EP2444979B1 - 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 PDF

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Publication number
EP2444979B1
EP2444979B1 EP10195259.6A EP10195259A EP2444979B1 EP 2444979 B1 EP2444979 B1 EP 2444979B1 EP 10195259 A EP10195259 A EP 10195259A EP 2444979 B1 EP2444979 B1 EP 2444979B1
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EP
European Patent Office
Prior art keywords
paste
glass frit
solar cell
particles
oxide
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Application number
EP10195259.6A
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German (de)
English (en)
French (fr)
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EP2444979A1 (en
Inventor
Seok Hyun Jung
Jung Chul Lee
Jae Hwan Oh
Jae Ho Kim
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Cheil Industries Inc
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Cheil Industries Inc
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Publication of EP2444979A1 publication Critical patent/EP2444979A1/en
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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

Definitions

  • the present invention relates to a paste for solar cell electrodes and solar cells using the same. More particularly, the present invention relates to a paste for solar cell electrodes, which includes nanometer and micron scale metal oxide particles and exhibits superior printability and conversion efficiency, and to solar cells using the same.
  • a solar cell is formed to generate electric energy using the photovoltaic effect of a p-n junction which converts photons into electricity.
  • a front electrode and a rear electrode are formed on a front surface and a rear surface of a semiconductor wafer or substrate with the p-n junction, respectively. Then, the photovoltaic effect of the p-n junction is induced by sunlight entering the wafer and electrons generated by the photovoltaic effect of the p-n junction provide an electric current flowing to the outside through the electrodes.
  • the electrodes of the solar cell are formed on the wafer by applying, patterning, and burning a paste for electrodes.
  • the conversion efficiency of the solar cells is a value that indicates a conversion amount of incident light into electrical energy and is expressed as the ratio of the maximum output to incident energy. Characteristics of electrodes are an important factor in improving the conversion efficiency of the solar cells, and a paste for front electrodes configured to receive incident sunlight generally includes conductive particles, glass frit powders and a vehicle provided as a liquid carrier.
  • EP 1 713 092 A2 disclosing a thick film conductive composition comprising: a) electrically conductive silver powder; b) zinc-containing additive; and c) one or more lead-free glass frits; all dispersed in d) organic medium.
  • the thick film conductor compositions include one or more electrically functional powders and one or more glass frits dispersed in an organic medium.
  • Another conventional method using 7 to 100 nm average diameter zinc oxide powder suffers disadvantages such as an increase in viscosity of pastes, pattern losses due to poor printability, and decrease in conversion efficiency.
  • the inventors developed a paste for solar cell electrodes and a solar cell using the same, which has improved paste printability while exhibiting superior conversion efficiency.
  • the paste for solar cell electrodes 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 ⁇ m.
  • the conductive powder may include at least one selected from the group consisting of silver (Ag), gold (Au), palladium (Pd), platinum (Pt), copper (Cu), chromium (Cr), cobalt (Co), aluminum (Al), tin (Sn), lead (Pb), zinc (Zn), iron (Fe), iridium (Ir), osmium (Os), rhodium (Rh), tungsten (W), molybdenum (Mo), nickel (Ni), and indium tin oxide (ITO).
  • the glass frit may include a leaded glass frit, a lead-free glass frit or a mixture thereof. Further, the glass frit may be selected from a crystallized glass frit, a non-crystallized glass frit, and a mixture thereof.
  • the organic vehicle may include an organic binder and a solvent.
  • the metal oxide particles may include at least one selected from the group consisting of zinc oxide (ZnO), lead oxide (PbO), copper oxide (CuO), silicon oxide (SiO 2 ), and titanium oxide (TiO 2 ) particles.
