CN103531267A - Conductive composition used for forming collecting electrode of solar cell and solar cell unit - Google Patents
Conductive composition used for forming collecting electrode of solar cell and solar cell unit Download PDFInfo
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- CN103531267A CN103531267A CN201210232334.2A CN201210232334A CN103531267A CN 103531267 A CN103531267 A CN 103531267A CN 201210232334 A CN201210232334 A CN 201210232334A CN 103531267 A CN103531267 A CN 103531267A
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Abstract
An objective of the invention is to provide a conductive composition which is excellent in printability and capable of forming an electrode with a high aspect ratio and used for forming a collecting electrode of a solar cell and a solar cell unit. The solar cell unit uses the conductive composition. The conductive composition used for forming the collecting electrode of the solar cell contains ball-shaped silver power (A) with an average particle size of 0.5-5.0 mum and sheet-shaped silver power (B) with an average thickness of 0.05-0.2 mum and an apparent density of 0.4-1.1 g/cm<3>.
Description
Technical field
The present invention relates to solar cell current collector forms with conductive composition and solar battery cell.
Background technology
The current known following method that has: will by thermoplastic resin (for example add in the electroconductive particles such as silver particles, acrylic resin, vinyl acetate resin etc.) or thermosetting resin is (for example, epoxy resin, unsaturated polyester resin etc.) etc. the adhesive, organic solvent, curing agent, catalyst etc. of formation the silver that is obtained by mixing stick with paste (conductive composition) and (be for example printed onto on synthetic resin base material, polyester film etc.), to form predetermined circuit pattern, and it is heated and forms the conductivity wiring that forms conductor circuit, thereby manufacture circuit substrate.
For example, in patent documentation 1, recorded: " a kind of conductor paste is that 3 ~ 8 μ m, apparent density are 0.4 ~ 1.1/cm by laser diffractometry 50% particle diameter
3and BET method specific area value is 1.5 ~ 4.0m
2the flake silver powder of/g and resin form, and it is characterized in that, described conductor paste has the peak value of resistance value between 150 ~ 200 ℃ " ([claim 5]).
In addition, in patent documentation 2, recorded: " a kind of conductive paste composition, it contains average grain diameter, the 1.5 ~ 4.0m with 3 ~ 8 μ m
2the specific area of/g and 0.4 ~ 1.1g/cm
3laminar silver powder A, the average grain diameter with 3 ~ 10 μ m, the 0.6 ~ 1.2m of apparent density
2the specific area of/g and 1.5 ~ 2.1g/cm
3laminar silver powder B and the resin of apparent density, wherein, so that the ratio that laminar silver powder A is 30 ~ 95 weight portions with respect to 100 parts of the total weights of laminar silver powder A and laminar silver powder B contains laminar silver powder A, and so that the mode that the total of laminar silver powder A and laminar silver powder B is 35 ~ 85 % by weight with respect to the solid constituent of conductive paste contains laminar silver powder A and laminar silver powder B " ([claim 1]).
And then, in patent documentation 3, recorded: " a kind of conductive composition, it contains resistivity is 20 * 10
-6metal material below Ω cm (A), there is the fatty acid silver salt (B) of an above hydroxyl and be 200 ℃ of binary of fatty acids silver salt (C) that following binary of fatty acids obtains by using boiling point " ([claim 1]); and recorded the film-forming resins such as epoxy resin ([0061]) as optional member, use in an embodiment silver powder as metal material (A) ([0071]).
Patent documentation 1: TOHKEMY 2003-55701 communique
Patent documentation 2: No. 3955805 communique of Japan Patent
Patent documentation 3: TOHKEMY 2010-92684 communique
But, the inventor is studied the paste material of recording in patent documentation 1 ~ 3, result is known, when there is the solar cell current collector of circuit pattern of a large amount of line width in formation, because producing to break, to crawl, ooze out etc., cause printing variation, and the ratio of the height and the width in the cross section of electrode (height/width) (following, to be called " aspect ratio ") also reduces.
Particularly know, on the surface of the silicon wafer of silicon type solar cell, be formed with pyramidal fine suede structure, sometimes easily produce according to the paste material after the shape of matte, printing the phenomenon (oozing out) of wetting diffusion occurs along the groove of matte.
Summary of the invention
Therefore, problem of the present invention is, provides printing solar cell current collector good and that can form the electrode that aspect ratio is high to form with conductive composition and the solar battery cell that uses this conductive composition.
The inventor conducts in-depth research in order to address the above problem, found that, the composition of the ball shape silver powder with predetermined average grain diameter also being used with the flake silver powder with predetermined average thickness and apparent density and being prepared, there is good printing, and can form the electrode that aspect ratio is high, thereby complete the present invention.That is, the invention provides following (1) ~ (11).
(1) a current collector formation conductive composition, it contains the ball shape silver powder that average grain diameter is 0.5 ~ 5.0 μ m (A) and average thickness is that 0.05 ~ 0.2 μ m and apparent density are 0.4 ~ 1.1g/cm
3flake silver powder (B).
