CN102403047B - Paste for solar cell electrode and electrode using the same and solar cell using the same - Google Patents
Paste for solar cell electrode and electrode using the same and solar cell using the same Download PDFInfo
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- CN102403047B CN102403047B CN201010597609.3A CN201010597609A CN102403047B CN 102403047 B CN102403047 B CN 102403047B CN 201010597609 A CN201010597609 A CN 201010597609A CN 102403047 B CN102403047 B CN 102403047B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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Abstract
Disclosed herein are pastes for solar cell electrodes exhibiting superior printability and conversion efficiency. The paste includes (a) a conductive powder, (b) a glass frit, (c) an organic vehicle, and (d) metal oxide particles comprising nanometer scale particles having an average particle diameter (D50) of 15 to 50 nm and micron scale particles having an average particle diameter (D50) of 0.1 to 2 [mu]m. The present invention also discloses an electrode formed of the paste for solar cell electrodes, and a solar cell comprising the electrode, which has improved paste printability while exhibiting superior conversion efficiency.
Description
Technical field
The present invention relates to a kind of electrode of solar battery slurry and use its solar cell.More specifically, the present invention relates to a kind of electrode of solar battery slurry, it comprises nanometer and micro-sized metal oxide particle and excellent impressionability and conversion efficiency is shown, the invention still further relates to the solar cell using this slurry simultaneously.
Background technology
Along with fossil fuel as oil and coal soon will be exhausted, the solar cell of the sunlight energy is as an alternative utilized to attract attention.Forming solar cell becomes the photovoltaic effect of the p-n junction of electricity to produce electric energy converting photons to utilize.In solar cells, front electrode and rear electrode are formed at respectively and have on the semiconductor wafer of p-n junction or the front surface of substrate and rear surface.Then, utilize the photovoltaic effect injecting the initiation p-n junction of wafer and the electronics produced by the photovoltaic effect of p-n junction provides electric current, this electric current is extremely outside by electrode stream.The electrode of solar cell is formed on wafer by coating, patterning and sintered electrode slurry.
The standard evaluating solar cell quality is conversion efficiency.The conversion efficiency of solar cell is the value that an instruction incident light converts the conversion amount of electric energy to, is expressed as the ratio of maximum output and projectile energy.Electrode characteristic improves a key factor of conversion efficiency of solar cell, and the front electrode slurry being designed to receive incident sunlight generally includes conductive particle, glass frit powder and is provided as the carrier of liquid-carrier.
Recently, the great majority improving conversion efficiency of solar cell make great efforts all to concentrate in these components of slurry.
But, traditionally solar cell size being printed on before and after wafer on side and after drying, during sintering, silver ions permeate silicon wafer, and making prepared solar cell cause series and parallel connections resistance variation due to the low distribution of the ion on electrode, the conversion efficiency of solar cell can not significantly be improved thus.
Another conventional method adopts the Zinc oxide powder of 7 ~ 100nm average diameter, and have some shortcomings, the viscosity as slurry increases, and cause pattern to lose, and conversion efficiency reduces due to impressionability difference.
Because inventor developed the solar cell of a kind of electrode of solar battery slurry and this slurry of use, it has slurry impressionability of improvement and demonstrates excellent conversion efficiency simultaneously.
Summary of the invention
One aspect of the present invention provides a kind of electrode of solar battery slurry.The metal oxide particle that this electrode of solar battery slurry comprises (a) electroconductive powder, (b) glass dust, (c) organic carrier and (d) have nanometer and micron particles, the average grain diameter (D50) of this nano-scale particle is 15-50nm, and the average grain diameter (D50) of this micron particles is 0.1-2 μm.
Electroconductive powder comprise in the group being selected from and being made up of silver (Ag), gold (Au), palladium (Pd), platinum (Pt), copper (Cu), chromium (Cr), cobalt (Co), aluminium (Al), tin (Sn), plumbous (Pb), zinc (Zn), iron (Fe), iridium (Ir), osmium (Os), rhodium (Rh), tungsten (W), molybdenum (Mo), nickel (Ni) and tin indium oxide (ITO) one of at least.
Glass dust can comprise flint glass powder, lead-free glass powder or its mixture.And this glass dust can be selected from glass ceramics powder, non-crystalline glass powder and composition thereof.
Organic carrier can comprise organic bond and solvent.
Metal oxide particle can comprise and selects free zinc oxide (ZnO), lead oxide (PbO), cupric oxide (CuO), silica (SiO
2) and titanium oxide (TiO
2) particle composition group in one of at least.
