CN103545016A - Crystalline silicon solar cell front electrode electrocondution slurry and preparation method thereof - Google Patents

Crystalline silicon solar cell front electrode electrocondution slurry and preparation method thereof Download PDF

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CN103545016A
CN103545016A CN201310495909.4A CN201310495909A CN103545016A CN 103545016 A CN103545016 A CN 103545016A CN 201310495909 A CN201310495909 A CN 201310495909A CN 103545016 A CN103545016 A CN 103545016A
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oxide
glass dust
silicon solar
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etching agent
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CN103545016B (en
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刘小丽
郭冉
李德林
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Shou Cheng new material Science and Technology Ltd. of Shenzhen
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SHENZHEN SOLTRIUM PHOTOVOLTAIC CO Ltd
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Abstract

The invention discloses crystalline silicon solar cell front electrode electrocondution slurry and a preparation method of the crystalline silicon solar cell front electrode electrocondution slurry. The crystalline silicon solar cell front electrode electrocondution slurry is composed of a corrosion etching agent, metal powder, an organic carrier and glass powder; the corrosion etching agent is a compound of one or more crystals, and the melting temperature of the corrosion etching agent ranges from 250 DEG C to 760 DEG C; the glass powder is of a non-crystal structure. In the sintering process of the electrode electrocondution slurry, the corrosion etching agent directly turns into a liquid from a solid so that the corrosion etching agent can flow easily; in coordination with the softened glass powder, the corrosion etching agent can easily etch and penetrate through an antireflection insulating layer on the front of a crystalline silicon solar cell so that the conductive metal powder and the crystalline silicon solar cell can form good ohmic contact; moreover, the conductive metal powder can be wetted, contact between the metal powder can be enhanced, and therefore a crystalline silicon solar cell front electrode with excellent conductivity is formed.

Description

Crystal silicon solar energy battery front electrode electrocondution slurry and preparation method thereof
Technical field
The invention belongs to technical field of solar batteries, relate to particularly a kind of crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
Background technology
Solar energy is a kind of inexhaustible clean type energy, along with the exhaustion day by day of the non-renewable energy resources such as coal, oil, develops, utilizes solar energy to become large focus, and solar cell is exactly a kind of important means of utilizing solar energy.Wherein, the crystal silicon solar batteries of having realized suitability for industrialized production is exactly a kind of in solar cell.
As the crystal silicon solar batteries part of core the most, cell piece, for by the electric current collection producing under illumination and derive, need to be made respectively an electrode on front and the back side.The method of manufacturing electrode is a lot, and silk screen printing and altogether burning are current the most general a kind of production technologies.
Crystal silicon solar batteries conductive slurry for front electrode and electrocondution slurry for backplate, aluminium back surface field are the same with slurry, are all to adopt the mode of silk screen printing to be coated on silicon chip, and at front side of silicon wafer, form front electrode by co-sintering.Crystal silicon solar batteries electrode after co-sintering must adhesion-tight, do not fall ash, silicon chip are not yielding, and is easy to welding, is convenient to electric current collection illumination being produced with wire and derives.Compare with electrocondution slurry with silicon solar cell back face electrode, silicon solar cell conductive slurry for front electrode must possess the ability that penetrates silicon nitride anti-reflecting film.
Traditional crystal silicon solar batteries front electrocondution slurry is comprised of silver powder, glass dust, additive and organic carrier, and its electrocondution slurry is printed on crystal silicon solar batteries front or plane of illumination conventionally, and then sintering forms front electrode.In sintering process, glass dust etching in electrocondution slurry the antireflective insulating barrier that penetrates crystal silicon solar batteries front or plane of illumination are as silicon nitride, titanium oxide, aluminium oxide, silica or silicon/titanium, make silver powder and crystal silicon solar batteries substrate contact, form front electrode.Conventionally glass dust has following effect in slurry: 1. soak metal powder, promote the sintering of metal powder; 2. etching antireflection layer, and promote metal and silicon face contact and guarantee cementation between the two.Glass dust is progressively softening in sintering process, in of short duration process cycle, is generally 1～2 minute, and when softening, segment glass powder rests in metal powder and flows, and another part glass dust softens to bottom and reacts with antireflection layer.