(2) the solar cell current collector formation conductive composition as described in above-mentioned (1), wherein, the content of above-mentioned flake silver powder (B) is below 30 quality % with respect to the gross mass of above-mentioned ball shape silver powder (A) and above-mentioned flake silver powder (B).
(3) the solar cell current collector formation conductive composition as described in above-mentioned (1) or (2), it also contains epoxy resin (C).
(4) the solar cell current collector formation conductive composition as described in any one in above-mentioned (1) ~ (3), it also contains fatty acid silver salt (D).
(5) the solar cell current collector formation conductive composition as described in above-mentioned (3) or (4), wherein, above-mentioned epoxy resin (C) is at least that epoxide equivalent is that bisphenol A type epoxy resin (C1) and the epoxide equivalent of 1500 ~ 4000g/eq is the polyalcohols glycidol fundamental mode epoxy resin (C2) below 1000g/eq.
(6) the solar cell current collector formation conductive composition as described in above-mentioned (4) or (5), wherein, above-mentioned fatty acid silver salt (D) is the polycarboxylic acid silver salt (D2) of the carboxylic acid silver salt's groups (COOAg) more than having carboxylic acid silver salt's group (COOAg) and each more than one fatty acid silver salt (D1) of hydroxyl (OH) and/or having three.
(7) the solar cell current collector formation conductive composition as described in above-mentioned (6), wherein, above-mentioned fatty acid silver salt (D1) is 2,2-dihydroxymethyl n-butyric acie silver salt and/or 2-hydroxy-iso-butyric acid silver salt.
(8) the solar cell current collector formation conductive composition as described in above-mentioned (6) or (7), wherein, above-mentioned polycarboxylic acid silver salt (D2) is 1,2,3,4-butane tetracarboxylic acid silver salt.
(9) the solar cell current collector formation conductive composition as described in any one in above-mentioned (3) ~ (8), wherein, the content of above-mentioned epoxy resin (C) is 2 ~ 20 mass parts with respect to total 100 mass parts of above-mentioned ball shape silver powder (A) and above-mentioned flake silver powder (B).
(10) the solar cell current collector formation conductive composition as described in any one in above-mentioned (4) ~ (9), wherein, the content of above-mentioned fatty acid silver salt (D) is 0.1 ~ 10 mass parts with respect to total 100 mass parts of above-mentioned ball shape silver powder (A) and above-mentioned flake silver powder (B).
(11) a kind of solar battery cell, it possesses surface electrode, semiconductor substrate and the backplate of sensitive surface side, and above-mentioned surface electrode and/or above-mentioned backplate form with conductive composition by using in above-mentioned (1) ~ (10) the solar cell current collector described in any one to form.
Invention effect
As follows, according to the present invention, can provide printing solar cell current collector good and that can form the electrode that aspect ratio is high to form with conductive composition and the solar battery cell that uses this conductive composition.
Particularly, solar cell current collector of the present invention forms with conductive composition (hereinafter referred to as " conductive composition of the present invention "), thin thread part (live width: printing approximately 50 μ m ~ approximately 100 μ m) is also good, therefore, can be suitable for silk screen printing.
In addition, as long as use conductive composition of the present invention, even calcine under low temperature (approximately 150 ℃ ~ approximately 500 ℃), also can suppress broken string and the generation of oozing out and form electrode, therefore, also have and can alleviate because heat for example, brings the effect of infringement to solar battery cell substrate (, silicon substrate etc.), therefore very useful.
Accompanying drawing explanation
Fig. 1 means the sectional view of an example of the preferred implementation of solar battery cell.
Fig. 2 utilizes scanning electron microscopy (SEM) ball shape silver powder using in embodiment (AgC-103, Bo Fen industrial group of FUKUDA METAL manufacture) to be taken and the photo that obtains.
Fig. 3 utilizes scanning electron microscopy (SEM) flake silver powder using in embodiment (Ag-XF301K, Bo Fen industrial group of FUKUDA METAL manufacture) to be taken and the photo that obtains.
Fig. 4 utilizes scanning electron microscopy (SEM) flake silver powder using in comparative example (AgC-A, Bo Fen industrial group of FUKUDA METAL manufacture) to be taken and the photo that obtains.
Label declaration
1 solar battery cell
2n layer
3 antireflection films
4 surface electrodes
5p layer
6 backplates
7 silicon substrates
Embodiment
[solar cell current collector formation conductive composition]
Conductive composition of the present invention is to contain the ball shape silver powder that average grain diameter is 0.5 ~ 5.0 μ m (A) and average thickness is that 0.05 ~ 0.2 μ m and apparent density are 0.4 ~ 1.1g/cm
3the solar cell current collector formation conductive composition of flake silver powder (B).
Below, to ball shape silver powder (A) and flake silver powder (B) and can contain as required other become to grade and be elaborated.
<ball shape silver powder (A)>
The ball shape silver powder using in conductive composition of the present invention (A) is that average grain diameter is the silver powder of 0.5 ~ 5 μ m.
At this, spherically refer to that the ratio of major diameter/minor axis is the shape of the particle below 2.
