SI'ECIFICATION
'I'lT1,E OF THE INVENTION
5 ELECTRONIC COMPONI',N'I; CONDUCTIVE PASTE, AND METHOD 1:OR
MANIJFACTURING ELEC'I'RONIC COMPONENT
TEC13NICAL FIELD
[OOOl]
10 The present invention relatcs to an electronic component comprising electrode
wirings, a cot~ductivep aste utilized to form the clcctrode wirings, and a manufacturing
method for the electro~licc omponent.
I3ACKGlZOUND A1U
IS [0002]
In solar battery cells? plasma display panels (I'III'), Liquid Crystal Ilisplays
(LCD), and clcctronic components stlch as ceramic multilayer wiring substrates or the
like, electrode wirings are formed. The electrode wirings are formed by utilizing
co~~ductivpeas tes. Silver (Ag) and alu~llirlt~(A~I~) ia rc utilized for nletal particles, in
20 the conductive pastes. The electrode wirings are formed by baking the corlductive
pastes in the atmosphere at thc l~igll temperature, however, the conductive pastes
contain glass particles in addition to the metal particles, and when the conductive
pastes are baked, by bcing hcated to the temperature which is grcatcr than or cqual to
the softcninp, poilit of the glass particles, the glass particles are softcncd and fluidificd,
26 and the electrode wirings bcco~nc morc compact and also adhere firmly to the
substratcs.
[0003]
Regarding the conductive paste utilizing the aluminum ~netal particles, the
conductive pastes utilizing the phosphate-type glass frit for the glass particles are
30 proposed (See Patent Literature 1 or the like). Furthermore, the cotlductive pastes
utilizing thc mixture ofthe aluminum metal particles and the silver metal particles for
the metal particles are proposed (See Patent Literature 2 or the like).
PRIOR ART REFER1;NCE
I'almt J,itcrilture
[00041
6 [Patent Literature 11 JP 2000-1 1927 A
[Patent Literature 21 JP 2008-1 08716 A
SUMMARY OF TI 1E 1NVI:N'I'ION
PROBLEMS '1'0 13E SOLVED BY TIIE INVEN'TION
10 r0005l
Since aluminum forms stable oxide fi1111s on the surpdce, the aluminum metal
parlicles show the sintering resistance. 'l'herefore, it is know11 to be sufficient that the
baking temperature is set greater than or equal to the melting point of aluminum, 660.4
degrees Celsius, in order to acquire the sufficient electrical characteristics with the
15 conductive pastes utilizing the alu~ninumm etal particles. As shown in Patent 1,iteraturc
1, if the baking tetnperature is lowered to 550 degrees Celsius to 600 degrees Celsius,
it becomes easy to manufacture the electronic components, however, it is deemed that
the suficie~e~lte ctrical characteristics cannot be acquired arid that the designing of the
electro~licc omponents is restricted in some cases. Patent Literature 2 has succeeded in
20 making the sintering temperature of the tnetal particles lower than that in the case that
the ~netalp articles are alu~~~il~buy lnrn,i xing the aluminum tnetal particles and the
silver ~netalp articles in the co~~ductivpea stes. 111 Palcnt 1,itcrature 2, the baking
temperature is lowered and the sufficient clcctrical characteristic can be acquired,
howevcr, it is decmed difficult to rcduce the cost. since silver is utili~edf or the uletal
25 particles.
[0006l
Therefore, an object of the present invention is to provide electronic
components comprising electrode wirings which are possible to acquire suficient
electrical characteristics even at the low baking temperature, the conductive pastes, and
30 a ~uanufacturingm ethod for the electronic con~ponentsa t a low cost.
MEANS FOR SOLVING 'TI-IE PROBLEM
[0007]
In order to ac,l~ievet he aforementioned object, the present invention is an
electronic component. comprising an electrode wiring having a plurality of particles
which consist of alu~ni~lul(nA l) andlor an alu~~~inu~~~-conatlaloiny,i nangd an oxide to
5 fix thc particles to a substrate, wherein the oxide includes phosphorus (P) and
alu~ninumin complete unity.
100081
Moreover, the present invention features a collductive paste, comprising a
phosphoric acid solution, and a plurality of particles which disperse in the phosphoric
10 acid solution and consist of aluminum andlor an aluminum-containing alloy.
[0009]
Furthermore, the present invention features a lnanufacturing method, coating a
substrate with a conductivc paste comprising a plurality of particles which consist of
alu~ninuma ndlor an aalumi~~um-cotltai~liall~logy dispersing in the phosphoric acid
15 solution, arid baking ihc conductivc paste which is coated and forming an clectrodc
wiring.
EFFECT OF TI-IE INVENTION
loolo]
20 The present invention can providc electronic components conlprising
electrode wirings which are possible lo acquire sufficient electrical characteristics cven
at the low baking temperature, the conductive pastcs, and a ~nanufacturingn ~ethodf or
the electronic co~npone~a~t tas l ow cost.
26 BRIEF DESCRIPTION OF 'I'HE DRAWINGS
[OOlll
FIG. 1 is a part of a sectional drawing of electrode wirings comprised by
electronic components with reference to the c~nbodi~nen1 to f the present invention;
FIG. 2 is a part of a sectional drawing of a plasma display panel (electronic
30 component) with rcference to the embodiment 2 of the present invention;
FIG. 3A is a botto~n view of a solar battery cell (electronic component) with
rcference to the embodiment 3 of the present invention;
FIG. 313 shows an arrow sectional drawing in A-A dircction of FIG. 3A, being
inverted upside down;
FIG. 4 is a sectional dra\ving of a ceramic multilajrer wiring substrate
(electronic componcnt) with reference to the embodiment 4 of the present invention;
5 and
FIG. 5 is one example of a temperature schedule whcn baking the ceramic
~iiultilayerw iring substrate (electronic co~i~poncnwt)i th rcferetice to the embodiment 4
of the present invention.
10 MODES FOR CARRYING OUTTI-1E INVENTION
LOO 1 21
Subscqucntly, the enibodinients of the present invention will be described in
depth with reference to the drawings, as required. Incidentally, in each drawing,
identical references arc put on tlic common parts, and the duplicated descriptions a e
1.5 omitted. lurtherniore, the present invention is not liniitcd to tlie individuals oi' a
plurality of embodiments described here, and may be combined, as required.
[00 131
(Bnbodinient I)
As shown in Table I , in the cnlbodiment I, electrode wirings of 13 types in
20 total, exaniples 1 to 12 and one comparison exariiple arc fbr~neda, nd the ~liiscella~leous
characteristics are evaluated. When forming thc clcctrode wirings, the co~lductive
pastcs are also ~iianufactured in riianufacturing conditio~is being changed for each of
the cxamplcs 1 to 12 and thc comparison cxamplc, and the baking conditions of the
conductive pastcs (clcctrode wirings) arc also changcd for each of the cxa~ilplcs1 in 12
25 and the comparison example. Incidentally, in thc tiianufacturing condition of the
conductive pastcs, the compounding ratio ofthe alu~iiinuni( Al) particles co~isistingo f
3 types of particle groups, and tlie weight ratio of the phosphoric acid solutiolis
consisting phosphorus pentoxide (PzOs), water (HzO), and ethanol (ClH50H) are
changed. Incidentally, in accordance with the change of the weight ratio of the
30 phosphoric acid solutions, the volume ratio of aluminum to the sum of the volume of
the aluminum and the phosphorus pentoxide is also changed. Moreovel; as the
characteristics which have been evaluated, peel tcsts, water-rcsislance tests, and the
measurelncnt of the specific resistallcc are perfornled to thc electrode wirings.
Hereinafter, the formation ofthe electrode wirings will be desclibed in dcpth.