In order to make metal powder and silicon face form good ohmic contact, require antireflection layer by etching completely, can not penetrate PN junction district again simultaneously.When selecting glass dust, the composition of glass dust, softening point, thermal coefficient of expansion, wettability, consumption etc. all can affect the physicochemical change in sintering process, and then affect the various performances of solar cell.If glass dust content is less, can not guarantee that itself and antireflection layer fully contact and complete reaction; If guarantee, antireflection layer is penetrated completely, needs to add the glass dust of q.s; If but the addition of glass dust is higher, the relative amount of conductive gold symbolic animal of the birth year is lower, the contact probability between metallic particles is fewer, will cause electrical property deteriorated; If glass dust softening point temperature is too high, can cause sintering to be difficult to control; If glass dust softening point temperature is too low, can stop up the interconnected pore between metal-powder, hinder effective discharge of organic carrier.The glass dust that traditional crystal silicon solar batteries front electrocondution slurry is used is amorphous material, in heating process, first there is whole solid deliquescing, there is no fixing fusing point, and just in a certain temperature range, occur to soften, this scope is called softened zone, start to occur softening temperature and be called softening temperature, softening temperature is a characteristic value of glass dust, and different glass has different softening temperatures, forms relevant with composition with its material.The atomic arrangement of glass dust inside is unordered, XRD(X-ray Diffiraction Pattern) test can demonstrate the lower bulge of a very wide intensity, unlike crystalline compounds, has sharp-pointed diffractive features peak.Glass dust is normally heated to melting by oxide, quenching or quenching and make.For example, the disclosed crystal silicon solar batteries of US Patent No. 2011/0308595 front electrocondution slurry, used plumbous tellurium oxide (Pb-Te-O) glass dust, its preparation method is: lead oxides and tellurium oxide are mixed, under air atmosphere or oxygen atmosphere, be heated to molten condition, then, the mixture of molten condition is quenched, grind and obtain its plumbous tellurium oxide (Pb-Te-O) glass dust.And for example, the disclosed crystal silicon solar batteries of PCT patent WO2012/129554 front electrocondution slurry, used plumbous tellurium oxide glass powder, its preparation method is traditional method for glass preparation: lead oxides and tellurium oxide are mixed, be heated to molten condition, then, the mixture of molten condition is quenched, grind and obtain its plumbous tellurium oxide glass powder.As described in PCT patent WO2012/129554, the inside atomic arrangement of their glass dust is unordered, and XRD test can demonstrate the lower bulge of a very wide intensity, unlike crystalline compounds, has sharp-pointed diffractive features peak.And for example, the disclosed crystal silicon solar batteries of US Patent No. 2011/0232747 front electrocondution slurry, used plumbous tellurium oxidate for lithium glass dust, its preparation method is: by TeO2, PbO, and Li2CO3 mixing, be heated to 900 ℃ of meltings, be incubated one hour, then quenching and make plumbous tellurium oxidate for lithium glass dust.And for example, the disclosed crystal silicon solar batteries of US Patent No. 2011/0232746 front electrocondution slurry, used plumbous tellurium boron oxide compound glass dust, its preparation method is by the mixture of plumbous tellurium boron, be heated to 800-1200 ℃ of melting, then the mixture quenching of fusing made to plumbous tellurium boron oxide compound glass dust, its glass dust is noncrystal, only have softening temperature, there is no specific melting temperature.
At present, the glass dust of front electrode slurry is selected Pb-Si glass system conventionally, has also occurred Pb-Te glass system simultaneously.
But no matter which kind of glass dust system is subject to the physical property constraint of glass dust itself, all there are the problems referred to above, make the manufacture difficulty of suitable glass dust and slurry large, operation window narrows.
Summary of the invention
An object of the present invention is to provide the front electrode electrocondution slurry that a kind of adhesion-tight, ohmic contact are good, can improve crystal silicon solar batteries combination property, is 100 parts of calculating according to total weight, comprises the component of following formula rate:
0.5～10 part, corrosion etching agent and glass dust,
Wherein, the weight ratio of described corrosion etching agent and glass dust is 5/95～95/5; Described corrosion etching agent is the crystalline compounds that lead, tellurium and/or the oxide that adds element form, and melting temperature is 250 ℃～760 ℃; Described glass dust is amorphization compound;
70～93 parts of metal powders;
5～25 parts of organic carriers;
Described metal powder, glass dust and corrosion etching agent are dispersed among organic carrier randomly.
Another object of the present invention is to provide the crystal silicon solar batteries front electrode electrocondution slurry preparation method that a kind of technique is simple, condition is easily controlled, production cost is low, comprises the steps:
Prepare described corrosion etching agent;
Prepare described glass dust;
Prepare described organic carrier; According to the formula of above-mentioned crystal silicon solar batteries front electrode electrocondution slurry, take described corrosion etching agent, glass dust, metal powder and organic carrier;
Described corrosion etching agent, glass dust, metal powder and organic carrier are mixed, grind, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
Another object of the present invention is to provide a kind of preparation method of high performance crystal silicon solar batteries front electrode, comprises the steps:
The crystal silicon semiconductor element that provides a kind of upper face to there is dielectric film, wherein, described dielectric film is at least one superimposed layer in silicon nitride, titanium oxide, aluminium oxide, silica;
The electrocondution slurry that the preparation method of 1～9 arbitrary described crystal silicon solar batteries front electrode electrocondution slurry or 10～18 arbitrary described crystal silicon solar batteries front electrode electrocondution slurries is obtained is printed on described dielectric film;
Sintering, the step of described sintering is: the described electrocondution slurry being printed on dielectric film is dried at 180 ℃～260 ℃, be heated to 700 ℃～950 ℃ sintering;
Cooling, obtain described crystal silicon solar batteries front electrode.
