CA1047171A - Manufacture of semiconductor insulating films by electrophoresis - Google Patents

Manufacture of semiconductor insulating films by electrophoresis

Info

Publication number
CA1047171A
CA1047171A CA243,160A CA243160A CA1047171A CA 1047171 A CA1047171 A CA 1047171A CA 243160 A CA243160 A CA 243160A CA 1047171 A CA1047171 A CA 1047171A
Authority
CA
Canada
Prior art keywords
slice
dispersion
semiconductor
glass
ion
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA243,160A
Other languages
French (fr)
Inventor
Maria A. A. A. Collaris
Henricus A. Debruijn
Petrus G. H. J. Smits
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Koninklijke Philips NV
Original Assignee
Philips Gloeilampenfabrieken NV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Philips Gloeilampenfabrieken NV filed Critical Philips Gloeilampenfabrieken NV
Application granted granted Critical
Publication of CA1047171A publication Critical patent/CA1047171A/en
Expired legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02142—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
    • H01L21/02145—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing aluminium, e.g. AlSiOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02142—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
    • H01L21/02161—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing more than one metal element
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02178—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing aluminium, e.g. Al2O3
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02142—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Formation Of Insulating Films (AREA)
  • Encapsulation Of And Coatings For Semiconductor Or Solid State Devices (AREA)
  • Conductive Materials (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Bipolar Transistors (AREA)
  • Liquid Deposition Of Substances Of Which Semiconductor Devices Are Composed (AREA)

Abstract

ABSTRACT

Manufacture of semiconductor devices in which a glass coating is provided on a semiconductor slice by means of electrophoresis from a dispersion of glass particles in a carrier liquid. A dispersion of the glass particles is used with a specific conductivity of at most 10-10 ohm-1 cm-1.

Description

I J 1~7 ~; 7 I r 131CS 1~1 :
. 17.1~-75 ,~
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~ etl]od Or manufac$urin~r~semiconductor clevices in whic}-a glas.s eoating is pro~ided, and semicollductor de~-i.ces manu~actured acoording to said method"~
~t ' sF~
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The invention relates to a method Or mallu- ~ ~
1~
facturing se]niconductor devices in which a glass coat-ing is provid~d on a semiconductor slice compris:ing one or more of' said scn2iconductor device~s in an :i.nter-mediate sta~re or in a ~inal stagre of` manu:~actllre, ~y mealls o~ elee-trophores:is usin~ a dlspe-rsi~n o:~ ~lass partielo~s ~ a l:l.qu2.clllledium, hereinafter tc:rmed dis~
r ~ c . ~ n~ 't. l ttl) C~ ~lt ~ ' ' 3 0 O ~ '; U L~ V' ~ IJ U ,~iJ.' U '~
tect vital parts of semicoi-iduc-tor device.s~ preseilt a~ s the surface, for exanlple, ~-junotions~ ending at t}le ~' surf'ace~which are to be cxpc)sed to comparal;ively h~6rh rcverse ~olta~e.s dur~ng use~, or parts wllich ar~ s-~,ns:L- `
tiv~ to atmoc;pherLc inf'luences, `, Upon providin6r such coatin6rs, lort~>-lastj.ng' t5 ~hormal troatlllents at modérately hiCrh teltlperal;ure ca~
ad~ersoly ;Lnfluence thc e1oc~r:Lcal propcrties o~ t]lû
. semLconductor devices. Witll a view to a reasollable protective effect against atmospheric influellces, the ~-.coatLng shoulcl bc sufficiently th:icl~. Howc~er in the ?0 case o~ large layer tllick~lesses, tllerllla11y causcd 5tre.s--se~ ma-~ occur and these Illay d~amag,e the semiconcluo~or ~' dev.l.ce. :~n order to ~ro~i.de a gla3s coa-t:Lngr with a '.
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PHN 7872 ,~
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reasonal~le thiekness and to avoid therma:L treatments ~, Of lon~ duration, aeeording to a known methocl the ~lass layer was cloposited e, ectrophoreticai.ly from a disporsion of fino-granular glass particles in a ~ f~
dispersion medium, for example, water, me-thanol or ethyl aeetate. The charge of the glass particles ori~
ginated from ions àdhering ~o the particlos. Such a deposited layer has suffieient adhesion to the device - to ~lithstand`, for example, rinsing treatmc-nts. For a better adhesion and screening ef:t`éc t j a thern1al trc~t me2nt at a moclerately hl~ll tomperaturo and o:~ on]y a ~ ~, . f short clurat~.on ma~ thon su:~:fiee . 1~ r~
~t has been louncl, howe~2rer, that the electro-~
phoretie depo.sition is of-ten n~ b produced uniforl11l 2~ 2;
over the semiconductor surfaee cmd the deposit is somot-:imes entiroly restricted to those parts of the i semieoncluct-or sli.ce surf~e which are present in the immediate proximit~ Or the eleetrode eonnec tion pro- i vidod for the eleetro~ ores~is. :I:t has furtIlerl11ore been establi.slled that non-uniforlll eoatiIl~s in the malIu:Eac-ture Or varlous types of semiconductor devlces occ~lr , to dif ferent extent . i~.
A first idea whieh has led to the present :;n- i-ventit>tI is that the above-ment.ioned phenomena may be relcl ed to rosistances in tllo slice itsel.f. As i.s ,, confir111ed by oxperiment-2, non-.unirorm deposits occur particulariy st;roI~ y :in those scmicond1lctol sl.ices '.