Metal oxide particle can comprise the particle with nanoscale average grain diameter (D50) and the particle with micron order average grain diameter (D50).Nano-scale particle can have the average grain diameter (D50) of 15 ~ 50nm, and is preferably 20 ~ 40nm, and described micron particles can have the average grain diameter (D50) of 0.1 ~ 2, and is preferably 0.1 ~ 1.5 μm.In one embodiment, the amount of nano-scale particle is 5wt% ~ 50wt% relative to the total amount of metal oxide particle.
In one embodiment, electrode of solar battery slurry can comprise the electroconductive powder of (a) 60wt% ~ 90wt%, the glass dust of (b) 1wt% ~ 10wt%, the organic carrier of (c) 8wt% ~ 20wt%, and the nanometer of (d) 1wt% ~ 10wt% and micro-sized metal oxide particle.Electrode of solar battery slurry can comprise additive further, as plasticizer, dispersant, thixotropic agent, viscosity stabiliser, defoamer, pigment, UV stabilizer, antioxidant, coupling agent etc., it can add according to consumption well known to the skilled person.
Provide the electrode formed by this slurry on the other hand.
Also have and provide the solar cell comprising this electrode on the one hand.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of the solar cell adopting slurry according to one exemplary embodiment to produce.
Embodiment
According to an execution mode, electrode of solar battery slurry comprises (a) electroconductive powder, (b) glass dust, (c) organic carrier and (d) nanometer and micro-sized metal oxide particle.
(a) electroconductive powder
Electroconductive powder can comprise conductive organic substance, Conductive inorganic material or its combination.
In one embodiment, electroconductive powder is inorganic powder, and is preferably metal dust.The example of described electroconductive powder can include but not limited to, silver (Ag), gold (Au), palladium (Pd), platinum (Pt), copper (Cu), chromium (Cr), cobalt (Co), aluminium (Al), tin (Sn), plumbous (Pb), zinc (Zn), iron (Fe), iridium (Ir), osmium (Os), rhodium (Rh), tungsten (W), molybdenum (Mo), nickel (Ni) and tin indium oxide (ITO).These electroconductive powders can be used alone or alloy as its two or more types uses.These electroconductive powders also can be used alone or its two or more type combination uses.
In one embodiment, electroconductive powder comprises silver (Ag) particle and can comprise nickel (Ni), cobalt (Co), iron (Fe), zinc (Zn) or copper (Cu) particle further.
Electroconductive powder can have spherical form, flake, combine without solid shape (amorphous shape) or its.In one embodiment, electroconductive powder can have spherical and improve activity coefficient, sintered density and UV transmitance further.
Electroconductive powder can have the average grain diameter (D50) of 0.1 ~ 10 μm, preferably 0.2 ~ 7 μm, more preferably 0.5 ~ 5 μm, and is more preferably 1 ~ 3 μm.Be scattered in isopropyl alcohol (IPA) at electroconductive powder ultrasonic wave under room temperature and measure average grain diameter by Model 1064D (CILAS Co., Ltd.) after lasting 3min.
The amount that electroconductive powder can exist is 60wt% ~ 90wt% relative to slurry total weight.Electroconductive powder consumption, within the scope of this, just may prevent from because resistance increases, conversion efficiency being deteriorated and the amount avoided due to organic carrier reduces and difficulty in formation slurry relatively.Electroconductive powder preferably exists according to the amount of 70wt% ~ 88wt%, and is more preferably 75wt% ~ 82wt%.
(b) glass dust
Glass dust can strengthen adhesive force between electroconductive powder and its lower substrate in burning process process and the deliquescing and reduce sintering temperature further when sintering.
Glass dust can comprise the glass dust of crystallization or amorphous glass dust.Glass dust can be the flint glass powder, lead-free glass powder and composition thereof of any type.Such as, this glass dust can include but not limited to be selected from following material one of at least: zirconia-silicas (ZnO-SiO
2), zinc oxide-boron oxide-silica (ZnO-B
2o
3-SiO
2), zinc oxide-boron oxide-silica-alumina (ZnO-B
2o
3-SiO
2-Al
2o
3), bismuth oxide-silica (Bi
2o
3-SiO
2), bismuth oxide-boron oxide-silica (Bi
2o
3-B
2o
3-SiO
2), bismuth oxide-boron oxide-silica-alumina (Bi
2o
3-B
2o
3-SiO
2-Al
2o
3), bismuth oxide-zinc oxide-boron oxide-silica (Bi
2o
3-ZnO-B
2o
3-SiO
2) and bismuth oxide-zinc oxide-boron oxide-silica-alumina (Bi
2o
3-ZnO-B
2o
3-SiO
2-Al
2o
3) glass dust.
