxtures*

Sam 1e

Res is t Lvlty of Cu"O (0. cfi)

H ( z)
50 50 20 20 10 10 10

Ar ("A)

sc (nA/cm,)

voc
V ol ts)

DLF-nVI-14-C AB.Pb-III.04-81 DLF-nV-17-K DTF-AI-III-04-B DLF-roV-14-B DLF-SL-rV-05-C DLF-CuBE-I-04-Fz

751 150 466 751 322 339 1050

50

l. 9 8 l. 9 4 2.08 2.O4 0. 26 0. 37

0. 630 0. 535 0. 491 o.577 0.370 0. 545

5o
80 80 90 90 90

N o P hotovol tal c E ffect Found

A11 cells

were PrePared under the normal bombardment condl tl ons snd 75 I bombardmenE ti me.

of

250 V bombardment voltage

24
TABLE 7
VarLance

ln

Vo" w l th of

B ombardment V ol rage

U sed in

P re p a ra ti o n

C u/ C u^ 0 C el l s z B ombardment (V ol ts V ol tase

Res is t ivi ty of Cu^O S ampl e

(f)'

"6)

oc

(V ol ts)

Art

DLF-mV-II-B DLF-mVII-C DLF-nV-II-D DLF-mV-II-E DLtr-mv-II-G

276 2A5 2L4 290 588

1250 r0q0
750 500 25A

0.545 0. 580 0.590 0.590 0. 545

I *:t I-01-E DLF-mVI DLF-mVII-01-G DLF-rnVII-01-B I-01-J DLF-nrVI I-01-H DLF-mVI 319 259 313 298 229 1250 1000 750 500 250

0,662 0.660 0.704 0.692 0. 680

'TDLF-MV-I

Cur0 samples were anneal ed

at

5O0o C onl y. anneal ed from 10000

rt* DL F- 6VI I - 01

Cur0 samples were successl vel y down to 5000 c.

\ \

l.l

\ c\| \ \

E (,

E v

f.o

o\

C'
a?

o.g

o.8

07

r||

250

750 lo o o 500 r250 t l o n Bo m b o r d m e n Vo lto g e ( vo lts)

Figure I

(Js" ) w l C h current .Va rL a ti o n o f C he short-ci rcuLt used l n the preparatl on of th e b o mb a rd me nE vol tage l on bombardmenE . by hydrogen CulCu^0 cells
L

26

o f t h e c u f l l m l s l e ss u n d e rh i g her bombardrnent tages voJ . Effect of Bombardrnent Ti rne. The I ength of time of bomb,ardment d woul b e c e r t a i n l y e xp e cte d h a veso m e to effect but the effect is not obvious,.9 . t h e f i l m t h i ckn e ssma yre a cha l i miting value with longer exposur e timesr i.d th e t h i c k n essa n d co n ti n u i ty o f the film s m ayhaveopposite effects especial l ,y on Jr. Preliminary experiments had shown that bombardment times of less than 45 s g a v ee r r a t i c re su l ts a n d o fte n n o photovo' ltaic effectr ur less Cu finger s were a p p l i e d . I n a syste ma ti ci n ve stigation at shor t exposur e es, it tim was found p o s s i b l e t o o b ta i n so me , u t p o o r , photovoltaicr esponse b for bom bar dment times a s s h o r t a s 1 5 s. T h l s i s sh o w n Table 7, TableA for 1000v and Table in B for 250V. Theseresults showthat the J.. values decrease the bombardment as tlme ls decreased. The Vo. was morelrregular but showed some tendencyto decrease wlth shorter bombardment tlme. L o n g e rb o mb a rd meti me s w e re also tr ied, up to 15 min. Table g shows nt a c o m p a r i s oo f ce l l s ma d e y 1 5 mi n bombar dment cells pr epar ed n b with at 60- 90 s on s i m i l a r C u t0 sa mp l e s. T h e ce l l s pr epar ed 15 min showed at both lower Vo. a nd lower ,1r.. HoYever, the Jr. values were not as low as mlght havebeenexpected f ro m t h e t h i cke r C u fi l ms, sh o w n Augermeasur ements. possible by A explanation ls t h a t t h e l mp ro ve d n ti n u l ty o f the thicker film s tendedto counter act co ln pa r t t h e e f f ect o f re d u ce di g h t transm ission. l Fromthe experlments,the optimum bombardment was chosento be 75 s time a n d t h l s w a s u se di n mo st o f th e o ther exper iments. Suoerimposed Evaporated cooperLavers. It was postulatedthat the good effects of hydrogen bombardment, high Vo.r could be attained with a very i.e. short bombardrnent time, and the better current collection could be achievedwith a n e v a p o r a t ed u o ve rl a ye r. A se ri es of r esults ar e shown Table 9 on C in cells d. c.

27

TABLE.&A -

Effect of short Bombardment Tirnes under 1000 v Bombardment Voltage on Cu/CurQ Cells* Reststtvtty
of

Sa

1e

(n. c6)
525 234 293 742 494 49L

Cu^O s-c (mA/cn2) V oIts

DLF-Sl.-rv-o5-82 DLF-nV-13-C DLF-Sb-In -I-05-D DLF-nV-12-F DLF-ltg-II-04-E DLF-nV-13-F

4s 4s
30 30 1.5 15

1.11 o.42 0.21 0 .23 0. 12 0. 04

0. 515 o.525 0.537 c. 580 0. 550 0.305

TABLE 88 -

Effect Voltage

of Short Bonbardment Tlmes Under 250 V Bombardmenr on Cu/CurO Cett.s*

Sa

1e

Resls t lvlty of CuoO (fl'c6)

exP s) 50 50 45 45 25 25 15 15
after

sc (mA/ cm

V ol ts

DLF-Pb- III.-05-D DI,F-Mg DLF-nV-11-K DLF-CuFr-III-03-C DLF-nVII-03-C DLF-Si-V-04-B DLF-mVI-14-D DLF-In-I-0l-C *Flngers were a p p l te d

232 1120 L24 305 357 341 774 206

t,o th e cel l s

2,35 1.87 0. 38 0.27 0. 63 0. 55 0. J.6 0. 65

bombardment.

0. 535 0.487 0.457 o.293 0,625 0.67 2 0.557 0.602

28

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whlch were made wlth bottbardment times of 5 - 30 s and followed inmediately b y c h e m l c al va p o ra ti o n f a C u fllm of 50- 60 I tnickness. It is seer rthat e o th e . J r . v a lu e sa re h l g h e r th a n values pr eviouslyobtainedwith shor t bombar dmenttimes without Cu overlayers but no higher than cells prepared with normal bombardment times. The Vo. values tendedto be lower than norma'l hydrogen reducedcells but somewhat higher than expectedfrom cells preparedby thermal e v a p o r a t l o n l o n e . T h e I-V ch a racter istics of a cell of this type is shown a in F i g u r e 9 . T h e secu rve sre se mb l e those of the evapor ated cell shown Figure in re in 2 A m o r et h a n th e h yd ro g e n d u ced.cellshown Figur e 2Br espcially in the a b s e n c e f th e ve ry h i g h re si sta ncein the dar k. This suggests o that the high r e s i s t a n c ein tri n si c l a ye r h a d b eenavoidedto som e extent. th I n g e ne ra 'l t a p p e a rs a t the r esults of these cells wer e inter mediate i reduced cells and the evaporated cel'ls. A between those of the hydrogen p o s s i b l ee x p l a n a ti o ni s th a t th e Cu film s pr oduced hydr ogen by bombar dmener e wt Cu d l s c o n t l n u ou s n d th a t th e e va p or ated films wer e ab' leto contact the Cur 0 a d i r e c t l y t h r o u g hh o l e s i n i n i ti a l Cu films. The r esu' ltson the composite l s cel

depending the r elative ar eas contacted. on ki th e n w o u l db e so me n d o f a ve ra ge w o T h i s i s r e mi n i sce n t f so me o rk on back- wallCulCur }r ectifier s by Br attain ( 12) whodlscussedthe modelof a patchy Junction. e. the exper im ents emade wer with the E f fe ct o f B i a s V o l ta q e . Nor m ally

were nndewith at samples grounddurlng borbardment.A series of experiments a b i a s v o l t a g e a p p l i e d to th e sa mple. lt shouldbe r ecalled that the ions af ter belng formd and acceleratedwere largely neutra'lizedby the neutralizer section may beam of the gun. Therefore, the effect of bias voltage on the composlte n o t b e e a s il y p re d i cte d . i Ex p e r in n n ta l l y t w a s fo u n d that a positive bias tendedto r educethe Jr. in in o f t h e c e l i s a n d p o ssi b l y a l so th e Vo., as shown Table 10. As shown Tabl e

TABLE 9

Ph o to v o l ta l .c Bombardnent

Result,s on CulCurO Cells prepared with Tlmes and wlth Evaporated Cu Overlayers

Shorr

Resis t tvlty of Cu,,O Bombardment (0. c6) Voltage (Volts)

exP s

SC

,r

vo i
Volts )

nA/"t"

DLF-nV-10-C2 DLF-Pb-r-05-Cl DLF-Pb-r-0 5-C2

296 201 . L76 L62 246 2220 929 929 830 L62 208 929 893 244 . 196 233 3960 198 L62

1000 1000 r.000 500 500 500 250 250 250 250 250 250 25A 250 250 250 250 250 250

30 1,0 10 15 10 10 20 t5 15 15 15 10 10 10 10 10 5 5 5

1. 0g 1. 18 1. 08

0. 560 0.540 0. 525 o.270 o.377 0. 513 0. 443 0. 340 0. 350 0. 280 0. 575 0. 455 0. 335 0. 500 0.350 0. 553 0. 400 0. 380 0. 360

DLF-Pb-I-03-Dl DLF-mII- Oz-Hz DLF-mIII-09'J

1. 23 1.59 1. 38

DLF-nIV-03-D DLF-nLV-03-D DLF-nIV-03-H DLF-Pb-I.03-D1 DLF-Pb-r-03-C DLF-mIV-03-D DLF-nIV-03-J DLF-Pb-I-03-A DLF-Pb-III-05-B DLT.Pb-III-05.F DLF-nIV-03-B DLr-Pb- r-03-B DLF-Pb-I-03-E

1. 03 1. 45 1. 32 1.33 1. 18 2. L3 1. 15 1, g5 L. 57 2. 10 0. 45 1. 13 L.7 2

31

f .50

o.75

Light

- o. I 5

o.60

-' o.75

- I.50

-2.?5

F lgur e

of a C ul C u2O cel l characterl sti cs C u rre n t,-V o 1 tn g e fo rm e d b y a s h ort exposure to hydrogen i on bombardof an evaporated C u overby addl tl on n e n g fo l l o w e d l a y e r.

32

ll'

n e g a t l veb i a s, u n d e rth e co nditionstr ied, did not degr ade the Vo., but s om e

small decreaseln Jr. could be noted. Anotherseries of experiments were performed w l t h l o w e r b o mb a rd me n tl ta g e sand with negativeblas. As seentn Table 12 , vo t h l s g a v el o w e r Jr.. b u t th e vo , valueswer e less affected. In sur mar y,it a p p e a r e dha t th e a p p l i ca ti o n o f bias voltage did not yield any im pr ovem ent. t
f. Surface Treatmen'!s. In the pr epar ati of cu/cur OcelI s by thenna l on

e v a p o r a t i on ,i t w a s fo u n d th a t etching of the Cur 0fo' l' lowed heating in a by Y a c u u m{ a sn e ce ssa ry o b ta i n goodcells. v to In the case of the cells pr oduc ed

by hydrogen the bombardment, surface treatmentwas less important but some the damaged face' left by po' lishing. sur e t c h i n g w a s n e ce ssa ry re mo ve to T a b l e l 3 sh o w s su l ts o n c e' lls made bombar dment sam ples polis hed re by of as w i t h 3 p o r 0 .0 5 u a 'l u mi n a . It is seenthat Jr . and Vo. ar e lower than nor mal with the finest polish,0.05 p. a n d t h a t t h e V o . w a s h i g h e st fo r the sam ples T a b l e 1 4 s ho w s su l ts'o n p a i re d sam ples re whichwer e tr eated with differ ent sam ples but the e t c h a n t s . T h e re su l ts w e ren u ch better than for unetched th d i f f e r e n c esb e tw e e n e e tch a n tswer e not gr eat in most cases. The Jr . was etch alone while the final NaCN better for the 8 M HN03 etch gave sonewhat a s l i g h t l y b e tte r V o . va l u e s. T a ble l5 shows com par ison samples of etchedw i th ( N a C lo n l y (A ) w i th sa mp l e s tch edin HN03 B) . The HN0,etchant appear s be { e to superi or. po' V e r y go o dsu rfa ce sca n b e o btainedby com bined lishing- etching whic h in t h e e t c h a n t i s u i e d a s a l u b ri ca nt on the polishing pad. Resultson sam ples p r e p a r e d n th i s ma n n ea re sh o v nin Table 16. The r esults ar e ver y good, r i the e s p e c i a l l y fo r V o ., a n d i n th e caseof NaCN, addition of the polishing d u r i n g e t c h i n g w a s b e n e fi ci a l . goodresults were obtainedw{th that reasonably In general lt appeared etchant, so that this was chosenfor nnst of the experiments. the 8 tl HN03

33

TABLE J,O

Cu/Cur0 Cells Positive

Prepared by Hydrogen

Bombardment with

BLas Voltages on the CelJ.s*

Sa

1e

ResistivJ.ty of Cu"O (O' cfi)

B Las V ol tage (V ol rs)

sc ,) (urA/crn 1. 45

voc
(V ol ts)

DLF-Sn-I-02-B

-354 466 53. 9 9L2 4L7 492 L260

200 200 200 270 270 400 400

0. 656

DLF-rnV-17-K

1. 53

0. 488

DLF-lO(-1L-J DLF-Sn-I- Az-D

L.7 3 0,2g

0,497 0. 495

DLF-rnVI-18-C

0. LJ. 0. 58

0.460 0. 613

DLF-Sn-I-02-A

DLF-nVI-18-F

0.50

0. 573

* All

of these cells

hrere prepared under the normal bombardment conditions

of 250 V bombardrnentvolcage and 75 s bombardment tLme.

34

TABLE 11

Ttre Best wlth

Cu/Cu,r0 Cells Prepared by Hydrogen Bombardment z NegatLve Bias Voltages on the Sanple * t

1e DLF-nVI-17-F DLF-nVI-17-H DLF-mVT-20-D DLF-nVI-22-A DLF-nVT-26-F DLF-nVII-05-D DLF-Pb-V-04-C DLF-Sl.-V-04-B DLF-Si-V- 04-D2 DLF-Sn-I-02-D

Reslsttvity of CurO (0. efi) 500 282 536 L366 42L 398 252 34L 235 4L7

B J.as V ol tage (V o 1t s)

sc) (mA/cm-) L.7 4 1, 63 1.59 L.7 3 1. 75 1. 91 1. 13 1.99 2. 18 l. 55

voc
V ol ts)

-275 \ -3 L 0 -3 8 0 -2 2 A -3 3 0 -230 -230 -230 -3 00 -3 3 0

o.67 4 0.700 o.7 02 0. 689 0.708 0. 655 0. 709 4.7 20 0, 698 0.705

A11 of these celIs

rJere prepared under the normal bombardment condltlons and 75 s bombardment tlne.

of, 250 V bornbardment voltage

Sornebf and all

these cel1s were among the samples vtith were made on successively anneaLed Cur0.

the highest

oc

val ues,

35

TASLE T2,

CulCuoO Cell.s Prepared by Hydrogen Bombardment at Low lVoltage and wLth Negati.ve Applted BLas Voltages on the Samples

Sanple DLF-nVI-25-B

ResLstivlty of CurO (O. c fi )

Bonbardment V o l ta ges (V ol ts)

t.* (s)

BJ.as Voltage sc2oc (V ol ts ) (aA/cm-) (volts)

JV

1330 L800

75

150

-6 0 -6 0 -6 0 -6 0 -7 5 -7 5 -37 5

0.55 0.28 0. 60 0.46 0.40 0,26 0.62

0.565 0.563 a.632 0.637 0.529 0.600 0.707r\

75 100 10c 100 100 10u

L50

llr-Pb-rv-04-B
DLF-nVT-20-A

1000 662 467 L790 282

75

DLF-nVT-20-F

75

DLF-nVT-?O-C

75

DLF-mVT-20-H

7s
75

DLF-nVI-I-7 -H

It

ls not understood why thls Bamples of thls

sarnple had such a hlgh Table.