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`~ 3L j6 ' ~ j which consist at least f or, the gr~3ater par t Or material o.f .a comparal;ively hi~,h res:isti.vity, : .
The invention is furthermore based on the idc.a p. that. in tl1e above-described 1;nown method the suspension , , used has a comparatively high conduc-t:ivit:y, so that the `, internal rcsistances between the electrode connect.ion ~`
provided on the slice and the varlous parts of the se-miconduc tor slice surface exposed to the suspensi.on, in particular those surfaoe par ts ~hich are present ~ at some dis,tan~oe from the connection-, need not be , ~ ,~
negligibly small witl1~ respect to the resistance be~
tween each o:E the sur*aco parts and the coul1ter-el~c- '" !~
,~ , troci e provid ed in iihe su s pen s io~ . , .
It has further been considered that the charge `~ `, I5 ~ of: the iOllS o:l~ la given sign adhering to the parti.cles ii'' .
are naturally: compensatec1 for b~ ions di~;solv~3d in'' the ; ' j dispersion medium. Both types o: ~ons are foLmed frol~ ,I .
dissoclable sul~ ~;ances ~ hereina*ter termed auxi,liary , .. . ~ disp~rsion aj~ents, suitable for that purpose and added .' 20 to the coDventional ~.ispersion media~ in w~1ioh the ( ions of one char6e type must be cQpable of adher:Lng l; .
to the sus,pended parl;:;oles and the ions of oppos:~,te Gharge type mu~;t preferably remain dissolve(l :Ln sai.d . i mediwn by ~):inding to the dipo1es o~ the molecules o~
the dlsperF;ion medluI,n *or wh.ich purpc se I;ho saic1 ions Or opposite charg(3 type shoul,d pre:C`erably be, comp.lra~
, tlvely small . Consequ(3l; l;:1.y the mobi.l.ity of sa:Ld i.ons ' , ' ' . . ' ~' ~

