CN108463500A - Conductive composition - Google Patents
Conductive composition Download PDFInfo
- Publication number
- CN108463500A CN108463500A CN201780006329.0A CN201780006329A CN108463500A CN 108463500 A CN108463500 A CN 108463500A CN 201780006329 A CN201780006329 A CN 201780006329A CN 108463500 A CN108463500 A CN 108463500A
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- Prior art keywords
- conductive composition
- cellulose
- electrode
- molecular weight
- average molecular
- Prior art date
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- 230000000149 penetrating effect Effects 0.000 description 1
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- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 238000010008 shearing Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
A kind of conductive composition being used to form electrode is provided through the invention.The conductive composition includes electroconductive powder, cellulose-based resin, butyral system resin and decentralized medium.The number-average molecular weight M of cellulose-based resinxFor 55000≤Mx, the number-average molecular weight M of butyral system resinyFor My≤100000。
Description
Technical field
The present invention relates to a kind of conductive compositions.More specifically, it is related to one kind to can be used in forming solar cell
Deng electrode pattern conductive composition.
In addition, this international application is advocated based on the Japanese patent application 2016- to file an application on January 12nd, 2016
No. 003756 priority, all the contents of the application are incorporated to as reference in this specification.
Background technology
From the viewpoint of the raising and the saving energy of environmental consciousness in recent years, the universal of solar cell rapidly promotes, with
It, it is desirable that the solar energy of better than the cellular construction of previous higher performance, i.e. photoelectric conversion efficiency and high-power cellular construction
Battery.As a scheme for realizing the requirement, the light for the every unit of cells area for expanding solar cell can be enumerated
The method of area.For example, in the light-receiving surface of solar cell, it is (non-as shading light part to be formed with the part of light-receiving surface electrode
Light part), thus as a method for expanding light-receiving area, desirably form the filament in the wire electrode of light-receiving surface
Change (fine line (fine line) change).
On the light-receiving surface at present as the so-called crystallization silicon type solar cell of mainstream, for typical, it be provided with and include
The filament formed by conductors such as silver finger-like (current collection use) electrode and the busbar electrode that is connect with the finger electrode.Hereinafter,
Those electrodes are referred to as light-receiving surface electrode.This light-receiving surface electrode contain the electroconductive powders such as the silver as conductor ingredient and
Include organic matchmaker's liquid (vehicle) ingredient of organic bond and solvent, and by the way that paste will be prepared into (comprising pulp-like, oil
Ink-like) material (hereinafter also referred to " conductive composition ", referred to as " composition " etc.) using the methods of silk screen print method with
Defined electrode pattern is printed on the light-receiving surface of solar cell (unit), is fired, to be formed.As in order to be formed
The light-receiving surface electrode of this solar cell and the relevant prior art of conductive composition used, such as patent text can be enumerated
Offer 1~patent document 3.
Existing technical literature
Patent document
Patent document 1：Japanese patent application discloses 2007-19106 bulletins
Patent document 2：Japanese patent application discloses 2013-165056 bulletins
Patent document 3：Japanese patent application discloses 2011-66134 bulletins
Invention content
Technical problems to be solved by the inivention
As described above, above-mentioned conductive composition is printed on light-receiving surface, thus its viscosity using the methods of silk screen print method
There is range appropriate.For example, in the case where being printed using mask (sieve etc.), it is desirable that have and show good mobility
And composition is made to be easy to leak out the viscosity characteristics of (and then the defects of broken string is less likely to occur) from the mask.In addition, via covering
After film is printed with defined pattern (be coated on light-receiving surface after in the state of), it is desirable that display inhibits the unexcellent of line width
The expansion (relaxation) of choosing and the good viscosity that can realize the graph thinning of electrode.
It has been recorded in above-mentioned existing technical literature and line width is formed containing ingredient etc. by research conductive composition
Wiring narrow, aspect ratio is high.However, even by this technology, meet the defects of breaking with fine lineization and inhibition abundant
The horizontal aspect of relevant requirement in recent years is still insufficient, expects further improve.
The present invention proposes that main purpose is to provide a kind of electric conductivity combination being used to form electrode in view of the foregoing
Object, can realize the graph thinning of electrode pattern, and be less likely to occur broken string the defects of.In addition, other be designed to provide
A kind of solar cell device that the function or performance that can be realized by using the conductive composition improve.
Technical solution for solving technical problem
To achieve the goals above, the electric conductivity that can be suitable for forming electrode (electrode pattern) is provided through the invention
Composition.The conductive composition includes electroconductive powder, cellulose-based resin, butyral system resin and decentralized medium.It is above-mentioned
The number-average molecular weight M of cellulose-based resinxFor 55000≤Mx, the number-average molecular weight M of above-mentioned butyral system resinyFor My≤
100000.Above-mentioned conductive composition has the viscosity characteristics suitable for printing.It therefore, can if using the conductive composition
Enough inhibit the defects of broken string and forms thin-line-shaped electrode.
In a kind of preferred mode of conductive composition disclosed herein, the equal molecule of number of above-mentioned butyral system resin
Measure MyNumber-average molecular weight M relative to above-mentioned cellulose-based resinxRatio (My/Mx) it is 0.2≤My/Mx≤1.2.By to become
Above-mentioned specific number-average molecular weight than mode cellulose-based resin and butyral system resin is applied in combination, can be made with higher level
The effect for the defects of graph thinning of electrode breaks with inhibition is simultaneously deposited.
In a kind of preferred mode of conductive composition disclosed herein, the equal molecule of number of above-mentioned cellulose-based resin
Measure MxWith the number-average molecular weight M of above-mentioned butyral system resinyRelationship meet following formula：10000≤My＜ Mx≤100000.Pass through
Make the number-average molecular weight M of butyral system resinyLess than the number-average molecular weight M of cellulose-based resinx, can more suitably play electricity
The graph thinning of pole and effect the defects of inhibiting to break.
In a kind of preferred mode of conductive composition disclosed herein, the content W of above-mentioned butyral system resinyPhase
For the content W of above-mentioned cellulose-based resinxRatio (Wy/Wx) it is 0.2≤Wy/Wx≤1.5.If being in such cellulose-based tree
The ratio between the content of fat and butyral system resin (Wy/Wx) in the range of, then can play better and with cellulose-based resin and
The effect of butyral system resin.
In a kind of preferred mode of conductive composition disclosed herein, above-mentioned conductive composition is totally set as
When 100 mass %, the content W of above-mentioned cellulose-based resinxWith the content W of above-mentioned butyral system resinyTotal amount (Wx+Wy)
For 0.1 mass % or more, 1 mass % or less.If the above situation, then it can make graph thinning and the inhibition of electrode with higher level
The effect of the defects of broken string is simultaneously deposited.
Also include silicone resin in a kind of preferred mode of conductive composition disclosed herein.Pass through this structure
At, compared with the case where not adding silicone resin, can more suitably play the graph thinning of electrode with the defects of inhibit to break
Effect.