[Table 11

[00 141
(1. formation of electrode wirings)
(I - 1. combination of aluminum particles)
5 Firstly, the aluminum was melted, and spherical particles were formed by the
water atomization method. 12rom a part of these particles, particles with particle
diameters greater than or equal to 8 pm wcre excluded by screening, and particles with
particle diameters less than 0.5 p1n were excluded by screening. 'rlie remaining
particles, in other words, the particles after excluding tile large particles and the srnall
particles by scrccning, wcrc further divided by screening into a particle group A having
a volume fraction greater than or equal to approximately 95% of particle diameters
5 which were within a range greater than or equal to 0.5 pm and less than 1.5 pm, and a
particle group 13 having a volu~nef raction greater than or equal to approxirnately 95%
of pa~~icdleia meters which were within a range greater than or equal to 1.5 pnl and
less than 8 pnl.
[OO 1 51
10 Moreover, tabular particles were ibrn~ed,b y treating a part of particles which
were formed by the water aton~ization method as they were, in thc organic solvent by
the ball tnills. Furthermore, in order to improve the thermal stability of these tabular
particles, annealing steps were performed in the reducing atmosphere at the
temperature of 700 degrees Celsius. From these tabular particles, particles with particle
15 dialneters greater ~hano r equal to 8 pn were excluclccl hy screening, and also pal.ticles
with particlc dialnctcrs lcss than 1.5 ptn wcrc excluded by screening. The rcmaining
particles, in other words, the particles after excluding the large particles and thc sinall
particles by screening, were a tabular-particle group having a volume fraction which
was greater than or equal to approximately 95% of particle diameters which werc
20 within a range greater than or equal to 1.5 pm and lcss than 8 pm, and wcre designated
as a particle group C.
[OOlC,]
As shown in Table 1, in the examples 1 to 11 and the comparison example, the
particles of thc particle group A and the particle group B wclc combined and utili~cd,
25 so that the particles of the particle group A could be 50 weight % and the particles of
the particle group I3 could be 50 weight %. In the example 12, the particles of the
particle group A and the particle group C were combined and utilized, so that the
particles of the particle group A could he 50 weight ?4 and the particles of thc particle
group C could be 50 weight %.
30 [0017]
(1 -2. formation of phosphoric acid solutions)
Subsequently, phosphoric acid solutions werc formed per the example 1 to 12.
?'he phosphoric acid solutions were formed by nlixing the phosphorus pentoxide, water,
and the ethanol in the weight ratio as shown in Table 1. Incidentally, the ethanol is
utilized in order to accelerate the evaporation/desiccation of the phosphoric acid
solutions and to suppress absorbing the moisture after the desiccation. In order from
6 the example 1 to the example 8, the weight ratio of the phosphorus pentoxide was
increased, the weight ratio of water was decreased, and the weight ratio of the sum of
the phosphorus pentoxide and water was made constant. In addition, the weight ratio of
the ethanol was made constant. The weight ratios of the phosphorus pentoxide, water,
and the ethanol in the example 9 to 12, were made 10 weight %, 80 weight %, 10
1.0 weight % and were made identical with the example 3. Incidentally, in place of the
phosphorus pentoxide, phosphoric acid (II3P04') may be utilized. In that case, the
volume of water is adjusted so that the densities of phospltorus atoms can be equivalent.
Moreover, for the cornparison example, the phosphoric acid solutions were not utilized,
but lead (Pb) glass was utilized instead.
15 [OOIX]
(1 -3. formation of conductive pastes)
Pcr thc cxa~nple1 to 12, for 100 parts by wcight ofalurl1i1lum particles wl~ich
were combined in 1-1, phospltoric acid solutions of 30 parts by weight which werc
fornled in 1-2, were added and mixed. By i~radiatingu ltrasonic waves to this mixture
20 for 10 minutes, the aluminum particles werc dispersed in thc phosphoric acid solutions
and thc conductive pastes were acquired.
[00191
In tlie comparison example, for 100 parts by weight of altnninu~n particles
which were combincd in 1-1, lcad glass powder of 10 parts by wcighi, 13utyl carbitol
26 acetate as the solvent, and ethyl cellulose as the binder were added and mixed. By
irradiating ultrasonic waves to this ~ttixturef or 10 minutes, the aluniinurn particles, ihc
lead glass powder, and the binder were dispersed in the solvent and the conductive
pastes were acquired.
[0020]
30 (1-4, baking of electrode wiring)
Per thc cxample 1 to 12 and the comparison exantple, the conductive pastes
were coated on the alumina (A12O3) substrate by a doctor blade method. After coating,
the conductive pastes were heated and desiccated in the atmosphere at the temperature
of 150 degrees Celsius for 30 minutes. Thereafter, the tentperature was raised to the
so-called baking temperature shown in the baking condition of Table 1 in an electric
furnace in the atmosphere at a temperature-ascending rate of 5 degrees Celsius/ntittute,
5 and the baking was performed by retaining the baking temperature for the so-called
baking time shown in the baking condition of Table 1, thereafter standing to cool By
this baking, electrode wirings were completed. The thicknesses of the film (electrode
wiring) after baking were approximately 10 pm in any of the example 1 to 12 and the
comparison example. The baking conditions of the examples 1 to 8, the example 12,
10 and the contparison example were made identical with the baking temperature of 700
degrees Celsius and the baking tinle of 30 minutes. In the examples 9 to 1 1 , the baking
temperature was changed to 400 degrees Celsius, 500 degrees Celsius, and 600 degrees
Celsius, and the baking time was made identical, being 30 minutes.
[0021]
15 (2. charaderistics of electrode wirings)
(2- 1 , pccl test)
I'er the example 1 to 12 and the comparison example, the strength of the
adhesion of tlte coittpleted electrode wi~ingsto the substrate was evaluated in a peel
test. In the pcel tcst, a commercial cellophane lape was pasted ovei the elect~odc
20 wirings, thereafter was peeled oft: Then, afer peeling off, the electrode wirings were
observed and evaluated. As the cvaluation criterion, a criterion was utilized with "u"
specified for the case that alntost all of the al~nninuinp a~ticlesw ere peeled off and that
the electrode wirings came into the breaking-wire condition, " A specilied for the case
that a part of the alu~iiinum particles wcrc peeled o f f and that a part of thc clcctrotic
25 wirings were missing but didn't come into the breaking-wire condition, and "on
specified for the case that the alurninuirt particles were not peeled ofr'(includit~gth e
extent that the aluminum particles on the surface of the electrode wirings were thinly
adhered to the cellophane tape) and didn't come into the breaking-wire condition. As
shown in Table 1, the results of the peel test showed "x" in the example 1 and tlte
30 example 9, "A" in the ekarqle 2, and "om in the examples 3 to 8, the exaniplcs I0 to
12, and the comparison example.
[0022]
By comparing the results of thc pccl test among the examples 1 to 8, it has
been clarified that having the weight ratio of phosphorus pentoxide greater than or
equal to 1 weight % and thc weight ratio of watcr less tlian or equal to 89 weight % is
preferable (the examples 2 to 8: the evaluation of "A" can be acquired, at least),
5 furthermore, that having the weight ratio of phosphorus pentoxide greater than or equal
to 10 % and the weight ratio of water less than or equal to 80 % is preferable (tlie
examples 3 to 8: the evaluation of " u" can be acquircd). As aforemcntioned, it 1s
deemed that the results of the pcel test depend on the weight ratio of phosphorus
pcntoxide in the phosphoric acid solutions because the weight ratio of this phosphorus
10 pentoxide relates to the volume ratio of phosphorus pentoxide to the aluniinum in the
electrode wirings. In other words, this is because that it is deemed that a volume of
phosphorus pentoxide greater than or equal to a certain ratio to the volume of
aluminum is necessary in order to fix tlie aluminum particles to the substrate. Table 1
has shown the volume ratio of aluminuni to the sum of the volume ofthc aluminu~n
15 and the phosphol.us peritoxidc, and it is clarified that having this volume ratio Icss than
or equal to 99.7 volume % is prefcrahlc (the exa~nples2 to 8: the evaluation of "A" can
be acquired, at least) whcn thc results oT the peel test were evaluated in this volume
ratio, and f~lrtherlnoreh, aving the volu~iier atio less tlian or equal to 97.4 volulne % is
preferable (the exainples 3 to 8: the evaluation of" o" can be acquircd).