, PllN 7P72 17.12.75 . ' " , ,' " ' ' ,. ~
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... , i 1 of opposite ehalge type i~ comparativcsly -lar~e~ An othor supposi-tion is, that said small ions should form a eomparatively clense cloud ln the po].ar mediul;lLIrollnd ~ each dispersed cliarged partiele so as to main-tain the dispersion. For such a comparatively dense ion cloud a correspondingly high ion concentration must be formed .- in the solution. The said comparatively hig]l concentra-tion Or dissolved ions and their eompnratively l~rge niobility are responsible for tlle comparatively ll:i~rh eonduetivity of the dispersions used :in thes abovc-me~nt:ioned lulown ritetllod It :i5 to be noted that clue to ~h~s very small mobil.ity o~ the disl~ersed parS;:ic].os, t ~ ~' , , Ille COnt'l'.ibUCiOn oI saicl a-t~spcriecl pa:r~icles to the ti - eonductivity of the dispersi.on is neg].igible.
~_1 s~
- ~ further iclea underlying tlle invention is .
that for t]le electrop~loretie deposit:Lon of glass on ~i semieonduetor slices, glass dispersion.~ of a con~e-niently lo~ conductivity may preferably be utiliYed.
Aeeording to th~s invention a method of manu-I`aetur~ng semicoIldtlctor desviees in ~llich a glass eoat-lng is provided on a semiconductor ~lice compr~.s one or Illore of said se~ico~dtlctor devices in an illter-mediate stage or in a final sta~re of manufacture~ by mecms of electrophoresis using a disp~srsion of glass particlei in a liquj.d di.spersion medium, is characteriz ed in that ~ disper.;ion of thc-, ~lass particles is used ~ith a sy~seific conductivi ty o~ at most 10 o}1m cm 1 ' . '' ' '' ' '" '; ' ~
, l !' l'llN 7872 . 17.12.75 ; 3L~4:7~L7~ ~ ~
It is to be noted that the fact should be takell i~ltO
acçount.that the dispc-~rsion medium in itsel~ llas a lower cond~ctivity tl1an.tlle dispersion preparec1 witl it so that the liqu:id dispersion mediwn should be .. , ~t~
chosen .from liquids having a speci.~ic cond1lctlvity of`
less than 10 ohm cm . l~rater and methanol, for examplc, have a spècif`ic concluc-tivity of more tllan 10 ohm cm . A lligher specif`ic concluctivity has ~ ! .
aLso been measured for etllyl acet:ate. Hydrolysls can ; ~ r increase t1le coMclllctivi-ty of etllyl acetate. ~ i~
It is to be noted that in ~:i.old3 otthor tllan sc~niconductor techl1ology, d:i.sporsions ~or e:Lcctro-~;LOre8:ig wltll a conduct:Lvity of le~s t~l.m 10 lû o}lm ICm ar~ known por se, ~or example, ~or the depos:ition of piglllents or carbon particles in the manu:~acture of disp~ay tube~
According to a proferred embodimc?nt, an apolar liquid dispersion mecliuln is u.æed. Such an apolar clis- .
pet~sion meclium has a conductivity o~ its o~n whicll is le~5 ~llan 1û 10 ollm 1Cm 1. 1.
It is recolmll~ndablo to C,]lOOSe tllo l~qu:Ld dispersion mediulll froln tlle hydrocarbons~ pre~erably tl1e sat~rated hydrocarbons. rhese have rl very low .
conduc-tl~rity o.~ tlleir own. The d:isper.sion mediulll need not cohs:i.st of a single liqllid llydrOC,arbOn bllt Illcly also cons.ist-oi a liquicl~nixtllre of hydrocarbons.
~ccordir3g to.a furt}lcl pre~orred embodimc?nt .' ' ' ~
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p~ T 7~72 ! ~-1 7 .1~ . 7~ I ~

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. . . ~ i the dispersion comprises at least one allxil:iary dis-persion agent in tho rorm of an ionisab~e material, Wh.iCll ..material compr.iscs a po].yvalent metal and at ~ least one ion ~ith at leasl. olle apolar orgc~ic group.
A polyvalent metal is to be eonsidered here as a Inetal having a valene)r larger than 1. Sueh auxiliary disper-sion agents are ~nown ~ fiO. Tho di:sociation of sueh an auxiliary di.spers:ion agent in an apolar d:i.sper.s:ion medium is proba~ly made possible by the occurrence o~ ~
Yan der Waals~ -rorces ~e-tween t}le apolar liqu:id and ! E
the apolar ~roup(s) o~ tlle above~ elltiolled ion, as a J'e9Ul t of Wlli,Ch SUC11 an lon :is di~so:Lved i.n ~he apola liqu:id. Tll~ pol~cl:L~ I.fl~ wi~ cr-~l.
thereto prol~ably forllls a morlovalent complo~ ion wh;.el is adher~d to the glass particles, so that sai~a par~
tieles obta:Ln a eertain eharge ~rhich i.s oî opposite . ï! ~
Si.6'11 Wit}l respect to the ehargo of tlle iO13S dissolv-ed in the di.spersioll medium. Thc gl'OUpS bound to the pluraly valent metal 3 in the monovalent eomple~ :ion n ~0 may provi.~le n contr:L~ution to the dispers:ion o.{ tho glass particles. ' 1 Yan der Waalsl ~orccs are g~nc:rally low with -res~ect to electrostatic bindin~r forces ~etweer~ :iotls .
of mutually opposite sign or ~ctween an ion and a ' ~:
dipole.mole~cul.e. In order to nlalie dissociation of ~h~ au~ili.ary.dispersioII agellt nevertlleless posslble, ~ .