In a kind of preferred mode of conductive composition disclosed herein, the metal kind of above-mentioned electroconductive powder is constituted
Class includes any one or two or more elements in nickel, platinum, palladium, silver, copper and aluminium.It, being capable of structure by this composition
At the electrode of excellent electric conductivity.
In a kind of preferred mode of conductive composition disclosed herein, shear velocity 0.1s-1When viscosities il0.1
For η0.1≤ 500Pas, shear velocity 10s-1When viscosities il10For 50Pas≤η10。
Herein, above-mentioned viscosity is using the value measured at 25 DEG C using commercially available rotational viscometer.For example, can be by making
It is measured under conditions of shear velocity region as described above used in the rotary viscosimeter (cone-plate type) of the field Plays viscous
Degree.
Conductive composition disclosed herein has viscosity characteristics as described above, as a result, is for example used via printing
When mask is assigned (supply) to the light-receiving surface of solar cell, show good mobility to which composition is from the mask
It leaks out good.Therefore, it is possible to inhibit the generation of broken string (that is, supply bad position).In addition, via mask with defined pattern
After being printed (that is, in the state of after being coated on light-receiving surface), high viscosity (shape maintenance performance) is shown so as to press down
The undesirable expansion of line width processed.That is, until in a period of before being fired, it is coated on the shape of the electrode pattern of light-receiving surface
It is not easy to infiltrate, therefore thin-line-shaped electrode pattern can be formed.Therefore, the conductive composition according to above-mentioned composition, can
It is stably formed the thin-line-shaped electrode of required line width (such as 45 μm or less, preferably 40 μm or less).
The present invention provides the electric conductivity having using recorded in any of the above-described in other aspects for achieving the above object
The semiconductor element for the electrode that composition is formed.For typical case, which can have comprising above-mentioned electric conductivity group
Close the solar cell device of the light-receiving surface electrode of the firing object of object.
Specifically, the conductive composition of the present invention is supplied such as utilizing silk screen print method to semiconductor substrate
Light-receiving surface in the case of, line width finer electrode pattern and electrode can be stably formed.Thus it is for example possible to
Further fine line is realized in the printing of the electrode pattern of various semiconductor elements, reaches semiconductor element to realize
Further miniaturization and highly integrated high-performance semiconductor element.In addition, for example to form solar-electricity by being applied to
The light-receiving surface electrode of pond element, can increase the light income of the per unit area of light-receiving surface, generate more electric power, thus especially
It is preferred that.
Description of the drawings
Fig. 1 is the sectional view of an example for the structure for schematically showing solar cell.
Fig. 2 is the vertical view of the pattern for the electrode for schematically showing the light-receiving surface for being formed in solar cell.
Specific implementation mode
Hereinafter, being illustrated to the preferred embodiment of the present invention.In addition, other than content specifically mentioned in this specification
Technology item and the required item of implementation of the present invention can setting as those skilled in the art based on the prior art
Item is counted to hold.The present invention can be based on the common technical knowledge in technology contents disclosed in this specification and the field come real
It applies.
＜ conductive compositions ＞
It is combined for conductive composition typical case disclosed herein for the electric conductivity of electrode can be formed by firing
Object.The conductive composition includes electroconductive powder, cellulose-based resin, butyral system resin and decentralized medium.Hereinafter, to this
A little each integral parts illustrate.
＜ cellulose-based resins ＞
Conductive composition disclosed herein includes cellulose-based resin.Herein, so-called cellulose-based resin is to include
The concept of cellulose and various cellulose derivatives (modifier etc.).As cellulose derivative, can enumerate will be as cellulose
Component units glucose residue hydroxyl (OH) etherificate or esterification made of derivative.As cellulose ether, second can be illustrated
Base cellulose (EC), methylcellulose (MC), hydroxy ethyl cellulose, hydroxy-methyl cellulose, hydroxy ethylmethylcellulose,
Hydroxy propyl cellulose, HYDROXY PROPYL METHYLCELLULOSE, ethyl hydroxyethyl cellulose, carboxy methyl cellulose etc..It can also
Use the salt of carboxy methyl cellulose sodium salt etc.As cellulose esters, cellulose acetate phthalate ester, nitric acid can be illustrated
Cellulose esters, cellulose acetate ester, cellulose acetate-propionate ester, cellulose acetate butyrate (CAB) ester etc..Wherein, from realize can be into
From the viewpoint of the viscosity characteristics of the good printing of row, EC can be illustrated and be used as cellulose-based tree particularly preferred for the purpose of the present invention
Fat.Above-mentioned cellulose-based resin can be functioned appropriately as organic bond and viscosity (mobility) conditioning agent.
The number-average molecular weight M of cellulose-based resinxFor 55000≤Mx.By by the number-average molecular weight M of cellulose-based resinx
The effect for the defects of being set as 55000 or more, the graph thinning of electrode can be made to break with inhibition with higher level is simultaneously deposited.From zero defect
From the viewpoint of ground obtains fine wire electrodes, the number-average molecular weight M of cellulose-based resinxPreferably 60000 or more, more preferably
65000 or more, and then preferably 70000 or more.In a kind of preferably mode, the number-average molecular weight M of cellulose-based resinxIt can
Think 75000 or more, such as can be 80000 or more.In addition, the number-average molecular weight M of cellulose-based resinxIt is for typical case
200000 hereinafter, preferably 150000 hereinafter, more preferably 120000 hereinafter, in turn be preferably 100000 or less.This place is public
The technology opened can be with the number-average molecular weight M of cellulose-based resinxFor 55000≤Mx≤ 100000 mode and be preferably carried out.
In addition, the number-average molecular weight M as cellulose-based resinx, the value found out by chromatography may be used.
Weight average molecular weight Mw about above-mentioned cellulose-based resinxAs long as the number-average molecular weight M of cellulose-based resinxMeet
Above range is then not particularly limited, and is 10 × 10 for typical4More than.The viscosity of good printing can be carried out from realization
From the viewpoint of characteristic, the weight average molecular weight Mw of cellulose-based resinxPreferably 13 × 104More than, more preferably 15 × 104With
On, and then preferably 18 × 104More than.In addition, the weight average molecular weight Mw of cellulose-based resinxPreferably 30 × 104Hereinafter, more
Preferably 25 × 104Hereinafter, being preferably 20 × 10 in turn4Below.
The number-average molecular weight M of above-mentioned cellulose-based resinxWith weight average molecular weight MwxRelationship be not particularly limited, from combination
The viewpoints such as the stability of object consider, such as molecular weight distribution (Mw can be preferably usedx/Mx) be 4.0 or less (such as 3.0 with
Under) resin.The Mw of cellulose-based resinx/MxPreferably 2.8 hereinafter, more preferably 2.6 hereinafter, in turn be preferably 2.5 or less
(such as 2.4 or less).In addition, theoretically, Mwx/MxIt is 1.0 or more.From the easy availability of raw material or the viewpoint of synthesis easiness
Consider, Mw can usually be preferably usedx/MxFor the cellulose-based resin of 1.1 or more (preferably 1.5 or more).