  • the metal oxide particles may include particles having a nanometer scale average particle diameter (D50), and particles having a micron scale average particle diameter (D50).
  • the nanometer scale particles may have an average particle diameter (D50) of ⁇ 15 to ⁇ 50 nm, and preferably ⁇ 20 to ⁇ 40 nm
  • the micron scale particles may have an average particle diameter (D50) of ⁇ 0.1 to ⁇ 2 ⁇ m, and preferably 0.5 to ⁇ 1.5 ⁇ m.
  • the nanometer scale particles may be present in an amount of ⁇ 5 to ⁇ 50 wt% with respect to a total amount of the metal oxide particles.
  • the paste for solar cell electrodes may include (a) ⁇ 60 to ⁇ 90 wt% of the conductive powder, (b) ⁇ 1 to ⁇ 10 wt% of the glass frit, (c) ⁇ 8 to ⁇ 20 wt% of the organic vehicle, and (d) ⁇ 1 to ⁇ 10 wt% of the nanometer and micron scale metal oxide particles.
  • the paste for solar cell electrodes may further include additives, such as a plasticizer, a dispersant, a thixotropic agent, a viscosity stabilizer, an anti-foaming agent, a pigment, a UV stabilizer, an antioxidant, a coupling agent, etc., which may be added in amounts well known to those skilled in the art.
  • Another aspect provides an electrode formed of the paste.
  • a further aspect provides a solar cell including the electrode.
  • a paste for solar cell electrodes includes (a) a conductive powder, (b) a glass frit, (c) an organic vehicle, and (d) nanometer and micron scale metal oxide particles.
  • the conductive powder may comprise a conductive organic material, a conductive inorganic material, or a combination thereof.
  • the conductive powder is an inorganic powder, and preferably a metallic powder.
  • the conductive powder may include, but are not limited to, silver (Ag), gold (Au), palladium (Pd), platinum (Pt), copper (Cu), chromium (Cr), cobalt (Co), aluminum (Al), tin (Sn), lead (Pb), zinc (Zn), iron (Fe), iridium (Ir), osmium (Os), rhodium (Rh), tungsten (W), molybdenum (Mo), nickel (Ni), and indium tin oxide (ITO).
  • These conductive powders may be used alone or as an alloy of two or more kinds thereof.
  • These conductive powders may also be used alone or in a combination of two or more kinds thereof.
  • the conductive powder includes silver (Ag) particles and may further include nickel (Ni), cobalt (Co), iron (Fe), zinc (Zn) or copper (Cu) particles.
  • the conductive powder may have a spherical shape, a flake shape, an amorphous shape, or a combination thereof. In one embodiment, the conductive powder may have a spherical shape to further improve fill factor, sintering density and UV transmittance.
  • the conductive powder may have an average particle diameter (D50) of ⁇ 0.1 to ⁇ 10 ⁇ m, preferably ⁇ 0.2 to ⁇ 7 ⁇ m, more preferably ⁇ 0.5 to ⁇ 5 ⁇ m, and still more preferably ⁇ 1 to ⁇ 3 ⁇ m.
  • D50 average particle diameter
  • the average particle diameter was measured by Model 1064D (CILAS Co., Ltd.) after dispersing the conductive powder in isopropyl alcohol (IPA) with ultrasound waves at room temperature for 3 minutes.
  • the conductive powder may be present in an amount of 60 to ⁇ 90 wt% with respect to the total weight of the paste. With the conductive powder in this range, it is possible to prevent deterioration in conversion efficiency due to an increase of resistance and to prevent difficulty in forming the paste due to a relative reduction in amount of the organic vehicle.
  • the conductive powder is preferably present in an amount of ⁇ 70 to ⁇ 88 wt%, and more preferably ⁇ 75 to ⁇ 82 wt%.
  • the glass frit may enhance adhesion between the conductive powder and the underlying substrate during a burning process and is softened upon sintering to further lower a sintering temperature.
  • the glass frit may comprise a crystallized glass frit or non-crystallized glass frit.
  • the glass frit may be any of a leaded glass frit, a lead-free glass frit and a mixture thereof.
  • the glass frit may include, but are not limited to, at least one selected from zinc oxide-silicon oxide (ZnO-SiO 2 ), zinc oxide-boron oxide-silicon oxide (ZnO-B 2 O 3 -SiO 2 ), zinc oxide-boron oxide-silicon oxide-aluminum oxide (ZnO-B 2 O 3 -SiO 2 -Al 2 O 3 ), bismuth oxide-silicon oxide (Bi 2 O 3 -SiO 2 ), bismuth oxide-boron oxide-silicon oxide (Bi 2 O 3 -B 2 O 3 -SiO 2 ), bismuth oxide-boron oxide-silicon oxide-aluminum oxide (Bi 2 O 3 -B 2 O 3 -SiO 2 ), bis