20 100231
111 addition, by comparing the results of the peel test alllong the exa~nplc3 , the
examples 9 to 11, it has been clarified that the evaluation shows "x" at the baking
temperature of 400 degrees Celsius (tlie example 9) of the baking condition, howcvcr.
the evaluation of "om can hc acquired at 500 dcgrccs Celsius (thc example lo), 600
25 degrees Celsius (the example I]), and 700 degrees Celsius (thc cxample 3).
Accordingly, it is deetned that the electrode wirings of the present invcniion don't stick
to the substrate at the baking temperature less than or equal to 400 degrees Celsius and
are easily peeled off, however, become more compact and stick to the substrate over
400 degrees Celsius, for example, at greater than or equal to 500 degrees Celsius.
30 [0024]
Moreover, by comparing the results of the peel test betwecn the exa~ilple3 and
the example 12, it has been clarified that the evaluation of "o" can be acquircd,
whichever of the particle group B (the example 3) and the particle group C (the
example 12) is utilized. Moreover, it has been clarified that the evaluation of "0" can
be acquircd also in thc comparison example.
lo0251
5 (2-2. water-resistance test)
Per the example 1 to 12 and the comparison exainple, the corrosiveness of the
completed electrode wirings to water was evaluated by a water-resistance test. In the
water-resistance test, the electrode wirings were dipped in warm water of 70 degrees
Celsius for 30 minutes. After dipping, the electrode wirings were observed and
1.0 evaluated. As the evaluation criterion, a criterion was utilized with "x" specified for
the case that the electrode wirings showed black-coloring after testing, "A" specified
for the case that the electrode wirings showed a slight color change, and "0" specified
for the case that the color was hardly changed. As shown in Table 1, the results of the
peel test showed "x" in the example 1 and the exarnple 9, "A" in the exanlple 2, and "0"
16 in the exanlples 3 to 8, the exan~j>lc1s0 to 12, and the comparison example. As shown
in Table 1, the results of the water-resistance tesl showed "x" in the exainple 9 and the
comparison example, " A in the example 1, and "0" in the examples 2 to 8 and the
examples 10 to 12.
j 00261
20 By conlparing the results of the water-rcsislance test among the examples 1 to
8 and the coillparison example, it has been clariiied that having the weight ratio of
phosphorus pentoxide greater than or equal to 0.5 wcight ?4 and the weight ratio of
water less than or equal to 89.5 weight O/o is preferable (the examples 1 to 8: the
evaluation of "A" can hc acquircd, at least), liirtl~ermoret, hat having the weight ratio
25 of' phosphorus pentoxide greater than or equal to 1 weight % and the weight ratio of
water less than or equal lo 89 weight % is prererable (the examples 2 to 8: the
evaluation of " 0" can be acquired). To the contrary, it has been clarified that the
comparison example shows "x". It has been clarified that the electrode wirings of the
examples 1 to 8 are superior in the water-resistance, compared to the comparison
30 example. Furthermore, by evaluating the results of the water-resistance test in the
volume ratio of the aluminum to the sum of the volunle of the aluminum and the
phosphorus pentoxide, it has been clarified that having less than or equal to 99.9
volu~ne% is preferable (the examples 1 to 8: the evaluation of "A" can be acquired, at
least), furthermore, having less than or equal to 99.7 volr~nle % is preferable (the
examples 2 to 8: the evaluation of" o" can be acquired).
LO0271
5 In addition, by comparing the results of the water-resistance test among the
example 3, the examples 9 to 1 I , it has been clarified that the evaluation shows "x" at
the baking tcnlperature of 400 degrees Celsius (the exalnple 9) of the baking condition,
however, the evaluation of "0" can be acquired at 500 degrees Celsius (the example
lo), 600 degrees Celsius (the example ll), and 700 degrees Celsius (the example 3).
10 Accordingly, it is deemed that the electrode wiri*n gs of the present invention have
aluminum particles not covered with compact oxides and cannot acquire the high
water-resistance at the baking temperature lower than or equal to 400 degrees Celsius,
howcver, the oxides to cover alunlinum particles becorne Illore compact and the high
water-resislance can be acquired, over 400 degrccs Celsius, for cxample, at greater
15 than or cqunl to 500 degr'ccs Celsius. To the contraly, in thc comparison examplc, even
at the baking tetnperature of 700 degrces Celsius, thc water-resistance cannot he
acquired and the evaluation shows "x". 'l'his is because the Sonnation neth hods of the
oxides to cover alutninum particles are different among the cxa~nple3 , the examples 9
to 1 I, and the cornparison example.
20 10028)
Morcovcr, by comparing the results of the water-resislance test between the
example 3 and the exanlple 12, it has heen clarified that thc evaluation of "0" can be
acquired, whichever of the particle group 13 (the cxa~nple 3) and the particle group C
(the example 12) is utilized.
25 [0029]
(2-3. specific resistance measurement)
I'er the example 1 to 12 and the comparison example, the specific resistances
of the completed electrode wirings were measured. In the specific resistance
measurement, the electric resistances and the film-thicknesses of the electrode wirings
30 were measured, and on the basis of these electric resistances and the film-thicknesses,
the specific resistances were calculated. By comparing the results of the specific
resistancc measurement among the cxamples 1 to 8 and the conlparison exa~nplei,t has
been clarified that the specific resistances become lower in the examples I to 7, than
5.0~10.' Qcm which is less than the specific resistances (5.6~10.' Qcm) of the
co~nparisone xample. In addition, by comparing among the exatnples 1 to 8. it has been
clarified that the specific resistances show the minimum value in the exainple 3 and
5 become 0.681~0" Qcm.
[0030]
In accordance with the increase from 0.5 weight % to 10 weight % in the
weiglit ratio of phosphorus pentoxide (from the examples 1 to the exa~nple 3), the
specific rcsistanccs decreased and the specific resistances showed the mini~num value
10 (0.68~10-' Qcm) in the 10 weight % (the example 3), then, in accordance with the
increase from 10 weight % to 70 weight % (from the example 3 to the cxample 8), the
specific resistances increased. The specific resistances became less than or equal to
1.0~10Q-~cm in a range from 1 weight % to 15 weight %, in thc weight ratio of
phosphorus pentoxide (the examples 2 to 4). The specific resistances bccarnc lcss than
16 5.0~10.I~~ CII\Iv Iiic11 is less tllan tlie specific resistances (5 6x10.' LZcm) of the
comparison cxamplc, in a range from 0.5 weight % to 65 weight %, in tlie weight ratio
of pliospliorus pcntoxide (the exainplcs 1 to 7).