-tl-le apol.ar part of the ions d:issolved in the clispel-s:ion '. ' ' . . . '' ,, '~ ' '. . ' ~ _ " ~

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. . ~'IIN 7~7.
. 17.~2..75 .~ ' ' .'"'"' , ' . ~

mecIium should be ~airly Iarge. For exaIllpIe, the apola.r part may consist o~ a cha.ln of an alipIatic hydrocarbon grollp having a conveniently large number o~ carboII atomsr The mobllity of the lon which is a dec.isive ~actor oi`
the conductivity of the dispersion, is very small clue . to the compara-tive size of` the ion.
Fur-tIIerlllors~ the lo~ conductivity Inay also be ascribed to the low concentration of dissolved iOllS, '.
inter alia by a low degree of dissocia-(;ion of' the All~i-li.ary clispers:ion agent. For ch.arge compeIlsation a cloucl Or dissolv0d ions are f`ormed around the disp~r~cd glass ' particles whicIl cloucl is ratI~ r :klli.n~ .,th.eiapolar:.di:G~.
r ~ .L o ~ e d iun ~ocordln~ to ~ :.~urth0T pre~orred omhodiIllont a ,.
polyIller is added to the disp~rsion as a binder f`or the ~lass part:icl0s, As a result o~ this the adhesion b~
twoen the deposited glass particlcs is improved. ~s ,l ~
is kr~own ~r so, S~ICh a polymer binder may provide c~n ~ ~
~f'f~ctive contrl~ut~.on to the dispersion of solicl par~
ticl~s in an apo:Lar di.spersion mc3dium as a reinforci.n~
and stabilizing agcnt. Xn particular in the preseIIt case o:f th-3 suspension o~ lass particl0.s which hav a polar strllct~re thQms~lves, polymors wh:ich ma~ be active as r0inPcircin~ cmd stabiliY;ing agc3n tS OE~ Qtic~larly ~`S~[Lil. l;~ur thern~oro the polymers ma~r adhere t:o the par~
ti.cles and ~ I;heir apt-lar p~rt S till~U Late a V~l dcr 1 , Wnalst bon~ to th~ mc)lecll]:es o~ the apolar Illo~ium. 'J'l-le . ~.

~ 8 .

- -~ n~N 7~72 `
17,12,75 7~7~ :
.., . 1~
polymer may compr:ise side chains of at least 4, fo example, 10-20, carbon atoms. Polylne-thaciy:l:Lc acicl compounds may be very useful. In a short duratio thermal treatment possibly sucoeeding the depositlon of the glass coating, such compounds may rapicll~ dis- `i appear, also due to depolymcr:isation. '~ ~-It has no-~ ~een found that it is poss:ible by ~;
means Or the method according to tlle invent:ion, to ef~icaciously pro~ide glass coatings of uniform thick- ,.
ness on semieonductor slices of comparative1y higrh resistances ln lateral directiorls, e~ren on 91:iccs t~
av;n~ an average ~ ternal resistance in lateral t dlrectiorls oi` at loast 500 ohnls per squaxe.
Glass eoatings are partlcularly usefu] for ¦
semlconductor devices having pn-junctions, for which a high brea~clown voltage is roquired. In thct manufac-ture of such devices use is made of a semiconductor slice of high resistivi-ty in ~-hich, one or more æones of opposito con~uctivi-ty types are pro~ided, for c~ampl~,by d:ifrusion. A sliee thus treatcd s~
consists Or the original high-ohmic material for -the , greater part Or its thickness. In particular in that ¦
- càse non-uniform glass depo~its are obtained witl~
the ~l0~ method. The method ~ccording to the inventic~
llo~ makes it possible to suGcess~ully cone slices }liCh conslst of sellliconductoL Inaterial having a re-siistivity Or at least 20 Ohm.cnl over the greatex part ' ' ' '' ~