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention is by adopt corrosion etching agent and glass dust simultaneously, and this corrosion etching agent is at least one crystal structure, and it has special internal structure and atomic arrangement; Glass dust is at least one non-crystal structure.When co-sintering, organic carrier is removed by volatilization, described corrosion etching agent directly becomes liquid by solid, become easy flowing liquid, itself and the glass dust coordinative role of having softened, thereby be easy to corrode and penetrate the antireflective insulating barrier in crystal silicon solar energy battery front, make conductive metal powder and crystal silicon solar energy battery form good ohmic contact, and can soak conductive metal powder, contact between reinforcement metal powder, form the good crystal silicon solar batteries front electrode of electric conductivity, than the independent use glass dust in traditional handicraft, there is better characteristic
Crystal silicon solar batteries front electrode of the present invention has been owing to having adopted above-mentioned electrocondution slurry, has that Stability Analysis of Structures, ohmic contact are good, the excellent combination property such as conduct electricity very well.
Accompanying drawing explanation
Fig. 1 is the method process flow diagram that the present invention prepares crystal silicon solar batteries front electrode electrocondution slurry;
Fig. 2 is used electrocondution slurry of the present invention to prepare the method process flow diagram of crystal silicon solar batteries front electrode;
Fig. 3 is the partial structurtes schematic diagram of crystal silicon solar batteries before sintering of having printed electrocondution slurry;
Fig. 4 is crystal silicon solar batteries partial structurtes schematic diagram after sintering of having printed electrocondution slurry;
Cooling chart when Fig. 5 is preparation corrosion etching agent crystalline compounds;
Fig. 6 a is the exemplary survey map of XRD of a Pb-Te-Li-O system crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval;
Fig. 6 b is the exemplary survey map of XRD of a Pb-Te-Li-O system glass dust, demonstrates the lower bulge of the very wide intensity of distribution in low-angle interval, there is no sharp-pointed diffractive features peak;
Fig. 7 a is the exemplary survey map of XRD of a Pb-Te-Si-O system crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval;
Fig. 7 b is the exemplary survey map of XRD of a Pb-Te-Si-O system glass dust, demonstrates the lower bulge of the very wide intensity of distribution in low-angle interval, there is no sharp-pointed diffractive features peak;
Fig. 8 a is the exemplary survey map of XRD of a Pb-Te-Ba-O system crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval;
Fig. 8 b is the exemplary survey map of the XRD of a Pb-Te-Ba-O glass dust, demonstrates the lower bulge of the very wide intensity of distribution in low-angle interval, there is no sharp-pointed diffractive features peak;
Fig. 9 a is the exemplary survey map of XRD of a Pb-Te-Bi-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval;
Fig. 9 b is the exemplary survey map of the XRD of a Pb-Te-Bi-O glass dust, demonstrates the lower bulge of the very wide intensity of distribution in low-angle interval, there is no sharp-pointed diffractive features peak;
Figure 10 a is the exemplary survey map of XRD of a Pb-Te-Bi-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval;
Figure 10 b is the exemplary survey map of the XRD of a Pb-Te-Bi-O glass dust, demonstrates the lower bulge of the very wide intensity of distribution in low-angle interval, there is no sharp-pointed diffractive features peak;
Figure 11 a is the exemplary survey map of XRD of a Pb-Te-Bi-Li-B-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval;
Figure 11 b is the exemplary survey map of the XRD of a Pb-Te-Bi-Li-B-O glass dust, demonstrates the lower bulge of the very wide intensity of distribution in low-angle interval, there is no sharp-pointed diffractive features peak;
Figure 12 a is the exemplary survey map of XRD of a Pb-Te-Bi-B-Ti-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval;
Figure 12 b is the exemplary survey map of the XRD of a Pb-Te-Bi-B-Ti-O glass dust, demonstrates the lower bulge of the very wide intensity of distribution in low-angle interval, there is no sharp-pointed diffractive features peak.
Figure 13 a is the exemplary survey map of XRD of a Pb-Te-Bi-Ti-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval;
Figure 13 b is the exemplary survey map of the XRD of a Pb-Te-Bi-Ti-O glass dust, demonstrates the lower bulge of the very wide intensity of distribution in low-angle interval, there is no sharp-pointed diffractive features peak
Figure 14 a is the exemplary survey map of XRD of a Bi-Te-B-Li-O crystalline compounds corrosion etching agent, demonstrates sharp-pointed diffractive features peak in low-angle interval;
Figure 14 b is the exemplary survey map of the XRD of a Bi-Te-B-Li-O glass dust, demonstrates the lower bulge of the very wide intensity of distribution in low-angle interval, there is no sharp-pointed diffractive features peak
Embodiment
In order to make object of the present invention, technical scheme and advantage clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
The embodiment of the present invention provides a kind of crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof, and uses this electrocondution slurry to prepare the method for crystal silicon solar batteries front electrode.