  • the glass frit may have an average particle diameter (D50) of ⁇ 0.1 to ⁇ 5 ⁇ m, preferably ⁇ 0.5 to ⁇ 3 ⁇ m. Within this range, curing of a deep part through UV irradiation is not interrupted and generation of pinholes does not occur in a developing process when forming the electrodes.
  • the average particle diameter was measured by Model 1064D (CILAS Co., Ltd.) after dispersing the glass frit in isopropyl alcohol (IPA) with ultrasound waves at room temperature for 3 minutes.
  • IPA isopropyl alcohol
  • the glass frit may have a transition point of ⁇ 300 to ⁇ 600°C, and preferably ⁇ 400 to ⁇ 550°C.
  • the glass frit may be present in an amount of ⁇ 1 to ⁇ 10 wt%, and preferably ⁇ 1 to ⁇ 7 wt% with respect to the total weight of the paste. Within the range, it is possible to prevent deterioration in conversion efficiency due to an improvement in resistance, sintering properties and adhesion of the conductive powder, while preventing an excessive amount of glass frit from remaining after burning, which can cause an increase in resistance and deterioration in wettability.
  • the organic vehicle may comprise an organic binder which provides liquid properties to the paste.
  • the organic vehicle (c) may comprise an organic binder and a solvent.
  • the organic vehicle (c) may include ⁇ 5 to ⁇ 40 wt% of the organic binder and ⁇ 60 to ⁇ 95 wt% of the solvent.
  • the organic vehicle (c) may include ⁇ 5 to ⁇ 30 wt% of the organic binder and ⁇ 70 to ⁇ 95 wt% of the solvent.
  • organic binder examples include, but are not limited to, acrylic polymers obtained by copolymerization with hydrophilic acrylic monomers such as a carboxyl group; cellulose polymers, such as ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and hydroxyethyl hydroxypropyl cellulose, and the like. These binders may be may be used alone or in a mixture of two or more kinds thereof.
  • the solvent may be an organic solvent having a boiling point of 120°C or more.
  • the solvent may include, but are not limited to, methyl cellosolve, ethyl cellosolve, butyl cellosolve, aliphatic alcohol, ⁇ -terpineol, ⁇ -terpineol, dihydro-terpineol, ethylene glycol, ethylene glycol mono butyl ether, butyl cellosolve acetate, texanol, etc. These solvents may be used alone or in a mixture of two or more kinds thereof.
  • the organic vehicle may be present in an amount of ⁇ 8 to ⁇ 20 wt% with respect to the total weight of the paste, and preferably ⁇ 10 to ⁇ 15 wt%. Within the range, it is possible to prevent inefficient dispersion or excessive increase in viscosity after preparation of the paste, which can lead to printing difficulty, and to prevent an increase in resistance and other problems that can occur during the burning process.
  • the metal oxide particles improve contact resistance of electrodes and promote crystallization of the paste.
  • the metal oxide particles may include, but are not limited to, at least one of zinc oxide (ZnO), lead oxide (PbO), copper oxide (CuO), silicon oxide (SiO 2 ), and titanium oxide (TiO 2 ).
  • the metal oxide particles include a mixture of particles having a nanometer scale average particle diameter (D50) and particles having a micron scale average particle diameter (D50).
  • the nanometer scale metal oxide particles may have an average particle diameter (D50) of ⁇ 15 to ⁇ 50 nm, and preferably ⁇ 20 to ⁇ 40 nm.
  • the micron scale metal oxide particles have an average particle diameter (D50) of ⁇ 0.1 to ⁇ 2 ⁇ m, preferably ⁇ 0.1 to ⁇ 1.5 ⁇ m.
  • the average particle diameter was measured by Model 1064D (CILAS Co., Ltd.) after dispersing the metal oxide particles in isopropyl alcohol (IPA) with ultrasound waves at room temperature for 3 minutes. Within this range, the paste may have good fill factor and conversion efficiency.
  • IPA isopropyl alcohol
  • the metal oxide particles formed of the nanometer scale particles and the micron scale particles may be present in an amount of ⁇ 1 to ⁇ 10 wt% with respect to the total weight of the paste, and preferably, in an amount of ⁇ 1 to ⁇ 8 wt%. Within this range, it is possible to prevent deterioration in resistance and conversion efficiency due to deterioration in sintering properties during the burning process, and to prevent poor printing due to an increase in resistance and viscosity of the paste.