[003 11
By evaluating the results of thc specific resistmce ~neasurement in the volunic
20 ratio of the aluminu~n to the sulu ofthe volume of the aluminum and the phosphorus
pentoxide, in accordance with thc decrease fiom 99.9 volumc ?4 to 07.4 volume % in
the volume ratio (fiorn the example 1 to the example 3), tlie specific resistances
decreased, and the speciiic resistances becarne tlie minimum value (0.68x10~~1cmin )
the 97.4 vol~lme O/o (the example 3), then, in accordance with the dCcrcasc frotn 97.4
25 volume % to 84.2 volu~ne % (fron~ the example 3 to the cxa~nple 8), the specific
resistances increased. The specific resistances became less than or equal to 1.0x10.'
ficm in a range from 99.7 volume % to 96.1 volume %, in this volume ratio (the
examples 2 to 4). The specific resistances became less than 5 . 01~0. ' ficm which is less
than the specific resistances (5.6~10f-i~cm ) of the comparison example, in a range
30 from 99.9 volume % to 85.1 volume %, in this volume ratio (the examples 1 to 7).
[0032]
By coinparing the results of the specific resistance measurement among the
example 3, the examples 9 to 11. and the comparison example, it has been clarified that
the specific resistances become lower in the exa~nplc 3, the cxa~nplc 10 and the
example I 1 than 5 . 01~0 " $2cm which is less than the specific resistances ( 5 . 6 ~10 .'
Rcm) of the comparison examplc. In addition, by comparing among the example 3 and
5 the exa~nples 9 to 11, it has been clarified that the specific resistances show thc
minimum value in the example 3 and become 0 . 6 81~ o e5C lem.
[0033]
In accordance with the increase from 400 degrees Celsius to 700 degrees
Celsius in the baking temperature of the baking condition (from the examples 9, 10, 11
10 to the exa~nple 3), the specific resistances decreased and the specific resistances
became the ~ninimumv alue (0.68~10R-~c ~n)a t 700 degrees Celsius (the exa~nple3 ).
'fhe specific rcsistances became less than or equal to 1.0~10b-2~cn 1, in a range fro111
600 degrees Celsius to 700 degrees Celsius, in the baking temperature (the example 11
and the exantple 3). The specific resistances becanle less than 5 . 0 ~ 1 0iZ' ~c1 11 which is
15 less than the specific resistances (5.6~10" Qcin) of the compitrison example at the
baking temperature over 400 degrees Celsius, for example, greater than or equal to 500
dcgrces Celsius (the examl~le1 0, the exa~nple1 1, the example 3).
[0034]
Moreove~; by comparing the results of the specific resistance measurement
20 between the example 3 and the exa~nple 12, it has been clarilied that the specific
rcsistances can be rcduced by utilizing t:ltc particle group C (tabular particles : the
example 12) rather than the particle group I3 (spherical particles : the example 3).
(00351
(2-4. optimization of matiufacturing condition)
25 By evaluating thc volumc ratio of the aluminun~ to the sun1 of tltc volume of
the aluminun~ and the phosphorus pentoxidc from the results of pccl tests,
water-resistance tests, and the specific resistance measurement, it is clarified that the
iavorable adhesion (peel test result) and the favorable water-resistance
(water-resistance test result) can be acquired when this volume ratio is in the range less
30 than or equal to 99.7 volume % and greater than or equal to 84.2 volunle % (the
examples 2 to 8). Incidentally, when this volumc ratio is re-written in the volume ratio
of phosphorus pentoxide, the value to subtract the volurnc ratio of alulninum from I00
volu~ne% becomes the volunle ratio of phosphorus pentoxide, therefore, the favorable
adhesion (peel test result) and the favorable water-resistance (water-resistance test
result) can be ac,quired when being in the range greater than or eqnal to 0.3 volnnle %
and less than or equal to 15.8 volu~ne% (the examples 2 to 8).
5 COO361
Furthermore, it has been clarified that the favorable adhesion (peel test result),
the favorable water-resistance (water-resistance test result), and the favorable specific
resistance (specific resistance measurement result) can be acquired, when this volume
ratio is within the range less than or equal to 99.7 volume % and greater than or equal
10 to 85.1 volume % (the examples 2 to 7). In addition, it has been clarified that the Inore
favorable adhesion (peel test result), favorable water-resistance (water-resistance test
result), and the more favorable specific resistance (specific resistance measurement
result) which is the specific resistance less than or equal to 1.0x10~%cm can be
acquired, wllen this voluine ratio is within the range less than or equal to 97.4
15 volutnc % and grcatcr than or cqual to 96.1 volu~ncO /o (thc cxamplcs 3,4).
[0037]
Moreover, by evaluating the baking temperature, it has been clarif ed ihai ihe
favorable adhesion (peel test result), the Favorable water-resistance (water-resistance
test result), and the favorable specific resistance (specific resistance measurement
20 result) can he acquired, when this baking tctnpcrature is within the range greater than
or equal to 500 degrees Celsius and less than or equal to 700 degrees Celsius (the
examples 10, 11, 3). In addition, it has been clarified that the favorable adhesion (peel
tcst rcsult), tllc favorable water-rcsistancc (water-resistance test result), and the morc
favorable specific resistance (specilic resistance measurement result) which is the
25 specific resistance less than or equal to 1.0x10~' dZcn1 can be acquired, when this
baking tcmperaturc is within thc range grcatcr than or equal to 600 degrees Celsius and
less than or equal to 700 degrees Celsius (the examples 1 1, 3).
100381
Furthermore, by evaluating the combination of the particle group B and the
30 particle group C of alutninum particles, it is clarified that the favorable adhesion (peel
test result), the favorable water-resistance (water-resistance test result), and the specific
resistance (specific resistance measurement result) which is more favorable than that in
the case to utilize the particle group R of the exa~nple3 , can be acquired. when the
particle group C is utilized instead of the particle group I3 (tlie example 12)
[0039]
FIG. 1 shows an enlargement of a par1 of a sectional drawing of an electrode
5 wiring 2 comprised by an electronic conlponent 1 with reference to the e~nbodiment 1
of the present invention. The electronic component 1 comprises an alunliua substrate 3
and the electrode wiring 2 which is adhered and fixed on the alunliua substrate 3. The
electrode wiring 2 has a plurality of particles 4 which consist of aluminum (Al) andlor
an alunlinun1-containing alloy, and an oxide 5 which fixes the particles 4 to the
10 substrate 3.
[0040]
FIG. 1 is on the basis of the results to observe the electrode wiring 2 which
was generated, for example, in the example 1 1 of Table 1, by utilizing the Scanning
Electron Microscope-Energy 1)ispcrsive X-ray Analyzer (SEM-EDX). A plurality of
15 the particles 4 are combined (neclting) each othc~ by sintering. The layer of the native
oxidc of alun~inunw~a s not observcd in this neckiug co~nbinations cction 6, l h m thc
analysis result by thc Energy Dispersive X-ray Analy~er( MIX).
1004 I ]
lhe oxide 5 included phosphorus oxide which has phosphorus and oxygen (0)
20 as the chief ingredients, and the coutcnt ratio of the phospl~orus was greater than or
cqual to 50 atom % in the ingrcdicnt ratio without respect to oxygen. Morcovel;
alutninunl was also detected in the oxide 5, in addition to phosphorus. Accordingly, it
has been assumed that the native oxide layer of alutninutn which covered the surface of
the particles 4 dispersing in the phosphoric acid solutions bcfore the baking (11. during
25 the baking of the conductive pastes was melted by the phosphoric acid solutions, and
aluminum liquated in the phosphoric acid solutions, eventually, these phosphoric acid
solutions including alun~i~lurbne came the oxide 5 including phosphorus and aluminum,
by the baking. Since the native oxide layer of aluminum which covered the surface of
the particles 4 of the aluminun~ and the aluminum alloy was missing when baking, it
30 has become possible to generate the necking combination section 6 easily, and the
specific resistance of the electrode wiring 2 could be reduced.