It ls possl bl e

voc
that

in comparison the hlgh bias

to the other voltage

used contributed

to thLs.

36

TABTE 13 -

of cu/curO cerls prepared by Hydrogen goubardrnent of As-Pollehed CurO Sanples prepared l{Lthout characterlstics Chenl.cal Etchl.ng
ResLstlvtty
of Cu20 Bombardment O. c m ) /o l ta ge (V ol ts) exP . oc V ol ts

El C

Sample

Grit S l ze of FLnal P ol tsh

m

mA/cmo

DLF-XX-II-E DLF-mVI-21-B DLF-nIVII-10-C DLF-nVII-10-F DLF-nVII-10-H

78.8 599 iSO 393 461

250 1250 250 250 250 250 250 250

360 7.5 120 7s 75 90 75 75

0. 63 0. 45 0. g0 1,0 0. 64 0.56 0. 15 0. 37

0.095 0. 095 0. 345 0. 135 0. 102 0.173 0.26 0.268

3 3 0. 05 3 3 3 0. 05 0. 05

DLF-mVII-12-G1 --DLF-MVII-13-E fu3OO DLF-IoVII-13-F tu300

37
TABTEL4 'Effe c ts Ce1ls of Va rl ous E tchants Ln the P reparaE l on of

C u/ C urO

by Hydrogen

Bornbardment*

Sarnple

ReslstLvlty of Cu20 O'cm

Etc h ants U sed

E tchl ng Ti me(s)

exP sc (s ) (mA/cm2)

voc
(V ol ts )

DLF-mV-10-J2 DLF-nV-10-J1

227 227

8M HNO: 8M HNO3, 57" NaCl Llr NaCN

15 15 30 L0 15 20 10 10 t5 20 10

90 90

1. 96 L.7 2

0. 595 0. 590

AB-Zn-II-05-82*rt AB- Zn'I l-Qs-Blttlt

371 2L7

8M HNO3 8M HNO3, 5"1 NaCl

75 75

3. 04 2.2L

0.626 0.693

2r4NaCN, 57. NH3

DLF-AI-III-04-A DLF-AI-III-04-B 952 75L 8M HNo3 8M HNo3 8I'{ HN03, 57" NaCl 214NaCN, 57. NHg DLF-mVI-26-H** DLF-nVT-26-F** 242 42L 8M HN03 8M HNO3, 57" NaCl 2l'l NaCN, 5"1 NH3

L20 120

1. g2 1.49

0. 595 0.607

75

o.g2

0.694
0.709

T\so 15 s etches
One 20 .75 1.75 s+ fi ro 5 s etches

DLF-rnVT-24-Hrtrt DLF-pVT-24-Glt*

277 210

8M HNo3 8M HNO3, 57. NaCl

10
Treo 15

75

1.83

0.67 5 0. 5gg

s+

75 1.49 One 10 s etch

2t4 N aC N , 57"NH3 DLF-Sb-Zn-I-04-C 322 DLF-Sb-Zn-I-04-A 388 AB-Mg-II-03-Bl AB-Mg-II-03-ClA 322 797
8M HNOg 8M HNO3r 57,,NaCl 8l'l HNOg 8M H N O3, 5Z LlCl lll
NaCN

20 15 15 15 15 30 60 60 75 75 2.43 J..52 2,25 1.80 0.527 0. 570 0.592 0.502

* All

eamples lrere prepared wlth

a bombardment voltage

of 250 V.

** These Cu20 saurpleg were successLvely hlgher voltages than the other

annealed and typlcally

dlsplay

samples whlch were annealed only at

5oooc.

38

TABLE

Effect Cells

of

NaCN Etchants

in

the

Preparatlon

of CulCurO

by Hydrogen

Bombardment*

Results on Samples Prepared with NaCN Etchants Resistlvlty of Cu,r0 (o. cf ) tu 300 J

Sanple

Etchant U s ed zYI NaCl{,

Et,ching TLne ( s

exP
s

sc mA/crn 0. 94

oc ol ts

DLF-mVII-13-C

57. Mg

20 10 L5 60 60

95

0.567

zlq NaCN, 5Z Mg

DLF-nVII-13-B DLF-nV-L4-A DLF-nV-14-B

tu 300 45I. 322

2 H N a C N , 57. Mg LM NaCN l H N a C N , 27" NH3

75 60 60

1. 28 L. 88 2. 03

0. 553 0. 505 0.5L3

Results

on Sl,rnJ.lar Samples Prepared

with

HNO3 Etchant

DLF-nVII-13-D DLF-nVII-13-F DLF-nVII-13-H

tu tu

300 300

8M N03 8M NOg 8M HNO3

6 6 5

100 tu 1.40 g0 tu 1.60

0.605 0.555 0.600

tu.300

50 tu1.70

* These samples were alL prepared uslng a 250 V bombardment voltage.

39
T

TABLE 16

Effect

of PolLsh-Erching
I

wLth NaCN Etchanrs Ln the by Hydrogen Bonbardment*

Preparatlon

of Cu/CuoO Cells

Results

on sanples Polish-Etched
Resls tLvLty of Cu"O (f,I'cfi)

wlrh NacN

Sarnple

Etchant Used

Etchtng TLme (s )

IJ v exP sc ,oc (s) (mA/cn -) (V ol t s)

DLF-mVI.-25-D DLF-Pb.IV-04-C

569 851

2M NaCN, s7 Mg ' 2M NaCN, 5 7 Mg

90 90

75 75

1.10 1.09

0. 580 0. 650

Rasul te on Sltntlar

Samples wlth

Normal 8M NOg Etchanr

DLF-Pb-rV-04-C DLF-nVI- 25-C

851 649

8M HNO3 8l'I No3

10 10

50 75

1.34 1. 50

0.700 0. 6gg

* These samples were iff

prepared wlth

a250V

bombardment voltage.

40

9.

H e a tl n qo f S a mp l e s. In the pr epanatlon Cu/Cur O of cells by ther mal

e v a p o r a t i o n 'a p re -h e a ta t l 0 0 o Cfor l0 min is necessar y obtain goodcells. to Presumably thls ls necessary remove to water vapor or other adsorbed gases. Slmilar treatmentswere tried with the cells preparedby hydrogen bombardment. I n t h e fi rst se ri e s o f e xp er im ents, cell was pr epar ed mallywithout a nor p r e - h e a t l n g . T h e sa me mp l e f cur 0 was then r epolishedand etched,and the n sa o heatedat l30oCfor 10 min and cooled before hydrogen bombardment. The results a r e s h o w n n T a b l e l 7 A ' a s p a i re d cells. i Fur ther exper iments e doneon wer

sl m i l a r s a m p l e s'so me i th h e a ti ng and some w without. Theser esults ar e show n i n F i g u r e l 7 B . It d o e sn o t a p p earthat pr e- heatingis necessar y for the hyd r og e n b o m b a rd mep ro ce ss. T h i s can be explainedby the fact that the Cu/Cur O nt is bombardment made invas:ion the Cur0 so that the by of iunction in hydrogen p Ju n c t i o n i s ma d e a rt w a y i n to the inter ior of the or igina' l sample. For the th e r m a l l y p re p a re d l l s' th e C u film is deposited ectly on the sur face, s o ce dir th a t t h e i mp u ri ti e s o n th e su rfa cewouldbe mor eimpor tantin this case. The fact that pre-heating is not necessary the hydrogen in process bombardment si m p l i f l e s an d sp e e d s p th e p ro cessing. u wasmalntainedat the pre-heat temperature In some experlments,the sample durlng the hydrogen Again no definite differences were observed bombardment. b e t w e e nh e se ce l l s a n d ce l l s w l thout heating. t An o t h erva ri a ti o n w a s to h e at the cell in a vacuum nnediately ir after the hydrogen This might be expectedto anneal the lntrinslc CurO bombardment. l la y e r a n d p erh a p s a n g ets p ro per ties. The r esults ar e shown Table 18. ch in At the lower temperatures, there did not seem be any effect but at 400"C, to there was a tendency towarda lower Vo. and higher Jr. due to the heatlng. This i e f f e c t i s a l so sh o w nn F i g u re 1 0. Since the high dar k r esistanceof the cell b w a s e c r e a s ed y h e a ti n g , i t l s p o ssible that the intr insic layer wasaffected. d

41

TABLE 17. '

Effect of Pre-Hearing of the curO Before cell by Eydrogen Bombardrnent

samples
J

preparation

Experlments on Re-Processed rdentlcaL

Reststlvtty
of Cu^O (fl. "61 DLF-XX-14-G* DLF-JO(-14-Grt DLF-Sb-I-05-Drt iLF-sb-r-05-Drt DLF-C.F2-I-D5-B* DLF-CuF2-I-05-Btt 181 L81 781 781 581 681 130 130 None 10 130 None None

8C

voc
Vol ts

nA/cm- )

l. 6 8 10 L.27 1. 05 10 1. 33 L.L2 0. g6

0. 545 0. 530 0.515 0.590 0. 520 o. 595

ExperLments

on Slnllar

Sanrples

DLF-n-14-C* DLF-Sb-I-05-82* DLF-nV-05-A1* DLF-nV-05-A2* DLF-nV-OS-B* DLF-uV-05-82* DLF-nV-OS-C* DLF-rnVII-05-A** DLP-nVII-05-B** DLF-nVII-05-C** DLF-UVII-05-D** DLF-nVII-05-c*tr DLF-uVII-05-lt**

280 637 357 357 3520 3520 3070 73g 474 526 398 516 340

135 130 None None None 130 130 4OO 400 None None None None

10 10

1.35 1.15 L.20 1.10 I.1O

0.525 0.560 0.430 0.280 0.545 0.495 0.540 0.670 0.664 0.651 0.655 0.696 0.685

10 10 10 10

0.92 1.28 L.82 L.74 1.66 1.91 1.63 I.30

* These eamples were prepared wlth 500 v bombardment voltage and 120 e bonrbardnent tlne. ** Ttrese sarnples nere prepared wlth 250 V bornbardrnent voltage and 75 s boubErdnent tLme.

42
I

TABTE 18

Effects

of Postheatlng

CulCuoO Cells Made by ltydrogen

Bonbardment*

Postheated Cu/CurO Sanplee ReelatLvlty of Cue0 lleatLng J

qeqpte
DLF-Pb-V-04-A1 DLF-Pb-V-O4-!c DLF-S1-V-04-B DLF-InVII-04-A DLF-nVII-05-D DLF-mV-14-A DLF-nVII-04-C DLF-nVII-04-C AB-Zn-I-02-A1

in:lfi
428 338 341 673 398 45L 354 325

(oc)
140 140 L50 240 250 400 400 400 400

Mr-nutes t*i!"t
10 .10 10 10 10 10 10 10 10 1. 15 1. 30 1. 53 L. 81 1. 87 2.53 2.24 1. 94 3. 31

voc
(V ol ts)

0.575 o . 6 74 0.583 0. 649 0.642 o. 455 0. 585 0.605 0. 483

Unheated StmLlar Sanples DLF-nV-14-A DLF-nV-14-B DLF-nVII-04-G DLF-nVII-05-C DLF-nVII-05-D DLF-nVII-05-G DLF-nVII-05-H DLF-Si-V- O4-A2 DLF-St-V-04-B DLF-Pb-V-04-C *'A11 cellg

45L 322 325 526 398 516 340 253 34L 252

1. 88 2,03 L.62 1. 56 1. 91 1. 63 1. 30 1. 95 1. gg 1. 13

0. 505 0. 513 0. 660 0. 65L 0. 655 0. 696 0. 695 0. 695 4.72A 0. 709

were prepared under the normal bourbardnent condl.tlona of and 75 e bonbardnent tlne.

250 V bombardnent voltage

|',

O r+. EO T' l. Ul

qt

-o
e

r0u p .r{ E !, oqr

.()
JA

o
e

()

Io
( ) ED E
\l

co oU .r{
d

'r{ l.

O
l.l

ho

l'.
l I

= o \

(9()

o o \r
o {!t c,
a-

rU

o-to-\ o

OE : fo' +r a

g:5

fl.

oqt o0t OU L. "o ql h,tr srJ SH "tt

>\o
qt

HE H E5 E
,=l

q) .C,
a-

c'

o\.,

v, o

ofr E} ko o,tr t+{q.

.O
F{ F{ q, O F{

o o
t

q, lf)
-..L !rt
a-

o
L-

]L JJ

tL

."{ lJ

o0 tr

UO
F O o{ J

oo

? C)

Oc)
+E, ttl
.'_!

e\\

NE ]550 (J=A
U

4(!0 L)
t+{

.r
L

ttttE o 0,
'lt !J

C'

o
o

F?

5 tJO O |t, o 'r{ C> t,

}.l.t

ocu )o 6 'rf uu,o ."{

rJO U &J A qt( ( ' l {E qto SLt- C

otr

o(0u

o s. c .o t(u
rr!l r A qt
t, F{ OF{ AF{

O 'r{

OOar 3 qt cn

(Jlr,

O E F{ la U 'r{ l. 'F,l E A S, 'rf

u?r
-l

o
r-{

,l

( z w c / v tl l )

lu a r r n c

I
I
I

'.d

a o0

fr

44

h.

Effect of Varlatlons ln Cuprous Oxldg. A large variable in these experl-

m e n t sl s t h e q u a l l ty o f th e C u rO. Thls depends the lm pur ltles ln the star tl ng on C u , t h e r e mo va o r a d d l tl o n o f l rnpur ltlesdur lng the oxldation and pr ocessln g, l a n n e a l l n gc on d i tl o n s, e tc. T h e sefactor s mayinfluence the gr ain slze, r esls tl v l t y , d l f fu sl o n l e n g th , l n te rface states, tc., which dir ectly affect the

p r o p e r t l e s of th e ce l l s. o l ) So urce f C o p p e r. T h e b est high pur ity Cu available cor m er ciallyls Cor 9 9 . 9 9 9 + fC u , su p p l {e db y Ma te rl a ' lsResear ch por ation, l Gallar d- schlesinger , grade is OFE,99.95+X ASARCO, others. The best normalcottvnerclal and Cu. A bom bar dment var ious star ting Cu is b fr om c o m p a r l s o of ce l l s ma d e y h yd rogen n g l v e r rl n T a b l e 1 9 . T h e re su l ts o f this study ar e inconclusive. Fr oma r eview thic the sour ceof the Cu is not impor tant . o f t h e r e s u l ts o n e ml g h t co n cl u de e Cu T h i s c o n c l usi o nl s q u e sti o n a b 'l since the impur ity content in 99.999+f is the car r ier concentr ation 100Q.cm in o a s m u c h s l 0 p p m r l 0 l 8 cm-3w her eas a

Cu r ois 1 o l4 c m-3

ar T h u si t i s e vident that the impur ity concentr ations e

s u f f i c i e n t to a ffe ct th e e l e ctri cal pr oper ties and it is pr obablethat all of t h e s o u r c e so f C u co n ta l n crl ti ca l im pur ities that ar e in par t hannful. A f u r t h e r d i s cu ssi o no f i mp u ri ti e s was given in the ear lier r epor t ( 2d) . It w o u l db e u s e fu l to h a veh i g h e r p u r ity Cu available, at least for tests. Pr oby c e d u r e sf o r p u r{fyl n g C u h a veb e endeveloped Le H6r lcy, t al. ( fg) . wer e usedas oxldl z ed of A o 2 ) S u c ce ssl ve n n e a l i n g f C u20. Sonpsam ples Cur O annealat 500"Cin order to lower at ,\,1000"C nrostwere given a subsequent but the reslstivity. anneal of Recentlywe have found it useful to use a prograrmed

cells 1 0 0 0 o r9 0 0 o r8 0 0 o r7 0 0 " 16 0 0 o ,5 00ofor I hour each. The r esults on some p r e p a r e d n th l s ma n n ea re g i ve n in Table 20. The Vo. valueswer e conslsten tl y r l impr ovem ents Jr . In h l g h , a l l l n e xce sso f 0 .6 4 V a n d as high as 0,72 U. Som e cells on sim ilar samples Cur O( 2d) of w e r e a l s o o bta i n e do n th e rma l l ye vapor ated

45
f'l

Ta b l e1 9

Comparl of Cu/ son Sol Cuo0 ar CelI s Made Hydrogen Bombardment by c

of Cu^0Obtalnedfrom Dlffer ent Star tl ng Cu * c

Startl ng Cu and Cu20Preparatl ** on l) l ' |' a l-b 2-b 3-d 3-d 3-a 4-d 4-a 4-d 5- a 5-a 5'a 5-c
5-C

vo.