  • the nanometer scale particles may be present in an amount of ⁇ 5 to ⁇ 50 wt% with respect to the total weight of the metallic oxide particles, preferably ⁇ 25 to ⁇ 50 wt%, and still more preferably ⁇ 25 to ⁇ 40 wt%. Within this range, the specific surface area and volume of the metal oxide particles increase to provide more spaces for reaction with the glass frit, thereby providing desired effects.
  • the paste for solar cell electrodes may further include typical additives, as needed, to enhance flow properties, process properties, and stability.
  • the additives may include, but are not limited to, a plasticizer, a dispersant, a thixotropic agent, a viscosity stabilizer, an anti-foaming agent, a pigment, a UV stabilizer, an antioxidant, a coupling agent, etc. These additives may be used alone or as a mixture of two or more kinds thereof. These additives are well known to those skilled in the art and are commercially available.
  • additives may be added in an amount of ⁇ 0.1 to ⁇ 5wt% with respect to the total weight of the paste, but this amount may be changed, as needed.
  • FIG. 1 shows a solar cell according to one exemplary embodiment of the invention.
  • a rear electrode 210 and a front electrode 230 may be formed by printing and burning the paste on a wafer or substrate 100 that includes a player 101 and an n-layer 102, which will serve as an emitter.
  • a preliminary process for preparing the rear electrode 210 is performed by printing the paste on the rear surface of the wafer 100 and drying the printed paste at 200 to 400°C for 10 to 60 seconds.
  • a preliminary process for preparing the front electrode 230 may be performed by printing the paste on the front surface of the wafer 100 and drying the printed paste. Then, the front electrode 230 and the rear electrode 210 may be formed by burning the wafer 100 at 400 to 900°C for 30 to 50 seconds.
  • Example 2 The same process as in Example 1 was carried out except that the nanometer scale metal oxide particles were not used.
  • Example 1 The same process as in Example 1 was carried out except that the micron scale metal oxide particles were not used.
  • Each of the pastes for solar cell electrodes prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was deposited in a predetermined pattern on a front surface of a wafer by screen printing, and dried in a UV furnace. Then, an aluminum paste was printed over the rear surface of the wafer and dried by the same method. Cells prepared by this process was subjected to a burning process at 400 to 900°C for 30 to 50 seconds using a belt type furnace, and fill factor (FF, %) and conversion efficiency (eft, %) of each solar cell were measured using CT-801 (Pasan, Co., Ltd.). The results are shown in Table 2. Table 2 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 FF (%) 74.1 71.5 72.2 73.15 60.8 51.3 Eff. (%) 17.1 16.675 16.625 17.005 13.3 11.21
  • the pastes prepared by mixing the leaded or lead-free glass frit with nanometer scale and micron scale zinc oxide particles exhibited superior fill factors and conversion efficiency.
  • Such improvement in fill factor and conversion efficiency is believed to be due to promotion of paste crystallization by the glass frit and zinc oxide powder during a cooling process after drying and sintering the paste printed on the front and rear sides of the silicon wafer such that the paste is crystallized on a layer (or an emitter layer) of the silicon wafer to prevent silver (Ag) ions from entering the silicon wafer and to improve surface distribution of the silver ions.
  • the nanometer scale zinc oxide particles were mixed in an amount of 5 to 50 wt% with respect to the total weigh of zinc oxide particles, the specific surface area and volume of the metal oxide particles increased to provide more spaces for reacting with the glass frit, thereby providing desired effects.
  • the mixed amount of the nanometer scale zinc oxide particles exceeded 50 wt% with respect to the total weigh of zinc oxide particles, the metal oxide particles caused rapid increase in viscosity of the paste and in pattern loss resulting from poor printability due to excessive increase in specific surface area and volume and, thereby causing significant deterioration in fill factor and conversion efficiency.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Photovoltaic Devices (AREA)
EP10195259.6A 2010-09-15 2010-12-15 Paste for solar cell electrode and electrode using the same and solar cell using the same Active EP2444979B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR20100090672 2010-09-15