100421
Furthentlore, due to the high ltydropl~ilicityo f the surface of the particles 4 of
thc aluminu~tal nd the aluminum alloy by the addition of ethanol or the like, tlte whole
surface of the particles 4 becomes drenched by tlte phosphoric acid solutions, and
covered by thc phosphoric acid solutions. Therefore, by baking, the whole surface of
5 thc particles 4 excluding the necking combination section 6, is to be covered by the
oxide 5. Incidentally, sincc the ~tativco xide layer of alurninunt is excluded, the oxide 5
directly contacts the particles 4, and the oxide 5 beco~nes not the dual-layer but the
single-layer, therefore, phosphorus (P) atoms and aluminum atoms are included in the
oxide 5, in complete unity in the whole film.
10 [0043]
Moreover, it has bcen clarified that the elcctrodc wiring 2 shows the superior
conductivity evert at the baking te~nperature less than or equal to tltc melting point of
alu~ni~~oufn 6t6 0.4 degrees Celsius, as shown in the exa~nple1 0 and tlte example 11 of
Table I . Coi~ventionally, it is deemed that thc sintcring of alumi~tum doesn't proceed
15 l>ccausco f tllc oxidc film (native oxide iil~n)a nd tllat tlic bilking Lcmpcratulc greater
than or cqual to the melting point is required in order to destroy this oxide film. In tlte
electrode wiring 2, the oxide film of thc surface of tltc particles 4 of alu~ttinum is
etched and excluded in the pl~osphorica cid solutions which are acidic. In other words,
during the baking, the aluminum ingredients liquate in the phospltoric acid solutions,
20 and prccipitatc in the phosphoric acid solutions or in the oxide 5 of phospl~orica cid as
the oxide colnpound of pl~osphorus and aluminum, oxide aluntiniim or the like. It is
assumcd that the sintering of aluminum was accelerated because the oxide fihu was
excluded, and that the favorable conductivity appeared even when baking at tlrc
tcrnpcraturc lowcr thatt the melting point.
25 [0044]
12urllternlorc, thc phosphoric acid solutions coat the surface of the particles 4,
and when baking, phosphoric acid and the liquated aluminum ingredient react and thc
oxide 5 to be the co~npound (oxide compound) is formcd. In the electrode wiring 2, it
is deemed that the factor which improved the water-resistance is that the sparsc oxide
30 film was excluded from the whole surface of the particles 4 of alumi~~urann,d that the
homogeneously compact compound of phospl~orus and aluminum is formed on the
whole surface of the particles 4 of aluminum, therefore, the surface of thc particles 4
wasn't exposed and the chenlical stability was improved. Howevel; regarding the
water-resistance, in the case to bake over 400 degrees Celsius. for example, at greater
than or equal to 500 degrees Celsius, favorable water-resistances could be acquired.
LO0451
6 To the contrary, when the electrode wiring 2 generated in the comparison
example shown in 'Table 1 is observed by utilizing the Scanning Electron
Microscope-Energy Dispersive X-ray Analyzer (SEM-EDX), lead (Pb) metal has
precipitated in the interface between the particles 4 of aluminum, and the segrcgation
of the glass ingredient was observed. It is deerned that this was precipitated because
10 the lead ofthe Pb glass was deoxidized by the oxidation by the Pb glass of the particles
4 of aluminum. Accordingly, it is assumed that, in the case of the Pb glass
conventionally utilized, thc surfacc of the particles of alunli~~uinsl further oxidized,
keeping the sparse oxide film of the surfacc of the particles of aluminum remained,
therefore, the newly generated oxide fi1111 was also sparse oxide fill11 and could not be
15 coated cotnpactly.
100461
For thc particles 4, not only the particles 4 of aluminum, but also the particles
4 which consist of an alnminum-containing alloy can be utilized. As thc
a1uminu111-containing alloy, at least one type of chemical element out of silver (Ag),
20 copper (Cu), silicon (Si), nlagnesiuln (Mg), and calcium (Ca) is included. For example,
by adding silver, it is possible to increase the clect1.i~c onduc,tivity of the alloy (AI-Ag).
Moreover, by adding copper, it is possiblc to increase the strcngth ofthe alloy (AI-Cu).
By adding silicon, it is possible to incrcase the abrasion resistance ofthe alloy (AI-Si).
I3y adding magnesium and calcium, it is possible to increasc the strength and the
25 corrosion resistance of the alloy (AI-Mg, Al-Ca).
[0047]
The particles 4 consist of a particle group A (first particle group) 4A having a
volume fraction of approximately 95% of particle diameters which are within a range
greater than or equal to 0.5 pm and less than 1.5 pm, and a particle group B (second
30 particle group) 4B having a volume fraction of approximately 95% of particle
diameters which are within a range greater than or equal to 1.5 pm and less than 8 pm.
The total wcigl~to f a plurality of pa~ticles4 of ihc particle group A (4A) and the total
weight of a plurality of particles 4 of the particle group B (4B) are substantially
equivalent. Accordingly, the particles 4 of the particle group A (4R) having small
particle diameters go into the clearances among the particles 4 of the particle group B
(413) having large particle diameters, and the density of the particles 4 can be increased,
5 therefore, it is possible to form the compact electrode wiring 2.
100481
(Embodiment 2)
FIG. 2 shows a part of a sectional drawing of a plasma display panel (PDI':
electronic component) 1 l(1) with reference to the embodiment 2 of the present
10 invention, In the embodiment 2, as the electronic component 1 to which the present
invention can be applied, the plasma display panel 11 is described as an example. For
the display electrode 20 and the address electrode 21 of the plasma display panel 11(1),
the electrode wiring 2 of the electronic component 1 of the present invention is utilized.
The plasma display panel Il(1) is arranged with the front panel 12(3) and the rear
15 pa~iel l3(3) kced will1 a 100 lo 150 pni-gap, and thc gap betwce~tlh c front ],anel 12(i)
and the rear panel 13(3) is retained by the diaphragm 14. The circumference parts of
the front panel 12(3) and the rear panel 13(3) are ailtightly sealed by the sealing
material 15, and noble gases are filled in the interior of the panel in thc gap of the front
panel 12(3) and the rear panel 13(3).
20 On the li.ont panel 12(3), the display electrode 20(2) is formed. The front
panel 12(3) corresponds to the substrate 3 of the embodiment 1, and the display
electrode 20(2) corresponds to the electrode wiring 2 of the e~nbodiment 1. ?'he
dielectric layer 23 is for~ned on the display electrode 20(2), and on the dielectric layer
23, the protective layer 25 (Ibr cxample, the cvaporatcd film of oxide magncsiuru
25 (MgO)) to protect the display electrode 20(2) or the like from the electric discharge, is
formed.
1:0049]
On the rear panel 13(3), the address electrode 21(2) is formed. The rear panel
13(3) corresponds to the substrate 3 of the embodiment 1, and the address electrode
30 21(2) corresponds to the electrode wiring 2 of the embodiment 1. In the planar view,
the address electrode 21(2) is formed to meet the display electrode 20(2) at right angles.
The dielectric layer 24 is formed on the address electrode 21(2), and on the dielectric
layer 24, the diaphragm 14 to constitute the cell 16 is provided. The diaphragm 14 is a
stripe-like, or lattice (box)-like structure.
[0050]
The microscopic space divided by the diaphragm 14 in the gap between the
5 front panel 12(3) and the rear panel 13(3) becomes the cell 16. The fluorescent
niaterials 17, 18, 19 are filled in the cell 16. 1 pixel consists of three pieces ofthe cell
16 corresponding to three primary colors of the cell 16 filled with the red fluorescent
material 17, the cell 16 filled with the green fluorescent material 18, and the cell 16
filled with the bluc fluorescent material 19. Each pixel can light-emit various colors in
10 accordance with the signals applied to the display electrode 20(2) and the address
electrode 21 (2).