Jsc (mA/ ) cmz

Sampl e RI-J-Marl B II- 0 3 -D RI-?-l4arz B V I-0 4 -E B DLF-m III-05- C RI-GS -I-J RI-GS .I.5 RI-GS .I-3 A DR.I-3 A DR-I-5 ADR. -6 I RI-3-03-B RI- 3- 03-C RI- 3-03-D RI-3-10-B RI-3-J0-C RI - 3-04-C

(Q'cm)

(v)
0. 635 0. 550 0. 605 0. 580 0. 583 0. 608 0. 630 0. 583 0.65.| 0 .622 0.620 0.640 0. 582 0. 523 O.6JB

I 370 1378 I 821 1257 577 897 983 518 513 452 607 300 268 298 280

2.43 2. 30 2.56 3.03 2.54 2.63 2.04 2 .35 2 .29 2.48 2.77 2.62 2.70 3. 05 2. 58

2) 3)

4)

5)

5-a

Prepared at 25A V and 75 s bombardment

** For detalls, see Tables t9B and 19C

TableI 98

Types CuUsed Starting Materialfor the Preparation of as of Cur0Samples

Cor in C M R Z g r a d eC u (9 9 .9 9 9 % u ) suppliedby M ater ials Resear ch por ation 3/4" diannter rods. The slices cut from the rod were melted and rec r y s t a l l i ze d i n g ra p h i te cru cible - then r ol' ie,j into a r ibbon of desir ed t h l c k n essa n d cu t l n to re cta ngularsamples. in Cor C Z 2 . l t l ARg r a d eC u (g g .9 9 9 % u ) su ppliedby M ater ials Resear ch por ation t h e f o r m o f 0 .6 n n th l ck ri b b on. 3. by Company in C H l g h p u r i ty C u (g g .g g g Z u ) supp' lied Gallar d- Schlesinger 3,/4r'dianeter rods. The s'lices of 'r,1 rm thickness were cut directly from the rod. 4. (d C u o b t a in e dfro m A S A R C Oo u blyr efined) high pur ity Cu whichwasm elted a n d r e c r ysta l l i ze d (i n o u r l a bor ator y) in a gr aphite cr ucible as a 3/4" r o d . Sl i ce s o f n ,l n m th i cknesswer e cut dir ectly fr om the as- gr oi{ n n a t e r i a l. 5. 9 C o r n n r c l a lOF E 9 .9 5 f C u su p plledln 0.82 r m thick r lbbon sheets

47

Tablel9C

Heat Treatment the As-Grown Cur0Crystals of

After oxidation a t l 0 o o -1 0 1 o o c(.l5- 30 h) , the as- gr own Cur 0crystal s were t subjectedto the fol 1owing hea treatments
a. Step cool i ng down: 900"C for 2 h , 8 0 0 o Cf o r 2 h , 7 0 0 o Cf o r 2 h , 600 " C f o r 2 h , a n d 5 0 0 o Cf o r 2 h .

;.

for I h, I Step coo i ng with a l o n g er heat tr eatm entat 500oC: 900"C for t h, 8 0 0"Cfor I h, 700' Cfor ' l h, 600"C for 4 h. a n d 500"C

c.

j over 1.5 h - then r apid S J co n tin u o u sco o 'ln g from I000" to 500oC ow q u e n ch l n g ro o mte mP er atur e. to

d.

ture . ng d Rapl quenchl f rom I 000"C to room ternpera

4B

TAEIE20

Ilplcal

Cu/Cur0 cells

Prepared by Hydrogen Bombardment

on SuccessLvely Annealed CurO Samples*

Samples

ResLstlvlty of Cur0 (n'cfi)

Bombardment Vol tage (V ol ts)

sc (mA/crn 1. g3

voc
(V ol ts)

DLF-nVT-24-H

-277 229

250 254 250

0.675 0.680 0, 650 0. 660 0. 696 0.685 0. 640 0, 543 0.690 0, 685 o"720 0. 643

DLF-nVIf-0l-H -' DLF-nVII-.09-FI

2. 01

2.25

DLF-mVII-04-G

325 516 340 435 ?74 150 253 34L 249

250, -230 v B l as 250, -2 3 0 V B i.as 250, -2 3 0 v B l as 250, -23 0 V B Las 250 250 254 250, -23O V BJ.as 250, -2OOV Bias

1. 62

DLF-nVII-05-G

1. 53

DLF-nVII-05-H

1. 30

DLF-nVII-07-K DLF-In-I-01-D

1. 71 1. 41

DLF-Pb.II-03-B L-V-04- .,,2 DLF.-S

r . 39 1. 95
1, gg

DLF-Si-V-04-B

DLF-SD,-I-02-C

L.22

* A11 sanples were prepared wlth a 75 s bombardment tLme.

49

T h u st h e s u cce ssl ve n n e a l i n g rocess p a appear s be beneficial. Twoof the to p o s s i b l ee x p l a n a ti o n s re (l ) th e depar tur efr om stoichiom etr y adjustedmor e a is favorably and (Z) sone impuritles are removed from the bulk of the CurOgrains by nucleation and growthof separatephases A 3 ) D o o e d u p ro u s d eS a mo' les. number cells fr om doped C Oxi of sam ples of C u r O e r e i ncl u d e di n th e re su l ts alr eadydiscussed. These w wer e usedpar tly b e c a u s eh e y w e re a va i l a b l e fro m other r esear ch t and par t' ly to detect possibie e f f e c t s o f do p a n ts. U su a i l y n o g r eat differ enceswer e obser ved because the of normalscatter in the results. A comparison between cells from undoped and

d o p e d u r 0 sa mp l e ss sh o w nn T ab' le21. In this par ticular gr oup, the doped i i C higher Vo., but the Jr. values were comparab'le. samples tendedto have somewhat r L e a da n d t i n w e re n o te d to b e mo s t beneficial and some esults ar e given in Table2?. wer eaddedto a base99.999+fl I t s h o u l db e me n tl o n e d a t the dopants th Cu ce w h l c h o l r e a d y co n ta l n e d rta l n i mpur itles. The var ious lmpur ities could d i s t r i b u t e i n so me a y i n th e ca sting and r olling. w Som e impur ities wer e lost

I n t h e o x l d a tl o n b y vo l a tl l l za ti o n or segr egatlon the gr owinglnter face. at pr co A f u r t h e r s e g re g a ti o n u l d o ccu r in the annealing ocess,and, wher eim por tant, or t h e e t c h a n t c o u l d d i ffe re n tl a l l y remove leave impur ities at the sur facc. more Therefore, to properly studJ the effect of impurities wil'l require much her d e t a i l e d i n t ve stl g a ti o n s th a n a ttempted e, and for this it wi' ll be necessar y t o p r e p a r ea h i g h l y p u ri fi e d b a seCu. Cur 0cell s wer e prepa by hydrogen a red 4 ) E le ctro p la te d C u e O. S e verJ Cul i of bombardnrent el ectroplated Cur0f i I ms (t q ) deposted o n g o ld c o v e re d s u b s t ra t e s . Th e f l l m s w e re 3 - 2 5 u m th i ck a n d no etching was usedin mo s t c a s s r s in c e it in T w a s f e l t t o b e u n n e ce ssa ry. h e results ar e shown T a b le 2 3 . F o r p re l imi n a r y r nrents the results were qui te good with Vo. up t o 0 . 4 8 V a n d J r. u p t o experl ,

50

TABTE 21

of Cu/Cur0 Ce1ls Prepared by Hydrogen Bombarduent of Doped and Undoped Gu.O Sanples*

Conparlson

Undoped CurO Saraples Annealed ar 5OOo C

Sample

ResistLvity ' o f C u ,r0 (f,l. c6)

J
SC ?t

voc
V oLts

(mA/ cm4

DIJ-XX-1l-J DIJ-nV-09-D DLF-nV-10-H DLF-nV-12-E DLF-nV-14-C DLF-nV-17-J DLF-rnV-17-K

53. g 589 256 296 242 588 466

2. 00 2. 30 1. 40 1. 93 2,25 l. g g 1, gg

0.469 0. 519 0. 567 0.559 0.430 0. 497 0.512

Doped Cur0 Samples Annealed a r 5 0 0 0 c DIJ-AI.I-03-A DLT-AI.II-04-B DLF-AI-LI-,04-C DLF.AI-III-04-C DLF.AI-III-04-D DLF-In-II-05-B DLF-I{B-II-03-BI DLF-Pb.I-03-E DLF-S1-rV-05-C DLf-Sb-Sr1- I-05-C

337 164 180 .796 s74 451 322 L62 339 580

1.76 2. 13 2. 05 2.6L 1. 49 2. 08 2,25 1. 66 L. 67 L.77

0.594 0.642 a.627 0.575 0. 502 0. 495 0. 592 0.617 0.550 4.622

* These Banples were all

prepared under the normal bornbardment condltlons and 75 I bombardment t Lme.

.of 250 V bonbardment voltage

5l

TABLE 22 . A

Best cu/cuoO ceIls Prepared by Hydrogen Bombardmenr on z Doned CurO Samples Gells t"* (s) """ , (mL/cn') Vo. (Votts)

HLgh Current

Sarnple

ReaLstLvLty of Cuo0 Bombardment (O. c6) Voltage(Volts)

fig-fn-Il-05-82 *. [g-lp-Il-05-82 * AB-Zn-II-02-B AB-Pb-III-04-D rt DLF-A1-rrr-04-C AB-Zr-II-05-A* * DLF-Pb-V-04-A1 DLF-Sn-I-05-C2

37L 37L 148 138 796 267 428

250 25O 250 250 250 250 .250

75 75 7i 75 75 75 120 75

3. 04 2.76 2.66 2.65 2. 61 2. 50 2.50 2.54

0.626 o.632
0. 565 0. 665 0. 575 0.649 0. 663 0, 575

7g4 250, -230 V BLas

Hlgh V.rltage Cells

DLr-S1-V-04-B* DLi.'-Pb-rr-03-B* * DLF-Pb-V-04-C DIJ-Sn-I-02-D * DLF-Pb-IV-04-C t DLF-Sn-I-02-B*

34L 250, -230 V Blas 160 250 252 250) -nA V B ia s 4L7 250, -330 V Bias 85L 25A, -200 V Bias

75 90 75 75 50

1. g9 1. g3 1. L3 L. 55 1. 34 L. 19 1. 05 2.27

4 . 72 0 0.710 0.709 0.705 0,700 0. 5gg 0. 698 0.697

354 250, -375 V Bl,as 7 s 250 75 DLF-Pb-rr-03-D* . 160 24A 250 A3-Pb-rrr-04-81 * 150
* Ttrese CurO Bamples were auccessLvely annealed

from 10000 c t o 5 O O o . c

52

TABLE23

Hydrogen Reduced Electroplated

Cur0 Samples *

*tffie'' sanple
RKP {IL RKP #2

Etchant

Area (ctn21

Bombardment V ol tage (V ol te)

e:(P (s)

acaoc (nA/cE')

JV

(volts)

None

0. 65 1.0 1.0

2s0
250

60 60 60

0.18 0.90 1.00

0.325 0.115 0.325

2 .5 5 .0

None

T-tt
AR #1 AR #1 AR IIZ

None

2so

None

1.0 J..0 1.0

2 5 0 (-1 9 0 V Blas ) 2 5 0(-1 9 0 V Blas ) 250(-330 v BLas)

75 75 75

0.30 0.30 0. 01

0.482 0.475 0.425

None

None

RKP-32

23

5 I wtth 8M HNO30.56

250

60

0.96

0,422

*No reslsttvlty

values were avallable

for

these samples, but the reslstLhigh.

vLty of electroplated

Cur0 is normally

quite

53

I fiA/cmo. The chlef pnoblem wlth the electr oplatedcur Ois its high r esistivity , t 1 0 4o . c ma n d th l s co u l d ca u sesome the lower ingof Vo. and Jr .. of Fur ther

devel opnnnton the bulk properties of el ectroplated curOwi I I be necessary n i order to pursuefurther cel I work. ' 3 . Ph vsfca lE xa mi n a tl oo f Cooper n Film s The fllms produced hydrogen by bombardment examined several techniques were by ln o r d e r t o esta b l i sh th e co mp o s ition the film s, the thicknessas affected of b y b o m b a r d me n tl ta g e a n d ti me , nucleationand gr owthof the film s, and the vo e l e c t r l c a l c on tl n u l ty o f th e fi l ms. Themethods usedwer eAugersur faceanaly s i s ,

s u r f a c e r e s i sti vi ty me a su re me n ts, electr on m icr oscopy diffr action. and and a. AuqerStudles. The satnples were preparedjust before the Augerexamina-

tion (within a few hours) and were transported in a vacuum vessel. Total survey scansat varlous depths showed that only Cu and 0 were present, except for the usu a l , c o n t a mi n a tl o n th e su rfa ce. The sputter etching r ate with Ar + wa; cal i at brated wlth a thermally preparedCulCur0 cell of known thickness of Cu, shown In Figurell. F i g u re 1 2 sh o w s d epth pr ofile for a cell pr epar ed hydr ogen a by

bombardment. outer part of the sample The was i,100t| Cu, which verified experimentally that the effect of hydrogen bombardment to reducethe top surface was o f t h e C u r 0t o C u . E ve n tu a l l yth e depth pr oflle r eached the [Cu]/[0] r atio of 2' r e p r e s e n ta ti ve f b u l k C u r0 . A s seenby the Augerexper im ent, o the tr ansitio n from Cu to Cur0was not sharp (ttris was also true for the evaporated film on Cu Cu r 0 ) , s o t h at th e th l ckn e sso f th e Cu fllm could not be accur atelymeasur ed. As l n d f c a t e d In F l g u re 1 2 , th e l n ter face was chosen the polnt wher ethe Cu at pe a kf e l l t o h a l f o f l ts e xce ssva l ue over the bulk value. . th F l g u r e 1 3 sh o w s e re su l ts o n cells pr epar ed var ious bombar dment at voltages .

A t l o w v o l t a g e s' th e Ju n cti o nw a smor eshar ply definedand the conver sion Cu to

54

G| N

q, .

rHd

to
o< 'r
Y rlO

r0
; o =E H

F {H .r{ tct . ${ >\O

oo o0 oo

= qt =fa

!o |

g
E

o'g u.l t{ gl rn -cl

@ tf

Yl tJH

eE8 OE
O IH O oF l N >,F O tl

r, 3
F
tF

.m =.r {tn E E '- 1

N
I

e.

c o

I .=

E
x
o
b

Cl CL

s
o C)

rt, c.l

E X rif 'r 3J

.U 8,3H
tu\fg tl r St H cJ r! cn d E ( tto

ruoqt 60rr Ntr

lr rJ O 'r{ OOAH 5 >\ O

L at e

A"'/
Fl

({ o \r uoflotlugcuoO

l'{ it
tF

l.Al

quJoly

b0 'rl

tr{

N N

n
0,

o<o u
F{

.}1

' il

htr

'r{

o aE
Y
lr

(o ? r,
a-

h AE

o \t q,
f.t r

rrt
IF I tl .r f $f

68
q' t, h I. (J

t !D OF Cqf A-

\rg

co .5

'CtHAF {q lr O () a O F{ t+{ T r F {O

(,

Ot-

a l"
N
(F

o-

rt

E qtr

r{ O O O'd h c{r, Ft 3 ltt Ct() lo tr\ GIS A (.) (|

o o oc

uN
Ot ,,tr rl rtl o A
O

U
tI' a Efa

o E
o ! rt FF
l-

c! Gt o v{ hu
Ul

s q5
CV (F
(F

tt

v,
o e e o
f.

tH U F{ H .F{ O a cL E o >\}r rro t{ S O ql r| o0 A ${ h

t F{ Ft

rI' ru

tJ F l

Jd (U A O t{ O H 2 ! S n l rqt00 OA O E .F{ l. ,E H 6 A

tr'E

()

d trr

H t 00

(% )

u o tl o Jl u ts u o S

9tl l rol v

l'ktlttn at tar-t t n r r r t " t n . | '| | t -.trlf,lt ! _ +,r * _ * R ,5 .

