Академический Документы
Профессиональный Документы
Культура Документы
,..... ______
-------------~""" " __ , __
____ _________
....;.;..._~ .;... .,:_
:,:
:~orio TA.l':ICUC
7okyo Scie nce ~nive~si~y
I,od<',- shi , Chiba-ken , 27c Japa n
Abstrac'.:
'Nano-technology' is the prod\.c.;io:r. tec:mology ~o get t:-:e extra
high accur acy anci ultra fine diT!!en:;ion5, i . e . ~he nreci sei:es s :rnd
fineneso of the order of 1 nm (riano rnei;er) , ·, o-9 1:; in - length . The name
of '~iauo-technoloey ' origir.a tcs fro m t::i~: nano:net cr . In the processing
o! ~atsrials, ~he s~allest bi.; size o~ ai;ock re~oval, accretio n or flo~
of mat~rialsis proba:i J.yof cne ato:r. o::- one ::io l e::ule , nar.:cly O. 1~ 0 . 2 :im
in length . Therefore, the expe cte d limit size o! fineness ~oulci be of the
order of 1 nm. Acco1·dingr y , 'li,illO-tecru"lology' n;ainly consists of the
pr oce ssing of · separation , consolidation -, Lion of meteriuls
a11.:: ciefo ::-m:
by one atom or one ,r.ole :::ule . Neeo.less to say , ~he 11easurement ,rnd cont-
ro ll techn ique s to assu re-t~e preciseness snd ficenenn of 1 n~ play
very irr.portant role in this tecnnology.
In the present paper, the basic concept of 'i'ano-t echno logy • in
materia ls proce ssing is discussed on the busis of ~icroscopic behaviour
o: materials :.-1.iAasa result_ the ior. sputter-:nachini11g is introduced ns
the ::ios, proraissing proceGs for the technology .
- IP.-
Supplied by the BritishLibrary- 'The world's knowledge"www.bl.uk
r·
!
I
I
_ __---
_____ _.:...: -·•-·- --·~- - ---- - -- - ···- -· - - ·- ··
.1
'i'1::ble ·, . Ki ndo l, ;· :1,c1t,erials process i r.e ·oy on e ::,tom or one :aolecule
J
1 mech an::sm __kinds
____ __ _ _,______ of pr ocess i ng
---- --=~
-- -- ------- 7-+
( ch emic&]_ de co ~posi~ion ch emi cai etching ( photo - etcting),
I i~~ chemic a:i. nolish i r.g
I ,-.::8 m glectro - chemical c."eco ,r.posi tio,, I ele c n ·oly tic p ol i sh i n.::;, el ectr o- ch e rdca1
J ·~ tt
g ":
.-,-----,-,--..,,.-- -- --- ~
' me.chi r:.i.ng ____ ·- ·· . ·····-·- -- ---- ---,- ---- --l
I i
1-·"'~
I
o P-c
0
(
7
ev.!:rn·o-r
.Ytio r, , ,: lsso l u tion
, f1e::-mal)
i-, ~ :,:1-- -'--..;;..;.;..;.;::.c..;_;
.c:c.:._.=- "
electron b e a:r; 11
;ac h i.ning , li;ser r2.y machining ,
cle c "trc d :.s cll::.rg e mach . , dissolu t ion ma.ch. ,
I spi.;.l, terine; 1uy:-::a:nic r.lJ 10:-:: sp 11tt(: r m,,ch in i ng
I )~ i
1
p:1y1:;icz•.l a nd ...{heri:;c,. l a c cre· cion v ar.o ur d1e:pc-s it :i.on , sputter cleposi ti on , io ni c
I ! -~ !- -,-.- .,..-.,. ,- -- - t-,--,-_
__ _____ ...,.. dei,oni t:i.or. . .
::ucm::.c &;. acc1 ·e ·.te n ch emic a l plating O'.!'.'aer o sition
'1 l~
-...,
electro - J.ytic P.c cret i on el~c t"1;-o- plating , ele c tro c a s ting
' ::a
.