The crystal silicon solar batteries front electrode electrocondution slurry that the embodiment of the present invention provides, is 100 parts of calculating according to total weight, comprises the component of following formula rate:
0.5～10 part, corrosion etching agent and glass dust,
Wherein, the weight ratio of described corrosion etching agent and glass dust is 5/95～95/5; Described corrosion etching agent is the crystalline compounds that lead, tellurium and/or the oxide that adds element form, and melting temperature is 250 ℃～760 ℃; Described glass dust is amorphization compound;
70～93 parts of metal powders;
5～25 parts of organic carriers;
Described metal powder, glass dust and corrosion etching agent are dispersed among organic carrier randomly.
Fig. 1 is the method process flow diagram that the embodiment of the present invention is prepared crystal silicon solar batteries front electrode electrocondution slurry, comprises the steps:
S01A, prepares described corrosion etching agent;
S01B, prepares described glass dust;
S01C, prepares described organic carrier;
S02, takes described corrosion etching agent, glass dust, metal powder and organic carrier according to the formula of above-mentioned crystal silicon solar batteries front electrode electrocondution slurry;
S03, mixes described corrosion etching agent, glass dust, metal powder and organic carrier, grinds, and obtains described crystal silicon solar batteries front electrode electrocondution slurry.
Particularly, in step S01, preparation corrosion etching agent can adopt one of following method: cooling method is controlled in liquid-phase chemical reaction method, chemical vapour deposition, melting and vacuum fusion is controlled cooling method.
In a preferred case study on implementation, the preparation method of above-mentioned corrosion etching agent is: the lead acetate solution that by the temperature of 0.1～6mol/l is telluric acid solution, tellurous acid solution, tellurate solution or tellurite solution and/or the 0.1～10mol/l of 60-90 ℃ mixes, and then adds the salting liquid of at least one interpolation element in lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium; While only comprising tellurium and lead in mixed solution, tellurium and plumbous mol ratio are 0.1/10～10/0.1, be preferably 1/5 – 5/1 stirs the solution mixing at 50 ℃～250 ℃ again, maintain mixing speed within the scope of 1000～1500r/min, reaction time is 2～5hrs, generate precipitation, the speed with 1000r/min at 80 ℃ that is preferably stirs 3 hours; Then carry out successively Separation of Solid and Liquid, washing, until filtrate PH is 5～7; Regather solid, at 150 ℃, dry 2～3hrs, obtain above-mentioned corrosion etching agent crystalline compounds, then pulverize, after milled processed, obtain described corrosion etching agent crystalline compounds particle.
In another preferred case study on implementation, the preparation method of above-mentioned corrosion etching agent is: at least one steam adding in element in the steam of lead and/or tellurium and lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium is imported in the reative cell that contains oxygen atmosphere by a certain percentage continuously; In mist, only comprise tellurium and when plumbous, tellurium and plumbous mol ratio are 0.1/10～10/0.1, are preferably 1/5 – 5/1; When comprising tellurium, lead and adding element in mixed solution, summation and the mol ratio of adding the summation of element plumbous, tellurium are 90/2 – 80/20, are preferably 95/5 – 85/15; It is reacted 1～4 hour at 1000～3000 ℃, be preferably and at 1000～2000 ℃, react 2 hours; After naturally cooling to 25 ℃, obtain above-mentioned corrosion etching agent crystalline compounds; Then pulverize, after milled processed, obtain above-mentioned corrosion etching agent crystalline compounds particle.
In another case study on implementation, the preparation method of described corrosion etching agent is: the oxide of tellurium and/or plumbous oxide are mixed with the oxide of at least one interpolation element in lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium; In mixture, only comprise tellurium and when plumbous, tellurium and plumbous mol ratio are 0.1/10～10/0.1, are preferably 2/5-5/2; When comprising tellurium, lead and adding element in mixture, plumbous, tellurium element summation is 98/2 – 80/20 with the mol ratio of adding element summation, is preferably 95/5 – 85/15; Then in irreducibility atmosphere (comprising oxygen atmosphere, air atmosphere, nitrogen atmosphere, argon gas atmosphere etc.), be heated to 700～1200 ℃, it is reacted 30～120 minutes under molten condition, be preferably at 800-1100 ℃ 2 hours; Naturally cool to 25 ℃ or cool to 25 ℃ with the furnace, then pulverize, after milled processed, obtain described corrosion etching agent crystalline compounds particle.
In another case study on implementation, the preparation method of described corrosion etching agent is: at least one oxide that adds element in the oxide of tellurium and/or plumbous oxide and lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium is mixed; While only comprising tellurium and plumbous oxide in mixture, tellurium and plumbous mol ratio are 0.1/10～10/0.1, are preferably 2/5-5/2; When comprising tellurium, lead and adding the oxide of element in mixture, plumbous, tellurium element summation is 98/2 – 80/20 with the mol ratio of adding element summation, is preferably 95/5 – 85/15.; Then in the atmosphere of vacuum, be heated to 700～1200 ℃, it is reacted 30～120 minutes under molten condition, be preferably at 1000 ℃ 2 hours; Naturally cool to 25 ℃ or cool to 25 ℃ with the furnace, then pulverize, after milled processed, obtain above-mentioned corrosion etching agent crystalline compounds particle.