,]
? I

55

A ppro x lr n q t e 74

Thlckness t49

A)
r86
223 260

ro 0\,
E

\\\_\_ \_=

.9 aC'
L ar

Copper

\i.--

&t c o C)

E C,

.3 4 0 E
o
a-

Bombor dmenl Volto

fooov
750v 500v

z s ov
2.4 ,c|
3.6 J.b 4.9 4.9
6.0

7,2

8.4

S p utter lng Rofe

( minutes)

Flgurc 13. '

Auger gurfacc analysis depth profJ.les of Cu/Cu2O cclls prcpared by hyllrogen ion bonbardment undlr (Bombardment tlne, 75 s.) varl,ous bonbardment voltages.

at the surfacetrashlgher, whereas hlghervoltagesthe Junction at wasmore graded. Thenomlnal fllm thickness,as definedabove,increased wlth bombardment voltage. Thedata are given in a different form in Fig. 14. Theamount..of nretal Cu twlce the pertentage 0 from the total percentage of wascalculatedby subtractlng as the of Cu (ttrts assumes 0 ls present CurO). TheI of Cuols plotted against to sputterlng time ln Flgure14. Theareaunderthe curvewasintegrated 7.2 min of of to yfeld a valueof the total percentage Cuoin that thickness film. This wlth of on ls lndlcated eachcurve. It ls seenthat the percentage Cuolncreased at of converslon Cur0to Cuo any point variedfrom70 to voltage. Themaxlmum 909. and times at Some cells prepared variousbombardment wereexamined the of profiles are shown Flgure15. It is seenthat the amount conversion ln Auger as tlme. bombardment Thenonlnalfllm thickness definedin Flgure Increased\wlth
the per centage tlme. Flgur e l6 shows o lZ l s s e e n \ t o b e l n d e p e n d e n tf b o mbar dment to o f C u ot n t h e to p l a ye r co rre sp o n ding 3.6 r nin of sputter etching ( n,100l) . time. of Thls showt dh.t the amount Cuoformedincreasedwith exposure 15 ln The eff ct o f a ve ry l o n g b o mbar dmentr mln' is shown Flgur e 17. Thi s
\

fllm to converslon Cuoto a depthof 'r,75A. Thenomlnal nearly omplete shows

the T,50[ obtalnedfor was ve d to 'r,1 3 0l , su bstantlally beyond thl ckness at in shorter bomba nt tlmesshown Figure15. A]l cells weremade 250V. b. Su r f a conductorsol ar cel I s -semi stl Resl vl ty l,leasUfercnlg. In nretal '

value ln that the fllm t he t h l c k n e s so f i h e mta l fl l m sh ouldhavean optlm um lateral conductlvlty and thln enough d shoul be thl ck e oughto have adequate t o h a v eh l g h lfsh tra n smi ssi o n . F ur ther ' the conductivity of the fllm depends a s w e l l a s th e thickness

uponI ts contlnult

by of were Su r f a c ere sl st vl ty measurements made the Cu fi lms produced

57

A p p r o xlm f e o

T h lc k n o s g

(i)
223

r oo

5 6 flz

r67
Bombo r d ment Volfoge

I
3 (J

A
\\

looo v
\\\ \\ I ,'\
/

80
'

zl- -

750 V 500v 250V

\

r-ra -Ir--I

-----II

t|-

o /
E C-

\\l

o
tr

60
I I l. I

I I

\\

E'
.a -

u i
\ ,\ \ \

)S-z- 4g.g "h \

\ \

E c,. (, c, o C) t)

42.1 ',h
\ \ \ \

tf
tl

lt 40 '-l
I I

E o
iF

t I I 3f .6 olo

\
a\

20

'\

ot

o
14.

1.8 S putt e r in g

3.6 T im e

5.4 ( m in ue s ) f

7.2

Flgure

of Cuo on Cu/CurO cells prepared by hydroDlstributlon gen ton bombardment at varLofis bombardment voltagee and a 7-c s bombardment tl.ne.

58

tooP
'(n

37

A ppr o x im o t e 74

T h ic k n e s s il2

(i)
t49 186

/ /

80
v
-r--trrrr----

oe

Co pper
e-

. .......-;...Fi l

.rur

.-,

c o

60

{E

C'
L. t-

c c, (, c
C)

()

40
'a a t t'

.g E o a-

20
\

od

v,
///

"""

,4;:
l .? 2.4 S pu t le r ln g

B o m b o r d r n e n t T im e 75s 60s 45s 3Os f5 s 3.6 T lm e 4.8 ( m in u le s ) 6.O

Flgure 15.

of Cu/Cu2O Cells Augar surface anal;vsls depth profiles prepared by h;rdlsgen lon bonbardnent nt 250 V wlth various 'bombardnent tlmes.

59

I
c 3 (J
t-

o
II

a-

c o C' c o ()

L. a-

20

.9 E
o
ap

15

30

40 TIme (s)

B ombord m e n f

Flgure 15.

Amount of Cuo formed on Cu/Cu2Ocells prepared by 8E 250 V-with varlous bonbardinent hydrogen bombardmenE ttmeg.

60

A p p .r oximo.t: r3^ 0 Point A

T hickn es s

( A)

r95

260

CoPPer
^
v

r-->

De

c o
a-

.a-

t+-

c c,
(.t

c () ()

40

C' .E
a-

o xygen ru

2.1 S putteri n g

4.2 T im e

6.3 ( m in u t e s )

8.4

of a Cu/Cu20 cell Flgure 17.., Auger eurface analysis depth proflle prepared by hydrogen 1on bombardment at 250 V hrlth s. 15 rnlnrrle borabardnent t,Lme.

61

hydrogen bombardmnt hf gh reslsfivity of

( > lo4 n.cm) curO preparedby the

g r a l n g r o w t hme th o d ) w fth o u t a low tem per atur e (a anneal. Typically the bomb a r d m e n t a sd o n ea t 2 5 0 V fo r 7 5 s. w 0n a number individual cel' ls, the of

su r f a c er e s i stl vi ti e s ra n g e dfro m 66 to 2300n/squar e. This is r elatively h i g h s o t h a t fi n g e rs a re n e ce ssa r y lower the cell r esistance. In applying to flngers, it was found necessary make to contact to the bombarded surface on'ly, because any evaporated cameinto contact with untreatedcu"0, the vo. if cu of the cell was found to be lowered. A s e t o f U s" i ..L g a su re ments shown Figur e 18. Resistivity measu r eme is in m n t s w e r em a d e fte r e a ch l 0 s o f bom bar dment. is seenthat the sur face a It re s l s t l v l t y fe l l sh a rp l y i n th e re gion of 50- 90 s. Beyond s, the decr eas e 80

f n r e s i s t i v l t y w a s l e ss. T h i s i s consistentwith the empir ica] choiceof 75 s as a n o p t i m um o mb a rd me nme . The Augerr esults also suppor tthis choice. b ti t c. El e ctro nMi cro sco p S tu d ies. It was of inter est to exam ine m or e the

phologyof the Cu film formedon Cur0 by hydrogen bombardment to correlate and t h i s w l t h t h e A u g e ra n d su rfa ce re sistivity m easur ements. number electr o n A of m i c r o s c o p t e ch n i q u e s e ree xp l o red( scanning lectr onm icr oscopV, ansm ission e w e' tr y e l e c t r o n m i c ro sco p o f re p l i ca sa mp' tes, etc.) and the successfu'appr oach l that wa se v o l v e dw a s tra n smi ssi o n l e ctr on m icr oscopy thin sectionsof Cur } . e of S a m p l eo f fl o a t zo n ere fi n cd single cr ystals of Cur 0wer e cut into thin s s e c t i o n s ' f u r th e r th i n n e db y p o l i shing, and finally wer e thinnedby ion m illing at un t i l p e r f o r ate d . T h e e d g e so f th e sam ple the ho' lewer esufficiently thin f o r e l e c t r o n tra n smi ssi o n d i e s. Var iousar eas could be identified and located stu a g a l n i n l a t e r e xp e ri me n ts.T h e sam ples eexamined wer befor e and after a hydr ogen usedwer ebr ight fie' ld and dar k field b o m b a r d m e ne a tme n t. T h e te ch n i ques tr t a ima g l n g n d s e l e cte da re a e l e ctro n diffr action ( SnO) . This allowedone to n d is t i n g u i s hb ei w e e C u a n d C u rO.

62
DA
. L.J I l

a^

o
L

o = trr

"t ,

aE
o-

=
3l'

=c) Yt ct CE

' (, c' ||t-

A4

40 B om b o r d m e n t
18.

60
-Ft

80 (s)

f oo

I I me

F lgur e

resl stl vl ty o f Ehe surface Va ri a ti o n of the C u fi l m a s a fu n c ti o n ' of the bombardment tl me by hydrogen lons.

63

Reprtsentatfve SADpatterns before and after hydrogen bombardment are shown Figures l9A and B. The pattern ln Figure l9A is that of a well ln orlented single crystal of Cur0. This spot pattern was indexedfrom known crystallographic data (15) and the assignments shown Figure 20. Figure are in pattern of the sample l98 shows the SAD after hydrogen bombardment. baslc The p a t t e r n i s s tl i t tt.t o f C u r0b u t the patter n containsm any mor espots, ar ising

from the Cu fonnedby the bombardment. .Thelndexlng of the spots in this pattern is g i v e n i n F i g u re 2 1 . A mo red e tailed identification of the doublediffr action s p o t s l s g l v e n i n F l g u re 2 2 . It can be seen that the Cu spots form an :'Centicalpattern to that of Cur0 b u t s l i g h t l y e n l a rg e d . B o th C u a nd Cur 0havecubic str uctur eswith ' lattice p a r a m e t e i s f 1 .8 0 8a n d 2 .1 3 5A , r.tpectively, so that the Cur 0' lattice is o diffr l5 % l a r g e r t h a n th a t o f C u . T h u sthe comesponding action patter ns ar e that Cu for msas a sing' le c . l o s e r t ot h e ce n tra l b e a m. T h u sthis patter n shows c r y s t a l o n C u r0a n d th e re l a ti ve spot positions showthat Cu for m sepitaxially th o n t h e C u r O . A n a l ysi s sh o w s a t the Cu { 100} planesar e par allel to the o t l0 0 ) p l a r r e s f C u r0a n d th e C u <.|00>dir ection is par aliel to the Cur 0 < .|00 > d i r e c t l o n . It i s i n te re sti n g th a t these or ientations occur in spite of the l5? i m l s m a t c hn l a t.i ce co n sta n ts. f Additional spots occur aroundthe primary diffraction spots by the phenomenon o f d o u b l ed l f fra ctl o n (1 6 ) a n d th e s e ar e often ca1ledsatellite spots. Double strongly diffracted by one set of rllffractlon occurs whenan electron beam p ltself and is diffr acted a second time by , p l a n e sa c t s a s a se co n d rl ma ryb e am se a fa v o r a b l y ori e n te d se co n d t o f cr ystal planes. Epitaxial layer s on a cr ys tal diffr action ( 17) . Double diffr acti on pr o v i d e v e r y fa vo ra b l eco n d i ti o n sfor doub' le o c a n r e s u l t i n th e a p p e a ra n cef fo r biddenspots as well as satellite spots. In these Cu on Cur0 patterns, both forbidden and satellite spots occur. The forbidden

' t-. 'i

.1r'**-

patcerns of an ton thtnned FICUREf9.- Selected area electron dlffractton Gu20 crystal (A) before and (B) efter hydrogdn ion bonrbardvollago ond 150 r bonbnrdruonttlnc. nGnt ot 250 V bombardrnent

65

o
.. rr-

o
t-

o
rra

o "o4

r3 l

o22

f t3

z
r--

t20
-a

o o -rl
o ooo o

z
to 2

z
2 r3

o
trl

o
rtl

o
?22

z
ar--

z
-t

z
e3l

I 02

O II

t20

o
- t-

o
o "2
IID

o
l3
( ce n te r Sp o t)

o
240

il3

o z

= U n d i f f r o c t e d Be o m = C uo O S p o t s
c

a F o r b i d d e n D o u b le Diffr o ctio n Sp o fs

FLgure 20.

Indexlng of the slngle found ln Figure 27A.

crystal

Cuoo spot partern

66

-x

(o 2? l
A

Ao B

BX AOA B

( f T3)

x (2O4)

AoA

B AO A B

B AZA B B A O X (llt) B B A Z A B B AOA BX

AZA

o
B A OA B .B AOA

AO AX

Qzzl

z
o

A Z A

x (o22't

AOA
( I3 I)

X Q 4ol

O= U n d i ffroc l ed B eom (C e n le r S p o t ) O= CuDO S pots C

z = Fo r bi dden
X= A= B=
Cu S pofs So te l l l fe So tr l fi te

D oubl e D i ffr oction

Spots

D oubl e D oubl e

20 (o22)c, :::::::::::::: ::jtcu ::j,,, zuc,

20-

Flgure 21.

Analysls of the extra spotF appearing in FLgure 278 after the cu20 sample (whose sAD partern is shoun in Ftgure 27A) was exposed to hydrogen ion bombardment at 250 v bombardment voltage and a 150 s bombardment tLme.

-<t---r--ir--t*-ts

67

c
A

c
A

D E
@=

D E

Cu,-O Spot c. Doubfe Diffroction Double Diffrocfion Double Dif f roction Double Diffroction Double Diffroction

A B

(lll)cu

(o2zl

zo

( il t ) A t,U

c
D E

Cu ZO

(o?zt
ilT3),

Cu

ilTs l' Cu !A

0u

?-?) "O cu zo (2o4) cu zo

ez 4 UU A

(2o4r, "Cu

Flgure 22.,

o f th e doubl e dtffractLon Analysis spots w hi ch coul d exlst a ro u n d e a ch prl mary C ur0 spot, as found l n F l g u re 2 7 B ..

68

spotsoccurln both the pureCurO the Cu/CurO patternswhen electron and an beam dlffracied by oneset of Cur0nlanesundergoes dlffractlon by anotherset of Cur0plahes. These ldentlfled ln Figures and22. Thesatellite are 2l spots, shown Figure22, anddenoted ( in as )CueO ( )gu spots, occur

froma particularset of planes the Cu lattice is when the,diffracted beam in diffracted by a similar set of planes the Cur0lattice. in Parallel rnolr6 fringeswereobserved the bright field images the in of Cu/Cr4'r} as in fringes result fromthe overlap samples shown Figure23. These slight'ly different lattice parameters of ltto single crystals having whichare
o r f e n t e d w i th p a rti cu l a r crysta l ' lattices par a' lle' lto eachother . The spacing s b e t w e e nh e frl n g e s., D , i s re l a ted to the lattice par am eter of Cu and Cur 0, d1, t a n d d r , w h i ch co n tri b u te to th e fringe for m ationthr oughthe equation D = d l d . l l \ - d.l (1 6 ). T h e me asur ed value of the m oir 6 fr inge spacingwas
I

r u1 4 . 3 5[ , w h i ch co mp a refa vo ra b' ly with the va]ue of ' 13.65 calcu]atedfr om s A ll t e r a t u r e va l u e so f d ., a n d d r. A fur ther conclusion that can be dr awnfr om the

i m o i r 6 f r i n g e i ma g e s s th a t th e Cu on the sur faceof the Cur 0 is pr esentin p s m a l l l n t e r c o n n e cte d a tch e s. T his is par ticular ly clear in the vicinity of t h e d a r k e x ti n cti o n co n to u rw h e rethe fr inge patter n is m ost clear ly visible. I t i s p o ssi b l e to a d j u st th e obiective aper tur eto excludesom e diffr acte d e l e c t r o n s r el a ti ve to o th e rs a n d thus cr eate dar k field or br ight field lmages . S t u d yo f s u ch l ma g e s p p e a rto sh owthat the Cu is pr esentas sm all inter a on l c o n n e c t e dsl a n d s'e p i ta xl a l l y g ro wn the Cur O. It is posslblealso that the slightly with f l l m i s c o n ti n u o u s i th sma l l p o rtions, its islands, m isor iented w re s p e c tt o ea cho th e r b u t sti l l Coatinqs 4. Added Antireflection coatings were used to reducethe reflection losses and attack on the cells. w v a r i o u s e n c a p su l a n ts e re u se dto pr eventatmospher ic e pitaxial with r espectto the Cur 0.

ll O.Olpm

lfcuffA]-

rlcrogrnph hoEor of obrervcd ln th. brlSht fl.ld.l.ctron frln3rt rlrl hrrlhl r.ductlonr utlng hydrogan lon bonberdncnt, of lon thhrncd by prrtl.l Cu ftlnr forrd rhovr l hr r.l Gct.d aroa ol cctron dl (fracti on ( th r ln r r t P rtt.rn corr!.cu 2 0 [r p lr r p o ia r n r to th l. r r tlo n ) .