In addition, average grain diameter refers to the mean value of the particle diameter of spherical silver powder, and refers to the 50% volume accumulation diameter (D50) obtaining by using laser diffraction formula particle size distribution device to measure.It should be noted that, as the basic particle diameter of calculating mean value, be in oval-shaped situation in the cross section of spherical silver powder, refers to the mean value that the aggregate value with its long and short diameter obtains divided by 2, in orbicular situation, refers to its diameter.
For example, silver powder (the AgC-103 using in embodiment described later, the manufacture of Bo Fen industrial group of FUKUDA METAL) silver powder shown in photo (Fig. 2) belongs to spherical silver powder, in embodiment described later and silver powder (the Ag-XF301K of use, Bo Fen industrial group of FUKUDA METAL manufactures) photo (Fig. 3) and in comparative example and the silver powder (AgC-A of use, the manufacture of Bo Fen industrial group of FUKUDA METAL) silver powder shown in photo (Fig. 4) does not belong to spherical silver powder, and belongs to sheet (scale) shape silver powder.
In addition, from making printing reach better reason, the average grain diameter of preferred above-mentioned ball shape silver powder (A) is 0.7 ~ 5 μ m, from making sintering velocity suitably make the reason that operability is good, more preferably 1 ~ 3 μ m.
In the present invention, can use commercially available product as above-mentioned ball shape silver powder (A), as its concrete example, can enumerate: AgC-102 (average grain diameter: 1.5 μ m, Bo Fen industrial group of FUKUDA METAL manufactures), AgC-103 (average grain diameter: 1.5 μ m, Bo Fen industrial group of FUKUDA METAL manufactures), AG4-8F (average grain diameter: 2.2 μ m, DOWA ェ レ Network トロニク ス company manufactures), AG2-1C (average grain diameter: 1.0 μ m, DOWA ェ レ Network トロニク ス company manufactures), AG3-11F (average grain diameter: 1.4 μ m, DOWA ェ レ Network トロニク ス company manufactures), EHD (average grain diameter: 0.5 μ m, company of Mitsui Metal Co., Ltd. manufactures) etc.
<flake silver powder (B)>
The flake silver powder using in conductive composition of the present invention (B) for average thickness be that 0.05 ~ 0.2 μ m and apparent density are 0.4 ~ 1.1g/cm
3silver powder.
At this, sheet refers to that the ratio of major diameter/minor axis surpasses 2 shape, and as mentioned above, for example, the silver powder shown in Fig. 3 and Fig. 4 just belongs to this type of, and wherein, the silver powder shown in Fig. 3 belongs to flake silver powder (B).
In addition, average thickness (d) refers to the specific area of the silver powder of measuring by BET method (gas adsorption method) is made as to S (m
2/ g) and by following formula (i) calculate and the value that obtains.
d=0.19/S…(i)
In addition, apparent density refers to the value that the method mensuration by recording in JIS Z2504:2000 " metal powder-apparent density assay method " obtains.
In addition, from making the reason of the better and easy gelatinization of printing, the average thickness of preferred above-mentioned flake silver powder (B) is 0.05 ~ 0.1 μ m.
Similarly, the apparent density of preferred above-mentioned flake silver powder (B) is 0.4 ~ 1.1g/cm
3, 0.5 ~ 1.0g/cm more preferably
3.
In the present invention, the preparation method of above-mentioned flake silver powder (B) is not particularly limited, and can prepare by the method such as recording in [0007] of patent documentation 1 ~ [0015] section etc.
In addition, can use commercially available product as above-mentioned flake silver powder (B), as its concrete example, can enumerate: Ag-XF301K (average thickness: 0.1 μ m, apparent density: 0.82g/cm
3, Bo Fen industrial group of FUKUDA METAL manufactures) etc.
In the present invention, by by above-mentioned ball shape silver powder (A) and flake silver powder (B) use, the printing of resulting conductive composition of the present invention becomes well, can form the electrode that aspect ratio is high.
Its detailed reason is not yet clear and definite, but the inventor is presumed as follows.
First, for common paste material, the surface area of the inner powder existing is larger, and thixotropy more improves.And, compare with common flake silver powder, the flake silver powder using in the present invention (B), surface area is very large, give thixotropic effect high, so printing is good.In addition, by ball shape silver powder (A) and flake silver powder (B) are also used, ball shape silver powder (A) is difficult to mobile by flake silver powder (B) clamping, and then make to wrap between flake silver powder (B) in optional member described later (epoxy resin, fatty acid silver salt, solvent etc.), therefore can form the electrode that shape retention is good, aspect ratio is high after printing.
In addition, in the present invention, from making thixotropy and viscosity suitably and the better reason of printing, the content of preferred above-mentioned flake silver powder (B) is below 30 quality % with respect to the gross mass of above-mentioned ball shape silver powder (A) and above-mentioned flake silver powder (B), more preferably 1 ~ 20 quality %, more preferably 5 ~ 20 quality %.
<epoxy resin (C)>
Conductive composition of the present invention, preferably also contains epoxy resin (C) as required as film-forming resin.
As above-mentioned epoxy resin (C), can use existing known epoxy resin.