Publications (2)

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EP2444979A1 EP2444979A1 (en) 2012-04-25
EP2444979B1 true EP2444979B1 (en) 2013-07-17

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EP (1) EP2444979B1 (ko)
JP (1) JP5568001B2 (ko)
KR (1) KR101374359B1 (ko)
CN (1) CN102403047B (ko)

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KR101557536B1 (ko) * 2012-12-21 2015-10-06 제일모직주식회사 태양전지 전극용 페이스트 조성물 및 이로부터 제조된 전극
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
KR101596548B1 (ko) * 2013-03-27 2016-02-22 제일모직주식회사 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
KR101648242B1 (ko) * 2013-03-27 2016-08-12 제일모직주식회사 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
KR101396444B1 (ko) * 2013-05-06 2014-05-22 한화케미칼 주식회사 태양전지의 전극의 제조방법 및 이를 이용한 태양전지
KR101590228B1 (ko) * 2013-07-19 2016-01-29 제일모직주식회사 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
KR101648253B1 (ko) * 2013-09-13 2016-08-12 제일모직주식회사 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
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
KR20150054352A (ko) * 2013-11-12 2015-05-20 엘지전자 주식회사 유리 프릿 조성물 및 이를 포함하는 태양 전지 전극용 페이스트 조성물, 그리고 태양 전지 모듈
CN103559940A (zh) * 2013-11-14 2014-02-05 盐城工学院 一种铜系电子浆料及其制备方法和应用
CN103714912B (zh) * 2013-12-30 2016-04-20 无锡市儒兴科技开发有限公司 一种uv环保型硅太阳能电池背场铝浆的制备方法
KR101693078B1 (ko) * 2014-05-15 2017-01-05 제일모직주식회사 태양전지 전극 형성용 조성물 및 이로부터 제조된 전극
KR101721731B1 (ko) * 2014-07-11 2017-03-31 삼성에스디아이 주식회사 태양전지 전극용 페이스트 및 이로부터 제조된 전극
CN104157327B (zh) * 2014-08-05 2017-09-05 上海蓝沛新材料科技股份有限公司 一种应用于低温共烧陶瓷的灌孔导电金浆及其制备方法
CN104200865B (zh) * 2014-08-05 2017-09-05 上海蓝沛新材料科技股份有限公司 一种应用于低温共烧陶瓷的表面导电金浆及其制备方法
KR101598501B1 (ko) * 2014-08-25 2016-03-02 한국에너지기술연구원 실버프린팅을 이용한 태양전지의 투명전극의 제조방법과 이를 이용한 태양전지의 제조방법
US10636540B2 (en) 2015-03-27 2020-04-28 Heraeus Deutschland GmbH & Co. KG Electro-conductive pastes comprising an oxide additive
EP3076401A1 (en) 2015-03-27 2016-10-05 Heraeus Deutschland GmbH & Co. KG Electro-conductive pastes comprising a metal compound
GB201520077D0 (en) 2015-11-13 2015-12-30 Johnson Matthey Plc Conductive track or coating
WO2018032351A1 (en) * 2016-08-16 2018-02-22 Zhejiang Kaiying New Materials Co., Ltd. Thick-film paste for front-side metallization in silicon solar cells
CN106935311A (zh) * 2017-04-14 2017-07-07 北京市合众创能光电技术有限公司 一种低烧结温度的光伏导电油墨
EP4073008A2 (en) * 2019-12-12 2022-10-19 Bert Thin Films, LLC Pastes for solar cells, solar cells, and methods of making same
CN114203334A (zh) * 2021-11-25 2022-03-18 大连海外华昇电子科技有限公司 一种水性晶体硅太阳能电池用背面铝浆及其制备方法

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Also Published As

Publication number Publication date
KR20120028789A (ko) 2012-03-23
EP2444979A1 (en) 2012-04-25
CN102403047B (zh) 2015-07-22
CN102403047A (zh) 2012-04-04
JP5568001B2 (ja) 2014-08-06
JP2012064916A (ja) 2012-03-29
KR101374359B1 (ko) 2014-03-18

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