G
:: ~ ? ~ ` ~

!
., . . ,~,~
PIIN r/~72 ¦ ~

47~7~ , ~

of their thicl~ness.
- . Xn semiconductor dev~.ces wlt;}~ higrll-oll~ic sub-strates, f`or example, diodes ~Yith h:igh brea~idown voltlge ~ and many thyristors, glass coatings are u.secl in order to obviate lo~ breakdo-~n volttges by peri.pher~l dis-turbances wllere ~-jw~ctions are encling ~ the semi-conductor surfaoe. In a pre~errecl embodiment a ~serni~
conductor s~ice_is used WhiCll comprises a higll-o]lmic .
eubstrate on which on a-t least one side at leas-t one .
semieonductor zono of a diiferel1t conducti.vil:y .nd/or conductivity type :is l~rov.iclecl. Accordingr to 9aid pJ'e-fcrled el~ odilllont, on the sicle o:C tlle providocl sem:i-concluc~or Y.onetSj a net~York Or grooves is proviclecl do~Yn to in the hig}l-ohmic substratej after which the ;
glass coating i5 also deposi-ted in the grooves f`roIll the dispersion in the apolar disp-rsion medium. In this ~;
manner~ junctiolls debouch;.n~; into the grooves~. .
may be covered with a stabilising glass layer. S:ince - the groovos extend lnto tho hig}l-ohmic nlaterial the ~ various senliconduc-tor parts enclosed by the grooves are connec-ted tog-3t}ler only by h:igh-ohin:ic su~stra-te material causing non-negli~rible lateral resistances in the slice. When g1ass coatings are fornied oii sen conductor slices using knot~7ri ~ispersions of glass ~5 partic1es :i.n l;olar dis},ersiol1 me~licl the coatirig.s pl-O-~ .
duce~ ma~r le of non~uI~ ornl thi.c]clless or ~na~ 1e-ve . ~.
parts of t}le sllce uncoated, whereas a glas~s COting i ,' ~
.'' ''. ` . '' '' ' ~
, ' _ 11)''- . ', ' ' ; .~", ~ IN 7872 " , , , , . 1 17.12.75 ~7~L7~

on the sen1iconductor surfa.ce o r a substantially ~Ini-form thic];ness is obtained over the whole are of tlle slice by m~clns Or the metllod according to the inven- , tion. , , - ~ further ilnportant aspect of the mcthod ac-cord.ing to -the invention is as folLows. In the l;nown ,deposition~ only exposecl senliconductor and possib:Ly metallically conducti~e surI`ace parts are covered, whereas insu'Lating layers already present, also i~
these are eon~paratively thin, remain uncoverecl. By ~ E
means oI` t;ho method aecording to the invention, S~II'- ' ~.
' ~no(3 parts consistin~ o~ insulAI;Ion nl~terial are aL,so ~overe~l witn tho giass pa~t~e-.es. ~s a result of` thls j an improved protection o-f vi.tal parts Or the semicon~
ductor device t.o be manufactured oan be obt~ined.
The invention furthormore extonds to semicon~
ductor devices obtained by meaIls of -the methocl accord-' ,, ing to the iDvention. ' , 'I ' ~;
The inventi.on wlll now be dcseribed in greater , .
,20, dotAil Wit]l rc:~ercnco to an elJIbodilllent.
ln t,his embodilllent,a glass coa-tinG is,provid- ~ ~' ' ed on a silico~ slice which has been'obtQined, for i example~ as follows~
, Startin~ material, is a disc-shaped sliee :'o~ , 2S . monocrystallinf~ sllicon }iav:in~ a resistivity of approx.i- -~ . .
matel~ 50 oI~nl.em. ~Yle s:Lice has. a diameter o~ approxi-m~toly 50 nlln and a thic~ ess o~ 200/unl. ~t has been . '' ' '' ' ' '' ~
.

' ! g~

I~lN` "7 8 7 2 , ~ 17. i2.`~ ~., .'' ' `' ~ ",' ~ ,~, .
~47 . i i,, obtained frolu a rod-shape(l sin~le crystal by sawing in the direction Or r 100~ -planes~ a~ter ~hich the slice has bQen ~iven thc above thicl~ness by grinclin~, ~ polishing and etchine One or more zones destined fGr semiconclucto devices to be n~anurac-turecl are provided on one side by means of ~o~Yn metllods, for example, by d:ifIusion and pos.sibly ep.itaxial dcposition, ~-thlch zonc o:r Y,OIleS `
differs or dirfer in conductivity type and/or conduc- `~
tivity from tllose Or the rema:in:ln~r pc~rt o~ the origi-n~l mater~al of tho slice. Saicl remalnln~r part ~YhiC]~.
constitutes the ~reator ~art o:E` the thicl~.ness o:~` the Slj ce ~rill hereinafter be re~errecl to as the hi~?h-O}l!l~j_C
~ ~substrate. A layer of insulatiug matcrial, ~or e~am~le t5 Or silicon oxide, may be providecl according to a desir- --ed.pattern on the scmiconciuctor surface on -tlle siclc? o~
the proviclc?d zone~s).
On l;he rele~ant side of the sl:ice ~here the ,, r~
zonc(s) is (nrc) sl.tuated g:rc-oYes are no~r for~i~ecl, :
~0 ex~mple, accord:illg to a net~-rork of scr:ibirl~ lan~s alon~
wh:ich the s.l.:ice can be sevc?red into a number of semicon- ~ ~`
ductor clevices. Said ~rooves may be prov:Ldcd in kno~rn manll-?r, in ~Yhich first a possiblc layc~r of insulation ~.
matcrial accordine to the pattern Or grooves is re- `
moved Accordingr to the ciesirecl pattcrn o~ ~rooves, t;]le silicon iS ctch(cl anisotropically (US:).}l~,' an e l;C]I~
resistan-t mask.in~) do~Yn to a de~th cxcceclin~; t}le thic3i- -~

~ .