\ \ \ \ \
I I I I

. d . A n tl re fl e ctl o n C o a tl n q s..Antir eflection coatingsof SiO* ( t < x< z) were applled to cells by sputtering from an SiO, target with argon. The optirnum thlckness of 775A r.r calculated from t = (l /4)^/n where), = 4550A ana n was t a k e n a s 1 . 5, th e re fra cti ve i n d e x of Si0r . re T a b l e 24 sh o w s su l ts o b ta i nedon cel' ls befor e and after application of a n t l r e f l e c t f on co a tl n g s. It l s seenthat substantlal impr over nents, to n,5 0X, up w e r eo b t a l n edfo r Jr. w h i l e th e V o. wasnot affected appr eciably. Similar 4. re s u l t s a r e sh o w n l se w h e ren T a b' le e l b. E n ca p su l a ti o S ta b i l i tv Studies. A num ber cells wer e encapsulat ed n of

in e p o x yr e s i n s u n d e rg l a ss to p rotect themfr om atmospher ic attack. In gene r al , w t h e p r o c e d ure a sq u i te su cce ssful. The Vo. of the cells changed y litt' le ver o v e r w e e k s ,as sh o w nn F i g u re 2 4 . The Jr . almostalwaysim pr oved, i som etimes gr lrm e d l a t e l y up o ne n ca p su l a tl o n n d sometimes adually. The impr ovem ent a was

l0 to 57% overa number cells. Possible of explanations this are an. for improvement light transmission, morelike'ly, that the top layer of the or, in
Cu w h l c h h a d a l re a d y su ffe re d so tne oxidation by air was r educed back to Cu by t h e e p o x y , t hu s i mp ro vi n g e co n ductivity' of the film. th Thesecells did not hav e

a n a n t i r e f l e cti o n co a ti rrg . P a rt o f the im pr ovem ent antir ef' lection coatings by re p o r t e di n t h e p re vi o u sse cti o n m ayalso havebeendue to a sim ilar chem ical re d u c t i o no f su rfa ceo xi d e s. F i g u r e 25 sh o w s e va ri a ti o n of c o n v e rs io n e f f ic ie n c ie s o f s e v e ra l c e lls th ur i t h t l m e . A g a i n l t ca n b e se e nthat t h e re is s o me t ime s t e n d e n c yf o r a n a ln lm p r o v e m e nt p ro p e rtl e sw i th ti me. T h i s s u g g e s t s t h a t i t ma y b e a d v is a b le t o processthe cel I s compl u etely i n vacuum n t i I t h e c e l I s h a v e b e e n e n c a p s ua t e d . l

71
I

'FAD? .t llDlrg

OI.. l$t

Inprovements Coatlngs*

Ln Cu/Cu^O Cells

Due to StO

AntLrefLectlon

MeasurCurrent-Voltage ments luuuedLately Before CoatLns Sanple

StO_- Cunent-Voltage *. lrlgasureme,nts -,r . coatLng ::::.lrter

"iii J
915 915 775 775

J_ _ 8c rmProvement

(z)

DLF-nVI-25-C DLF-nVT-26-G pLF-nVI-25-D DLF-Pb-IV-04-C

-1.10 1.18 1.08 1.01

0. 633 0.652 0.636 0. 602

1. 70 L. 44 1.58 l. 37

0.629 0.630 0.650 0.607

35 22 46 36

A11 cells

$rere made wLth the normal

bombardment ti.me,

condLtLons cel l s

of

250 V " r2

bombardment voltage active areas.

and 75 s exposure

and aII

had I.0

72

.tt
l, ql F,l

o
t o

ul ) z rc l V

cs
It

o q

o
@

qr

o q o

rr)

o U c o 'o . ct tr r, c

O.

CV

o o o o o

lt t{ G ,o E o p

U E

o
C\I o

.fl

a o
a o oo o
h

oc -.3
o/ o,

cN -

ro
lf)

-9,,_= !{-q
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.o -r (l,

'o

t"l

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(ro >,:. \. o

o
lf

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.q tt'f
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sqg o
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93
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-.:
ct

a-

b
t-

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F{ F{

a.

(.,
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Al. (J

\o

qtx

o o o
oO

r!.

o
o

oo hqa g t

o
O

o o

.r{ r-f C .r{ .d 3S OtJ &, .r{ 3n'

o q o
( si l o ^ )

o \t
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ton

o o o

.S

.t-l frr

.\| o l' a oo

o:l
DL F - A I

o.6

o.5
DL F . M Z - B I - 0 4 . G 2
; { 0i,

o.4

C'

o.3

g .9 99r

DL F - m E

- 14 - G

lI.J

135

r80

T im e

( doys )

Flgure 25.

Cu/Cu2o VarLatton of the efflcLency of.3 dtfferent cells prepared by hydrogen ion bombardment and encapsulated ltlthln an ePoxy resLn'

74

and D. Sunmar.v Dlscussion l. P rl n ci p a l R e su l ts

The most important result of this researchwas a large improvernntin the of with a pr eviousm aximun o p e nc i r c u i t p o te n ti a l , u p to 0 .72U, as com par ed 0 . 3 5 V . T h e fi l l , to fa cto r a l so w a s impr oved 0.56. Howeverthe shor t cir cui t

ce]ls preparedby thermal evapocurrent tendedto be lower than for comparable for^ value obtainedwas 5.28 nrA/c,nz, a cell with Cu ratlon of Cu. The maxlmum f i n g e r s a n d a n S i 0 *a n ti re f.te cti o ncoating.However ,theseoptimumvaluesw er e attained efficiency was 1.3% . ce n o t o b t a i n e dl n th e sa n re l l , S o that the m aximum
Z. Method Bombardment Analvsis of the Hv_droqen

0.

on Formati of the Cu/Cu Juntli * ' 20

The ef fect of hydrogeni on bombard-

a the top surfaceof the Cut0to Cu, thus producing rnent Curgis to reduce of barrier iunction' i.. a junction. Thejunction is therefore Schottky CulCur1 junction, whichproduces rectifying andphotovoltaic the a metal-to-semiconductor effect. from is hydrogen to be expected of Therecluction Cur0to Cuby'ionized analysis by and considerations, this wasverified experimentally Auger thermcdynamic
a n d b y e l e ctro n d i ffra cti o n . is of A n advantage the method that the Cu is fo r m ed b y i n v a s l o no f th e C u r0so th a t sur face impur ities ar e' left behindand a cleaner inter face states m ayincr easethe bar r i er of J u n c t i o n i s fo rme d . T h e a b se n ce some h e i g h t a n d th e re fo re vo ., b u t th e data to pr ovethis ar e inconclusive. The at reducedconcentrationof surface states mayreducethe recombination the in the dar k' by i n t e r f a c e an d th i s i s su p p o rte d the lower r ever secur r ent b. C Effect of Bombardment ' The distribution of it Experimental'ly by is cu formedby bombardnrent shown the Augerresults. as deeperinto the sample the bombardment was found that the cu profile moved

75

Yoltagewas increased. The amount Cu formedincreasedwith bombardment of time, w h l c h d e te rmi n e d e to ta l l o n dosage. Thuslower voltages, B.g. 250V, wer e th Pr e f e m e d,si n ce th e se g a veth i nner films, whichgavebetter light tr ansm i s s i on r n d t h e r c fo re b e tte r Jsc. A t l east a cer tain bom bar dment time, .g. n,75 s , w as co r c q u l r e d to l n su re a d e q u a te ntinuity in the film and sufficiently 1owsurfac e rcsistivity. This contributed to an inprovedJr.. Longerbombardment times

g a v et h i c k e r C u fi l ms, w h i ch l e d to r educed light tr ansmission and lower Jr .. it A s a fl rst a p p ro xi ma ti o n can be assum ed that the distr ibution of Cu w as d e t e r m i n e d y th e d i stri b u ti o n of hydr ogen the sample. Ther eis a cons i der abl e b in into m ater ia'l s , b o d yo f l i te ra tu re (1 8 ,1 9 ,2 0 )o n the penetr ationof ion beams of b u t t h e i nte re st i n l a rg e l y o n ion implantation,invo' lvjngbeams sever a l h u n d r e d e Va n d fa i rl y l i g h t d osages. This is differ ent fr om the condition sof k e can t h e p r e s e n tre se a rch ,b u t so xn c onpar isons be m ade. sample tends to be a Gausslan T h e d l stri b u tl o n o f l o n s l n a bombar ded d i s t r i b u t i on , a n d fo r l i g h t i o ns at low voltages, the cur ve is tr uncatedat the pr by s u r f a c e . T h e p e n e tra ti o nd e p th is char acter ized a mean ojectedr ange , m squar e R ^ , w h i c h l o ca te s th e ma xi muo f the distr ibution, and a r oot m ean Pf l u c t u a t i o n , a F '', w h i ch d e scri besthe str aggling of the ions. In the case of deviation i n d a G a u s s i a n i stri b u ti o n , A F pca n be identified with the standar d exp N (x) = N p , ( - XZ/Z) ( 4)

at at w h e r eN ( x ) i s th e co n ce n tra ti on depthx, Np is the peakconcentr ation x'Rpr i ! ,d X = (x-R p )/a n '. T hustl( x) = I' lo//Eat x = RptaRp.

S o m e l cu l a ti o n s o f ra n g esfor pr otonsin var iousmater ials havebeen ca a h m a d e y An d e rse n n d Z i e g l e r (2 1) . At the' lowest limit of their calculations , f o r I k e Vp ro to n s, th e ra n g ei n Si was foundto be l2O A and the str aggling , I Z Ol . F o r T i , th e ra n g efo r I keVpr otonsr epor tedwas 70 I and the str aggl i ng,

76

l0 O [ .

0 f t h e tw o , T i i s mo st n e ar ly compar able Cur O to since it has an atom i c

number 22 and a density of 4.5 g.cm-3.otpu."d with an averageZ for Cur0 of of 2 2 a n da d e n si ty o f 5 .0 g .cm-3 . In Figur es13 and 14, it is seenthat the Cu A u g e rc u r v e f or 1 0 0 0V h a s a p e a kat n,50[, which is qualitative' ly simi' lar to Ti. I n F i g u re 2 6 ' th e d a ta fo r th e d t est f o r a G a u ssi a n i stri b u ti o n . .|000 V cur ve in Figur e 14 ar e r eplotted to

The plot is for 1og [Cuo] in % vs. the squar e

o f t h e d i s t a nce i n to th e sa mp 'l e .The str aight l' ine plot shows r em ar kably a g o o df i t t o a Ga u ssi a n i stri b u t'i o n. Fr omthe cur ve the str aggling, ARp,is d est i m a t e dt o b e 6 5 A , a n d R Oi s ta ken as 60 A. A:;lr i:lar tr eatner l vr asapplie d in t o t h e 2 5 0 V c u rve o f F i g u re 1 4 a n d this is shown Figur e 27. The fit to a

G a u s s i a nu n cti o n i s fa i rl y g o o da nd the cur veyields values of RO= 28 A ancl f A R -= 4 l I . P distr ibution maybe somewhat tuitous, sin c e for w T h e a g r ee me n t i th a Ga u ssi a n for the hydr ogen ar r iner t sample w in t he a n a l y s i s o f co n ce n tra ti o n a s not made b with ionized hydr ogen and b u t r a t h e r f o r th e C u op ro d u ce d y reaction of Cur O the values for ROand ARO appear t h i s a s s e e nb y th e A u g e rme th o d . Never theless, function is useful her e to , t o b e r e a s o n a b l ea n d , i n a n y cd S rthe Gaussian desc r l b ea n d p re d i ct th e [C u o ] d i str ibution, which is of pr im ar yinter est her e. H o w e v e rth e re i s a n o th e ri mp or tantfactor . , In ion implantaticln, the

distanceinto the sam ple o b J e c t i v ei s t o i n tro d u cel o w l e ve l s of dopantsom e in ke the wh i c h r e q u i r e s se ve ra l h u n d re d V , wher eas the pr esentexper im ents, o b j e c t i v e i s t o co n ve rta l 'l o f th e Cur 0at and near the sur face into Cuo. As provided the CurOnear the surface is convertedcompietelyinto Cuo, the hydrogen may et,idence by further bombardment be driven further into the sample. Some ed f o r t h i s i s p r o vi d e di n F i g u re 1 7 , but it m ustbe r em ember that this is for tne [Cuo] as seen by the Augermethod.

77

q,
F'

o (-, vf
3.rl

30

t-l (J l-t !a

Depth, *2/ l-04 Nz

Figure 25. of Cuo vs . dep th ln sarnPle of CucO bornbarded wlth Distrlbution . hydrogen ions at 1000 V . P l ot l s f or l .og [c"o3 f,". x?.

78

4A
rt\' (J U1

o a
)'!

Et

r-t
5 (J
L-l

30

ba

0 \ \

* 2 1t 0 3
Flgure 27,

i2
wl th

DtstrLbutlon of Cuo vs depth tn a s a m p l e o f C u o O b o m b a r d e d hydrogen lons at 2 5 0 V . Itl ot l s for rog [c""] r"l *2 .

79

The emplrlcal cholce of the optimum bombardment voltage of 250 V appears to be reasonable frlm the Augerresults also. In Cu/CurO cells preparedby

thermal evaporation,the optimum thickness of Cu has beenchosen n,60 A. at T h e p e a ko f 2 8 i p ro vi d e db y 2 5 0 V is in the m iddleof this 60 i and of cour se t h e r e l s s p r e a d l n g n b o th d i re cti ons i

Thecholceof 75 s for the optimum bombardment appears time neasonable from results in Figure'15,sincethis is the minimum required give the Auger time to nearlycornplete conversion Cuoat the peaklevel. to
S o m emp ro ve me nma yb e p o ss ible in the exper im ental l ts conditions. It m ay a be p o s s l b l e to p ro d u ce b e tte r d l str ibutlon of Cuoby using a pr ogr am sever al of doing the bombardment lower voltages or b.V througha mask. Techniques this of s o r t a r e u s edi n i mp l a n ta ti o ni n to semiconductor s. I t w a s po stu l a te dth a t th e re is a high r esistance' layerof Cur O Just be' low t h e C u f l l m a t th e su rfa ce . It i s pr esum ed that this layer consists of intr ins i c or n e a r i n t r i nsi c C u r0 , cre a te db y the action of small am ounts hydr ogen of in s u f f i c i e n t to ca u sere d u cti o nto Cuo. Since Cur 0 is known be a nonto s to i c h i o m e t r i cma te ri a l w i th a n e xcessof oxygen that causes to be p- type ( 2i l , it acts to r emove t h e e x p l a n a ti o nco u l d b e th a t h yd r ogen this oxygen excessbr ing i ng composition. Pr otonbom bar dm ent t h e m a t e r i a l to w a rda mo ren e a rl y stoich' iom etr ic (lO t o 5 0 0 k eV ) h a s b e e nu se d (2 3 ) to pr oduce high r eslstancelayer s 1n both p - t y p e a n d n -typ e Ga A s, s w e l l a s p- type ZnTeand n- and p- type Si. a The expl ana-

p t lo n o f f e r e d w a s'th a t h yd ro g e n ro videsdeeplying donor sand acceptor sln the s e phenom enon pr oton of ma t e r l a l s . I ' l h i l e th e se re su l ts su ggestthat the exper im ental c re bo m b a r d m e n t a ti n g h i g h re sl sta n celayer s is m or egener al,one wouldnot expec t gr on since it is unlikely to e t h e s a m e x p la n a tl o n h o l d i n C ur O chem ical ounds w t h a t a t o m i ch yd ro g e n o u l dco n ti n ueto exist in Cur 0without r eaction.