Particularly, can enumerate such as bisphenol-type epoxy resins such as bisphenol A-type, Bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF types, diglycidyl ether of ethylene glycol, ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentylglycol diglycidyl ether, poly-neopentylglycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, tripropyleneglycol diglycidyl ether, diethylene glycol (DEG) diglycidyl ether, polyglycereol polyglycidyl ether, polyethyleneglycol diglycidylether, two glycerol polyglycidyl ethers, polyglycerol polyglycidyl ether, sorbierite polyglycidyl ether, poly-1, 4-butanediol diglycidyl ether, pentaerythrite diglycidyl ether, pentaerythrite triglycidyl ether, polypentaerythritol polyglycidyl ether, trimethyl propane diglycidyl ether, four (glycidoxy phenyl) ethane, the polyalcohols glycidol fundamental mode epoxy resin such as three (glycidoxy) methane, the ethylene oxidic ester based epoxy resin of the synthetic fatty acids such as dimeric dibasic acid, N, N, N ', N '-four glycidyl group MDA (TGDDM), four glycidyl group diamino-diphenyl sulfone (TGDDS), four glycidyl group m-xylene diamine (TGMXDA), triglycidyl group para-aminophenol, triglycidyl group m-aminophenol, N, N-diglycidylaniline, four glycidyl group 1, the two aminomethyl cyclohexane (TG1 of 3-, 3-BAC), glycidol amine epoxy resin such as triglycidyl group isocyanuric acid ester (TGIC) etc., above-mentioned epoxy resin can be used, or two or more may be used separately.
In the present invention, from forming the reason of the electrode of good weldability, bisphenol A type epoxy resin (C1) and epoxide equivalent that above-mentioned epoxy resin (C) is also preferably 1500 ~ 4000g/eq with epoxide equivalent are the polyalcohols glycidol fundamental mode epoxy resin (C2) below 1000g/eq.
(bisphenol A type epoxy resin (C1))
The bisphenol A type epoxy resin that above-mentioned bisphenol A type epoxy resin (C1) is 1500 ~ 4000g/eq for epoxide equivalent.
The epoxide equivalent of above-mentioned bisphenol A type epoxy resin (C1) is in above-mentioned scope time, and the hardness after the solidifying of conductive composition of the present invention is good, and can maintain the good solderability to solidfied material (electrode).
In addition, ratio better to the solderability of electrode from making, cure shrinkage is little and can suppress the reason of the warpage of solar battery cell substrate, the epoxide equivalent of preferred above-mentioned bisphenol A type epoxy resin (C1) is 2000 ~ 4000g/eq, more preferably 2000 ~ 3500g/eq.
(polyalcohols glycidol fundamental mode epoxy resin (C2))
Above-mentioned polyalcohols glycidol fundamental mode epoxy resin (C2) for epoxide equivalent be the polyalcohols glycidol fundamental mode epoxy resin below 1000g/eq.
The epoxide equivalent of above-mentioned polyalcohols glycidol fundamental mode epoxy resin (C2) is in above-mentioned scope time, and the viscosity of conductive composition of the present invention is good, and printing is better.
In addition, the suitable reason of viscosity when making to carry out silk screen printing, the epoxide equivalent of preferred above-mentioned polyalcohols glycidol fundamental mode epoxy resin (C2) is 100 ~ 400g/eq, more preferably 100 ~ 300g/eq.
In addition, in the present invention, from forming the reason of the electrode good with the adaptation of solar battery cell substrate, preferred above-mentioned epoxy resin (C) the has been addition epoxy resin (C3) of oxirane and/or expoxy propane.
At this, the addition of oxirane and/or expoxy propane is such as carrying out as follows: while making bisphenol-A, Bisphenol F etc. react to prepare epoxy resin with chloropropylene oxide, by adding ethene and/or propylene, carry out addition (modification).
As above-mentioned epoxy resin (C3), can use commercially available product, as its concrete example, can enumerate: ethyleneoxide addition bisphenol A type epoxy resin (BEO-60E, new Japanese physics and chemistry company manufactures), expoxy propane addition bisphenol A type epoxy resin (BPO-20E, new Japanese physics and chemistry company manufactures), expoxy propane addition bisphenol A type epoxy resin (EP-4010S, ADEKA company manufactures), expoxy propane addition bisphenol A type epoxy resin (EP-4000S, ADEKA company manufactures) etc.
In the present invention, from forming the reason of the electrode better with the adaptation of solar battery cell substrate, content while preferably containing above-mentioned epoxy resin (C) is 2 ~ 20 mass parts with respect to total 100 mass parts of above-mentioned ball shape silver powder (A) and above-mentioned flake silver powder (B), more preferably 2 ~ 10 mass parts.
<fatty acid silver salt (D)>
Even calcine and also can form electrode and can further alleviate the reason of the infringement bringing to solar battery cell substrate because of heat from the temperature lower (approximately 150 ℃ ~ approximately 200 ℃), preferred conductive composition of the present invention also contains fatty acid silver salt (D).