The content W of cellulose-based resin in conductive compositionxIt is not particularly limited, such as 0.05 matter can be set as
Measure % or more.From the viewpoint of playing the effect using cellulose-based resin better, preferred content WxFor 0.1 matter
Measure % or more, such as 0.2 mass % or more.Additionally, it is preferred that by above-mentioned content Wx5 mass % are set as hereinafter, being more preferably set as 1 matter
Measure % or less (such as 0.5 mass % or less).
＜ butyrals system resin ＞
In conductive composition disclosed herein other than above-mentioned cellulose-based resin, also contain butyral system tree
Fat.Herein, so-called butyral system resin is that polyvinyl alcohol is instigated to be reacted (acetalation) in acid condition with butyraldehyde
And the polymer obtained, further include polymer made of making remaining hydroxyl and other compounds react and import acidic group etc.
Concept.Above-mentioned butyral system resin can be adjusted together with above-mentioned cellulose-based resin as organic bond and viscosity (mobility)
Section agent functions.
The number-average molecular weight M of above-mentioned butyral system resinyIt is 100000 or less.By the way that the number of butyral system resin is divided equally
Son amount My100000 are set as hereinafter, the graph thinning of electrode and effect the defects of inhibiting to break can be made with higher level and deposited.
The number-average molecular weight M of butyral system resinyPreferably 90000 hereinafter, more preferably 70000 or less.In a kind of preferred mode
In, the number-average molecular weight M of butyral system resinyCan be 40000 hereinafter, for example can be 20000 or less.In addition, butyral
It is the number-average molecular weight M of resinyIt is 5000 or more for typical case, preferably 8000 or more, more preferably 12000 or more, in turn
Preferably 15000 or more.Techniques disclosed herein can be with the number-average molecular weight M of butyral system resinyFor 10000≤My≤
100000 mode and be preferably carried out.In addition, the number-average molecular weight M as butyral system resiny, may be used and pass through chromatography
The value that method is found out.
Conductive composition disclosed herein is preferably the number-average molecular weight M of cellulose-based resinxWith butyral system tree
The number-average molecular weight M of fatyRelationship meet following formula：10000≤My＜ Mx≤100000.By keeping the number of butyral system resin equal
Molecular weight MyLess than the number-average molecular weight M of cellulose-based resinx, the graph thinning of electrode can be made to break with inhibition with higher level
The defects of effect and deposit.
In a kind of preferably mode, the number-average molecular weight M of butyral system resinyNumber relative to cellulose-based resin is equal
Molecular weight MxRatio (My/Mx) it is about My/Mx≤ 1.2, preferably My/Mx＜ 1.0, more preferably My/Mx≤0.9.Preferred one
Can be M in kind modey/Mx≤ 0.8, such as can be My/Mx≤0.7.By with as specific number-average molecular weight than side
Cellulose-based resin and butyral system resin is applied in combination in formula, the graph thinning of electrode can be made with higher level and inhibits broken string etc.
The effect of defect is simultaneously deposited.My/MxLower limiting value be not particularly limited, preferably 0.2≤My/Mx, more preferably 0.23≤My/Mx。
As the preference of conductive composition disclosed herein, can illustrate：The number-average molecular weight of cellulose-based resin
MxFor 55000≤Mx≤ 200000 and butyral system resin number-average molecular weight MyFor 5000≤My≤ 100000 composition；It is fine
Tie up the number-average molecular weight M of prime system resinxFor 60000≤Mx≤ 150000 and butyral system resin number-average molecular weight MyIt is 10000
≤MyThe composition of ＜ 60000；The number-average molecular weight M of cellulose-based resinxFor 70000≤Mx≤ 100000 and butyral system tree
The number-average molecular weight M of fatyFor 15000≤My≤ 40000 composition；The number-average molecular weight M of cellulose-based resinxFor 80000≤
Mx≤ 90000 and butyral system resin number-average molecular weight MyFor 18000≤My≤ 22000 composition etc..If in such
In the range of cellulose-based resin and the number-average molecular weight of butyral system resin, then it can make the graph thinning of electrode with higher level
With inhibit broken string effect and deposit.
About the butyralization degree of above-mentioned butyral system resin, as long as the number-average molecular weight M of butyral system resinyIn satisfaction
Range is stated, then is not particularly limited.From the viewpoint of the viscosity characteristics that realization can carry out good printing, for example, 60 rub
You are % or more, can be 63 moles of % or more, such as 65 moles of % or more for typical.Techniques disclosed herein can more than
The butyralization degree for stating cellulose-based resin be, for example, 60 moles of % or more, 80 moles of % or less (for typical for 63 moles of % with
Upper 74 moles of % or less) mode and be preferably carried out.In addition, so-called butyralization degree, refers to constituting butyral units
In total molal quantity of Component units, vinyl alcohol units and vinyl ester units, constitute shared by the Component units of butyral units
The ratio of molal quantity.
The content W of butyral system resin in conductive compositionyIt is not particularly limited, such as 0.01 matter can be set as
Measure % or more.From the viewpoint of playing the effect using butyral system resin better, preferred content WyFor 0.02 matter
Measure % or more, such as 0.04 mass % or more.Additionally, it is preferred that by above-mentioned content Wx3 mass % are set as hereinafter, being more preferably set as
0.7 mass % or less (such as 0.3 mass % or less).
From the viewpoint of effect from performance better and with cellulose-based resin with butyral system resin, butyral system
The content W of resinyContent W relative to cellulose-based resinxRatio (Wy/Wx) it is preferably 0.2≤Wy/Wx.By to become special
Determine content than mode cellulose-based resin and butyral system resin is applied in combination, the graph thinning of electrode can be made with higher level
With broken string the defects of inhibition and deposit.Above-mentioned content ratio (Wy/Wx) it is preferably 0.4 or more, more preferably 0.6 or more.Wy/Wx's
Upper limit value is not particularly limited, preferably Wy/Wx≤ 1.5, more preferably Wy/Wx≤ 1.2, and then preferably Wy/Wx≤1.0.This
Technology disclosed in place for example can be with WxWith WyRelationship be 0.2≤Wy/Wx≤ 1.5 (such as 0.5≤Wy/Wx≤ 1.0) side
Formula and be preferably carried out.
When conductive composition to be totally set as to 100 mass %, the content W of cellulose-based resinxWith butyral system tree
The content W of fatyTotal amount (Wx+Wy) it is preferably 0.02 mass % or more, 10 mass % or less.Preferred total amount (Wx+Wy) be
0.05 mass % or more, such as 0.1 mass % or more.Additionally, it is preferred that by above-mentioned total amount (Wx+Wy) be set as 10 mass % hereinafter,
More preferably 5 mass % are set as hereinafter, being preferably set to 1 mass % in turn hereinafter, being particularly preferably set as 0.5 mass % or less.