: ~ ~:
l"lN.7872 7:
2~ 75 , ~47~ ~
- .
ness of the provide.d zone(s) 011 t~lC relevant si.de of t}le sliee. Julletions in the semieoncluctor mat.erial, for example, between SUCll a zone ancl t]le substrate ~ material, may mer~e at the surraee~ a-t the ~alls Or ;
the grooves A dispersioll of glass par-tieles in a su.:Ltable ;
liquid disporsion n~edi.um is preparod for use in the elcetropllore-tie deposition Or a glass eoati~g on the :
. se~nieondue-tor sliee surfaee. The glass parti.elcs eon- '.. .
sistof a su:Lta~le high-ohlllie ~lass on the basis o:~
sil.ieon oxide, lead oxide and alu~i.n.iulll o~i.clo~ u.ld.
hio]l glass ~oI`volls at app:roxilnato:l.y 8~oo to 850C .
~ ~cc ^~ th:7.~ ~ i.J ~ v~ ?:L' ~ î ~r .~m:i- r :
eondlletor uses. . ! 1 Tho gra.in dian~eter of the glass particles i5 '~ .
between approximately 0.1 ancl 10/um ~ith an a~rerage , ~nlue Or approximately 3/um. ;
~ As a liquivl dispersion llled:iuln is usod a mix- ..
t~lro Or isopnrarri.ns havillg 9-12 earbon atoms por molo-~20 eule, il~ tl~is eas0 a mixtvu:rc? whieh :is eommc?reially .
available as "Sholl Sol T0".
~ .
~or the auxiliary dispersion agents to be addcd is used a mixture eomprisillg --1 part by ~eight Or a ealcium soap of dide-25. eyl estc?r o.~ suJ.rJllosuceil]ie aeidj 1 par~ by ~eig]lt o~ a ehrorlliuln soap o~ a .mlxture Or allc)rl salieyla.tcs, the all;yl group o~ whieh . " ," ~
~. , . ' , . . ' ~
. ~ 13 - - ~
.',,` ' '." .' "' ` ~

PllN 7~7'.
. . 17.12.75 7~
comprises 8~ carbon atoms.
1 part by we:ight; of a co-polymer of lauryl stcaryl methacrylate c~nd 2-methyl,5-vinyl pyridinc~ d ~ 3 parts ~y wcight of a suitable solven-t, Por example xyleno.
Such a 7nixture is commercially ~vailab]e as ~'A S ~ - 3i' o~ Shell Cy. 0.75 g of said m:ixture is dlssol~.ed in 1 l of the abo~e~montiome~l isoparaPri mixture. OP this mixture tlle calciuln soap and the c~lromlum soap :~orm the ionisab].o aux:i.liary clisper~sio a~en~.s. Tho co polymer ~orllls a re:inforcin6r c~nd sta-bili.~.inGr agenl In the present example a furtller re:;nforci.ng .
- and stabiliz.in~r agent in the form of a lauryl st~aryl polym~thacrylate solution of 20 g per litre of the al- `.
ready mentiollecl isoparafrin mixture is us~
The suspension is prepared by add.intr~r;
10 g oP the ~rlass parti:cles to be suspendec1 20 lnl Or tlle ~A.~.~.3~-sv:Lution clnd 10 ml of -tho lauryl stearyl polymethacry].~-te SOltltiOll ~ ~, to 1 litre of the isoparclffin n1ixture "Shell So]. T0".
The specif`lc conclucti~;ity of the dispersion is 5x10 2ol~m crn ~n.c~g~ por-l;:;on oP th6 serlliconduc~or sl.ic~
to bc covered is connected to c~n electric :Load melllbor .cons:i.stin~r of p].atinulll by means oP a cj.a~ and hullg '', ' - ' ~
, IN r/ 8 7 2 . . 17. I~ . 75 , ~L'~'k`7~.7~L .