Further, above-mentioned corrosion etching agent is crystalline compounds, for spherical, class is spherical, at least one in sheet, graininess, colloid particle, is of a size of 0.1～10.0 μ m.
The method that the step of mixing in step S03 particularly, can take substep to mix:
In one embodiment, above-mentioned corrosion etching agent, glass dust and metal powder are pre-mixed, then this is pre-mixed to thing mixes with organic carrier, then carry out milled processed, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, by above-mentioned, corrosion etching agent, glass dust and organic carrier are pre-mixed, then add metal powder in this mixture, then carry out milled processed, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, metal powder and organic carrier are pre-mixed, then are pre-mixed in thing and add corrosion etching agent, glass dust at this, then carry out milled processed, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, 20-60 weight portion metal powder and 20-60 weight portion organic carrier are pre-mixed, again 40-80 weight portion corrosion etching agent, glass dust and part organic carrier are pre-mixed, and then be pre-mixed thing mixing by two kinds, milled processed, obtains described crystal silicon solar batteries front electrode electrocondution slurry.
Fig. 2 is used above-mentioned electrocondution slurry to prepare the method process flow diagram of crystal silicon solar batteries front electrode.The preparation method of the high-performance crystal silicon solar batteries front electrode that the embodiment of the present invention provides, comprises the steps:
S04, the crystal silicon semiconductor element that provides a kind of upper face to there is dielectric film, wherein, described dielectric film is at least one superimposed layer in silicon nitride, titanium oxide, aluminium oxide, silica;
S05, is printed on above-mentioned crystal silicon solar batteries front electrode electrocondution slurry on the dielectric film of step S04;
S06, sintering; The step of this sintering is: the described electrocondution slurry being printed on dielectric film is dried at 180 ℃～260 ℃, be heated to 720 ℃～900 ℃ sintering, in sintering engineering, described corrosion etching agent becomes liquid, easily flows, and it and softening glass dust coordinative role, corrode and penetrate the antireflective insulating barrier in crystal silicon solar energy battery front, wetting conductive metal powder, urges into the combination between metal powder, makes conductive metal powder and crystal silicon solar energy battery form good ohmic contact; Cooling, obtain described crystal silicon solar batteries front electrode.
Fig. 3 is the partial structurtes schematic diagram of crystal silicon solar batteries before sintering of having printed described electrocondution slurry.It is worthy of note, this figure is an example, and it should be as the restriction scope of application of the present invention.As shown in Figure 3, crystal silicon solar batteries consists of semiconductor chip 100, emitter 102 and insulating barrier 110, P/N interface is between semiconductor chip 100 and emitter 102, and electrodes conduct slurry 120 is employed on the surface 121 that screen printing technique is optionally printed on insulating barrier 110 parts.Electrodes conduct slurry contains metal dust 122, corrosion etching agent 126, glass dust 124 and organic carrier 128. according to the needs of solar cell design and application, the printing width of electrodes conduct slurry 120 is 30 μ m-～2mm, the printing width of its thin gate electrode is 30～70 μ m, and the printing width of main grid electrode is 1～2mm.
Fig. 4 is the partial structurtes schematic diagram of crystal silicon solar batteries after sintering of having printed described electrocondution slurry.It is worthy of note, this figure is an example, and it should be as the restriction scope of application of the present invention.As shown in Figure 4, electrocondution slurry, through oversintering, is transformed into electrode 200.Sintering is to be heated to 180 ℃ of-260 ℃ of oven dry from 25 ℃, is then heated to 700 ℃ of-950 ℃ of sintering, then cooling, forms electrode 200.In sintering process, along with temperature raises, organic carrier in electrocondution slurry is removed, and corrosion etching agent is molten into liquid 210, to surface of insulating layer 110, flows, along with temperature further raises, glass dust softens (as shown in 230), and the corrosion etching agent 210 of fusing and softening glass dust 230 same functions corrode and penetrate the dielectric film 110 of crystal silicon semiconductor element surface, metal powder is directly contacted with the matrix of crystal silicon semiconductor element, form ohm layer 240.The corrosion etching agent of fusing and softening glass dust are when corroding and penetrating the dielectric film 110 of crystal silicon semiconductor element surface, also effectively soak conductive metal powder, strengthen the contact between metal powder, form the good metal powder combination 220 of electric conductivity, it forms ohmic contact by ohm layer 240 and semiconductor 102, forms the good crystal silicon solar batteries front electrode 200 of electric conductivity.
Further, in front electrode 200 of the present invention, contain after corrosion etching agent and glass dust sintering mixture. above-mentioned corrosion etching agent is for plumbous, tellurium and/or interpolation element (as: lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, at least one in germanium) the formed crystalline compounds of oxide, its melting temperature is 250 ℃～760 ℃, above-mentioned glass dust is Pb-Si-O, Bi-Si-O, Pb-B-O, Bi-B-O, Pb-Te-O, Bi-Te-O, P-Zn-Na-O, B-Al-Na-O, B-Zn-Ba-O, at least one in V-P-Ba-O system glass dust, wherein, described glass dust contains Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, at least one in the oxide of P or Bi, this glass dust is non-crystal structure, and its softening temperature is 250 ℃～650 ℃.