"' ch e mi c r.l 2.nd eiec:-t:( ·::-- eche:, ,ical thin f il m ( anod·ic ox idatio n, oxidation ,
j.. ~,;: ~ ..,.c
..:c
o.:.::in~p:..:o..:.:s:..,
.-! "'· i:...
t:.::i.;:..·
c:1r:
;.'-,- ..,.---=-:
---,.-- -,- ....--'-- --l --,•n~;.;.
i:;.. "• 1.;.·
t..;.r,..c
·l:l
c....., ;...:;:gasc ou s , 1 1.q
o;:..r
:...
1_,. · ui d _ ) _____ _ _ _ ___ ......,
o o implantati on l dyna rnca l ) ·1·on irr.plantatio21-· -· ·----·-·- ---·-·
I g~
! (.)
e>
hen :.:
·- --·.....··--·.-4
-~- c; c.. t-a-· i_· f_ ='
_· u_
s_i_o_;t_( _ t_h_"'......,.'
'IL_
3_l_!_ -,-.,-- ----+ -s-u_r_f_'"
_'_c_
e_t_r_e_a_t_:n_e_r_, ~
" , ___s_i_
· n_t_e_r_1_n_g
_ _ ________ _ -··- ··----
c rys tnl gro wt h (ti:le r mal ) e pitaxial , mole c•.1Jar bean:
!'
..-.,,.---,----,-,-,-
-- ~ ....-----· .. ·- ----+- d-fppI-a-:r.t-:,i-:-nccg-
,-z"'"h""
e_r__m_
a"'"l..,.f
,...u"""s-,
1_0,_,.
r.-.-- - ------- ·---·
I f usio n {ti'le r :ncl)
1 ~[3 :;;·..u·face : l ow ( t hermal) flow fi n 1nsh1.n g (ga s flame, high :rrouer.cy, --
;;.:~ u i1eat i-cy , elec t 1·on beam , lase r r ay )
~ •-1 o 1--v-i_
s_c_o_
u_s_ f~l- o-·,-1-ar.-.~d
- a_b_r_a_s..,i_o_r_1-- -+-~f,;:l:..::o:..::
1s
:..:
· :..1
.,;1;..:n::.,/...1sfi
il 1g ( vi cftl tl on- $11arng , l1qu '""'
1,.,o.'·
,__,
g'"a"'1::s,,....,./--
~~ ~ (dynanicH l )
,,,
"A a c t iv a t ed
state
~ E"°
0
;,, j ___ -
'-1
~~ .(1G
.;:i J!., fflirl s1;~t i c
'C:
j_ ___ _
;::
0 Gr
.o sta ti c state
i11t C!'t1.1omi c sp:::ci n g a re:?.c t.;d..on
,.,,
,
free f'nergy 01: tl.e ~.cti vn ted
free P.Yiergy on the stat ic (0 °K)
before th e re: , ction
free energy on the s t ~tic(0 °K)
~fier ~he rcsc~ion
....