＜ electroconductive powders ＞
In conductive composition disclosed herein other than above-mentioned cellulose-based resin and butyral system resin, also wrap
Containing electroconductive powder.Electroconductive powder is the ingredient of the main body of the solid constituent as conductive composition.As electric conductivity powder
End, it may be considered that include the various metals for having required electric conductivity corresponding with purposes and other physical property etc. or its conjunction
The powder of gold etc..As an example for the material for constituting above-mentioned electroconductive powder, can illustrate：Golden (Au), silver-colored (Ag), copper (Cu), platinum
(Pt), metals and their alloy such as palladium (Pd), ruthenium (Ru), rhodium (Rh), iridium (Ir), osmium (Os), nickel (Ni) and aluminium (Al)；Charcoal
Black equal carbonaceous materials；It is expressed as LaSrCoFeO3It is oxide (such as LaSrCoFeO3)、LaMnO3Be oxide (such as
LaSrGaMgO3)、LaFeO3It is oxide (such as LaSrFeO3)、LaCoO3It is oxide (such as LaSrCoO3) etc. transition gold
Belong to the conductive ceramic etc. representated by perovskite (perovskite) type oxide.Wherein, as particularly preferred composition conduction
The material of property powder, can enumerate monomer and their alloy (Ag-Pd alloys, Pt-Pd alloys including noble metals such as platinum, palladium, silver
Deng) and nickel, copper, aluminium and its alloy etc. material.In addition, it is cheaper from cost, electrical conductivity is high etc., and viewpoints consider, especially
It is preferable to use the powder (hereinafter also referred to as " Ag powder ") for including silver and its alloy.Hereinafter, for the conduction of the present application
Property composition, to use Ag powder as illustrating in case of electroconductive powder.
The grain size of Ag powder and other electroconductive powders is not particularly limited, can be used corresponding with purposes each
The powder of kind grain size.For typical case, be suitably the average grain diameter based on laser light scattering diffraction approach be 5 μm of powder below, it is excellent
Choosing uses the powder that average grain diameter is 3 μm or less (being 1 μm~3 μm, for example, 1 μm~2 μm for typical).
The shape for constituting the particle of electroconductive powder is not particularly limited.For typical case, it can be suitble to use spherical, scale
Shape (flake), coniform, rodlike particle etc..Being filled with property it is good and be easy to be formed the reasons such as fine and close light-receiving surface electrode and
Speech is, it is preferable to use spherical or squamaceous particle.As used electroconductive powder, preferably have sharp grain size distribution (narrow)
Powder.For example, it is preferable to use the conduction having sharp grain size distribution as the particle for being substantially 10 μm or more not comprising grain size
Property powder.As its index, the grain when cumulative volume 10% in the size distribution based on laser light scattering diffraction approach can be used
The ratio (D10/D90) of diameter (D10) and the grain size (D90) when cumulative volume 90%.In the whole equal feelings of the grain size for constituting powder
Under condition, the value of D10/D90 becomes 1, conversely, size distribution becomes wider, then the value of the D10/D90 is closer to 0.It is preferable to use
The value of D10/D90 is the powder that size distribution is narrow as 0.2 or more (such as 0.2 or more 0.5 or less).
Use the electroconductive powder of the conductive composition with this average grain diameter and the electroconductive powder of grain shape
Fillibility it is good, fine and close electrode can be formed.This is advantageous when forming fine electrode pattern with good form accuracy.
In addition, the manufacturing method etc. of the electroconductive powders such as Ag powder is not particularly limited.Such as it can will utilize many institute's weeks
Wet-type reduction method, gas-phase reaction method, gas reduction method for knowing etc. are come electroconductive powder (typical for be Ag powder) root for manufacturing
It is used according to being classified.Above-mentioned classification is implemented such as can use the classifying equipoment using centrifugal separation.
When composition to be totally set as to 100 mass %, in conductive composition shared electroconductive powder containing than
Example is more preferably set as 85 mass %~95 suitable for being set as about 70 mass % or more (being the 70 mass % of mass %~95 for typical)
Quality % or so, such as be preferably set to 90 mass % or so.From the sight for the pattern for forming the good and fine and close electrode of form accuracy
Point considers, preferably improves the content ratio of electroconductive powder.On the other hand, if the content ratio is excessively high, there are the operations of cream
Property or the case where to declines such as the adaptability of various printings.
＜ decentralized media ＞
For typical case, in addition to above-mentioned cellulose-based resin, butyral system resin in conductive composition disclosed herein
Also include decentralized medium other than electroconductive powder.As decentralized medium, preferably boiling point is about 200 DEG C or more and (is for typical
About 200 DEG C~260 DEG C) organic solvent.More preferably using boiling point be about 230 DEG C or more (be substantially 230 DEG C for typical case~
260 DEG C) organic solvent.As this organic solvent, can be suitble to use：Butyl cellosolve acetate, butyl carbitol second
Acid esters (BCA：Butyl carbitol acetate) etc. ester series solvents, butyl carbitol (BC：Diethylene glycol monobutyl ether) etc. ethers system
Solvent, ethylene glycol and diethylene glycol derivative, toluene, dimethylbenzene, solvent naphtha (mineral spirit), terpinol
(terpineol), menthol (menthanol), one isobutyl ester (TEXANOL) of 2,2,4- trimethyl -1,3- pentanediols etc. are organic
Solvent.As particularly preferred solvent ingredient, can enumerate：Butyl carbitol (BC), acetate of butyl carbitol (BCA), 2,2,
4- trimethyl -1,3- pentanediol mono isobutyrates etc..
Conductive composition disclosed herein for example can be with its solid component content (nonvolatile component, non-
volatile content；NV be 70 mass of mass %~99 % and remainder be decentralized medium (it is) organic molten for typical
Agent) mode and be preferably carried out.More preferably above-mentioned NV is the mode of 90 mass of mass %~95 %.
The other ingredient ＞ of ＜
In the range of not departing from the purpose of the present invention, other than conductive composition disclosed herein can include above-mentioned
Various inorganic additives and/or organic additive.As the preference of inorganic additive, can enumerate frit, it is above-mentioned other than
Ceramic powders (ZnO2、Al2O3Deng), various fillers in addition to this.In addition, the preference as organic additive, such as can
Enumerate the additives such as surfactant, antifoaming agent, antioxidant, dispersant, viscosity modifier.
Frit is the ingredient that can be functioned as the inorganic bond of above-mentioned electroconductive powder, and performance makes composition
The conductive particle of electroconductive powder each other, the work that improves of the associativity of conductive particle and substrate (object for forming electrode)
With.In addition, in the case where the conductive composition is for example used to form the light-receiving surface electrode of solar cell, pass through the glass
The presence of material, conductive composition can penetrate through the antireflection film as lower layer in firing, can realize good with substrate
Bonding and electrical contact.
This frit is preferably regulated as and electroconductive powder is same or its size below.For example, being dissipated based on laser
The average grain diameter for penetrating diffraction approach be preferably 4 μm hereinafter, be suitably for 3 μm hereinafter, for typical case be more preferably 0.1 μm or more 2 μm with
Lower left and right.