80

3 . A n al .vsl s f E l e ctrl ca l P roper ties o a. G e n e ra l . Ge n e ra d i scu ss ions the electr ical pr oper ties of photol of

v o l t a l c c e l l s h a veb e e ng i ve n b y tl olf and Rauschenbach , by Hovel ( eS) , Uy ( 24) Ha l l ( . e e ) ,a nd b y Gre e n(2 7 ). T h e d i s cu ssi o nl s u su a l l y ma de ter msof an equivalentcir cuit, as show n in ln F l g u r e 2 8 . In th i s ci rcu i t, th er e is a cur r ent gener ator ,which pr ovides t h e p h o t o g e n e ra te d me n t, a d i o de which r epr esents cu the r ectifying junction a n d a s e r i e s a n d a sh u n t re si sta n ceas well as the load r esistance. The net c u r r e n t i n t o th e l o a d i s g i ve n b y J=JL -Jo -JS | ( 5)

cu wh e r eJ , i s t h e p h o to g e n e ra te d rr ent, JD is the cur r ent thr oughthe diode an d J St i s t h e c urre n t th ro u g hth e sh untlngpaths. JD is given by
JD = Jolexp( (q/n k r) (v + J Rs) )

-u

( 6)

w he r e R, i s the series resistance, V a n d J a re t h e v o l t a g e a n d c u rre n t a t t h e J o ad , J0 is the dark reverse saturat io n c u rre n t f o r t h e d io d e a n d n is t h e n o ni d ea lity fa ctor. The shunt resistan c e is g iv e n by

r, J s n = (V+ J R , r n = G s ( V+ J Rs )/n )
is whereGSf, the shunt conductance.

(7 )

F o r t h e ca se o f J = 0 a n d Jrn = 0, the opencir cuit potential Vo. is given by

voa= (nkT/q snt (.1LlJ ) + tl ) o

(B)

i i convers on effi ci ency R, s h o u ld b e a s l o w a s p o s s b Je , RS ns h o u ld mum Thus for maxi b e htgh an d J0 should be low.

81

F lgur e

ZB.

Eq u l v a l e n t

c L rcuJ.t

f or a photovol t,al c cel l .

b.

Relation of Vo. to Barrier Height. Experimental values for the barrier

he l g h t w e r e ob ta l n e db y p l o ttl n g the logar ithmof the dar k cur r ent vs. the J u n c t i o n p o t e n tl a l , V J = V - IR s' to obtain JO by extr apolation. The bar r ier he l g h t 0 5 w as ca l cu l a te dfro m th e Richar dson equatlonas descr lbed lier . ear Va l u e so f 0 . 5 8- 7 0 w e re typ i ca l l y obtainedalthoughone value of 0.87 was found. T h e s ev a l u e sa p p e a rto b e to o 'l o w to explaln the high valuesof Vo" by any s i m p l em o d e l . O n ec a n a rrl ve a t a n e stl ma teof the r equlr ed bam ier height by calculating J O f r o m t h e R l ch a rd so e q u a ti o nfrom assumed values of 0b and then ca' lculatln g n Vo . f r o m Eq ua tl o n 8 . T a b l e 2 4 sh ows the r esults of these calculatlons assumi ng J r = 0 . 0 0 5A cm-2 . It ca n b e se e nthat lar ger va' lues 0o wouldbe r equir ed of t h a n t h o s e o b ta i n e de xp e ri me n ta l ly. ^( . S t i l l h i g h e r va l u e so f 0 b mi ght be expected. As shovr n Figur e' , the in b a r r l e r h e i g h t l s e q u a l to th e F e rmiener gyplus the built- in potential. The .|00 as F e n n i e n e r g yi n C u r0ca n b e e sti mated 0.35 eV ( .fr om r esistivity of a o' c m an d a m o b i l i ty o f 1 0 0 cm2 .V -l .r-l ). If one assum es that the built- in potential

ls g r e a t e r t h a n V o ., th e n fro m th e highest value of Vo.,.0,72 Vr on wou' ld e x P e c t0 b t 0 .3 5 + 0 .7 2 = 1 .0 7 V . c. An a l ysi s o f S e ri e s a n d S huntResistances.As shown above,the conve r s i on

by' e f f l c i e n c y o f so l a r ce l l s ca n b e i mpr oved lower ingthe ser ies r esistanceand in c r e a s i n gt h e sh u n t re si sta n ce . paths suchas cur r ent L o ws h u nt re si sta n ce sca n a ri se fr om var ious leakage at lo s s e s o v e r t h e ce l l e d g e so r sh o r ting spots on the sur face, per haps gr ain , from the slope of the boundaries. Experinentalevaluation of Rrn was made c u r r e n t - v o l t ag e rve sa t l o w vo l tages ( 26) . For the hiSh Vo. cells,0.68- 0.72U , cu cells preparedby therm.al values of Rrn of 20- 60 kOwere obtained. For CulCur0

83

CUAO

Semlconductor

Mc t o l

Evo cu u m

E Conductlon

E F e rm l E v o le n c e

Q ,u
J

= w o r k F u n c t i o n o f cu
= Wo rk F u n ctl o n cf Cu 20

y Cu Z= -O

QU xcu 20

Borrfer Heighf ! E l e c fr o n A f f i nity o f cu 2 0

'Ferml E nergY

A=
Eg

= B ondoP E nergy

vbl

= B ul l f-ln P otenti o t
-z .r energy band d firgram f or the Cu lCu^0 sys tem.

Flgure 28a. Detalled

84

Yalues RSh 0.4 to 2.0 kOwereobtalned. This supports evaporatlon, of of the ' postulatethat hydrogen produces method bombardment cleanerjunctions, possibly wfth fewershortlng spots A detalledanalyslsof serles reslstance be made can followlngHall (26). Factors whlchcontrlbuteto the serles reslstance are the bulk reslstance the of semlconductor the resistance the contactssuchas the sheetresistance of and of of the top layer andthe resistance the grid. Thetotal cell resistance of reduced cells wasfoundto be 8-25 fl. A typlcal valuefor the the hydrogen
co n t r l b u t l o n o f th e b u l k to th e ser les r eslstancemaybe estimatedby assum l ng a n a r e a o f I cm2 ,a th i ckn e sso f 200 umand a r esistivity of 300 Q.cm,yielding a r e s i s t a n c eva l u e o f 6 a . T h e s h e e t re sl sta n cel s g i ven by ( 20) R = p rd " /1 2
t

( 9)

conduction ger s . fln w h e r eo 5 l s th e sh e e t re si sti vi ty and d is the distancebetween for For o, - 7g5?/square eO i Cu thickness and d = 0.2.| crlrroh obtains a value of 0.26 n. T h e r e sl sta n ceo f th e g rl d l s calculatedfr om ( 20)

Rn= or['dl3w

(ro)

of where ls the sheetresistance the metalfingers (Cu) L ls the length of the , o,

ng. For pm= flngers, w is the wldth of the fingersandd is lntergrid sPaci (for O.S7e/square 300I thlck Cu), d = 0.21 cm, I = I cm,and tv = 0.03 cm, one

o b ta l n sRg= 1.3 0.
t t h i l e a l l o f th e co n tri b u ti onsto the ser ies r esistancecould be r educe d,the m o s t i m p o r ta n to n e to co n si d e rfo r CulCur }cells is the bulk r esistance. At p r es ent

8s

the lorest raslstlvlty attalned 100 0.cft. Foran lso]ated ls film, the lowest
of ls thlckness fllm thrt canbe handled 100utn. Employlng thesewouldglve Rr'l 0. Furtherimprovement come fromlowering would the resistivity and

further reduction thickness, of .g. by usingsupported films.

T h e s he e t re si sti vi ty i s h i gher than that calculatedfr om the bulk pr oper ti es vs.2 so o f C u( 7 O ' n /sq u a re .9 .O/sq u ar e) that it wouldbe desir able to impr ove the c o n t i n u i t y o f th e fi l ms. by T h e g r i d re sl sta n ceco u l d b e lower ed incr easingthe thicknessof the m e t a l f i n g ers a n d th i s co u ]d b e doner eadily.

86

III.

PREPARED REDUCTION Cu 0 l,{ITHAT0MICHYDROGEN CELLS BY 0F A. I rtt_roduqti ot

I.

General

The hydrogen bombardment method for producingCu/CurO cells was especially ln p o r t a n t i n th a t i t sh o w e d a t l ar ger values of Vo., as high as 0.72U, cou'l d th be o b t a i n e df o r C u /C u r}j u n cti o n s. This impr ovem ent believedto ar ise fr o m was the fact that cleaner Cu/Cur0 iunctions were preparedby invasion of the Cur0 to pr o d u c e h e Cu , so th a t a n y su rfa ce im pur ities wer e left behind t However, by the cells produced hydrogen bombardment somewhat had lower v a l u e s o f J r . th a n th e ce l l s p re p ar ed ther malevapor ation onto Cur O. by' Cu T h u sl t w a s of l n ti re st to i n ve stl gate other less aggr essive ethods r educ i ng m of of the Cur0 to Cu' so that the advantages the bombardment method could be attained bu t w i t h o u t t h e d i sa d va n ta g e s.In par ticular , it wasplannedto confine the r e duction to thinner top layers of the Cur0, 2, Me P o s si b l eR e d u cti o n th o ds

methods investigated Some reduction that havebeen briefly are I ) reduction

}Jith molecular at hydrogen highertemperatures, reduction 2) with aqueous sc'lut i on s of reduclng agents suchas hydrazine,3) cathodic electrolytic reduction

and 4) reductlon with atomic hydrogen. The atomic hydrogen method had previousphotovoltalcJunctio ns , ly b e e nu s e d ln th l s l a b o ra to ry (1 0,31) to pr epar eCu/Cur 0 m for fur ther investigatlon. to an Cl t w a sJ ud g e d b e th e mo stp r omising ethod 3. Anal Thermod-vnamic vsi s

0n therrnodynamlc Arounds,one wouldexpect that Cur0 could be reducedby elther rnolecularor atomic hydrogen. Thus, the reactlons are l)

( c u r 0( s ) + H z( g ) = 2 c u ( s) + He o s) ( ( Cu r Os ) + 2 H ( g ) = 2 C u( s) + He On ,)

87

The calculated values for the standardfree energychange AGo 298Kare at -1 9 . 7 k c a l . mo l -l fo t. re a cti o n l ) and - 116.8 kcal.m ol- l fo. r eaction 2) . t.lhile

both reactlons are posslb'le' the reactlon with atomic hydrogen should proceed morereadily at roomtemperature. B . Exper imental l. Generatlon Atomic Hydroqen of

(28,29). The method for generatlngatomlc hydrogen There ane several methods u s e dh e r e w a s to p a ssmo l e cu l a rh ydr ogen over a hot tungstenwir e ( 10,30,31)at of 2 O 0 O : 2 5 0 0 'C .T h e tu n g ste nfi 'l a m entwasm ade 0.127nun e using a I0 cm wir i le n g t h , a n d th i s w a sw o u n dn to a 3 nmcoil of 6 to 7 tur ns. An ACcum ent bf th 2 . 5 - 3 A w a sp a sse d ro u g hth e coil to attain the desir ed temper atur e. No of th of a t t e m p tw a sma d e d e te rml n e e am ount conver sion molecu' lar atomic to to hydrogen 2. Apparatus fitted with a were done ln a stainless steel vacuum chamber The experlments m and nu m b eo f p o rts to p ro vl d ea cce ssfor evacuation,for mechanical anipulatlon, r diagr am the appar atus show n of is f o r e l e c t r l c a l a n d w a te r l e a d s. A schem atic in F i g u r e 2 9 . 3. Procedure

w T h e e t c he dC u r0sa mp l e a s p l acedin the holder ( HolderII in Figur e 29) , to u a n d t h e s y s t e m ta se va cu a te d 2 x lO- 5 tor r . The sam ple was cooledto OoC.

gas Hydrogen was introduced into the systemthrougha variable leak, and the pressurewas adiusted to I to 2 x l0-3 torr. The metal shutter wasmoved a to

a p o s l t l o n b e t we e n e sa mp l e n d th e filament. The fllam ent was tur ned on ( 3A) , th i the filam ent and the sample.to an d a f t e r 9 0 s th e sh u tte r w a s l o wer erto expose tinn was normally varied between and 20 5 the flow of hydrogen. The exposure wasbackfil' ledwith nitr ogen, and then the ml n . A f t e r th e tre a tme n t,th e system to systemwas opened allow removalof the sample.

88

TOP VIEW To dlf fuslon PUNP Elec tr lcal connections

To rough p To gaugea
Shut ter

Vacuun brake

SI DE VIETT

Flgure 29.

schernatic Dlagran of Atornic Hydrogen Apparatus

89

Twoprecautlonswere found to be necessary. The Cur0 sample had to be properly polished and etched. The tungstenfi'lament had to be properly cond i t i o n e d i n o rd e r to re mo ve rface oxideswhichcould other uisevolatilize su and contaminate the sample. A newtungstenfi'lamentwas heatedfor several hours ln hydrogen achieve this remova'l oxides. to of s T h e o t h e r p ro ce d u rew e re q u ite sim ilar to those descr ibed eviously. pr The Cur0was usually preparedby oxidation of Cu sheet at q,]oooocfollowed by a 5 0 0 o C n n ea l . T h e C u rO mp l e s e cut, polishedand etched, usually in a sa wer 8 M HN03. Gold contacts were used for resistivity measurements, the back and c o n t a c t w a s r e ta i n e d fo r th e ce l l s. Nor mallyfinger s wer e r 1ctapplied and an ti qbflection coatlngs were not used, but both of these could be expectedto increase the Jr. of the cells. The I-V measurements made usua'texcept that extra were as care was used to make contact with the probe
C. I. General Observiti ons E xpe rime n t a J s u t s _ Re l

The experirnents junctions were produced were successful in that Cu/CurO which p s h o w e de a s o n a b l e h o to vo l ta i cch ar acter istics. The r eductionof the Cur 0 to Cu r was provedby the fact that visible Cu films were produced prolongeC uncier treatrB n t . T h e f i l ms o fte n w e re n o t u nifor mso that the photovoltaicr esults wer e often not reproducible. Sonewhat better results were obtainedafter the precautions re n t i o n e dw e r e i n sti tu te d . T h e fi l ms wer eeasily dam aged that it was necess ar y so

t o u s e c a r e i n ma ki n g n ta ctsw i th the pr obefor I- v m easur cnents. co I n g e n era l ' th e V o . o f th e ce lls appear ed be mor er epr oducible to than the Jr.. l{oderatelygooddiode characteristics were obtained. Figure 30 shows the

I -V c h a r a c t eri sti cs i n th e d a rk a n d in the light for a fair ly goodcel' 1. It ca n be seenthat the curves resemble those for the therma'l)y evaporated cell shown in

90

Dark

c.1

0.2

0.4

V(Volts)

FLgure 30.

Atomic current-voltage characterj'sElcs of cu/curo cel1 Produced by Itydrogen Treatment,

91

Flgure 2A morethan those for the cells produced hydrogen by bombardnrent, as shown F{gure28. In partlcular, the hlgh dark r.esistances in exhlbiteC the by hydrogen bombardmnt cells are not presentin the cells nadeby the atomic hydrogen reductlonprocess. Howevef, dark reversecurrentsof thesecel.ls the appear be lowerthan for the thermallyevaporated to cells, drd this maybe lndlcatlveof a cleaner Junction. ThelowerJo appeared be attributableto to the coolingof the sample duringtreatment. 2. TheOpen Circuit Vo]tase {he Vo. of thesecells werenot as hlgh as thosefor the hydrogen bombarded cells but occasionally werebetter thanthoseusuallyobtained thennally for evaporated cells. Theresults on 100ce]'lsare shown frequency in distrlbution dlagranln Flgure31. It can be seenthat the Vo. vaiuesvariedfrom0.125V to > 0.40V. Thebest valueobtal.ned 0.415V. was
3 . T h e S h o rt C l rcu l t C u rre nt T h e J r . va l u e sw e remo reh i S hly var lable, appar entlydue to the hor r - ur if or m i ty of t h e f l l m s . T h e a ctl ve 'a re a w a s dlfflcult to m easur er ihd the var iation of

the output over the area was a great prohlem,but someinformation on this was ob t a l n e db y a l a se r sca n n e r th od, me whichwi' !l be discussed the next sectio n. in T h e d l s t r l b u t l o n o f th e co p p e r,w henvisible, appear ed occur in patchesand to sometlmes moreabundant appeared under the mask. .|.5 The averagevalue of Jr. was between and 2.5 mA/cmz aLout ten percent but of t h e c e l l s h a d Jr. b e tw e e n a n d 4nA/cn?. A better contr ol of the Cu film 3 thickness should improvethe Jr.. Further improvements could come from the use of

c o n d u c t { o ni n g e rs a n d a n ti re fl e cti on coatings. f 3. Reduction Process The AtomlcHydroqen

presentedsome The reduction of Cur0 by atomic hydrogen puzzllng aspects. In particular it was not expectedthat the Cu film would scmetimes growmorerapidly

I'f,gure 31.