A
., vJi- G1. < 0
,,
dri vir.g energy for
the 1·cact i on
.~C1 -= G 1 - G.x.> 0 rq,isting ene r gy fo:-
.'l
<.-
~r,,,
reactiOll
Q 0 ; ;;c"oivatiun ;,ne1·g:; or- barrier energy
0
r1·ct ,,:la(~!·g y ~
bot:d.ing pot en ti;;l e:iergy ·• kinetic
'c"!lE!'gy
r;, n2 Qo
idncti c energy
:! l-'ig . ·)
''
''')
:d
.d
\f Supplied by the BritishLibrary- "The world's knowledge"www.bl.uk
-l 9-
.,~
L
I
I I
aensity of worKing e~ergy, so ca~led, but vatio:1 energy Q 0 , and also ciepe ncis on
,str ictl y speak i ng , is c.i iierent from l ar·gcly i.he cor:c cntr8 ti or. o: re~.ct .ing subs -
sp ecif .Le stock remov:!.r,g·: ene::-gy or stock t~nceG . How€ver, :.t s~c~ld be not ee tha t
rerr.ovi r.g er.ergy o:f u n:. t vo J u:nc . ( 1) t he rate of r eaction tines not depend on
Conoequently , 1: a bit o~ ~rm·£~oing t!.e dri vi r.g energ_v o~· ?·e~i::.tin~ cne~·gy :or
en e::-gy large .i· tha r1 :he: bonc.ing energy reactio n 4 ~ or AGI ,rc sp ec ti 'le l y, ~n::.c~
were fed di::-ectly t o th e nuc le us of the corre~nonds to the c.i ffe renc e of bor.6i ng
ato~ of ~o~k-n~ece tie a t o~ potenLlal enc rg i~a be t ween be fore ar. d afier
nartic~lar 1
the re ac-:.io n . ?ur t.hcrmore , i n case of stock
;,o-..ilc. ·oe rerr.ovec. off :'::-oir. the ~i:.rfi,;ce of removir :g process , t l:c re!o i::it ir.g ene rgy be -
work-pie ce . Hxactly speak i ng , the pro ce ss- cc:~es ·, o be nearly eq_1. .l Lo the bondir.g
'.!:'
i ng ene-:-gy must ·oe larger than the !?. ct:.va-
ti on energy , wh:.c~ is discussec later . energy its el f and also tha act iv ation ener -
riowever, in the: stock re • oving process gy is la rg er than ;,hL va~ ~e o: tl.e boNiing
based on chemi cal , electro -c hemical a nd ener gy in gen er·al.
th er ~al reactions, the particular atom of Ther efo re, in o::-der t o get "the lar ee
work - piece reacted can not be directly fed r eactio n rate , it is neces:rnry to r :.se up
t:-ie l ocal t0 mnen,1ture of ·,;erk-piece ar. :l. a) so
the processing en~rgy fr o::i therefLCting atom of react i ng
statist ic ally only . In to increase t Sr concentrtition
, but can get
other words , at this kine. o:· nr oc1?ssing, su hota ~ce s o i ~he :oca l porLio~ of work-
~he r ate of ree.ction io s t&ti;tically 'det- pi ec e by re; :1ac i i.g the sub.star.ces sencr at.ed
ermined , as expla i ned by the ~heory of from the reaction te l y .
irn!!le:l:i.v
re~ction rate orocess .
NameJy , prior io t~e re a ctior., ra act cd 3 Evaporatio!"l process
t he In case of evaporation process ao t he
at om of wor k- piec e must stand on the procesr; i ng ene r gy is
act iva t ed state, on wtic h ~he free energy therr ;1al reactio:1,
of the atom is large r by t~e activation s uppli ed as the for m of the heat en ergy to
en er gy or barrier energy Q 0 , ( ,T/molecule ) , the particu:ar atom ar.d ther , the t empera -
t h!m the free cn <:lrgy of static state or · ture rises up to the evRpora.1.ion point s1t
0 ° K, ae sho.:n in :ig . ? schemstic2lly . ~hic n the ~eRn kinet ic ener gy of atoms E
is det er - beco::ies Lo be nea;::ly equ al ~o the a ctiv ::-. tion
According r y, tte rate of re2ction
mined by the p!·obabil i ty that the the ::-ma- ener gy , i . e . Q0 = E. Conoce:uently the rate
lly agit at ed ato r.i of wor k- piece co;,;.ld get of re actio l" approac he s t.0 the maxirnwr. ;:;.t
the free er.ergy , mai::l y kine ti c ene rgy , th e poin t , as seen in Bqu . 2 .