It about the composition of frit, is not particularly limited, the glass of various compositions can be used.For example, as generally
Glass composition, or those skilled in the art usual statement address, that is, so-called lead system glass, lead lithium system glass
Glass, zinc system glass, borate-based glass, borosilicic acid system glass, alkali system glass, unleaded system's glass, tellurium system glass and containing aerobic
Change the glass etc. of barium or bismuth oxide etc..Self-evident, those glass comprising the major glass occurred in above-mentioned address in addition to constituting
Other than element, can also include selected from Si, Pb, Zn, Ba, Bi, B, Al, Li, Na, K, Rb, Te, Ag, Zr, Sn, Ti, W, Cs, Ge,
Ga、In、Ni、Ca、Cu、Mg、Sr、Se、Mo、Y、As、La、Nd、Co、Pr、Gd、Sm、Dy、Eu、Ho、Yb、Lu、Ta、V、Fe、Hf、
One or more of Cr, Cd, Sb, F, Mn, P, Ce and Nb element.This frit is for example in addition to general amorphous glass
In addition, or include the sintered glass ceramics of crystallization in a part.In addition, frit can be used alone the glass of composition
The frit of two or more compositions can also be used in mixed way by glass material.
The softening point for constituting the glass of frit is not particularly limited, preferably 300 DEG C~600 DEG C or so (such as 400 DEG C
~500 DEG C).The glass that can be adjusted to as such as above-mentioned softening point in 300 DEG C or more 600 DEG C or less of range, specifically,
Such as the glass that combination includes element as shown below can be enumerated.B-Si-Al systems glass, Pb-B-Si systems glass, Si-Pb-Li systems
Glass, Si-Al-Mg systems glass, Ge-Zn-Li systems glass, B-Si-Zn-Sn systems glass, B-Si-Zn-Ta systems glass, B-Si-Zn-
Ta-Ce systems glass, B-Zn-Pb systems glass, B-Si-Zn-Pb systems glass, B-Si-Zn-Pb-Cu systems glass, B-Si-Zn-Al systems glass
Glass, Pb-B-Si-Ti-Bi systems glass, Pb-B-Si-Ti systems glass, Pb-B-Si-Al-Zn-P systems glass, Pb-Li-Bi-Te systems glass
Glass, Pb-Si-Al-Li-Zn-Te systems glass, Pb-B-Si-Al-Li-Ti-Zn systems glass, Pb-B-Si-Al-Li-Ti-P-Te systems
Glass, Pb-Si-Li-Bi-Te systems glass, Pb-Si-Li-Bi-Te-W systems glass, P-Pb-Zn systems glass, P-Al-Zn systems glass,
P-Si-Al-Zn systems glass, P-B-Al-Si-Pb-Li systems glass, P-B-Al-Mg-F-K systems glass, Te-Pb systems glass, Te-Pb-
Li systems glass, V-P-Ba-Zn systems glass, V-P-Na-Zn systems glass, AgI-Ag2O-B-P systems glass, Zn-B-Si-Li systems glass,
Si-Li-Zn-Bi-Mg-W-Te systems glass, Si-Li-Zn-Bi-Mg-Mo-Te systems glass, Si-Li-Zn-Bi-Mg-Cr-Te systems glass
Glass etc..Conductive composition containing the frit with above-mentioned softening point for example, if formed solar cell device by
Used when smooth surface electrode, then show it is good grill thoroughly (fire through) characteristic and contribute to form high performance electrode, because
And it is preferred that.
As the example of organic additive, silicone resin can be enumerated.By containing silicone resin, can realize better
It can carry out the viscosity characteristics of good printing (such as silk-screen printing).(silicone can also be referred to as silicone resin
(silicone)) organic compound for including silicon (Si), is used without special limitation, such as tool can be preferably used
There is the organic compound of the main framing of siloxanes key (Si-O-Si).For example, can be in main fram unbonded key (side chain,
End) on be imported with the straight chain type silicone of alkyl or phenyl etc..Alternatively, it is also possible to for by polyether-based, epoxy group, amido, carboxyl,
Other substituent groups such as aralkyl, hydroxyl are directed into the amylose modified silicone on side chain, end or both, or make polyethers
Replace the straight-chain block copolymer being combined into silicone.As silicone resin, specifically, for example can it is preferable to use poly-
Dimethyl siloxane and/or polyether modified siloxane.
This silicone resin has with weight average molecular weight MwzGet higher and can be formed the tendency of the electrode of high aspect ratio.
From the viewpoint of realizing high aspect ratio, the weight average molecular weight Mw of silicone resinzSuch as 1000 or more can be set as, preferably
3000 or more, more preferably 5000 or more, particularly preferably 8000 or more, such as 10000 or more.In addition, MwzThe upper limit do not have
Especially limitation, from broken string the defects of inhibition and low resistance from the viewpoint of, MwzPreferably 150000 hereinafter, more preferably
120000 hereinafter, be preferably 100000 hereinafter, particularly preferably 80000 or less in turn.
The content W of silicone resinzIt is not particularly limited, is totally set as by the conductive composition in addition to silicone resin
When 100 mass %, such as 0.01 mass % or more can be set as.From the viewpoint for playing the effect using silicone resin better
Consider, preferred content WzFor 0.05 mass % or more, such as 0.01 mass % or more.Additionally, it is preferred that by above-mentioned content WzIt is set as
3 mass % are hereinafter, be more preferably set as 1 mass % or less (such as 0.5 mass % or less).
＜ viscosity ＞
About conductive composition disclosed herein, shear velocity 0.1s-1When viscosities il0.1Can be η0.1≤
500Pas (such as 100Pas≤η0.1≤ 500Pas), preferably η0.1＜ 500Pas, more preferably η0.1≤
450Pas, and then preferably η0.1≤ 300Pas, particularly preferably η0.1≤ 250Pas (such as 200Pas≤η0.1≤
250Pa·s).It is 0.1s by shear velocity-1When viscosities il0.1It is set as η0.1The conductive composition of≤500Pas is for example being situated between
When being assigned by the mask of printing in (supply) to the light-receiving surface of solar cell, good mobility is shown, to combine
The leakage of object from the mask is good.Therefore, it is possible to generation the defects of (supplying bad position) that inhibits to break.
In addition, about conductive composition disclosed herein, shear velocity 10s-1When viscosities il10Can be
50Pa·s≤η10(such as 50Pas≤η10≤ 100Pas), preferably 52Pas≤η10≤ 80Pas, more preferably
55Pa·s≤η10≤70Pa·s.Conductive composition disclosed herein is by having such as 50Pas≤η10Such viscosity
Characteristic, can (be coated on light-receiving surface after in the state of) after being printed with defined pattern via above-mentioned mask,
High viscosity (shape maintenance performance) is shown so as to inhibit the undesirable expansion of line width.That is, until before being fired
During, the shape for being coated on the electrode pattern of light-receiving surface is not easy to infiltrate, therefore can form thin-line-shaped electrode pattern.Cause
This can be stably formed (such as 45 μm or less, preferably 40 μm of required line width according to the conductive composition of above-mentioned composition
Thin-line-shaped electrode below).
Herein, according to the opinion of the present inventor, although about without cellulose-based resin and butyral system resin or packet
Fibre-bearing prime system resin and butyral system resin but number-average molecular weight Mx、MyIt is unsatisfactory for the existing conductive composition of above range,
If increasing the additive amount of resin to inhibit line width to expand, the viscosity in high shear rates region is rising trend, but with
This correspondingly low shearing speed region viscosity also be rising trend.Therefore, it when only merely increasing the additive amount of resin, deposits
In following situation：Shear velocity is 0.1s-1When viscosity be more than 500Pas, generate printing it is bad, as a result can not stablize landform
At fine wire electrodes.