Further, in a preferred case study on implementation, in front electrode 200 of the present invention, contain through the coated metal powder of the non-silver of oversintering, comprise at least one in silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, manganese, palladium, rhodium.
In another one case study on implementation, in front electrode 200 of the present invention, contain through the coated metal powder of the silver of oversintering, comprise at least one in the coated copper of silver, iron, nickel, aluminium, zinc, titanium, cobalt, chromium, manganese, wherein, the thickness of silver coating is 10～2000nm.
In another one case study on implementation, in front electrode 200 of the present invention, contain the mixture through the coated metal powder of the above-mentioned non-silver of oversintering and silver-colored coated metal powder, the coated metal powder of wherein said non-silver is 5/95～95/5 with the weight ratio of silver-colored coated metal powder.
Start to discuss in detail each component of crystal silicon solar batteries front electrode electrocondution slurry provided by the present invention herein below, preparation method, and use.
i. corrode etching agent
Corrosion etching agent of the present invention is crystalline compounds, has fusing point, is different from glass dust.Described corrosion etching agent is plumbous, tellurium and/or the formed crystalline compounds of oxide that adds element (as: at least one in lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium), and its melting temperature is 250 ℃～760 ℃.
Corrosion etching agent of the present invention comprises the one or more kinds of mixtures in crystalline compounds below: PbTe 4O 9, PbTeO 3, PbTeO 4, PbTe 3O 7, PbTe 5O 11, Pb 2TeO 4, Pb 2Te 3O 7, Pb 2Te 3O 8, Pb 3TeO 5, Pb 3TeO 6, Pb 4Te 1.5O 7, Pb 5TeO 7, Pb 5TeO 7, PbTe 2O 5, Li 2TeO 3, Bi 6B 10O 24, Na 2B 8O 13, Bi 4TeO 8, Pb 6Bi 4O 18, PbBi 6Te 10, Bi 2TeO 5, PbBi 6TeO 12, BiTe 0.5Pb 0.5SrNb 2O 9, Pb 0.25SrBi 1.5Te 0.25Nb 2O 9, Pb 3Te 2Br 2O 6, Pb 3TeBr 2O 4, Pb 2CaTeO 6, Pb 2TeCoO 6, PbTe 2CuO 6, PbTeCu 3O7, Pb 3Te 2Fe 2O 12, Pb (Te 0.33Fe 0.67) O 3, Pb 2(Hf 1.5Te 0.5) O 6.5, Pb 2Te (Li 0.5Al 0.5) O 6, Pb 2Te (Li 0.5Bi 0.5) O 6, Pb 2TeLi 0.5Fe 0.5O 6, PbTeLiFeO 6, Pb 2Te (Li 0.5La 0.5) O 6, Pb 2(Ti 1.5Te 0.5) O 6.5, Pb 2(Ti 1.5Te 0.5) O 6.5, Pb 2(Li 0.5Sc 0.5) TeO 6, Pb 2Li 0.5Y 0.5TeO 6, Li 0.5Pb 2Yb 0.5TeO 6, Pb 2MgTeO 6, Pb 11Si 3O 17, Ba (Fe 0.5Mg 0.5) PbTa 0.5Te 0.5O 6, PbBaMgTeO 6, Pb 0.5BaNbTe 2O 9,BaTeO 5, BaTe 4O 9, Pb 2MgTeO 6, Pb 2Mg 0.5Fe 0.5(Ta 0.5Te 0.5) O 6, Pb 2MgSrTeO 6, Pb 2Mg (W 0.9Te 0.1) O 6, Pb 2Mg (W 0.7Te 0.3) O 6, Pb 2Mg (W 0.5Te 0.5) O 6, Pb 2Mg (W 0.4Te 0.6) O 6, Pb 2Mg (W 0.4Te 0.6) O 6,PbMnTeO 6, Pb (Mn 0.5Te 0.5) O 3, Pb 2MnTeO 6, PbMn 2Ni 6Te 3O 18, Pb (Na 0.4Te 0.6) O 3, Pb 2(Na 0.5Bi 0.5) TeO 6, Na 0.5Pb 2Fe 0.5TeO 6, Pb 2(Na 0.5La 0.5) TeO 6, Pb 2Na 0.5Sc 0.5TeO 6, Na 0.5Pb 2Yb 0.5TeO 6,Na 0.5Pb 2Y 0.5TeO 6, Pb 4Te 6Nb 10O 41, Pb 3Ni 4.5Te 2.5O 15, Pb 2NiTeO 6, PbSc 0.5Ti 0.25Te 0.25O 3, Pb 2Sn 1.5Te 0.5O 6.5, Pb 2(Sn 1.5Te 0.5) O 6.5, Pb 2SrTeO 6, Pb 2ZnTeO 6, Pb 3Zn 3TeAs 2O 14, Pb 2(Zr 1.5Te 0.5) O 6.5, PbTe 5O 11, Pb 3(Te2O 6) Cl 2, Pb 2ZnTeO 6In at least one.Described corrosion etching agent is all crystalline compounds, there is typical crystal characteristic, when being heated to its melting temperature, crystal starts fusing, becomes liquid, there is no softening temperature, physical aspects change in its heating process is: directly from the solid-state liquid state that becomes, and glass dust is non-crystalline compounds, the physical aspects change in heating process is: first from solid-state, become softening state, and then become-liquid state.