However, it is very difficult to con-
over the value of act i vation energy Q0 • the sufficient he at energy to
On t he oth er hands . the a ton:s of so 1 id centrate
,,..ith their the particular atom , because there are
rr.aterial s have the.distl"ibution
kin et ic energies as shown in ?ig . 3, there- two dif f iculties ; the first is of flo wing
f ore, th e pro ba bility abo ve mentio ned is t he hea.t ener gy thr ough suc h t ha t very
'·,·
given as fol l o~s; na r ro w path req ui red a11tl the se cond is of
(1) risicg only tle te~perature o~ s uch that
ex~( - (Q0 - B)/k~ ) ~exp( - Q0 /kT)
where .::. is th e rJe!m kin~t ic enerey of the very f in e i·egion to ev ;,-!)Or ation point ,
atoms at the -;;err.p()rature of T i<~li'mo
0
lecu le ) ; wi thstanding to the i n.'1erent prop erty of
2
k :aolt z~a r,n's co nstar.t 1 . 38x1• - J/1<.::iol e- heat cOJ!tiuct ion .
cule; and in t he ro0m ter:1peraii.:rc Q O is Tt e ty pic a ~ evapo rat io n p::-ocesoes ~or
ge ner all y pretty larger than E, and so app- the ultra fine fin is hi ~g are the ele ctron
roxiamtion form of right si de of Eq~ . 1 is bca:n processing anci thi, laser ray procesi:, -
used . , ing, buL th& electro - :iischarge :.1achinin g
Then the ratelof r ea c tion , the rate of the and the heat ray pr ocessing stand afte r .
oc cur ence of .mi t reaction or t~1e re:novii:g As to the elect::- on beam ;n ·oces sir.g ,
rate of a t o:n ::·o:n the wo::-k- niece :nate r ials , elec t::-or.s wit:1 hieh kinebc e~ergy, e .g .
de noted r, is giv~n as follo~s ; 100 kcV ~ 30keV, are pro ~ec tc o on the
( 2) surface of the ¼Ork- pi ece mat erials an d
r=Ae x-p(- ( Q0 - E) /k'T ) is evap orated
where A is the co nst ar.t of time r:e.te , i.e . ~he parLic ular atom projected
the tillie ra t e of r.u~bers of reacted ato~s by the heat co :.verte ci from tha proj ec ted
per uni t vo l ume concer neo , and expressed elecLro~ ene rgy.
as fo ll owing form by the t:ieory of statis- However, there are so~e troub~es to get
ti cal mecha~ i cs, the fineness of working o: 1 nm. That i s ,
A=f( c )p JI exp(S ,.../k) (3) the electron with suc h that hig ~ speed
In above formula , f(c ) is the functio:r: of c,n not oe gr asped by th e a Lorn on su r f, • ce ,
the co ncentr~tion c of r e~ctingsubstance s; but penetrates the pre-:.ty deep dep t h into
p the probability ~hat the a.torr. satisfie s materials, bec::,use an el .gctro~ h~s a very
the geometrica l and other cor,di tiorn; nece- small di arr.e Ler o:r 3x 10-1,crn co:npared wit h
ssa r y to the reaction i n the activated the suacine of atomic latt i ce and also,
state; v t he frequency of the ato: n to D?ecial ly ir. ca se of r.ie~ spee d elctron,
react , ato :nic fre quency of t he a t orr. in Lt passes through the oc.ter el ec tron sheJ l
so lid or a fre~uenc y of collision ofre2ct- of ato • of su r face . Namely, ~ost of elect-
in g ato~s in li c.uia or gas; SA t:ie d iffer- rons with hi gh k.;.r.ctic energy are captured
er.ce of entropy of the a torr.s 'between ':,y the o-.;.ter sne:il o:· atom la c<'.teci. a t t!'lc
before ai:d after the re ?.ction . ' e] ectror. range' ben ea:h th e surface and
.t.ccorc.i1:g ry, :.t can be ::-eg~.rded th3t converttheir energ ies to heat th ere .
in ~he above mer.tioned p rocesLee the rate The elec~ ron ra nge~ ~s gi ven by ~hep~rt-
of r eaction or th e rate of stoc k re~o v ing ly exn er i~ental ex press icn as fo llows;
:. ,.-2 .lx 10-1zv /f cm, ~.he re ·v is tr.e
4
increases ,:i th the ternp er£ature of re, ,ctin g
substances T, and r.e~re:.;ses w::.th the acti-
\
I
I accerelation yotential in V, and f is the obtainthe extrem fineness of the order o~
j density of the work-piece material in t nm, even thoug h th e rr:ost develored ;r.ethod
g/ cm3. Practical numer i ce.l va l uer; are of electron be;;.m process and le1se ray p:·o -
26µm on steel and 80,u:n on alumin um for cess could be applied .