Glass dust can have the average grain diameter (D50) of 0.1 ~ 5 μm, is preferably 0.5 ~ 3 μm.Within the scope of this, the deep solidification when forming electrode by UV radiation can not be interrupted, and can not produce pin hole in developing process.Be scattered in isopropyl alcohol (IPA) at glass dust ultrasonic wave under room temperature and measure average grain diameter by Model 1064D (CILAS Co., Ltd.) after lasting 3min.
In one embodiment, glass dust can have the softening point of 300 ~ 600 DEG C, and is preferably 400 ~ 550 DEG C.
Glass dust exists relative to the consumption of slurry total weight according to 1wt% ~ 10wt%, and is preferably 1wt% ~ 7wt%.Within the scope of this, just conversion efficiency may be prevented to be deteriorated due to the improvement of the resistance of electroconductive powder, sintering character and adhesive force, and after avoiding firing, there is excessive glass dust simultaneously, resistance can be caused to increase for these excessive glass dust and wettability is deteriorated.
(c) organic carrier (carrier)
Organic carrier can comprise for slurry provides the organic bond of liquid properties.In one embodiment, organic carrier (c) can comprise organic bond and solvent.Specifically, organic carrier (c) can comprise the organic bond of 5wt% ~ 40wt% and the solvent of 60wt% ~ 95wt%.In another embodiment, organic carrier (c) can comprise the organic bond of 5wt% ~ 30wt% and the solvent of 70wt% ~ 95wt%.
The example of organic bond includes but not limited to, by the acrylate copolymer obtained as carboxyl generation copolymerization with hydrophilic acrylic monomer; Cellulosic polymer, as ethyl cellulose, hydroxyethylcellulose, hydroxypropyl cellulose and hydroxyethyl hydroxypropyl base cellulose etc.These adhesives can be used alone or use with the mixture of its two or more types.
Solvent can be have 120 DEG C or more high boiling organic solvent.The example of solvent includes but not limited to methyl cellosolve, ethyl cellosolve, butyl cellosolve, fatty alcohol, alpha-terpineol, β-terpinol, dihydroterpineol, ethylene glycol, ethylene glycol monobutyl ether, butylacetic acid cellosolve (butyl cellosolve acetate), 2,2,4-trimethyl-1,3-pentanediol mono isobutyrate (texanol) etc.These solvents can be used alone or use with the mixture of its two or more types.
Organic carrier can exist according to the consumption of 8wt% ~ 20wt% relative to the total weight of slurry, is preferably 10wt% ~ 15wt%.Within the scope of this, just may prevent the dispersion deficiency after slurry preparation or excess stickiness from increasing, this may cause printing difficulty, and may prevent resistance increase and contingent other problem in burning process process.
(d) metal oxide particle
Metal oxide particle improves the contact resistance of electrode, and promotes the crystallization of slurry.
Metal oxide particle can include but not limited to zinc oxide (ZnO), lead oxide (PbO), cupric oxide (CuO), silica (SiO
2) and titanium oxide (TiO
2) in one of at least.
Metal oxide particle can comprise the mixture of the particle of nanoscale average grain diameter (D50) and the particle of micron order average grain diameter (D50).In one embodiment, nanosize metal oxide particle can have the average grain diameter (D50) of 15 ~ 50nm, and is preferably 20 ~ 40nm.In one embodiment, micro-sized metal oxide particle can have the average grain diameter (D50) of 0.1 ~ 2, is preferably 0.1 ~ 1.5.Continue after 3min metal oxide particle ultrasonic wave under room temperature being scattered in isopropyl alcohol (IPA), measure average grain diameter by Model 1064D (CILAS Co., Ltd.).Within the scope of this, slurry just can obtain good activity coefficient and conversion efficiency.
The metal oxide particle be made up of nano-scale particle and micron particles can exist according to the consumption of 1wt% ~ 10wt% relative to the total weight of slurry, and is preferably 1wt% ~ 8wt%.Within the scope of this, just may prevent because sintering character is deteriorated and makes resistance and conversion efficiency be deteriorated during burning process process, and prevent the printing that increases and cause due to resistance and slurry viscosity poor.
In addition, nano-scale particle can exist according to the consumption of 5wt% ~ 50wt% relative to metal oxide particle total weight, is preferably 25wt% ~ 50wt%, and is more preferably 25wt% ~ 40wt%.Within the scope of this, the specific area of metal oxide particle and volume increase and for providing more spaces with the reaction of glass dust, provide required effect thus.