Corrosion etching agent of the present invention is different from glass dust can be measured and be distinguished by X-ray diffraction (XRD).Each crystalline compounds of described corrosion etching agent, when XRD measures, all can demonstrate sharp-pointed diffractive features peak in specific angle of diffraction, and glass dust is noncrystal, only in low-angle interval, demonstrates the lower bulge of the very wide intensity of distribution.
Corrosion etching agent of the present invention can also be distinguished by transmission electron microscope (TEM) from the remarkable different of glass dust.When any crystalline compounds in corrosion etching agent of the present invention is detected by transmission electron microscope, will show orderly atomic arrangement face, and glass dust will show unordered atomic arrangement face.
Corrosion etching agent of the present invention be spherical, class is spherical, at least one in sheet, strip, dendritic, graininess, colloid particle, its size is not subject to concrete restriction.In a case study on implementation, its size is less than 15 μ m; In another case study on implementation, it is of a size of 0.1-10 μ m; In another case study on implementation, it is of a size of 0.1～7.0 μ m.
Described corrosion etching agent is prepared by one of following method: cooling method is controlled in liquid-phase chemical reaction method, chemical vapour deposition, melting and vacuum fusion is controlled cooling method.
Corrosion etching agent of the present invention can be standby by liquid-phase chemical reaction legal system, and its preparation process is: by tellurium salting liquid, lead salt solution is uniformly mixed at 80 ℃～250 ℃, then adds respectively lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, in germanium, at least one adds the salt compound of element, maintains mixing speed within the scope of 1500r/min, reacts 2～5hrs, generate precipitation, Separation of Solid and Liquid successively then, washing, regather solid, dry 1～3hrs for 150 ℃, obtain a kind of or two or more contain plumbous and tellurium and lithiums, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, in germanium, at least one adds element and the formed crystalline compounds of oxygen.
In a case study on implementation, by tellurium salt (as Na 2teO 3) solution and lead salt be (as lead acetate Pb (CH 3cOO) 2) solution is uniformly mixed at 80 ℃～250 ℃, then adds lithium salts as (LiCl or LiNO 3deng), maintain mixing speed within the scope of 1500r/min, react 2～5hrs, generate precipitation, Separation of Solid and Liquid successively then, washing, regathers solid, dries 1～3hrs for 150 ℃, obtains plumbous tellurium and be crystalline compounds and lithium tellurium and be the mixture of crystalline compounds as PbT eo 3and Li 2t eo 3the one or more kinds of mixtures of crystalline compounds.
In another one case study on implementation, by tellurium salt (as Na 2teO 3) solution and lead acetate (Pb (CH 3cOO) 2) solution is uniformly mixed at 80 ℃～250 ℃, then adds barium salt as BaCl 2with magnesium salts as MgSO 4, maintain mixing speed within the scope of 1500r/min, react 2～5hrs, stopping heating and obtaining containing plumbous tellurium with the cooling rear generation precipitation of room temperature is that crystalline compounds and barium tellurium are the mixture of crystalline compounds, as PbTeO 3, PbBaMgTeO 6and Pb 2mgTeO 6one or more kinds of its mixtures of crystalline compounds.
In another one case study on implementation, by tellurium salt (as Na 2teO 3) solution and lead acetate (Pb (CH 3cOO) 2) solution is uniformly mixed at 80 ℃～120 ℃, then adds lithium salts as LiCl, barium salt BaCl 2with bismuth salting liquid as Bi(NO 3) 2solution, maintain mixing speed within the scope of 1500r/min, reaction 2～5hrs, stopping heating, with the cooling rear generation precipitation of room temperature, to obtain plumbous tellurium be that crystalline compounds, barium tellurium are that crystalline compounds, bismuth tellurium are that crystalline compounds and lithium tellurium are the mixture of crystalline compounds, for example PbTeO 3, Li 2teO 3, Pb5Bi 4o 18, PbBi 6teO 12, Bi 2teO 5one or more kinds of mixtures Deng crystalline compounds.
In another one case study on implementation, by tellurium salt (as Na 2teO 3) solution and lead acetate (Pb (CH 3cOO) 2) solution is uniformly mixed at 80 ℃～250 ℃, then adds lithium salts as LiCl or LiNO 3with molysite as Fe (OH) 3maintain mixing speed within the scope of 1500r/min, reaction 2～5hrs, stop heating and precipitate with the cooling rear generation of room temperature, then Separation of Solid and Liquid successively, washing, regathers solid, dry 1～3hrs for 150 ℃, obtain the mixture of the multiple crystalline compounds that contains plumbous and tellurium and lithium, iron and oxygen formation as PbTeO 3, Li 2teO 3, Li 0.5pb 2f e0.5t eo 6one or more kinds of mixtures Deng crystalline compounds.