[OOSl]
Subsequently, the manufacturing method of the plasma display panel 11 (1) is
described.
15 [00521
(generation of conductive pastes)
I:irstly, the particle group A described in 'iablc 1 was prepared as the particles
to be contained in the conductive pastes. The particles were aluniin~u~mle tal particles.
The pa~ticlcs of the particle group A havc a volu~ile fiaction greater than or equal to
20 approximately 95% of particle diameters which arc within a range greater than o~ cqual
to 0.5 p111 and less than I .S pn. The particle group I3 and the particle group C wcre not
utilized, and the particle group A was utilized in the compounding ratio of 100
wcight %. I:urtl~ernlore, as thc phosphoric acid solutions, the phosphoric acid solutions
wllich have thc idcntical weight ratio wit11 ille example 3 of Tablc 1 wcrc prepal.cd. In
25 other words, tlie phosplioric acid solutions which have weight ratios of 10 weight % of
phosphorus pentoxide, 80 weight % of water, 10 weight % of ethanol wele prepal.ed.
30 parts by weight of these phosphoric acid solutions were added to 100 parts by
weight of tlie powder prepared in advance. By irradiating the ultrasonic waves to these
nlixtures for 10 minutes, the particles were made to be dispersed in the phosphoric acid
30 solutiolis and the conductive pastes were completed.
[0053]
(generation of plasma display panel)
Subsequently, the plasma display panel was generated. Firstly, the whole
surfaces of the front panel 12(3) and the rear panel 13(3) were coated with the
conductive pastes by the screen printing method, and were desiccated in the
atmosphere at 150 degrees Celsius. By the photo lithography method and the etching
5 method, the places having excessive coating fihn of the conductive pastes were
excluded, and the patterning of the display electrode 20(2) and the address electrode
21(2) was performed. Thereafter, by baking, in thc identical baking condition with thc
exalnple 11 of Table 1, in the atmosphere at the baking tetnpcrature 600 degrees
Celsius for 30 minutes of the baking time, the display electrode 20(2) and the address
10 electrode 21(2) were completed. In this baking, the baking atmosphere becomes an
acidic atmosphere, however, by this baking, the ~netal particles, especially of
aluminum, of the display electrode 20(2) and thc address electrode 21 (2) didn't change
in color by the che~l~ical-reactioonr the like.
LOO541
15 Subsequently, each of the front pancl 12(3) anti the rear panel 13(3) was
coated with the dielectric pastcs to be the dielectric layers 23, 24, and baked in the
atmosphere, at 610 degrees Celsius of the baking temperature, for 30 minutes of the
baking time. Incidentally, in this baking, the baking atmosphere beeonles an acidic
atmosphere, and thc dielectric layer 23 directly conlacts the display electrode 20(2) and
20 the dielectric layer 24 directly contacts the address electrode 21(2), howcver, the
dielectric layer 23 didn't chemical-react with the dispfay electrode 20(2) and the
dielectric layer 24 didn't chemical-react with the address electrode 21(2), by illis
baking. 'l'hc protective layer 25 was deposited by evaporation, liom the side of thc
dielectric layer 23 of the tront panel 12(3).
2 [0055]
The diaphragm 14 was generated by forming the material including at least
the powder-like glass colllposite and the filler in a stripe-like or lattice-like manner,
then, sintering this formed structure at 500 to 600 degrees Celsius. 'This diaphragm 14
was arranged on the dielectric layer 24 to constitute the cell 16. Thereafter, by filling
30 each of the cells 16 with the pastes for the fluorescent material corresponding to three
primary colors, and baking at 450 to 500 degrees Celsius, the red fluorescent material
17, the green fluorescent material 18; and the blue fluorescent nlaterial 19 were formed
in the cell 16.
[0056]
Subsequently, by the dispenser method, the printing method or the like, either
one of the circunlference parts of the front panel 12(3) or the rear panel 13(3) was
5 coated with the sealing material 15. Thereafter, the fi.ont panel 12(3) and the rear panel
13(3) were scaled. When sealing the fi-ont panel 12(3) and the rear panel 13(3), the
front panel 12(3) and the rear panel 13(3) were arranged to be faced each other by
precisely being aligned, and heated at 420 to 500 degrees Celsius. In this heating, the
gases in the cell 16 were exhausted and the noble gases were filled instead. Incidentally,
10 the sealing nlaterial 15 may be tentative-baked at the same time when the pastes for the
fluorescent material when forming the fluorescent materials 17 to 19 are baked. By
tentative-baking the sealing material 15, the air bubbles included in the sealing
material 15 can be reduced. Incidentally, in FIG. 2, the sealing material 15 and the
address electrode 21(2) directly contact, however, the display electrode 20(2) also
15 directly contacfs the sealing matcrial 15 in order to pull out the electrode lo the exterior.
The sealing material 15 is heated when tentative-baking and when glass-sealing, and,
in this heating, the baking aln-rosphcre becoi~~eans acidic atmosphere, however, by this
heating, the sealing material 15 didn't chemical-rcact with the display eleclrode 20(2)
and the address electrode 21(2). As aforcmcntioned, the plas~na display panel ll(1)
20 was completed.
lo0571
(evaluation of plasma display panel)
(visual inspection)
The visual inspection around the display electrode 20(2) and thc address
25 electrode 21(2) was perfonlled. In the interface section betwcen the display electrodc
20(7.) and the front panel 12(3) or in the interface section between the display electrodc
20(2) and the dielectric layer 23, neither the generations of the air-gap nor the changes
in color were observed. Furthermore, in the interface section between the address
electrode 21(2) and the rear panel 13(3) or in the interface section between the address
30 electrode 21(2) and the dielectric layer 24, neither the generations of the air-gap nor the
changes in color were observed. The plasma display panel 1 l(1) could be generated in
the favorable condition of appearances.
lo0581
(lighting experiment)
Subsequently, the lighting experiment of the generated plasma display panel
11(1) was pcrfornled. For the lighting (luminescence) of the cell 16 of the plasnla
5 display panel 1 1(1), a voltage was applied between the display electrode 20(2) and tlie
address electrode 21(2) of the cell 16 required to be lighted, and an address electric
discliargc was perforn~cd in the ccll 16, then, the noblc gases were excited into tlie
plasma condition to store tlie wall charges in tlie cell 16. Subsequently, by applying a
certain voltage to a pair of the display electrodes 20(2), the display electric discharges
10 were caused only in the cell 16 which stored the wall charges and the ultraviolet rays
22 were generated. Thereafter, by utilizing these ultraviolet rays 22, the lu~ninescence
of the fluorescent materials 17 to 19 was caused and the image (information) was
displayed.
LOO591
15 Ildore and alter the display of this image infomiation, the specific. resistances
of the display electrode 20(2) and tlic address electrode 21(2) didn't increase.
Furthennore, the withstand voltages didn't lower between the adjacent display
electrodes 20(2) cach other, and between the adjacent address electrodes 21(2) each
other, or the like, and it was possible to boost up tlic voltages and lo light the ccll 16.
20 Moreover, the migration phenomenon such as the electrode wiring of the silver thick
lilm was not caused, and other issues with particular diiliculties were not observed.
Since expe~isive silver is not utilized for the display electrode 20(2) and the addrcss
electrode 21(2) of the plasnla display panel 11 (1) of the embodinicnt 2, it is possible to
highly contribute for the cost reduction.