Electrode of solar battery slurry may further include typical additive according to required and strengthen mobile performance, processing characteristics and stability.Additive can include but not limited to plasticizer, dispersant, thixotropic agent, viscosity stabiliser, defoamer, pigment, UV stabilizer, antioxidant, coupling agent etc.These additives are well-known to those skilled in the art, and can be commercially available.
These additives can add according to the consumption of 0.1wt% ~ 5wt% relative to the total weight of slurry, but these consumptions can change according to required.
Other side of the present invention provides the electrode formed by electrode of solar battery slurry and the solar cell comprising this electrode.Fig. 1 shows solar cell according to one exemplary embodiment.
With reference to Fig. 1, rear electrode 210 and front electrode 230 can pass through slurry printing and fire on the wafer comprising p-layer 101 and n-layer 102 or substrate 100 and formed, and it will play the effect of emitter.Such as, the preliminary process process preparing rear electrode 210 continues 10 ~ 60s by the slurry of this printing dry on the rear surface that slurry is printed on wafer 100 and at 200 ~ 400 DEG C and completes.In addition, before preparation, the preliminary process process of electrode 230 can be completed by the slurry on the front surface that slurry is printed in wafer 100 also printed by drying.Subsequently, front electrode 230 and rear electrode 210 can be formed by firing the time of the lasting 30 ~ 50s of wafer 100 at 400 ~ 900 DEG C.
Then, the present invention is described in more detail with reference to embodiment.But, should notice that these embodiments only provide with the object illustrated and are not intended to limit the scope of the invention.
For clarity, the elaboration of apparent details will be removed for those skilled in the art herein.
Embodiment
Component used in following examples and comparative example is described in detail as follows:
A () electroconductive powder: spherical Ag powder, has the average grain diameter (D50) (AG-4-8, Dowa HighTech Co., Ltd.) of 2.0
(b) glass dust
(b1) low melting point flint glass powder, has the average grain diameter of 1.0 and the inversion point (Leaded Glass, PSL1004C, Particlogy Co., Ltd.) of 451 DEG C
(b2) low-melting point lead-less glasses powder, has the average grain diameter of 1.7 and the inversion point (CSF-6, Phoenix PDE) of 317 DEG C
(c) organic carrier: be dissolved in the ethyl cellulose (Dow Chemical Co., Ltd., STD4) in terpinol (Nippon Terpine Co., Ltd.) at 60 DEG C
(d) metal oxide particle
(d1) ZnO powder (Kanto Chemical Co., Ltd.), has the average grain diameter (D50) of 1.2
(d2) ZnO powder (SB Chemical Co., Ltd.), has the average grain diameter (D50) of 30nm
Embodiment 1 ~ 4
The composition of above-mentioned preparation is used with the ratio given in table 1, add the dispersant B YK111 (BYK-chemie) of 0.3 weight portion in addition wherein, the thixotropic agent BYK430 (BYK-chemie) of 0.3 weight portion, the defoamer BYK053 (BYK-chemie) of 0.1 weight portion also mixes with it, then adopt three-roll grinder to mill, be prepared into electrode of solar battery slurry thus.
Comparative example 1
Except not using nanosize metal oxide particle, implement according to the same procedure with embodiment 1.
Comparative example 2
Except not using micro-sized metal oxide particle, implement according to the same procedure with embodiment 1.
Table 1
In embodiment 1 to 4 and comparative example 1 and 2, the electrode of solar battery slurry of each of preparation is deposited on the front surface of wafer according to predetermined pattern by silk screen printing, and dry in UV stove.Subsequently, aluminum slurry be printed in wafer rear surface on and dry according to identical method.The battery prepared according to this process adopts band oven at 400 ~ 900 DEG C, stand burning process process lasts 30 ~ 50s, and adopt CT-801 (Pasan, Co., Ltd.) activity coefficient (FF of each solar cell is measured, %) with conversion efficiency (Eff., %).Result is as shown in table 2.
Table 2
As what can find out from these results, demonstrate excellent activity coefficient and conversion efficiency by the slurry that flint glass powder or lead-free glass powder are mixed with nanoscale and micron order Zinc oxide particles and prepared.
This improvement of activity coefficient and conversion efficiency it is believed that it is due to after being printed in the slurry before and after silicon wafer on side by dry and sintering, during process for cooling process, glass dust and Zinc oxide powder is utilized to improve slurry crystallization, to make slurry crystallization upper and prevent silver (Ag) ion to enter in silicon wafer and caused by the surface distributed improving silver ion in the layer (or emitter layer) of silicon wafer.