Above-mentioned fatty acid silver salt (D) so long as the silver salt of organic carboxyl acid be not particularly limited, for example can use: the fatty acid metal salts (particularly ternary aliphatic acid silver salt) of recording in [0063] ~ [0068] section of TOHKEMY 2008-198595 communique, the aliphatic acid silver of recording in [0030] section of No. 4482930 communique of Japan Patent, the fatty acid silver salt with more than one hydroxyl of recording in [0029] ~ [0045] section of TOHKEMY 2010-92684 communique, the binary of fatty acids silver salt of recording in the section of [0046] of TOHKEMY 2010-92684 communique ~ [0056] etc.
Wherein, preferably use the polycarboxylic acid silver salt (D2) that there is carboxylic acid silver salt's group (COOAg) and each more than one fatty acid silver salt (D1) of hydroxyl (OH) and/or there are three above carboxylic acid silver salt's groups (COOAg).
Particularly, for example, as above-mentioned fatty acid silver salt (D1), 2,2-dihydroxymethyl n-butyric acie silver salt, 2-hydroxy-iso-butyric acid silver salt can be preferably used, as above-mentioned polycarboxylic acid silver salt (D2), 1,2,3,4-butane tetracarboxylic acid silver salt can be preferably used.
In the present invention, from making the better reason of printing, the content of preferred above-mentioned fatty acid silver salt (D) is 0.1 ~ 10 mass parts with respect to total 100 mass parts of above-mentioned ball shape silver powder (A) and above-mentioned flake silver powder (B), more preferably 1 ~ 10 mass parts.
< cationic curing agent (E) >
In the situation that containing as required above-mentioned epoxy resin (C), preferred conductive composition of the present invention contains cationic curing agent (E) as the curing agent of epoxy resin.
Above-mentioned cationic curing agent (E) is not particularly limited, preferred amines system, sulfonium are, ammonium is,
the curing agent of system.
As above-mentioned cationic curing agent (E), particularly, for example can enumerate; Boron trifluoride ethylamine, boron trifluoride piperidines, boron trifluoride phenol, to methoxybenzene diazonium hexafluorophosphoric acid ester, diphenyl iodine
hexafluorophosphoric acid ester, tetraphenyl sulfonium, tetra-n-butyl
tetraphenyl borate, tetra-n-butyl
-o, o-diethyl phosphorothioate, the sulfonium salt that represented by following formula (I) etc., above-mentioned curing agent can be used, or two or more may be used separately.
Wherein, from shortening the reason of curing time, preferably use the sulfonium salt being represented by following formula (I).
In formula, R
1the alkyl or the halogen atom that represent hydrogen atom, carbon number 1 ~ 4, R
2represent the alkyl of carbon number 1 ~ 4, benzyl or the α-menaphthyl that can be replaced by the alkyl of carbon number 1 ~ 4, R
3the alkyl that represents carbon number 1 ~ 4.In addition, Q represents that X represents SbF by the group of any one expression in following formula (a) ~ (c)
6, PF
6, CF
3sO
3, (CF
3sO
2)
2n, BF
4, B (C
6f
5)
4or Al (CF
3sO
3)
4.
RO——(a)
In formula (a), R represents hydrogen atom, acetyl group, methoxycarbonyl or benzyloxycarbonyl.
In the sulfonium salt being represented by above formula (I), from forming the reason of the electrode of good weldability, preferably the X in above formula (I) is by SbF
6the sulfonium salt representing, as its concrete example, can enumerate the compound being represented by following formula (1) and (2).
In addition, in the present invention, the reason that makes the ring-opening reaction of epoxy radicals fully carry out from utilizing heat to activate, preferably the content of above-mentioned cationic curing agent (E) is 1 ~ 10 mass parts with respect to above-mentioned epoxy resin (C) 100 mass parts, more preferably 1 ~ 5 mass parts.
<solvent (F)>
From the viewpoint of the operability such as printing, preferred conductive composition of the present invention also contains solvent (F).
Above-mentioned solvent (F) so long as the solvent that conductive composition of the present invention can be applied on base material be not particularly limited, as its concrete example, can enumerate: butyl carbitol, methylethylketone, isophorone, alpha-terpineol etc., these solvents can be used, or two or more may be used separately.
In addition, the content while preferably containing above-mentioned solvent (F) is 2 ~ 20 mass parts with respect to total 100 mass parts of above-mentioned ball shape silver powder (A) and above-mentioned flake silver powder (B), more preferably 5 ~ 15 mass parts.
<additive>
Conductive composition of the present invention can contain the additives such as metal powder except above-mentioned ball shape silver powder (A) and flake silver powder (B), reducing agent as required.
As above-mentioned metal powder, particularly, can enumerate such as copper, aluminium etc., wherein preferably copper.In addition, preferable particle size is the metal powder of 0.01 ~ 10 μ m.
As above-mentioned reducing agent, particularly, can enumerate such as glycols etc.
On the other hand, from can further improving aspect ratio and suppressing the reason of the decomposition of above-mentioned epoxy resin (C), the content of preferential oxidation silver is below 5 mass parts with respect to above-mentioned solvent (F) 100 mass parts, more preferably, below 1 mass parts, most preferably do not contain in fact the mode of silver oxide.