Frequency DlstrlbutLon of V^^ Valuea ln Cu/CurO Cells Made by AtonLc Hydrogen Reductton \'\' SanPle*rt Vo" Frequency p (ft'cn)

Cu Source*

TOTAL
GS . GS GS GS

cs-R-Ir2r3 GS-B-IV.01 GS-B-Vrr-O1 AB-GS-B-Vr-05 #

---xtx- xx
U \x*xxxxx

tt

1155 563, 73g ,

I I xrurx-

242 428

GS

GS--Pb-Vr-0 6lt{l c-3-0 c-5-1 C-6-0-1

204-23L 180, t gg 238, 306 143, 153

OFE OFE

OFE

OFE

TJL-XXI-TI +
ntr\!nu\!ntA N C\N NN C\ F{ rl CU NF^rq

402s

IR E !R E i R E l,-l lcUfN St\lnnl-f

Voc LnVJ

*Gr Source: GS - Gallard-Schleslnger 99.999+2 Cu; OFE Orygen-Free Electronl.c 99.952 cu. All were ln eheet forrn except GS-R eanples whtch were allceg cut fron rod. **All Cu aamPlea rrere oxldlzed at n, 1000oc^and annelled at 5Q0oc for verl.oue t!.nae. 0ttrts aanple ltag program cooled fron 10O0oc to s0ooc tu lOOo-trrt"r,tet". ll#Tlne Cu wae doped wlth 0.22 Pb. I Thie lraa a slngle crystal rnade by graln growth.

93

under the maskthan on the exposed surfaces of the Cur0. A possible explanatlon for thls ls that the dlrectly exposed surfaces recelved some coatlng of tungsten a n d t u n g s t e no xl d e sr rrd th l s co uld haveinhiblted the for matlonof Cuo. An to of effort was made avoid this type of contamination,but the success the rnthod has not yet beencompletelytested. A n o t h erp o ssi b l e e xp i a n a ti o nis that the atomsin the str eamof hydr oge n a m l v l n g d l r e ctl y fro m th e fi l a ment wer e too ener geticto stick and r eact effectlvely. atomscould under go epeated r collisi ons U n d e rth e ma skth e hydr ogen

a b e t w e e nh e sa mp l e n d th e ma sk,thus incr easingthe pr obability of r eaction. t hydr ogen ' lO- 3tor r at 2700K at fre T h e c a l c u l a te dme a n e p a th o f (m olecular ) ls r u 8 0c m , a n d a t 3 0 0 K ,l t l s n ,9 cfir so that ver y few co' l]isions in the gas support phasewould be expectedunder the conditions of the experiment. Some in for this hypothesiswas obtalned from experiments which the shutter was 'left over the heatedtungstenfil awas in p l a c e w h i l e th e fl o w o f h yd ro gen m aintained nnnt. Eventhoughthere was no direct path from the fi'lament to the sample, iunctions wer e re d u c t i o no f th e C u r0su rfa ce sti 'll occur r edand photovo' ltaic have had to makeat least one atomswou'ld the obtained. Presumably hydrogen r co l l i s l o n w i th a ch a mb ew a l l b e for e amiving at the sample. Possib]ythe loss in kinetic energy. atomswere reflected at the wal'l with some hydrogen
a D . S unma ry n d Dis c u s s io n

results I n a reduction of the c th The treatmentof Cut0 bri atomi hydrogen a .junctlonwlth r ectifying and surface of the CutOto Cu p ro d u clng Cu/Cur 0 ' similar to the reduct'ionby photovoitaic properties. The processis somewhat in hydrogenbombardnnnt that the Cu metal is producedfrom the Cut0. The highest obtainedwith ther mal l y Vo . s o f a r a tta l n e d ,0 .4 1 5 V , i s higher than that nor m al' ly cells. bom bar ded ce e y a p o r a t e d l l s b u t l e ss th a n th at with hydr ogen The valuesof

ilr. were morevarlable and tendedoften to be low. The difficulty

with the

processln its present form ls that it produces non-uniform fi'lms of Cu metal, s o t h a t t h e fl l ms ma yb e to o th i ck in places to allow adequate iight tr ansm i s s l o no r ma yb e to o d i sco n ti n u ous places so that the cur r ent collection i.n is l n e f f i c i e nt. to a lower ed .. Jr .contr ibute could be im pr oved give Vo. valuei compar abl e I t i s p o ssl b l e th a t th e me th od to The atom ichydr ogen ethod' lssuper lor to m B o th o f th e se co uld

t o t h o s e o f hyd ro g e n o mb a rd e d lls. b ce

methodin that it avoids the productionof a high bombardment the hydrogen resistance layer of Cur0. of The best direction for further improvement the methodis to nodify the pr o c e s ss o a s to a ch i e vemo reu n i for mCu film s. Onepossibi' lity maybe to lnser t

path. Some variations in sampletemperature a baffle ln the beam and placement a n d o r i e n t a t io n ma ya l so b e u se fu l

95

SCANNER IV . LASER
A.

I ntrcductl on

valuesof the cells give average of Theusual I-V measurementsphotovoltaic the output. In som caseslt ls useful to examlne output In detall from polnt to polnt on the surfaceln order to checkthe uniformityof the output, or to variables. This canbe locatebadspotsandto correlatethesewlth processing the a by d,one conveniently moving small spot of light from a laser acnoss sample the outputon a suitableoscilloscope.Apparatus on a raster andthendisplaying (32). by ird developed severalgroupsr expecially Sawyer by to do this havebeen (33) that the method couldbe prellmlnary w0 experlrnents, haveshown In some Cut0 applledto Cur0cells. In order to havethe capabilityof further studylng was in apparatus constructed this laboratory. a celis ln this rnanner, laser scanner
B . Appar atus components.The was largely constructedfrom conmercla'l The apparatus prlnclprl components were two optlcal scanners(GeneralScannlng,Inc., Mode'l Scanning, Inc., Hodel co G- 3 0 0 P D )a chw l th a sca n n e r n tro' l- am plifier( Gener al e Inc., l- lodel ihd CR- 80- 2SP- BRH) , d a a CC X- l O 2 - 3 ) , h e l {u m-n e oln se r (Coher ent, of Tektrpnlx storuge oscllloscope (Tektronlx tlodel 5441). A number other parts wenesecuredor constructedto completethe assembly. A photoand components a ln graph of the apparatusls shown Flgure 32. Flgure 33 shows block dlagram of the apparatus. C . 0 o e ra tionof Laser Scanner l. G e ne ra l

hor l fro T h e b e am m th e H e -N ea se r ls swepttcr oss the sam p' le lzontally and signal fr om v e r t l c a l l y b y th e tw o o sci l l a ti n g mir r or s, eachdr iven by a sawtooth

Flgure 32.

Laeer

z lnput ce l I a trp l l fl e r

fupli fi er
E Canner d 1 f f e re n [ 1 a I a n p lif ie r

DIyci tirne ba se

Figure 33.

Block DLagran of Iaeer Scanner Apparatus

97

from lts control'

The photo-outputof the photovoltaic cell is addedto the y-

d e f l e c t l on sl g n a l r th d th e re sponse vlewed the stor ageoscilloscopea s a is on representatlonof the output of the cell as a function of "three dlnrenslonal" t h e p o s l tfo n o n th e su rfa ce . The dlsplay can be r ecor ded m ediate' ly ir with a Polarold camera attachment. A s ca no f a g o o dsi l i co n cell is shown Figur e 34. .Thehor izontal li nes in r e p r e s e n tth e l n d l vi d u a l sw e e ps the x dir ection. Eachsucceeding in sweeps i d l s p l a c e dre g u l a rl y u p w a rdn the y- dir ection by the scanner i contr o' land is f u r t h e r d lsp l a ce db y th e va ri a ble photo- output slgnal. The near ly ver tical f u r r o w s a re d u e to th e co n ta ct finger s blocking out the light and r educingthe o u t p u t . Be tw e e n e fu rro w s the output is r elatively constantindicating a th h i g h d e g re eo f u n i fo n n i ty i n this cell. T h e re so l u ti o n d e p e n d sn par t on the light spot size, which in these i e x p e r l m e n ts a s 1 0 0 u m. T h e si gnal fr om bhecel] can be chosen em phasi z e w to e i t h e r t h e vo l ta g e (V o .) o r th e cur r ent ( Jr .) . t h e h i g h i mp e d a n cef th e a mp l ifier is utilized. o In the voltage r node, Figur e 35A, In the cur r ent m ode,the c el l

i s l o a d e dw i th a l o w re si sta n ceload, as shown Figur e 358. The output of in a s i l l c o n ce l l a s a fu n cti o n o f load r esistanceis shown Figur e 35. The outin p u t l s l l n ea r u p to 1 0 0 A a n d tends to level off at ver y high r esistance, r ] F o r C u l C urO l l s' th e o u tp u t w as linear to 300o. ce v o l t a g e m o d e a su su a l l y u se d . w 2. ExampJ of U.se. es Sgme k O.

For gualitative studies , the

ti The out;:ut of a representa ve cel I madeby the atomic hydrogenreduction I I s shown n Fl gure 37. Fl gure 38 shows s u rf a c e s c a n o f a Cu / Cu r0c e l I mad e a

containinga n o t h e r s i n g l e c ry s t a l a re a a s n o t ed . w l t h a s i ng l e crysta l o f C u rO small dlfference ln o u t p u t b e t we e nt h e t wo a re a s , t h e re w a s l,lhf there was some le l n o a p p a r e n t o ss a t th e g ra i n b oundar y.

98

'FLgure 34.

photographof Display on Osctlloscope of a laser scan ofa StlLcon Cell. Dlstance betweenfrngers rs 3 D0.

o scllloscop
c e l1

oscllloscope

Flgure 35A

clrcuit

for

voltage

}Iode

Figure 358.. Clrcult

for

Current

llode

99

o
o

}{ a C'
H q, !
FT v
14

;) \./
,^a

H o q A

i
I

I l l i
I

.f

I o
I

\ \ \ \ \ \ \\ \ \ \ i \\ \ I \ \
I l I

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I

&

FT

o U

c Cr
,.\!, Yo

\-,

I
{
t,

o o OL . o

."{

."{
&

tlt a0 f, .r{ 6E

tr&

a' H oor+{

l I

"co 6
OH
FlA
l|f

$r,

OE A .f oA .r{ a rJ U ..
JO lqA

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t

\ \ \ \ \ \ \
{ F{ '

o '|.| q to o
F{ Fl l.a

o! C)O

Ot{ oo .r{ l{
-F { y . ra O sr ct)

tr

F{

t o

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(trTun r(rrrlTqrv)

lndrr

t,

100

t.

FLgure 37.

I,.aser Scan of Cu/CuoO Cell Made by Atonic Hydrogen Treatment ' 4.

frasFPS

FLgure 38.

Iaeer Scan of Cu/CurO Cell Showlng I\rc Slngle Crystal

Regtons

10 t

Flgure 39 showsthe surface scan of a Cu/Cur0 cell made atomlc hydrogen by t re a t m n t , s ho vti n g ve ry i rre g u l a r output. A single sweep oughthis cell i s a thr l s h o w nn F f g u re4 0 A ' i l l u stra ti n g the lar ge var iation in output. Figur e 40B s h o r s a s i m l l a r sw e e p n a C u /C u r0 o cell pr epar ed ther m alevapor ation, by which s h o r s a n p n eco n sta n to u tp u t. B y l oading the two cells with the sam e esistanc e, r on e c o u l d u s e th e th e rma l l ye va p o rated cell as a calibr ation to calculate the po s s i b l ee f f i ci e n cy o f th e e xp e ri mental celt if it had a unifor moutput equival ent to the peakoutput. D . Discussion aboveI 11ustrate the potential i ti es of the Ja s e r s c a n ne r The exampl shown es app a r a t u s s a d i a g n o sti c to o l fo r detecting faul ts i n photovol i c c e lls . a ta ( f ur t h e r d l s c u ssi o nh a s b e e ng i ve n b y Sawyer 32) .
A

ACTIVITIES V . OT HER A. Intr oduction

S e v e r a loth e r p ro j e cts h a veb eeninitiated with the expectationthat they of oxide photovo' ltaic c a n c o n t r l b u t e to th e fu rth e r d e ve lopntent cupr ous celis. Seve r a lo f t h ese w i l l b e d e scri b e dher e br iefly.
B. Float Zone . Re f in in g o f Cu r0

T h e p u r i f ica ti o n o f C u r0b y fl o at zoner efining is being investigated. Th e it which is l f lo a t z o n em e th o d s u se fu l b e ca u se is a cr ucible- fr ee method, C b n e c e s s a r y e c au se u r0re a cts w i th all cr ucible m ater ials jeading to contam inati on. VZA- 3 Float Zoner( 34). u T h e a p p ara tu s se dh a s b e e nmodlfledfr om a Siemens bV A m o l t e nz o n el s l n l ti a te d i n a 3 /8 " r od of Cur O induction heatingand the of through the rod by movement the induction coil. zone is passeiiupward Thls

102

: .

..,- ..

*.

..\

,Fi.gure 39.

Surface Scan of CulCurO Cell l{ade by Atomlc Hydrogen Treatment, Showlng Irregular Otrtput.

Flgure

40A.

Slngle SweeP on Cell tn Flgure 39.

'rtg,rr" 4oB.

sfuigis Sweep on Ar/Cuo0 Cell Hade by thenofil Euaporatlon

103

c a r r i e s t h e i mp u ri ti e s w i th th e me lt in faVor able casesand leaves behinda pur er re-grownrod. The processcan be repeatedto achievefurther purification. By u s e o f a sl n g l e crysta l se edat the tip it is possible to gr owsingle c ry s t a l s c f Cu r0 . S l i ce s fro m th e s e single cr ystals havebeenusedoccasional l y p t o t e s t t h e n e wce l l p ro ce ssi n g rocedur es. This is only of value for exper im ent al p t r p o s e ss i n ce th e p u ri fi ca ti o n and single cr ystal gr owthpr ocedur es e too ar invo l v e da n d exp e n si ve b e u se dfor makinginexpensive to cells. A n o t h e rasp e cto f th i s p ro Je ctwhich is Just being star ted is to intr oduc e lm p u r l t l e s i n to zo n ere fl n e d C u r0 , possibly in single cr ystals, by the method o f z o n el e v e l l i n g (3 5 ). T h i s w i ]l be donewith ir on, cobalt, and nickel, and per h a p s t h e r su i ta b l e e l e me n ts. T hesesamples will be studied by electr on spin o b res o n a n c w i t h D r. C . S ch w a a t th e Univer sity of Str asbour g oughan NSFe thr s p o n s o r e c o l la b o ra tl o n . d

c.
lnto Cur Ois being star ted with the objectlve A p r o J e cto n l o n i mp l a n ta tl o rr pof t r y i n g t o p re p a ren -typ e C u r0a nd thus pr oduce n junctions in Cur 0. The i d o p l n go f C u r 0w a s d l scu sse d n a p r eviousr epor t ( 2d) . Cur 0has beenpr epar ed onl y l n t h e p -typ e fo rm so th a t a l l cell wor k so far has beendonewith Schottky it tr b a n r l e r s a n d he te ro Ju n cti o n s.A p p ar ent' ly is not possib' le pr epar en- type it Cu r 0u n d e rt h e rma le q u i l i b ri u m co n ditions. l,lith ion im plantatio,r m aybe pos s i bl e especially in conjunction co with laser t o a c h i e v en o n -e q u i l i b ri u m mp o sitions in a n n e a l i n g . I f p -n i u n cti o n s ca n b e pr epar ed Cur O,this shour dgive higher V o . ( > 1 . 0 V ) a n d g re a te r e ffi ci e n cy. P554B impl.r nter ion has beensecur e d F o r t h e i o n i mp l a n ta ti o n ,a u sed0RTEC to and t h i s i s b ei n g p u t i n to co n d i ti o n for the exper im ents. It is planned use is f h a l o g e n so r t h e fi rst i mp l a n ta ti o ns. The' laserannea' ling being donewith a D ) pul s e dd y e l a se r (P h a se -R L -1 0 0 0oper atingat n,560nr n.