Simultaneously, when nanoscale zinc particles mixes according to the consumption of 5wt% ~ 50wt% relative to Zinc oxide particles total weight, the specific area of metal oxide particle and volume increase and provide more spaces to react with glass dust, thus provide required effect.But, when nanoscale zinc particles mixes according to the consumption more than 50wt% relative to Zinc oxide particles total weight, metal oxide particle causes the viscosity of slurry to increase sharply, increase sharply because specific area and volume excessive increases the impressionability the produced pattern loss caused that is deteriorated, and cause activity coefficient and conversion efficiency to be significantly deteriorated thus.
Although described some execution modes in the present invention, these execution modes only provide in the illustrated manner and have been not that anticipation limits the scope of the invention.Should be understood that, its various amendment, change and equivalent way just can be made by those skilled in the art of the present technique and can not depart from the spirit and scope of the present invention.
Claims (9)
1. an electrode of solar battery slurry, comprises: (a) electroconductive powder; (b) glass dust; (c) organic carrier; (d) comprise the metal oxide particle of nano-scale particle and micron particles, the average grain diameter (D50) of described nano-scale particle is 15-50nm, and the average grain diameter (D50) of described micron particles is 0.1-2 μm,
Wherein said nano-scale particle amount is 5wt% ~ 50wt% relative to described metal oxide particle total weight.
2. slurry according to claim 1, wherein said metal oxide particle comprises and selects free zinc oxide (ZnO), lead oxide (PbO), cupric oxide (CuO), silica (SiO
2) and titanium oxide (TiO
2) particle composition group in one of at least.
3. slurry according to claim 1, wherein said electroconductive powder comprise in the group being selected from and being made up of silver (Ag), gold (Au), palladium (Pd), platinum (Pt), copper (Cu), chromium (Cr), cobalt (Co), aluminium (Al), tin (Sn), plumbous (Pb), zinc (Zn), iron (Fe), iridium (Ir), osmium (Os), rhodium (Rh), tungsten (W), molybdenum (Mo), nickel (Ni) and tin indium oxide (ITO) one of at least.
4. slurry according to claim 1, wherein said glass dust comprises flint glass powder, lead-free glass powder or its mixture.
5. slurry according to claim 1, wherein said organic carrier comprises organic bond and solvent.
6. slurry according to claim 1, wherein said pulp bales is containing the described electroconductive powder of (a) 60wt% ~ 90wt%, the described glass dust of (b) 1wt% ~ 10wt%, the described organic carrier of (c) 8wt% ~ 20wt%, and described in (d) 1wt% ~ 10wt%, comprise the metal oxide particle of nano-scale particle and micron particles.
7. slurry according to claim 1, comprises further: the additive being selected from least one type in the group be made up of plasticizer, dispersant, thixotropic agent, viscosity stabiliser, defoamer, pigment, UV stabilizer, antioxidant and coupling agent.
8. an electrode, described electrode is formed by electrode of solar battery slurry according to claim 1.
9. a solar cell, comprises electrode according to claim 8.
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|---|---|---|---|
| KR20100090672 | 2010-09-15 | ||
| KR10-2010-0090672 | 2010-09-15 |
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| CN102403047A CN102403047A (en) | 2012-04-04 |
| CN102403047B true CN102403047B (en) | 2015-07-22 |
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Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2444979B1 (en) |
| JP (1) | JP5568001B2 (en) |
| KR (1) | KR101374359B1 (en) |
| CN (1) | CN102403047B (en) |
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| US9236155B2 (en) | 2013-02-04 | 2016-01-12 | E I Du Pont De Nemours And Company | Copper paste composition and its use in a method for forming copper conductors on substrates |
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| US9666731B2 (en) | 2013-10-21 | 2017-05-30 | Samsung Sdi Co., Ltd. | Composition for solar cell electrodes, electrode fabricated using the same, and solar cell having the electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101373794A (en) * | 2007-08-22 | 2009-02-25 | 中国科学院化学研究所 | Dye sensitization nano-crystal thin-film solar cell photoelectric pole and preparation method thereof |
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| Publication number | Publication date |
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| KR20120028789A (en) | 2012-03-23 |
| KR101374359B1 (en) | 2014-03-18 |
| CN102403047A (en) | 2012-04-04 |
| JP5568001B2 (en) | 2014-08-06 |
| EP2444979A1 (en) | 2012-04-25 |
| JP2012064916A (en) | 2012-03-29 |
| EP2444979B1 (en) | 2013-07-17 |
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