25 [0060]
(Embodiment 3)
FIG. 3A shows a bottom view (back side) of a solar battery cell (electronic
component) 31(1) with reference to the embodiment 3 of the present invention, and
FIG. 3B shows an arrow sectional drawing in A-A direction of FIG. 3A, with the
30 light-reception plane side (front side) up and the back side down. In the embodiment 3,
as the electronic co~nponent 1 to which the present invention can be applied, the solar
battery cell 31 is dcscribcd as an example. 1:ICi. 3A and FIG. 3U show the
back-contact-type (backside elcctrodc type) crystal silicon solar batiery cell 31(1) as
one example. For the backside p-type elcctrodc 37 of the solar battery cell 31(1), the
electrode wiring 2 of the electronic component 1 of the present invention is utilized.
Furlher~nore, the backside p-type electrode 37(2) is formed on the cell wafer 38 which
5 consists of the p-type silicon substrates. The cell wafer 38(3) corresponds to the
substrate 3 of the embodiment 1, and the backside p-type electrode 37(2) corresponds
to the electrode wiring 2 of the cnlbodinlcnt 1. In the solar battery cell 3 1 of the
back-contact-type (backside electrode type), the backside p-type electrode 37(2) and
the backside n-type electrode 36 are formed on the back side.
lo [0061]
In the cell wafer 38(1), a through hole 39 penetrating both of the front side
and the back side is formed, and the 11-type semi-conductor layer 33 is formed on the
side wall of the tlrough hole 39 and the light-reception plane side (front side) of the
cell wafer 38(1). In the through hole 39, a silver-made through hole clcctrode 34 is
15 embedded. In order to connect to thc throng11 hole clectrodc 34, a silver-made grid-likc
current-collecting grid clectrode 32 is for~ncdo, n the light-reception plane side (front
sidc) of tllc ccll wafer 38(1).
[0062l
011 the back side of the ccll wafcr 38(1), a high-density doping layer 35 is
20 formed, away from tile through holc 39 and tire through hole electrode 34. The
high-density doping layer 35 prevents thc rccombit~ation of the carrier. In order to
adjust the position to the high-density doping layer 35, aluminurn-made grid-like
backside p-type electrode 37(2) is fornled on the back side of ihc ccll wafer 38(1).
Moreover, in order to adjust thc position to ihe through llolc clcctrode 34, the
25 silver-made grid-like backside n-type electrode 36 is formed on the back side of the
cell wafer 38(1).
[0063]
Subsequently, the manufacturing method of the solar battcry cell 31(1) is
described.
30 [0064]
(generation of conductive pastes)
In tbc embodiment 3, as thc conductive pastcs, the identical conductive pastes
with the ones utilized in the example 2 of Table 1 wcre generated and utilized
[0065]
(generation of solar battcry ccll)
As the cell wafer 38(3), the p-type silico~l substrate was prepared.
6 Subsequently, the through hole 39 was formed in the cell wafer 38(3) by laser drilling,
etching or the like. Subsequently, though the drawing is omitted, in order to improve
thc light incidence efficiency, the tnixed solution of 1% caustic soda (sodium
hydroxide: NaOH) and 10% isopropyl alcohol (CI-13CI-I(OH)CI-I~w)a s utilized, and the
texture was formed by ctching the light-reception plane side (front side) of the cell
10 wafer 38(3).
[0066]
By coating the light-reception planc side (front side) of the cell wafer 38(3)
with the liquid i~lcludingp hosphorus pentoxide and treating at 900 degrees Celsius for
30 minutes, phosphorus (P) was ditli~sed from phosphorus pcntoxidc to the cell wafer
15 38(1) and the n-type semi-conductor layer 33 was foonned on thc light-rcccption plane
side. Incidentally, though the drawing is omitted, the anti-reflective fill11 of the silico~l
nitridc film (Si3N4) nlay be ii~r~ueidn the uniform thicknesses on the n-type
semi-conductor layer 33. This silicon nitride filtn can be formed by the plasma CVD
method with the mixed gas ofsilane (Sil-14) and arnmonia (NH3) as the material.
20 100671
Subsequently, by filling the intcrior of' the prc-lbrtned through hole 39 with
the cotnlnercial silver pastes by the printing method and further printing the
aforemetltioned silver pastcs on the light-reception planc side in the grid-like manner,
the through hole clectrode 34 and the cu~uent-collecting grid electrode 32 wcrc formed.
26 'The fornled through holc clectrodc 34 and the current-collecti~~ggri d electrode 32 were
desiccated at 150 degrees Celsius for 30 minutes.
100681
On the back side of the opposite side of the light-reception plane, the backside
11-type electrode 36 was fornied, by utilizing the silver pastes and printing in the
30 stripe-like manner by the screen print. Furthermore, on the back side of the opposite
side of the light-reception plane, the backside p-type electrode 37(2) was fornied by
utilizing the identical conductive pastes with the cunductive pastes utili~ed in the
example 2 and printing in the stripe-like manner by the screen print. The formed
backside n-type electrode 36 and the backside p-type electrode 37(2) were desiccated
at 150 degrees Celsius for 30 minutes.
100691
5 'The back-contact-type solar battery cell 31(1) was completed, by baking to
rclain the through hole electrode 34, the current-collecting grid electrode 32, the
backside 11-type electrode 36, and the backside p-type electrode 37(2) at 850 degrees
Celsius for 2 seconds. Incidentally, by this baking, aluminum is diffused from the
backside p-type electrode 37(2) to tlie cell wafer 38(3) of the lower part of tlie backside
10 p-type electrode 37(2) and the high-density doping layer 35 for preventing the
recornbination of the carrier is formed at the samc time.
[0070]
Further~i~oref,o r the comparison, the back-contiact-type solar battery cell
31(1) to ibrm the backside p-typc elcctrode 37(2) by utilizing the identical conductive
15 pastes with the conductive pastes utilized ill the comparison example of' Table 1 was
generated.
[0071]
(evaluation of solar battery cell)
It has been clarified that the back-contact-type solar battery cell 31(1) with
20 reference to tlie embodiment 3 shows the conversion efficiency which is the higher
elliciency than that in the solar battery cell generated for comparison. It seems because
the electric resistance value of the backside p-type electrode 37(2) could be lowered.
As aforementioned, it has been confirmed that the electrode wiring 2 (Sec 121G. I) of
thc present invention can be applied to the backside p-type elcctrode 37(2) of the
25 back-contact-type solar battery 31(1). Incidentally, the generation method of the
backside p-type electrode 37(2) of the solar battery cell described above is not limited
to tlie back-contact-type solar battery cell, but possible to correspond to the generation
rliethod of the p-type electrode of the various solar battery cells.
LO0721
30 (Embodiment 4)
FIG. 4 shows a sectional drawing of a ceramic rnultilayer wiring substrate
(electronic cori~poaent) 41(1) with reference to the embodiment 4 of the present
invention. In the e~nbodimen4t , an example to apply the clcctronic component 1 (See
FIG. 1) with reference to the preseut invention to the multi-layer wiring substrate, is
described. 1:lG. 4 shows the multi-layer wiring substrate 41(1) which consists of 5
layers of low temperature bake ceranlic (LTCC: Low Temperature Co-fired Ceramics)
5 as one exatuple of the multi-layer wiring substrate. For the through hole electrode
43(2) and the wiring 44(2) of the multi-layer wiring substrate 41(1), the electrode
wiring 2 of the electronic component 1 of the present invention is utilized. The wiring
44(2) is formed on the upper side and the lower side of each ceramic substrate 42(3).
In FIG. 4, thc wiring 44(2) is formed in 6 layers. The wirings 44(2) of each layer are
10 conllected by the through hole electrode 43(2). The through hole electrode 43(2)
penetrates the ceramic substrate 42(3). In the multi-layer wiring substrate 41(1), the
wiring 44(2) and the through hole electrode 43(2) are formed three-di~nensionallyT. he
ceranlic substrate 42(3) corresponds to the substrate 3 of the embodiment 1 and the
through hole electrode 43(2) and the wiring 44(2) correspond to the electrode wiring 2
15 of the emhodi~nentI. .