The manufacture method of conductive composition of the present invention is not particularly limited, and can be listed below method: utilize roll, kneader, extruder, omnipotent mixer etc. to mix above-mentioned ball shape silver powder (A) and above-mentioned flake silver powder (B) and the above-mentioned epoxy resin (C) that can contain as required, above-mentioned fatty acid silver salt (D), above-mentioned cationic curing agent (E), above-mentioned solvent (F) and additive.
[solar battery cell]
Solar battery cell of the present invention, possesses surface electrode, semiconductor substrate and the backplate of sensitive surface side, and above-mentioned surface electrode and/or above-mentioned backplate are by being used above-mentioned conductive composition of the present invention to form.
At this, for solar battery cell of the present invention, because the conductive composition of the invention described above can be applied to the formation of the backplate of full back electrode type (so-called back side contact-type) solar cell, therefore, also can be applied to full back electrode type solar cell.
Below, use Fig. 1 to describe the formation of solar battery cell of the present invention.
As shown in Figure 1, solar battery cell 1 of the present invention possesses: the surface electrode 4 of sensitive surface side, p layer 5 engage the pn forming and engage silicon substrate 7 and backplate 6 with n layer 2.
In addition, as shown in Figure 1, for solar battery cell 1 of the present invention, in order to reduce reflectivity, preference is as wafer surface implemented to etching and being formed pyramidal matte, thereby possesses antireflection film 3.
<surface electrode/backplate>
The surface electrode that solar battery cell of the present invention possesses and backplate, as long as wherein any one or both use conductive composition of the present invention to form, the configuration of electrode (spacing), shape, highly, width etc. is not particularly limited.It should be noted that, the height of electrode is usually designed to several microns to tens of microns, uses the aspect ratio of the electrode of conductive composition formation of the present invention to be adjusted to more than 0.4.
At this, as shown in Figure 1, conventionally there is several surface electrodes and backplate, for example, in the present invention, the part that can be only a plurality of surface electrodes is formed by conductive composition of the present invention, can be also that a part for a plurality of surface electrodes and a part for a plurality of backplates are formed by conductive composition of the present invention.
<antireflection film>
The film that the antireflection film that solar battery cell of the present invention can possess forms for the part that does not form surface electrode at sensitive surface (thickness: approximately 0.05 μ m ~ approximately 0.1 μ m), by forming such as silicon oxide layer, silicon nitride film, oxidation titanium film, their stacked film etc.
<silicon substrate>
The silicon substrate that solar battery cell of the present invention possesses is not particularly limited, can use the known silicon substrate (thickness of slab: approximately 100 μ m ~ approximately 450 μ m) that is used to form solar cell, in addition, can be also any one silicon substrate in monocrystalline or polycrystalline.
In addition, above-mentioned silicon substrate has pn and engages, and this face side that is illustrated in the first conductive-type semiconductor substrate is formed with the second conductivity type sensitive surface Impurity Diffusion region.It should be noted that, in the situation that the first conductivity type is N-shaped, the second conductivity type is p-type, and in the situation that the first conductivity type is p-type, the second conductivity type is N-shaped.
At this, as the impurity that p-type is provided, can enumerate boron, aluminium etc., as the impurity that N-shaped is provided, can enumerate phosphorus, arsenic etc.
For solar battery cell of the present invention, because surface electrode and/or backplate are used conductive composition of the present invention and are formed, therefore, can make the aspect ratio of electrode reach more than 0.4, and can extract efficiently the electromotive force that produced by light with the form of electric current.
The manufacture method of solar battery cell of the present invention is not particularly limited, and can enumerate the method that possesses following operation: conductive composition of the present invention is applied on silicon substrate and the wiring that forms wiring forms operation and resulting wiring is heat-treated and formed the heat treatment step of electrode (surface electrode and/or backplate).
It should be noted that, in the situation that solar battery cell of the present invention possesses antireflection film, antireflection film can form by known methods such as plasma CVD methods.
Below, wiring formation operation, heat treatment step are elaborated.
<wiring forms operation>
Above-mentioned wiring forms operation for conductive composition of the present invention being applied to the operation that forms wiring on silicon substrate.
At this, as coating process, particularly, can enumerate such as ink-jet, silk screen printing, photogravure, hectographic printing, letterpress etc.
<heat treatment step>
Above-mentioned heat treatment step is for forming to above-mentioned wiring the operation that the wiring (electrode) that obtains conductivity is heat-treated in the wiring obtaining in operation.
At this, above-mentioned heat treatment is not particularly limited, and is preferably the extremely processing of tens of minutes of heating (calcining) several seconds at the temperature of 150 ~ 800 ℃.Temperature and time within the scope of this time, even the in the situation that of being formed with antireflection film on silicon substrate, also can easily form electrode by the method for burning.
In the present invention, owing to using conductive composition of the present invention, therefore, even also can implement good heat treatment (calcining) under low temperature (approximately 150 ℃ ~ approximately 500 ℃).
It should be noted that, in the present invention, form being routed under ultraviolet ray or ultrared irradiation of obtaining in operation also can form electrode in above-mentioned wiring, therefore, above-mentioned heat treatment step can be the operation of utilizing ultraviolet ray or infrared radiation.
Embodiment
Below, use embodiment at length to describe conductive composition of the present invention.But the present invention is not limited to this.