100 keV, and. 6,µ.:JJ and 20f-n- : for 50 keV,
x·esoectivelv. 4 ch coica l and el ec Lro- cl',e;,~ico..:. re:r.oving
~herefore , in case of 10CkeV, the heat pr ocesses
is generated in the depth of se v era l ,JJ..m As easily seen, these pr·ocess e s :;,re very
beneath the surface of ~ark-piece and ~hen suitable for the ultra r.i.ne fir.ishing , ·oe-
c ondu cted to the surface ato:n . Accordingry, causetl!e remo v ing 1·eactioi1 is done by one
t:-,e stock removing due to the elctron beam ato m or one molecule . Por getting the ext -
·combarding can oe performed in the pretty reu: fineness of working , the accura-;;e po-
wide range as severul)'- m,l;ut :iot at the sitioning and fine localizing of re3c ti:ig
e:xtrem fine range as several· nm. subsiance is necess~ry, but it is very dif -
Not to say , using a lower energy elect- ficult in practice ,even for the order of
ron, it is able to make the electron range 1J£m in length , to make t he r:;ask hav i ng the
more shallo w, but it is not satisfied for accurate and fine patter:!". of clctrical ir: -
stock removing, because, in case of lower sulater or chemica l proof materials .
power density of electron beam , it is irr.po- Ho~ever, the new method combined ~ith
ss i ble to rise up the local temperature of the electron beam or laser ray in removing
the surface of work-piece to the evaporat- the weak points in these :.1rocess1nizs .
ion point against the heat dissipation due namely local i::ied hee. ting caused. by .:hese
to conduction. Besid es ,the processing u~ing energy bea: ns can er.hance the rc.,.ction r·ate ,
low energy electron .is 1·ealise6. in the elect - as explained by the reaction raLe theory .
ron exposure process for very fj_ne machini- Aft ·erall, thene processes .;.re not yet
ng . sufficient to get the preciseness 2.nd fine-
Namely, in order to evaporate the limit - ness of the order of 1 nm , because the
ed range of very fine dimensions, the elect- present roost succesfull technicue for mak-
ron beam used mus"s be appliec at ver1 hifh ing of the mask, i.e . photo - etching process ,
power densi ty,f or examole 10 ~ ~ 10 6 '11/cm is l imited to the order of 1~ m by the
for steel arid 10 6--. 10 '1 II'/cm2. for aluminu..'11, optica l wave length .
and also kep t its power only for very short
time duration, for e:xample,several microsec- 5 Ion sputter-machning or ion bombarding
onds y(iS )for s t eel and rno'r e short for alu- process
minum. These are deduced from the theory The sputtering is ba:::ica lly a knockin
of heat conduction of solid materials,repo- out of atoms of •,rnrk-piece due to bombard-
rted already in another paper . ( 2 ) ment of inert gas ions wi th high kinetic
Moreover, in the present stage, the dia- energy, namel y a bombardine;. ion makes
meter of electron beam can only reach to sequentia l elastic collioions with atoms
1µ m for low power , but 10 ,...,100 fA m for in taget materials and kn ocks out the atom
h igh power of several kilow;;.tts . from its sur f~.ce layer . Th2.t is , t!'!e nece -
By the above ment ion reasons, the attain- ssary removing energy of target materials,
able fineness obtained by the electron which corresponds to the acti,ation encrg;r
beam processing may be about 1~ ro. or bonding ene1·gy of the targe t atom, is
As to laser ray processir,g, the beam of supplied direct ly by a bom~ar d ing ion .