104

D . A n a l ysl s,a n dPur lfication of Cu and Cu20 A s d l scu sse d a rl l e r l n th l s r epor t and in the pr evlousr epor t ( Za) , ttre e q u a l l t y o f th e sta rtl n g C u a t 9 9 .999+% is pr obablynot goodenough. Better Cu q u a l l t y C u w o u l dyi e l d b e tte r C ur 0and this shouldlead to impr oved .. Thi s Jr 'raises the question of the methods determiningthe impurities at concentraof tlons of n,I ppm. m T h e f l r st p ro b l e m s to d e v elop ethods analysis in or der to deter ml ne l of w h i c h l m p u ri ti e s a re p re se n t, h o wtitey ar e r edistr ibuted in the var ious pr oces s l ng pur st e p s a n d h o we ffe cti ve p ro p o se d ificar ,icn pr ocedur es will be. The pr inc i pal u a n a l y t l c a l m e th o d se dp re se n tl y is atom icabsor ptionspectr oscopy which maybe that it deter m lnes y a d e q u a t eo r so me l e me n ts,b u t l t has the dlsaCvantage f e onl u a o n e e l e m e n t t a tl me . [,l ema y' s e the faci]itles of a local .lndustr ial labor ator y , wfth an lnductively coupled d w h l c h h a s a co mp u te rl zee ml ssl onspectr ogr aph preliminary analyseshave beenmade. plasmasourceand automaticread-out. Some i to f I n b o t h o f th e se me th o d st w l l l be necessar y developsuitable standar ds or th e a n a l y s es. in C h e m lcaa n a l ysl s ma yn o t b e sufficient in all cases. lor exam ple, the l or cooling, it m aybe that s om e a n n e a l i n go f C u rO,e i th e r a t 5 0 0 "C by pr ogr essive and thus ar e r emov ed lm p u r i t l e s arc, p re cl p l ta te d l n te rnally as separ atephases fr o m t h e C u r0 l a ttl ce . If th i s {s so, par t of the beneficial effect of the a n-

par tially in this m anner . Chemical analys l s n e a l l n g m a yb e to p u ri fy th e C u rO would not reveal this. of the total sample Onepossible method test for to

on to this condition is to use electron microscopy properly preparedsamples phases and then to analyzethese by electron mlcroprcbe. Iocate any segregated T h e p u rl fl ca tl o n o f th e co p perwouldbe a for mldableunder taklng. Le basedon careful electrorefinlng followed a Hdrlcy (.tg) has developed procedure by float zone reflnlng. in He succeeded reducingthe iron content in Cu to I

la'

t0s

part In 108. Slnce our requirements maybe satisfied wlth a lower degreeof p u r l f i c a t i o n , w e ma yb e a b l e to sl mpllfy the pr ocedur e, .g. by hor izontal z o n er e f l n l n g i n a b o a t, fo l l o w e d b y electr or eflning. Equipnnnt do this to prellminary experiments has beenassembled some and have beenundertaken. l l h e np u r lfl e d ra te rr.rl b e co mes available, lt will be posslble to take u p m o r . e e f l n l tl ve e xp e rl me n ts i th lntentional doplng. This could yield d w lo w e r n e s l s t l vl tv cu rOw h l chw o u l dl ead to lmpr oved l efficiency. cel'

VI.

SUMI,IARY DISCUSSION AND

method The hydrogen bombardment has shown that it is possible to prepare Cu/C u r 0 e l l s wl th a V o . rp to 0 .7 2 U. The Vo. was found to be r elatively c ln d e p e n d e n tf th e b o mb a rd me n tl tage' but the Jr . of the celJs incr eased vo o with loltage. lower bombardmenl processwas examined Augeranalysis and of The mechanlsm the bombardment by by electron mlcroscopy. Theseshowed that the effect of the hydrogen bombardmentwas to reducethe top layers of the Cur0 to Cu thus creating a Cu/Cur0 into the Cur 0followed a Gaussian J u n c t l o n . T h e p e n e tra tl o no f th e h ydr ogen d ls tr l b u t l o n w l th th e p e a ko f th e d l str lbutlon m ovlng lnwar dwlth incr easlng voltage. At lovrervoltages, the Cuowas concentrated bonrbardment near the yielde d s urfa c e s o t h a t th e C u fl l m w a s th l n ner and the better light tr ansm ission Jr.. an improved At least a certain bombardment was necessary obtain time to

a d e q u a t e o n t i nu l ty i n th e C u fi l m i n or der to havelow r esistancein the contac ts . c were a bonbardment voltage of 250 V and a bombardThe optlmuncondltlons f'ound mnt t l m o f 7 5 s. T h e ce l l s e xh i b ited a lar ge dar k r esistancewhichwasascr ibed

produced to a layer of lntrinsic Cur0Just belov the metal contact, presumably by of at a small amount hydrogen these depths. It is believed that further

lm p r o v e r c n t sn ce l l q u a l l ty co u l d be r m dewlth additlonal vari atl ons I n the l procedure,.9. a sequence low bombardment of voltages. T h e b e s t o ve ra l l co n ve rsi o n fficiency obtainedwith these cells was 1.3fl. e However, the best individual values for the parameters obtained in thls laboratory are Vo. = 0.72 U, Jr. = 7.0 rnA/crnz FF = 0.6. and If these were to be

c o m b l n e d a s i n g l e ce l l , th i s w o uldyield an efficiency of 3.0%. Sever al in n s m a l l l n c r e m en ta il mp ro ve me nits these par am eter Sr .g. l0% in each, could brin g t h e e f f i ci e n cy to 4 .0 %,th u s reachingthe near ter m goa' lof 4- 6%. Beyond

this; the theoreticalestimates the efficiencyare 13 to 22%. That these of be is by theoretical valuescou'ld approached supported the fact that for Si valuesof the efficiencyhavebeen brought andGaAs cells, the experimental closeto th e th eoteti c alv al ues . question whatefficiencyis necessary cormercial An important is for use.
efficiency that can be A pr e v a l ' e n t xp e rt" o p i n i o n i s th a t lOU is the m inimum "e a b us e d . H o w e v er, n a l yse s y S ch u e l er( 36) end by l,lolf ( 37) showthat efficiencie s belo w4 X c o u l d b e u se d l f th e syste n ls sul' ficiently low ln cost. 0f cour se, a la r g e r a r e a ls re q u l re d fo r l o w e fficiency cells and this m aybecome the lim i t i n g f a c t o r. A 5 X e ffi ci e n t ce l l can pr oduce 0.25 kt,{ .hr /m 2.day electr ica l of

a u ene r g y . F o r a h o u se h o l d sa g eo f l 0 kW .hr /day, photocell ar ea of 40 m2would be r e q u i r e d , o r l 2 x 3 0 ft2 , w h i ch c ould easily fit on the r oof of a house. ab A s s h o w n o ve ,e ffl ci e n ci e s fo r Cur 0cells of 4t can r ealistically be l0X are concelvable. The strategy expected. Efflclencles up to and exceeding that can be taken to achlevea 41 efficiency as a near tevrngoal is flrst to

and then to improvesome all of or comblnethe best values of the parameters these lncrementally. ln The large lmprovennnt Vo., uP to 0.7e V, obtalned by hydrogenbonrbardrnent str s ho w s h a t t h i s ca n b e o b ta i n e di n a CulCur 0 uctur e. This is not necessar ll y t

107

the llnit,

slnce a lowering of the Fermienergy (cf. Flgure 28A) can increase

the built-ln potential and therefore Vo.. Loweringthe Fermienergyfrom 0.35 eV t o 0 . 1 e V c o u l d ra l se th e V o . a b o v e0.9V. Larger values of Vo. could com from the use oi junctions other than Cu/Cur0, e.g . o t h e r S ch o ttkyb a mi e rs, i f they can be stabilized, heter ojunctions, a or p- n J u n c t i o n. H e te ro j u n cti o n s a vebeenstudied to some h extent in this labor a tor y (3 8 ) , b u t i t i s n o t p l a n n e d re tur n to this soon, as a m atter of expedienc y . to Th e p r i n c i p a l e ffo rt sh o u l db e p l a cedon im pr oving the CulCur 0 cel' l to achiev e the near tenn goal. Some effort wi'll be devotedto trying to producep-n equlpm ent it if J u n c t l o n sb y l o n l mp ]a n ta tl o n . T hls will be doneon the 0RTEC c a n b e m a d e e ra ti .o n aw i th th e resour ces op l available. In addition, som e explor ai w t o r y l m p l a n ta tl o n s i l 'l b e ma d e n a local industr ial labor ator y. The initial imp l a n t sw i l l b e d o n ew i th h a l o g e ns, g. fluor ine. e. nethod has the disadvantage bombar'dment The hydrogen that it gives cel'ls with lowet Jr. than other methods. This maybe due to the fact that the penetrais tion of the hydrogen too deepat the bombardment voltages used so that the Cu f i l m i s t oo th i ck, re d u ci n gth e light tr ansm ission, and that a high r esistanc e ln layer ls produced the Cur0. Thus it maybe desirable to re-examine the voltage to see lf these effects can be reduced reglon of low bombardment with a s h a l l o w e rl n t r o d u cti o n o f h yd ro g e n. Thls could be donewith a.pr ogr am low of vo b o m b a r d m e ntl ta g e s, fi rst sta rti ng with the lowest voltages, .g. 25- 50 V, a n d l n c r e a s l n gth e vo l ta g e i n ste p s to 100- 200 V. The initially fonnedCu wo ul d

bombardments. the succeeding act as a barrler to moderate Also a top layer of to Sl0 * c o u l d b e a p p l l e d fi rst b e fo re the bombar dment achievea slmilar effect. to it Howeyer, maynot be necessary makethe Junctions by the hydrogen bombombardment method. It maybe that the chief value of the hydrogen bardment th wlth ex p e r l r n n t sl s to d e mo n stra te a t'Vo. valuesup to 0,72 V ar e achievable

108

Cu/CuZ0 iunctlons.

It maybe possible to obtain the sannquality of Cu/Curo

Ju n c t l o n , l .e . a cl e a n Ju n cti o n , by other m thods, .9. by r educfionas wlth rtomlc hydrcgen by better prcparatlon of the Gur0 surface with better or etchants, followed by thermal evaporationof Cu. Some experinrents these of klnds have shown lmproved vo. but not yet ts consistenily as the hydiogenbombardment rnthod. Further lmprovements would come from lmprovements the quallty of the ln C u r o . T h e pa rtl cu l a r.q u a l l tl e s that ar e of lm por tance e the diffuslon len gth ar a n d t h e r e s l sti vl ty. T h e J.. d e pends the electr on diffusion iength, Ln. F or on la r g e L n ' t he th e o re ti ca l va l u e s for the lim it of Jr ..t (rg a s n , 2 0 m A/cm2 ). Al{ 0has beencalcul ated

F o r A l 'l l co nditions, the lim iting Jr . is estimatedto be

" , 1 7 n A/ c m2 . A b o u t7 5 1 o f th e l l mlting value could be obtainedwith a diffusl on I e n g t h o f r 'tO u m. l ,l e a su reva l ues of the Ln in cur O havebeen ' \,1- 2 um ( ld ) but d values up to 8 umhave beenreported by our Frenchcollaborators (40). The diffusion length depends the lifetime of the minority carriers. on the llfetim' To increase

one must reducethe number recombination of centers. Thls would b e a c h l e v e d p ro p e r p u rl fl ca ti o n and annealingof the Cur O. by L o w e r in g e re si sti vi ty co uld lm pr ove th both Jr " and FF ( 25) . Eventhe Vo. co u l d b e i m pro ve d , f th e l o w e re dr esistivity ' leadsto a substantial decr easen i i t h e F e n n l e n e rg y,a s l n d l ca te d a bove. At pr esent, the lowest r eslstfvity norm al l y o b t a l n e dl s q ,1 0 0O'cmb u t va l u e sdownto 60 Q.cmhavebeenobtalnedln lsolated ln s t a n c e s . At th e u su a l th l ckn e ssof Cur 0, thls glves a cell r eslstanceof 6- 12 o' nrd this needsto be loweredto lmprovethe efficiency. To sorne extent

t h l s c o u l d be d o n ew i th p re se n tmater lals by using thinner film s, c.9. r educlng the thlckness from 200 pm to 20 um. This would lncrease FF substanilally and the rlr. to some extent. The thlnner fllms would have to be supported.

109

The quallty of the Cur0 ls dependent the purity of the starting Cu and on materlal. the processlngprocedures. It rppears that CurOls a heavlly compensated F o r 9 9 . 9 9 $ t C u th e l mp u rl ty co n tent of ]0 ppm could glve an lmpur lty concentr atl on o f n ,l o l T - 1 0 l 8 .r-3 . with the nor malcar r ie r T h l s fs q u l te lar ge in compar ison purposes would be desirable For experimental it

concentratlonof . lOl4 .r-3.

by t o p u r l f y t h e C u su b sta n tl a l l y' p er haps electr or efining and zoner eflnlng. could A f t e r t h e o x ld a tl o n o f th e C u to Cur O,the native defect concentr ations at , b e m o d l f l e dby p ro p e ra n n e a l i n g ,p r esumably 500oC. Howeverlt wouldbe deslrab'leto add effectlve dopantsto the purified Cu or CurOto reducethe resl stl vl ty. to After the experlmentalfacts are understood,it maynot be necessary of p u r l f y t h e C u e xte n sl ve l y l f ce rtaln lm pur ltles or conbinatlons impur ltles ar e a v o i d e d . A n i n d i ca ti o n o f th l s ls that the highest Jr . attained so far , copper, with a nominalpurity was obtainedwith a 'lot of cormercial OFE 7 rnA/cn?, C of 9 9 . 9 5 + Z u . p especially the annealing,wouldalso ha v e T h e p r o p e r p ro ce ssl n g ro ce d ur es, m cer t o b e e s t a b l lsh e d . P a rt o f th e e ffect of the annealing aybe to r emove ta i n lm p u r i t y n n t al o xl d e s fro m th e C u r0lattice by inter nal pr ecipitation, e.g. at g ra i n b o u n d a ri e s. A fa cto r th a t could com plicate this, and mayhaveaffected the solublllty e a r l l e r r e s u l ts, l s th a t a ci d i c o xides suchas Sl0, could change o f b a s l c o x i d e s su ch a s !1 9 0 ,e tc. The annea' ling also adjusts the concentr ation

and oxygen vacancles, whlchar e o f t h e n a t l v e d e i e ctsr co p p ra to mvacancles can be th b e l l e v e d t o de te rmi n e e ca rri e r c oncentr ation. If effective dopants defect concentrationsby a found, lt maybe deslrable to reducethe competing l co c h a n g e n a n ne a l l n g n d i ti o n s.

f,

ll0

In sunmaryr for wide scale cormercial use of photovoltaic what ls needed c el l s f o r s o l a r e n e rg yco n ve rsi o ns not a technically excellent cell. i Such

c e ' l l s a l r e a d y e xi st, b u t th e y a re n ot wldely.used because cost. tlhat ls of n e e d e ds a c e l l o f a cce p ta b 'lq u a lity whichwi' ll m eetthe dem ands the l e of ma r k e tp l a c e in te rms o f co st. C u pr ous oxioe could pr ovide low cost cells ( 41) , in but must be lmproved somewhat efficiency. A possib'legoal to reach thls

ls a n e f f l c l e ncy o f 4 %, It l s re a l lstic to believe that this can be r eached wlt h C u r 0a s a n e a r te rm g o a l , w i th fur ther expectations eventually of reaching 10% greater. or

* 1,

lil

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