(embodiment 1 ~ 15, comparative example 1 ~ 3)
According to the ratio of components shown in following table 1, in mixer, add the ball shape silver powder shown in following table 1 etc., they are mixed, prepare thus conductive composition.
<silk screen printing>
By silk screen printing, the conductive composition preparing is applied to silicon substrate (silicon single crystal wafer, LS-25TVA, 156mm * 156mm * 200 μ m, the manufacture of chemical industrial company of SHIN-ETSU HANTOTAI) upper, forms wiring (live width: 80 μ m, length: 5cm).
Utilize light microscope to observe dry (calcining) the front wiring forming by silk screen printing.
Result, using break, crawl, ooze out with netted vestige all unconfirmed to situation as the extremely good situation of printing, be evaluated as " ◎ ", using unconfirmed to broken string but confirm crawl, ooze out with netted vestige in any one situation as the good situation of printing, be evaluated as " zero ", using unconfirmed to broken string but confirm crawl, ooze out with netted vestige in arbitrarily two or more situations as the poor situation of printing, be evaluated as " △ ", the situation using the situation that confirms broken string as printing extreme difference and be evaluated as " * ".The above results is shown in following table 1.
< specific insulation (than resistance) >
By silk screen printing, form after wiring, utilize baking oven to be dried 30 minutes at 200 ℃, make the sample of the solar battery cell of the wiring (electrode) that is formed with conductivity.
For the sample of each solar battery cell of making, utilization is used four terminal four probe methods of resistrivity meter (manufacture of ロ レス タYiGP， Mitsubishi Chemical Ind) to measure the specific insulation of electrode.The results are shown in following table 1.
<aspect ratio (after calcining)>
For the sample with above-mentioned each solar battery cell of similarly making, utilize laser microscope to observe electrode, measure height and width, obtain aspect ratio (height/width).
At this, by aspect ratio, be to be evaluated as aspect ratio high (can meet) more than 0.4 and lower than 0.8 sample, aspect ratio is evaluated as to aspect ratio low (can not meet) lower than 0.4 sample.These be the results are shown in following table 1.
Table 1 (3)
Each composition in table 1 is used following composition.
Ball shape silver powder A-1:Ag2-1C (average grain diameter: 1.0 μ m, DOWA ェ レ Network トロニク ス company manufactures)
Ball shape silver powder A-2:AgC-103 (average grain diameter: 1.5 μ m, Bo Fen industrial group of FUKUDA METAL manufactures)
Flake silver powder B-1:Ag-XF301K (average thickness: 0.1 μ m, apparent density: 0.82g/cm
3, Bo Fen industrial group of FUKUDA METAL manufactures)
Flake silver powder X:AgC-A (average thickness: 0.3 μ m, apparent density: 1.82g/cm
3, Bo Fen industrial group of FUKUDA METAL manufactures)
Bisphenol A type epoxy resin C1-1:YD-019 (epoxide equivalent: 2400 ~ 3300g/eq, chemical company of Nippon Steel manufactures)
Polyalcohols glycidol fundamental mode epoxy resin C2-1: polyethyleneglycol diglycidylether (Na ガ セ ケ ムテツク ス company manufactures for EX-821, epoxide equivalent: 185g/eq)
PO addition epoxy resin C3-1: expoxy propane addition bisphenol A type epoxy resin (ADEKA company manufactures for epoxide equivalent: 260g/eq, EP-4000S)
PO addition epoxy resin C3-2:350g/eq, expoxy propane addition bisphenol A type epoxy resin (EP-4010S, ADEKA company manufactures)
Isobutyric acid silver salt: first, 50g silver oxide (manufacture of Japan chemical industrial company), 38g isobutyric acid (manufacture of Northeast chemical company) and 300g methylethylketone (MEK) are put in ball mill, at room temperature stirred and it was reacted in 24 hours.Then, by suction filtration, remove MEK, by the powder for drying obtaining, prepare thus white isobutyric acid silver salt.
Neodecanoic acid silver salt: first, 50g silver oxide (manufacture of Japan chemical industrial company), 74.3g neodecanoic acid (manufacture of Japan Synesis Company) and 300g methylethylketone (MEK) are dropped in ball mill, at room temperature stir and it was reacted in 24 hours.Then, by suction filtration, remove MEK, by the powder for drying obtaining, prepare thus white neodecanoic acid silver salt.
2-hydroxy-iso-butyric acid silver salt: first, the 2-hydroxy-iso-butyric acid of 50g silver oxide (manufacture of Japan chemical industrial company), 45g (Tokyo changes into company and manufactures) and 300g methylethylketone (MEK) are put in ball mill, at room temperature stirred and it was reacted in 24 hours.Then, by suction filtration, remove MEK, by the powder for drying obtaining, prepare thus white 2-hydroxy-iso-butyric acid silver salt.
2,2-dihydroxymethyl n-butyric acie silver salt: first, by 2 of 50g silver oxide (manufacture of Japan chemical industrial company), 64g, 2-dihydroxymethyl n-butyric acie (Tokyo changes into company and manufactures) and 300g methylethylketone (MEK) are put in ball mill, at room temperature stir and it are reacted in 24 hours.Then, by suction filtration, remove MEK, by the powder for drying obtaining, 2 of preparation white thus, 2-dihydroxymethyl n-butyric acie silver salt.