the ray of high power density up to 10~~ 1oOJ Accordingry, the sputter - macLining is mat-
W/ crn2 can be used and projected pulsively eri all ya non - therma l process and not Lhe
with the pulse width of several µ s on the reaction rate process above ment i oned, dif-
surface of work-piece, and hence the parti- ferent from ~he electronheam processing.
cu lar atom of work-piece is evaporated by From this roint of view, the process is
the heat converted from the projected re.y. of an ideal stoc.:kremoving by one ato1r. or
For metals, the projected rays do not pene - one mole cule. Eowever, in order to eet the
tr.ateas an high speed electron, bu t it is h i gher ore.er of preciseness and fineness
also difficult to concen trate the heat ge- in the processsine, the flow or energetic
nerated by the projected ray to th e very ions must be bundlec. to ar, very fine beam
narrow portion of work-piece, because the andthe intensity and position of the ion
diameter of focused beam of the ray is beam sh ould ·oe controlleci precisely . These
limi t ed to sever ·al JJ-m by the optical wave techniques become to be possible by means
•
. '; length .
As to th e electro - discharge machining,
of electronic devices of high gr~de .
Most popular- type of ion nputtei ·- mach-
I
! the heat energy ge nera t ed fro • the electric ining :c.pparat '.l.S is the ion lie::>.mtype with
..
; dischargeis
high power density
supplied pulsively
of 10 6- 10? ~/ cm
wi-:t very duoplasmatron
Fig . 4 .
ion source, which i R shown i~
The argon e~:s ion ger.era Led by a
through the very na1-row path of 1 ~ O. 1 fa m elctl'ic discharge i n the ion source chamber
.! in diameter, in the insul ati on oil . Not to is ex:racted by the a c ce relation electro de
say, the mechanism of stock removing is aG a form of beo.;n a.'ld led onto the ,..ork -
the same evaporation process as the above piece in the machining chacber . Not to say,
two . However, the difficu}ties for ultra tr.e intcnr;i ty , the bearr. diameter and
fine finishing ex is t in the precise cont- focus, an6 other el ctric con~iti J ns are
rol of electrode and the ~aking of the con L.roll ecl oy the i\:.rnished electro:-iic
electrode of very fine dimensions . devices ·out t he poGi tion 2nd t he inci dei:t
In conseouence , the evaporation process angle of' i on beam to the ·,1ork-piccc tire
based on th; heating of the particular dterminod by the ~echan ical ci.cvices of s l id -
portion of work-piece i s not sufficient to i:'lg ,rot~Ling and swinging mechanisms . (3)
-21-
Supplied by the British Library- "The world's knowledge" www.bl.uk
-·--.
r
.p
As to the chemical and electro- che mical ~1
;
accretion or denosition, there are also
as chemical ·a
several usefull.vrocesses rl
platinB , oxidation and nit rat ion, etc .. Q)
·ri
'.:'ile ior . irr.plantation is the process >, Xe
r
that ions of 1:ig!I energy can invade into t::Jl
the work-piece pretty deep and make an ,::
·rl
,c
unelas tic cor 1is ion to combine direct l y ;...
(l)
with the atoE of the ma~eria l s . This is .,
~
··l
Fi g_~
Duo-plasmatro n
ion source
Sch emat ic d iag ra m of i o n beam
sput t er-machining apparat us.
I on gu n
To vacuum~
pump
t
16~1 67 Torr
I
'i Ion beam
Q/ a
/- showe r
~ I
:~ing
•'
Machini n g
I "'
vacuu m
:-,}.
chamber
'•
Swing-
To pump
motor
L==;;;;;;;;;.;;.=:=..J 1-'i g . G H. F. Io r, gun
f;e r.e-
r•,ito r
s pu~ te~ ~
ceps i"oi :.>n
f ie . 7 D.C. I on gun
g s.s ir. :'..e t vacut:.rn
.....
anod e t eated c athode
:n2.f:r.e:i c coil
iull rth
-
et 2..i.cctrntlce
wo:· k -
1:i€,c .; V8C UUr:l
- 2a-
Supplied by the British Library- "The world's knowledge " www.b l.uk