In contrast, conductive composition disclosed herein, by become specific number-average molecular weight Mx、MyMode
It is applied in combination cellulose-based resin and butyral system resin, the additive amount regardless of resin can make the shear velocity be
0.1s-1Neighbouring viscosity specifically declines.It the reason of as this effect is obtained, explains with being not particularly limited to, recognizes
It is for reason：With above-mentioned number-average molecular weight MxCellulose-based resin with have above-mentioned number-average molecular weight MyButyral system
The compatibility of resin is high, plays the effect for mitigating mutual cohesion.Thereby, it is possible to realize to be with shear velocity better
0.1s-1When viscosities il0.1For η0.1≤ 500Pas and shear velocity are 10s-1When viscosities il10For 50Pas≤η10It is this viscous
The graph thinning for meeting electrode and the defects of inhibition broken string two that can not be obtained in the past can be made in the conductive composition for spending characteristic
The best conductive composition of person.
As above-mentioned, conductive composition disclosed herein has the viscosity characteristics suitable for printing, thus for being suitable as
Such as be applied to silk-screen printing, intaglio printing, hectographic printing (offset printing) and ink jet printing printing composition
(there is also the situations of referred to as cream, slurry or ink etc.).Moreover, when the electricity for forming the defects of requiring fine lineization and inhibiting broken string
When pole figure case, it can particularly preferably be combined using above-mentioned electric conductivity using general-purpose printing methods as described above
Object.Thus, for example by taking the solar cell device as an example of semiconductor element as an example, shown on one side by being screen printed onto
The example that the comb-type electrode pattern comprising finer finger electrode is formed on the light-receiving surface, on one side to conduct disclosed herein
The solar cell device of semiconductor element illustrates.In addition, about solar cell device, in addition to feature of present invention
, can be same as existing solar cell other than the composition of the light-receiving surface electrode of property, for composition same and pass
It is not the characteristic point of the present invention, therefore omit detailed description in the part of material same used.
The solar cell device that Fig. 1 and Fig. 2 is the implementation that schematic illustration can be through the invention and suitably manufactures is (single
Member) 10 an example figure, be using the wafer comprising single crystals or polycrystalline or armorphous silicon (Si) as semiconductor-based
The so-called silicon type solar cell device 10 of plate 11.Unit 10 shown in FIG. 1 is solar-electricity of the general single side by light type
Pond element 10.Specifically, p-Si layer (p-type silicon metal) 18 of this solar cell device 10 in silicon substrate (Si wafers) 11
Light receiving side have the n-Si layers 16 formed by forming pn engagement bys, and have on its surface and pass through chemical vapor deposition
(CVD) antireflection film 14 comprising titanium oxide or silicon nitride of formation and by including the conduction as main body such as Ag powder such as
Property composition formed light-receiving surface electrode 12,13.
On the other hand, have in the back side of p-Si layers 18：It is equally combined by defined electric conductivity with light-receiving surface electrode 12
The back side external connection electrode 22 of object (for typical, electroconductive powder is the conducting cream of Ag powder) formation, Yi Jifa
Wave so-called back surface field (BSF；Back Surface Field) effect back side aluminium electrode 20.Aluminium electrode 20 is by will be with aluminium
Powder carries out printing as the conductive composition of main body and fires to be formed in substantially entire surface overleaf.In the firing
When form Al-Si alloy-layers (not shown), aluminium spreads in p-Si layers 18 and forms p+Layer 24.By forming above-mentioned p+Layer 24, i.e.
BSF layers, preventing the carrier of photogenerated, overleaf electrode is nearby carried out in conjunction with such as realizing short circuit current or open voltage
(Voc) raising.
As shown in Fig. 2, the sides light-receiving surface 11A of the silicon substrate 11 in solar cell device 10, as light-receiving surface electrode 12,
13, be formed with several (such as 1~3 or so) linear busbar (connection is used) electrode 12 being mutually parallel and with
The finger of the striated of more (such as 60~90 or so) being mutually parallel for being connect with the mode that the busbar electrode 12 intersects
Shape (current collection use) electrode 13.
It is formed with more finger electrodes in order to collect the photogenerated carrier generated by light (hole and electronics)
13.Busbar electrode 12 is the connecting electrode of the carrier progress current collection for will be collected by finger electrode 13.It is formed with this
The part of light-receiving surface electrode 12,13 forms non-light part (shading light part) on the light-receiving surface 11A of solar cell device.Cause
This, passes through the busbar electrode 12 and the (finger electrode especially more than quantity of finger electrode 13 for making to be set to the sides above-mentioned light-receiving surface 11A
13) fine line as much as possible, then the non-light part (shading light part) of corresponding degree reduce, per unit of cells area
Light-receiving area expand.This can improve the power of the per unit area of solar cell device 10 extremely simplely.
If at this point, at a part of position for generating relaxation or recess, above-mentioned relaxation or recess of the electrode through graph thinning
Resistance is caused to increase, current collection is lost.In addition, as long as the part in the electrode through graph thinning breaks, then it is difficult to lead to
Crossing above-mentioned broken string position makes generation current current collection (as the electric current to circulate in high-resistance substrate, become and produce current collection
Current collection is carried out in the state of loss).Therefore, in order to form the light-receiving surface electrode of solar cell device, it is desirable that electrical characteristic is worked as
It so wants high, and passes through the excellent conductive composition of the shape stability of printing.
In summary, this solar cell device 10 is manufactured by technique as described below.
That is, preparing suitable Silicon Wafer, the general skill such as thermal diffusion method or ion implantation (ion plantation) is utilized
Method adulterates defined impurity to form above-mentioned p-Si layers 18 or n-Si layers 16, thus makes above-mentioned silicon substrate (semiconductor substrate)
11.Next, such as forming the antireflection film 14 comprising silicon nitride etc. using skill and technique plasma CVD.
Then, in the back side sides 11B of above-mentioned silicon substrate 11, first, using defined conductive composition (for typical,
Electroconductive powder is the conductive composition of Ag powder) silk-screen printing is carried out with defined pattern, it is dried, is thus formed in
Become the back side side conductor coating material of back side external connection electrode 22 (referring to Fig.1) after firing.Next, overleaf side
Entire surface is coated with (supply) using aluminium powder as the conductive composition of conductor ingredient using silk screen print method etc., is done
It is dry, aluminium film is consequently formed.