in -the suspellsiol~, the sl:i.ce forlIlin~,r on~ e].cc trocle in the electrop]loresis bat~l, A p1.ati.nurll coullter--c.1.ectrodc in -th~ rorm of a d:isc having a diamctcr of 5 Clll iS ar-~ i~arc,ed diroctly opposite thQ s~.cle ~:ith l;he groovcs, so tllat tlle mutual d:Lstance be twee,n t]-le slice *o bc treatod an~l the platinum counter-electrode :is approxi-- mately 1~ mm everywhore. ' ' . A volta~e o~ 200 volts i.s thcn appliec~ acros~s tho electrodes, the semiconductor slico being nogat:ive-ly b:Lasecl rolat.Lve to the cowlter-ei.ecl:rod~. A~tc,~r ~p-prox:Lmatoly 1 mLnute a unLform i.ayor ap])rox:i.mclteLy 'l5/u th:Lcl~ htl5 beon provided on tlle semicollductor s i. Lcc ~sur-~aco on the side with the groovo.s and covers the sc.~nli-conductor slicc surrace and, iLf preserlt, insulating , layei~ portlons.
Aft~.?r dryill~, thc sltce witll the result:Lng coati..ng,of glass particles, mainly bonclccl by mctll.c~- ;
crylato~ :is s~lLj'ected to a tllermal tro.ltlllcllt in air 1t: 1 telllpcra~ul~o o:~ 500C ~or 10 Ill:L31u~o.s, c~ ? 01' -~20 ganic chcllllcal con~t:Ltuellts, for cxalllple, tho nletha- ~' crylate, dis~u~pear.ing par-tly by depolynler:isa*:Lon .~ld' ~ ~ evuporltion, and partly by oxlclation~ Tlle glass par-- . ticles arc then fuscd to rorm a dcnsc glass layer by llcating at ~OO~C for approx,inlatcly 7 nlinutos.
I~or conlpari.so)~, silllilar solnico3lductor sl:i.ces erc Sll~J ecl:~d to c:Loctrop~lo:rctic coa-Ling t:reatlllellt~
.Ln 1 dis~C?rC;.iOIl of ~lus9 p~J~tiC~.CS il3 1lieth~llo.1. as t~
.. , ;

, ,' ' ' ''' ' "' .
.. - , ~

- 17.12.75 dispersion med:ium and ~lC13 lS an auxil~ary d:ispersion agent The speeific condllc-t:ivity of the dispersioll in Dlethanol was between 6~10 5 o]lnl cm and 10~10 501lm cm dispersion in eil-lyl.lc~tate was also usecl wl~ich had a specific conducti~ity o~ 3xlO 90hlll Clll 1, Mle slices were not coated electr-opll.oretically ~ith a layer of glass par-tieles or we]-e only eoated elecl:rophoretieally near tlle provided ~leetrod~ con)lee-t:Lon. l~rhen using an~ of said d:Lsper.sio*s ~:itll polar cl.L.~p~r.ioll med:ia 1n no deposit:ion o:~ ~J.ass plr-ticle~ ~as Obta.:LrlC`CI clt .. ln~' sur~aec3 portiolls a~ which insu].atin~ layorc~ olo a:l.-ready pres~llt.
Results sirnilar -to the glass coat;in~ proee~s according t;o the abov~ eJllbodlment are obt:a:ined in si-. .
mil.lrly treating semiconductor slices clest:incd for th~rristors, in whieh on eitller sid~ ~ones have been dif~sQd in a hi.gl--ohmie silieon .sl:ie6 and. a networl~
o~` grooveci llave been prov:i.decl on both sic1'3s down l;o the substl~ate. Tl~e lat~ral rosistaneo Oe saicl slico9 iS on , 20 an average 200 ohms per square. T~o dise-s~lapecl eounter-olec-trodes are usecl,one on each s.ide o~ the selniconduc-tor slice ancl at equal distances t]ler~.~roin.
It ~-lll be obviou~ l;llat the invention is not restrictecl to the above embodinlQnts W:it]l d:ispers:ion.s ~5 -:i.n apo.lar media and l:llat .~mic.olJdue1;or .ql.iees Or selni-eondue-tol materi..l:l. other than silieon and/or i.i.t]l hetero~ nctions ean be provi.dod with ~la.ss eoatin~S
~ ec~rresI)orldi~l~JJIlmner ~it]lout ~ p~:rtin~ :t`30JII t~e .~e~ e c~:e tl~o ~ l.i.on.