200731
Subsequently, the manufacturing method of the multi-layer wiring substrate
41(1) is described.
/0074:1
20 (getteration of conductive pastes)
In the cnlbodime~lt4 , as the conductive pastes, the identical conductive pastes
wit11 tllc conductive pastes utilized in the exa~nple2 of 'G~blc1 were gencratcd and
utilized.
1007.51
25 (gcncration of multi-layer wiring substrate)
Firstly, a plurality of green sheets kneading the glass powder, thc ceramics
powder, and the binder were prepared. The green sheets becomc the ceramic substrate
42(3) of each layer by the baking to be described later. Subsequently, the thmugh holes
are opened at the required position of the green sheets. The green sheets with the open
30 through holcs are coated with the identical conductive pastes with the one utilized in
the example 2, by the printing method in the required wiring pattern. I-lcrc, the through
holes are also filled with the conductive pastes. The conductive pastes coatcd in the
wiring pattern become the through hole electrode 43(2) and the wiring 44(2), by the
baking to be described later As required, for example, the back side of tlie green sheet
of the bottom layer shown in FIG. 4 is also coated with the conductive pastes by the
printing method, and the wiring patterns are formed. In the case to coat the back side of
5 the green sheet, it is performed afier desiccating the conductive pastes to coat the
surface with.
coo761
A plurality of green sheets which formed the prescribed wiring patterns are
laminated and baked as a wl~ole. FIG. 5 shows one example of the temperature
10 schedule when baking. As shown in FIG. 5, the temperature-ascending process from
the room temperature to 700 degrees Celsius was in the atmosphere, the process in the
temperature range (including the 60-minute retaining time at 900 degrees Celsius)
from 700 degrees Celsius to 900 degrees Celsius was in the nitrogen attnosphere, and
tlie temperature-descendi~igp rocess fiom 700 degrccs Celsius to the room temperature
15 was in the atmosplicre, again, Incidcntaliy, the. te~~~perature-ascendirnatge and the
temperature-descendi~~rgat e were at 5 degrees Celsius/minute. Incidentally, the baking
temperature schedule is not limited to FICi. 5. Inciden~ally, the reason why the
temperature range from 700 degrees Celsius to 900 degrees Celsius was in the nitrogen
atmosphere is to suppress the oxidation of the particles 4 in thc conductive pastes.
20 LO0771
(evaluation of multi-layer wiring substrate)
The visual inspection around the wiring 44(2) was performed. In tlie interface
section between the wiring 44(2) and the ccraniic substrate 42(3), neither the
generations of the air-gap nor the changes in color were observed. 'fhe multi-layer
25 wiring substratc 41(1) could be generated in tlie Ptvorable condition in appearances.
By measuring the specific resistances of the wiring 44(2) and the through hole
electrode 43(2), the values which are similar to the example 2 of Table 1 could be
acquired, as designed. Subsequently, the section-observation of the generated
multi-layer wiring substrate 41(1) was performed. As a result, the generated
30 multi-layer wiring substrate 41(1) was baked colnpactly enough. Therefore, it is
deemed that the specific resistances also sliowed the favorable values as designed. It
was considered that thc dcbinding was substantially iully completed in the green sheets
in the tcmperaturc-ascending process to 700 degrees Celsius. Furthennore, it was
confirnled that the glass powder of the green sheets didn't chemical-react with the
through hole electrode 43(2) and the wiring 44(2) and that the air-gaps were not
generated in the vicinity of the mutual interface, either. As aforementioned, it was
6 confirmed that the electrode wiring 2 (See FIG. 1) of the present invention can be
applied to the wiring 44(2) and the through hole electrode 43(2) of the multi-layer
wiring substrate 41(1). Since it is not necessary to utilize the electrode wiring of the
expensive silver thick film for the wiring 44(2) and the through hole electrode 43(2), it
is possible to highly contribute for the cost reduction.
10 [0078]]
In the embodiments, the cases that the electronic coinpollent 1 is the plasma
display panel 11, the solar battery cell 31 and the ceranlic mounted substrate 41, were
described, however, the electronic component 1 is not limited to these, and it is
possible to extend the application range to which the electrode wiring of alunlinu~nc an
15 bc applied.
[0079]
1 electronic component
20 2 electrode wiring
3 substrate
4 particles
4.4 particle group A (first particlc group)
413 particlc group 13 (second particle group)
26 5 oxide
6 necking combination section
1. An electronic component, comprising an electrode wiring havine
a plurality of particles which consist of aluminunl (Al) andlor an
5 aluminum-contailling alloy; and
an oxide to fix the particles to a substrate, wherein the oxide includes
phosl~horus (P) and alutninutn in conlplete unity.
2. An electronic component according to claim 1, wherein the particles
10 include at least one type of chemical elcment out of silver (Ag), copper (Cu), silicon
(Si), lnagnesium (Mg), and calciunl (Ca).
3. An electronic component according to claim 1 or claim 2, wherein
in the electrode wiring, the particles are greatcr than or equal to 84.2 volurne O/o and
15 less than or equal to 99.7 volume %.
4. An electronic co~nponcnat ccording to either one of the clainl 1 to 3,
wherein
a plurality of the particles coilsists of
20 a iirst particle group having a volutne fraction of approximately 95%
of particle dia~nctcr.: which arc within a rangc greater than or equal to 0.5 it111 and less
illan 1.5 pln, and
a second particle group having a volume fiaction of approxinlately
95%) ofpiirlicle diameters which arc within a rangc greater than or equal to 1.5 pm and
25 less than 8 pm; and
the weights of the first particle group and the second particle group arc
substantially equivalent.
5. An electronic component according to either one of the claim 1 to 4,
30 wherein the particles include tabular particles.
6. An electronic component according to cither one ofthe claim 1 to 5,
wherein the oxide has phosphorus and oxygen (0) as chief ingredients, and a content
ratio of pliospliorus is greater tlian or equal to 50 atom % in an ingredient ratio without
respect to the oxygen.
7. An electronic component according to either one of the claim 1 to 6,
wherein a plurality of the particles are combined each other by sintering.
8. A conductive paste, comprising:
a phosphoric acid solution; and
a plurality of pariiclcs which disperse in the phosphoric acid solution and
consist of aluminum andlor an aluminum-coritaining alloy.
9. An electronic component, comprising an electrode wiring in which a
conductive paste according to claim 8 coats a substrate and is baked, wherein the
16 electrode wiring comprises:
a plurality of the particlcs cotilbined each other by sintering; and
a phosphorus oxide which is fonned from the phosphoric acid solution and
adheres the particles to a substrate.
10. An electronic conll)onent, according to either onc of thc clainl I to 7,
or the claini 9, wherein a specific resistance of thc electrode wiring is less tlian 5x 10."
Ocm.
11. An electronic component, according to either one oftlie claini I to 7,
25 and the claim 9 to 10, wherein a specific resistance of the electrode wiring is less than
I 1 o -L~Z C~I.
12. An electronic component, wherein the electronic component is either
of a plasma display panel, a solar battery cell, or a ceramic mounted substrate, in the
30 electronic component according to either one of the claim 1 to 7, and the claim 9 to 11.
13. A manufacturing nlelhoci,
coating a substrate with a conductive paste comprising a plurality of particles
which consist of alurnin~~a~nnd lor an aluminum-containing alloy dispersing in a
phosphoric acid solution; and
baking the conductive paste which is coated and forming an electrode wiring,