Next, on being formed in the antireflection film 14 of the surface side of above-mentioned silicon substrate 11, for typical, it is based on screen printing
Brush method prints the conductive composition of (supply) present invention with Wiring pattern as shown in Figure 2.Printed line width is without spy
It does not limit, by using the conductive composition of the present invention, it is 45 μm or so or its following (preferably 30 μm that formation, which has line width,
~45 μm or so of range, more preferably 30 μm~40 μm or so, and then preferably less than 40 μm) finger electrode electrode figure
The film (block letter) of case.Next, suitable temperature region (be 100 DEG C~200 DEG C for typical, such as 120 DEG C~
150 DEG C or so) in make drying substrates.Content about preferred silk screen print method is as described later.
The baking furnace of such as near infrared ray rapid firing stove etc is used in air atmosphere, it will be as described above on two sides point
It is not formed with the silicon substrate 11 of cream coating material (dry membranaceous coating material) with firing temperature appropriate (such as 700 DEG C~900
DEG C) be fired.
By above-mentioned firing, used with light-receiving surface electrode (being Ag electrodes for typical) 12,13 and back side external connection
Electrode (being Ag electrodes for typical) 22 together, forms and fires aluminium electrode 20, in addition, being formed simultaneously Al-Si alloys (not shown)
Layer, and aluminium spreads in p-Si layers 18 and forms above-mentioned p+ layers (BSF layers) 24, makes solar cell device 10.
It is carried out at the same time firing as described above in addition, substituting, such as can also implement to be used to form light-receiving surface 11A respectively
The firing of the light-receiving surface electrode (typical for be Ag electrodes) 12,13 of side and be used to form the back side sides 11B aluminium electrode 20 and
The firing of external connection electrode 22.
According to conductive composition disclosed herein, such as can be by silk-screen printing, it will with required electrode pattern
Conductive composition supplies (printing) on silicon substrate 11.Above-mentioned conductive composition due to above-mentioned viscosity characteristics,
Such as the electrode for being obtained after firing, it can be in the state that the generation of the thicker of line or broken string be greatly reduced, high quality
Ground forms the finger electrode 13 that line width is 45 μm or less (preferably 40 μm or less).It, also can be in high quality about busbar electrode
Form the busbar electrode of such as 1000 μm~3000 μm or so of line width.If as described above, realizing the graph thinning of electrode wires, pass through
The width of finger electrode 13 and radical are designed as best combination, provide photoelectric conversion efficiency high solar cell device.
Hereinafter, illustrating several embodiments related to the present invention, but it is not intended to limit the invention to above-mentioned
Content shown in embodiment.
＜ conductive compositions ＞
The conductive composition for being used to form electrode is prepared by step as shown below.That is, preparing number-average molecular weight
MxDifferent a variety of ethyl celluloses (EC) are used as cellulose-based resin and number-average molecular weight MyDifferent a variety of polyvinyl alcohol
Butyral (PVB) is used as butyral system resin.By those EC and PVB, as the silver powder of electroconductive powder, as frit
Pb systems glass, the dimethyl silicone polymer as silicone resin, the butyl diglycol acetic acid esters mixing as decentralized medium, system
The standby total amount comprising 90 mass parts of silver powder, 2 mass parts of frit, EC and PVB is 0.5 mass parts, 7.5 mass of decentralized medium
The conductive composition of the example 1~24 of part.About the conductive composition of each example, by the number-average molecular weight M of used PVBy、
The number-average molecular weight M of butyralization degree, ECx, the degree of polymerization, the content of PVB/EC summarize than the content (mass parts) of, silicone resin
It is shown in Table 1.In addition, replacing PVB using polyvinyl alcohol (PVA) in example 17.
In addition, the number-average molecular weight M of the cellulose-based resin and butyral system resin of each examplex、MyIt is to use Co., Ltd. island
Tianjin makes manufactured size exclusion chromatography method (Size Exclusion Chromatography, SEC) device in following conditions
Under find out.
(1) the number-average molecular weight M of cellulose-based resinx
Column：GPC KF-806L (Showa Denko K. K's manufacture)
Eluent：THF (tetrahydrofuran)
Flow：1ml/ minutes
Column temperature：40℃
Standard substance：PS (polystyrene)
(2) the number-average molecular weight M of butyral system resiny
Column：GPC KF-806L (Showa Denko K. K's manufacture)
Eluent：THF (tetrahydrofuran)
Flow：1ml/ minutes
Column temperature：40℃
Standard substance：PS (polystyrene)
[table 1]
Table 1
＜ viscosity ＞
The Haake Mars rheometers viscosimeters manufactured using commercially available Thermo scientific companies are with 25 DEG C of liquid temperature
And shear velocity 0.01s-1~100s-1Range the viscosity of the conductive composition of example 1~5,11,16 is measured.It will knot
Fruit is shown in Table 2.
[table 2]
Table 2
As shown in table 2, number-average molecular weight M is used in combinationxFor 55000≤MxEC and number-average molecular weight MyFor My≤ 100000
The conductive composition of the example 1~3 of PVB is compared with example 4,5,11,16, the viscosity higher in high shear rates region, Neng Goushi
Existing 50Pas≤η10This high viscosity.In addition, the conductive composition of example 1~3, compared with example 5,11,16, low sheraing is fast
The viscosity spent in region is lower, can realize η0.1This extremely low viscosity of≤500Pas or less.
The making ＞ of ＜ experiment solar cell devices (light-receiving surface electrode)
Using the conductive composition of the example 1~24 of above-mentioned acquisition come formed light-receiving surface electrode (that is, comprising finger electrode and
The comb-type electrode of busbar electrode), thus make the solar cell device of example 1~24.
Specifically, first, preparing the p-type list used for solar batteries of the size of commercially available 156mm cubic (6 inch square)
Crystalline silicon substrate (plate thickness is 180 μm), to its surface (light-receiving surface), is etched, thus using the nitration mixture of hydrofluoric acid and nitric acid
Damaged layer is removed, and forms concave-convex texture structure.Next, by being coated with solution containing phosphate for above-mentioned texture structure face,
Implement heat treatment, to form the n-Si layers (n that thickness is about 0.5 μm in the light-receiving surface of the silicon substrate+Layer).Next, at this
On n-Si layers, the silicon nitride film that thickness is about 80nm or so is made using plasma CVD (PECVD) method, as antireflection
Film.
Next, in the back side of silicon substrate, using defined silver electrode formation cream, to become outside back side later
The mode of connecting electrode carries out silk-screen printing with defined pattern, makes it dry, back side electrode pattern is consequently formed.It connects
It, overleaf the entire surface silk-screen printing aluminium electrode formation cream of side, is dried, aluminium film is consequently formed.
Then, using the conductive composition of each example, in air atmosphere, silk screen print method is utilized at ambient temperature,
The electrode pattern that light-receiving surface electrode (Ag electrodes) is printed on above-mentioned antireflection film, is dried with 120 DEG C.Specifically,
As shown in Fig. 2, being formed comprising 3 linear busbar electrodes being mutually parallel and with the busbar electrode just by silk-screen printing
The electrode pattern of 90 finger electrodes handed over and be mutually parallel.
It is the range that line width becomes 35 μm~40 μm as the size after the firing of the finger electrode pattern of target.In addition,
Busbar electrode is set in such a way that the line width after firing becomes about 1.5mm.
It, will be as above with 700 DEG C~800 DEG C of firing temperature using near infrared ray rapid firing stove moreover, in air atmosphere
The substrate for being printed with electrode pattern respectively on two sides is fired, and thus makes the solar cell of evaluation.