.
. ~ 16

Claims (10)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of manufacturing semiconductor devices in which a glass coating is provided on a semiconductor slice comprising one or more of said semiconductor devices in an intermediate stage or in a final stage of manufacture, by means of electrophoresis using a dispersion of glass particles in a carrier liquid, characterized in that a dispersion of the glass particles is used with a specific conductivity of at most 10-10 ohm-1 cm-1.
2. A method as claimed in Claim 1, characterized in that an apolar liquid dispersion medium is used.
3. A method as claimed in Claim 1, characterized in that the liquid dispersion medium consists of one or more hydrocarbons.
4. A method as claimed in Claim 3, characterized in that the liquid dispersion medium consists of one or more saturated hydrocarbons.
5. A method as claimed in Claim 1, characterized in that the dispersion comprises at least one auxiliary dispersion agent in the form of an ionizable material, which material comprises a polyvalent metal and at least one ion with at least one apolar organic group.
6. A method as claimed in Claim 1, charactierzed in that a polymeric binder for the glass particles is added to the dispersion.
7. A method as claimed in Claim 1, characterized in that the slice to be treated has an average internal resistance in lateral directions of at least 500 ohms per square.
8. A method as claimed in Claim 1, characterized in that the slice to be treated consists for the greater part of its thickness of semiconductor material having a resistivity of at least 20 ohm cm.
9. A method as claimed in Claim 1, characterized in that the slice to be treated comprises surface parts bearing an insulating coating, and on other surface parts the semiconductor material is exposed, and that the glass layer is provided over the whole surface of the slice.
10. A method as claimed in Claim 1, characterized in that the semiconductor slice comprises a high-ohmic sub-strate on which on at least one side semiconductor zones of different conductivity and/or conductivity type are pro-vided and on the side of the provided semiconductor zones a network of grooves is provided down to the high-ohmic sub-strate after which the glass coating is also provided in the grooves.
CA243,160A 1975-01-16 1976-01-08 Manufacture of semiconductor insulating films by electrophoresis Expired CA1047171A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
NL7500492A NL7500492A (en) 1975-01-16 1975-01-16 PROCESS FOR THE MANUFACTURE OF SEMI-GUIDE DEVICES, IN WHICH A GLASS COVER IS APPLIED, AND SEMI-GUIDE DEVICES MANUFACTURED ACCORDING TO THIS PROCESS.

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Publication Number Publication Date
CA1047171A true CA1047171A (en) 1979-01-23

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CH (1) CH599677A5 (en)
DE (1) DE2600321C3 (en)
FR (1) FR2298189A1 (en)
GB (1) GB1532471A (en)
IT (1) IT1054204B (en)
MX (1) MX143640A (en)
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IN147572B (en) * 1977-02-24 1980-04-19 Rca Corp
IN147578B (en) * 1977-02-24 1980-04-19 Rca Corp
GB2158463B (en) * 1982-04-06 1986-11-19 Stc Plc Forming ceramic films
GB2117796B (en) * 1982-04-06 1985-06-19 Standard Telephones Cables Ltd Forming ceramic layers; dielectric structures
GB2117795A (en) * 1982-04-06 1983-10-19 Standard Telephones Cables Ltd Fabricating capacitors; forming ceramic films
DE4343810C1 (en) * 1993-12-22 1995-04-20 Roland Man Druckmasch Photoelectric measuring head

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US3303399A (en) * 1964-01-30 1967-02-07 Ibm Glasses for encapsulating semiconductor devices and resultant devices
IE33405B1 (en) * 1968-12-09 1974-06-12 Gen Electric Semiconductor wafers sub-dividable into pellets and methods of fabricating same
US3895127A (en) * 1974-04-19 1975-07-15 Rca Corp Method of selectively depositing glass on semiconductor devices

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DE2600321A1 (en) 1976-07-22
FR2298189A1 (en) 1976-08-13
DE2600321C3 (en) 1981-09-03
MX143640A (en) 1981-06-17
SE7600278L (en) 1976-07-19
JPS556292B2 (en) 1980-02-15
DE2600321B2 (en) 1980-12-04
CH599677A5 (en) 1978-05-31
NL7500492A (en) 1976-07-20
AU1018776A (en) 1977-07-21
AU504812B2 (en) 1979-11-01
GB1532471A (en) 1978-11-15
IT1054204B (en) 1981-11-10
FR2298189B1 (en) 1982-04-16
JPS5197375A (en) 1976-08-26

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