1,2,3,4-butane tetracarboxylic acid silver salt: first, by 1,2,3 of 50g silver oxide (manufacture of Japan chemical industrial company), 25.29g, 4-BTCA (new Japanese physics and chemistry company manufacture) and 300g methylethylketone (MEK) are put in ball mill, at room temperature stir and it are reacted in 24 hours.Then, by suction filtration, remove MEK, by the powder for drying obtaining, 1,2,3 of preparation white thus, 4-butane tetracarboxylic acid silver salt.
Curing agent: the aromatic series sulfonium salt (manufacture of Sl-100L ，San Xin chemical industrial company) being represented by above formula (1)
Solvent: alpha-terpineol
Result is as shown in Table 1 known, the comparative example 1 that only uses flake silver powder (B) to prepare, and owing to observing broken string, therefore, and printing extreme difference, aspect ratio is also low to moderate and cannot measures, and specific insulation also increases.
In addition we know, and with ball shape silver powder (A) and the comparative example 2 that does not belong to the flake silver powder of flake silver powder (B), compare with comparative example 1, although make moderate progress on the whole, printing is still poor, and aspect ratio is also low, and specific insulation also increases.
In addition we know, the comparative example 3 that only uses ball shape silver powder (A) to prepare, although printing is good and specific insulation also reduces, aspect ratio reduces.
On the other hand, known and with ball shape silver powder (A) and flake silver powder (B) and the embodiment 1 ~ 15 of preparation, printing is good and aspect ratio is also high, and specific insulation also reduces.
In addition we know, add fatty acid silver salt and the embodiment 4 ~ 15 for preparing, compare with embodiment 1, specific insulation reduces, and aspect ratio also increases slightly.
Claims (11)
1. a solar cell current collector formation conductive composition, it contains the ball shape silver powder that average grain diameter is 0.5 ~ 5.0 μ m (A) and average thickness is that 0.05 ~ 0.2 μ m and apparent density are 0.4 ~ 1.1g/cm
3flake silver powder (B).
2. solar cell current collector formation conductive composition as claimed in claim 1, wherein, the content of described flake silver powder (B) is below 30 quality % with respect to the gross mass of described ball shape silver powder (A) and described flake silver powder (B).
3. solar cell current collector formation conductive composition as claimed in claim 1 or 2, it also contains epoxy resin (C).
4. the solar cell current collector formation conductive composition as described in any one in claim 1 ~ 3, it also contains fatty acid silver salt (D).
5. the solar cell current collector formation conductive composition as described in claim 3 or 4, wherein, described epoxy resin (C) is at least that epoxide equivalent is that bisphenol A type epoxy resin (C1) and the epoxide equivalent of 1500 ~ 4000g/eq is the polyalcohols glycidol fundamental mode epoxy resin (C2) below 1000g/eq.
6. the solar cell current collector formation conductive composition as described in claim 4 or 5, wherein, described fatty acid silver salt (D) is the polycarboxylic acid silver salt (D2) of the carboxylic acid silver salt's groups (COOAg) more than having carboxylic acid silver salt's group (COOAg) and each more than one fatty acid silver salt (D1) of hydroxyl (OH) and/or having three.
7. solar cell current collector formation conductive composition as claimed in claim 6, wherein, described fatty acid silver salt (D1) is 2,2-dihydroxymethyl n-butyric acie silver salt and/or 2-hydroxy-iso-butyric acid silver salt.
8. the solar cell current collector formation conductive composition as described in claim 6 or 7, wherein, described polycarboxylic acid silver salt (D2) is 1,2,3,4-butane tetracarboxylic acid silver salt.
9. the solar cell current collector formation conductive composition as described in any one in claim 3 ~ 8, wherein, the content of described epoxy resin (C) is 2 ~ 20 mass parts with respect to total 100 mass parts of described ball shape silver powder (A) and described flake silver powder (B).
10. the solar cell current collector formation conductive composition as described in any one in claim 4 ~ 9, wherein, the content of described fatty acid silver salt (D) is 0.1 ~ 10 mass parts with respect to total 100 mass parts of described ball shape silver powder (A) and described flake silver powder (B).
11. 1 kinds of solar battery cells, it possesses surface electrode, semiconductor substrate and the backplate of sensitive surface side, and described surface electrode and/or described backplate require in 1 ~ 10 the solar cell current collector described in any one to form by right to use to form with conductive composition.
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| CN104335358A (en) * | 2012-07-18 | 2015-02-04 | 横滨橡胶株式会社 | Conductive composition and solar cell |
| CN110692126A (en) * | 2018-03-30 | 2020-01-14 | 京瓷株式会社 | Resin composition for bonding electronic component, method for bonding small chip component, electronic circuit board, and method for manufacturing electronic circuit board |
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| CN110692126A (en) * | 2018-03-30 | 2020-01-14 | 京瓷株式会社 | Resin composition for bonding electronic component, method for bonding small chip component, electronic circuit board, and method for manufacturing electronic circuit board |
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