＜ line widths ＞
For the light-receiving surface electrode (finger electrode) of the solar cell of such as above-mentioned making, line is measured by following steps
It is wide.About the line width of electrode, by shape analysis laser microscope (Co., Ltd. keyence manufactures) to the solar-electricity of each example
The line width of any position of the light-receiving surface electrode in pond is measured.Its result is shown with the average value of the value to 30 Site Determinations
In the corresponding column of table 1.Herein, the case where line width being less than 40 μm is evaluated as " ◎ ", by 40 μm less than 45 μm of feelings
Condition is evaluated as "○", and 45 μm or more of situation is evaluated as "×".
＜ broken strings ＞
In addition, for the light-receiving surface electrode (finger electrode) of solar cell, broken string number is measured.About broken string number, use
Solar battery electroluminescence (Electro Luminescence；EL) check device, the broken string of the electrode of specific every 1 plate base
Position measures its quantity.Specifically, being biased to solar cell, the turning part of electrode is made to shine.At this point, EL is sent out
The non-conduction part of electrode shows black because of shading in light image, thus the quantity of the light shielding part as broken string position and is measured its number
Amount.It the results are shown in the corresponding column of table 1.Herein, broken string number the case where being less than at 10 it will be evaluated as "○", more than at 10
And the case where less than at 45, is evaluated as " △ ", by more than at 45 the case where is evaluated as "×".
As shown in table 1, the number-average molecular weight M of the EC of example 4,5xLess than 55000, and the number-average molecular weight M of PVByFor
100000 or less.In addition, the number-average molecular weight M of the EC of example 10xIt is 55000 or more, and the number-average molecular weight M of PVByFor
100000 or more.About the electrode for using these conductive compositions to be formed, confirm compared with example 1~3,6~9, line width has
It anticipates thicker.That is, learning using number-average molecular weight MxThe conductive composition and use number-average molecular weight M of EC less than 55000y
It can relax for the block letter (film) of the conductive composition of 100000 or more PVB, thin-line-shaped electrode can not be formed.
In addition, number-average molecular weight M is used alonexFor 55000 or more EC example 11 compared with example 1~3,6~9, line width
It is intentionally thicker, and in printing, composition is deteriorated from the leakage of mask, and mostly occur broken string.Divide equally in addition, number is used alone
Son amount MyAlthough the example 16 for 100000 PVB below can make line width attenuate, leakage of the composition from mask in printing
It is deteriorated, mostly occur broken string.In addition, number-average molecular weight M is used in combinationxAlthough the example 17 for 55000 or more EC and PVA can make line width
Attenuate, but composition is deteriorated from the leakage of mask in printing, mostly occur broken string.
In contrast, number-average molecular weight M is applied in combinationxFor 55000 or more EC and number-average molecular weight MyIt is 100000 or less
PVB example 1~3,6~9 conductive composition compared with above-mentioned example 4,5,10 and 11, the thin electrode of line width can be formed.
That is, the undesirable expansion that can inhibit film is confirmed, so as to form thin-line-shaped electrode.In addition, example 1~3,6~9
Conductive composition can reduce broken string number compared with above-mentioned example 11,16 and 17.That is, combination can be made in printing by confirming
Object becomes good from the leakage of mask, so as to form broken string the defects of few electrode.
In addition, here for the conductive composition of experiment in the case of, the content ratio of PVB/EC is set as 0.5 or more
In 1.5 examples 4,13~15 below, compared with example 12, the electrode of further graph thinning is obtained.In addition, by silicone resin
Content is set as in the example 22~24 of 0.1~0.5 mass parts, compared with example 18~21, obtains the electrode of further graph thinning.
More than, by preferred embodiment, the present invention is described, but above-mentioned description and non-limiting item, certainly
It can carry out various changes.
Industrial availability
In accordance with the invention it is possible to provide a kind of graph thinning that can realize electrode pattern and the disconnected of electrode pattern can be inhibited
The conductive composition of line.
Claims (9)
1. a kind of conductive composition, is used to form electrode, which is characterized in that, including：
Electroconductive powder；
Cellulose-based resin；
Butyral system resin；With
Decentralized medium,
The number-average molecular weight M of the cellulose-based resinxFor 55000≤Mx,
The number-average molecular weight M of butyral system resinyFor My≤100000。
2. conductive composition as described in claim 1, it is characterised in that：
The number-average molecular weight M of butyral system resinyNumber-average molecular weight M relative to the cellulose-based resinxRatio My/Mx
For 0.2≤My/Mx≤1.2。
3. conductive composition as claimed in claim 1 or 2, it is characterised in that：
The number-average molecular weight M of the cellulose-based resinxWith the number-average molecular weight M of butyral system resinyRelationship meet under
Formula：
10000≤My＜ Mx≤100000。
4. conductive composition according to any one of claims 1 to 3, it is characterised in that：
The content W of butyral system resinyContent W relative to the cellulose-based resinxRatio Wy/WxFor 0.2≤Wy/Wx
≤1.5。
5. conductive composition as described in any one of claims 1 to 4, it is characterised in that：
When the conductive composition is totally set as 100 mass %, the content W of the cellulose-based resinxWith the butyral
It is the content W of resinyTotal amount Wx+WyFor 0.1 mass % or more, 1 mass % or less.
6. such as conductive composition according to any one of claims 1 to 5, it is characterised in that：
It also include silicone resin.
7. such as conductive composition according to any one of claims 1 to 6, it is characterised in that：
Shear velocity is 0.1s-1When viscosities il0.1For η0.1≤ 500Pas,
Shear velocity is 10s-1When viscosities il10For 50Pas≤η10。
8. such as conductive composition according to any one of claims 1 to 7, it is characterised in that：
The metal species for constituting the electroconductive powder include any one or two kinds in nickel, platinum, palladium, silver, copper and aluminium
Above element.
9. a kind of solar cell device, which is characterized in that have：
The light-receiving surface electrode of firing object including conductive composition according to any one of claims 1 to 8.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016003756 | 2016-01-12 | ||
| JP2016-003756 | 2016-01-12 | ||
| PCT/JP2017/000139 WO2017122570A1 (en) | 2016-01-12 | 2017-01-05 | Electrically conductive composition |
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| Publication Number | Publication Date |
|---|---|
| CN108463500A true CN108463500A (en) | 2018-08-28 |
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|---|---|---|---|
| CN201780006329.0A Pending CN108463500A (en) | 2016-01-12 | 2017-01-05 | Conductive composition |
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| Country | Link |
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| JP (1) | JP6826542B2 (en) |
| KR (1) | KR20180103110A (en) |
| CN (1) | CN108463500A (en) |
| TW (1) | TW201736527A (en) |
| WO (1) | WO2017122570A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP6826542B2 (en) | 2021-02-03 |
| TW201736527A (en) | 2017-10-16 |
| JPWO2017122570A1 (en) | 2018-11-01 |
| WO2017122570A1 (en) | 2017-07-20 |
| KR20180103110A (en) | 2018-09-18 |
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