Change the chemical reaction condition of above case study on implementation, comprise change chemical composition or reaction temperature time, can obtain the similar or approaching crystalline compounds of performance.
Corrosion etching agent of the present invention also available melting is controlled cooling method preparation, and its preparation process is: the oxide of tellurium is mixed with plumbous oxide, then optionally add respectively lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the oxide of a kind of or two or more interpolation elements in germanium, more further evenly mix, be then placed in crucible, put into the irreducibility atmosphere of heating furnace at 800 ℃～1200 ℃ and (comprise oxygen atmosphere, air atmosphere, nitrogen atmosphere, the mixing of argon gas atmosphere or above gas) in, in molten condition, it is reacted, then from heating furnace, take out, be positioned over that in air atmosphere, (or reducing atmosphere comprises oxygen atmosphere, air atmosphere, nitrogen atmosphere, the mixing of argon gas atmosphere or above gas), naturally cool to 25 ℃ or cool to 25 ℃ with the furnace, pulverize, after milled processed, obtain one or more by plumbous and tellurium and interpolation element lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the formed crystalline compounds of at least one in germanium and oxygen, its melting temperature is 250 ℃～760 ℃.
Crystalline compounds of the present invention comprises a kind of or two or more in following crystalline compounds: PbTe 4O 9, PbTeO 3, PbTe 4O 9, PbTeO 3, PbTeO 4, PbTe 3O 7, PbTe 5O 11, Pb 2TeO 4, Pb 2Te 3O 7, Pb 2Te 3O 8, Pb 3TeO 5, Pb 3TeO 6, Pb 4Te 1.5O 7, Pb 5TeO 7, Pb 5TeO 7, PbTe 2O 5, Li 2TeO 3, Bi 6B 10O 24, Na 2B 8O 13, Bi 4TeO 8, Pb 6Bi 4O 18, PbBi 6Te 10, Bi 2TeO 5, PbBi 6TeO 12, BiTe 0.5Pb 0.5SrNb 2O 9, Pb 0.25SrBi 1.5Te 0.25Nb 2O 9, Pb 3Te 2Br 2O 6, Pb 3TeBr 2O 4,Pb 2CaTeO 6, Pb 2TeCoO 6, PbTe 2CuO 6, PbTeCu 3O 7, Pb 3Te 2Fe 2O 12, Pb (Te 0.33Fe 0.67) O 3, Pb 2(Hf 1.5Te 0.5) O 6.5, Pb 2Te (Li 0.5Al 0.5) O 6, Pb 2Te (Li 0.5Bi 0.5) O 6, Pb 2TeLi 0.5Fe 0.5O 6, PbTeLiFeO 6, Pb 2Te (Li 0.5La 0.5) O 6, Pb 2(Ti 1.5Te 0.5) O 6.5, Pb 2(Ti 1.5Te 0.5) O 6.5, Pb 2(Li 0.5Sc 0.5) TeO 6, Pb 2Li 0.5Y 0.5TeO 6, Li 0.5Pb 2Yb 0.5TeO 6, Pb 2MgTeO 6, Pb 11Si 3O 17, Ba (Fe 0.5Mg 0.5) PbTa 0.5Te 0.5O 6,PbBaMgTeO 6, Pb 0.5BaNbTe 2O 9, BaTeO 5, BaTe 4O 9, Pb 2MgTeO 6, Pb 2Mg 0.5Fe 0.5(Ta 0.5Te 0.5) O 6, Pb 2MgSrTeO 6, Pb 2Mg (W 0.9Te 0.1) O 6, Pb 2Mg (W 0.7Te 0.3) O 6, Pb 2Mg (W 0.5Te 0.5) O 6, Pb 2Mg (W 0.4Te 0.6) O 6,Pb 2Mg (W 0.4Te 0.6) O 6, PbMnTeO 6, Pb (Mn 0.5Te 0.5) O 3, Pb 2MnTeO 6, PbMn 2Ni 6Te 3O 18, Pb (Na 0.4Te 0.6) O 3, Pb 2(Na 0.5Bi 0.5) TeO 6, Na 0.5Pb 2Fe 0.5TeO 6, Pb 2(Na 0.5La 0.5) TeO 6, Pb 2Na 0.5Sc 0.5TeO 6,Na 0.5Pb 2Yb 0.5TeO 6, Na 0.5Pb 2Y 0.5TeO 6, Pb 4Te 6Nb 10O 41, Pb 3Ni 4.5Te 2.5O 15, Pb 2NiTeO 6, PbSc 0.5Ti 0.25Te 0.25O 3, Pb 2Sn 1.5Te 0.5O 6.5, Pb 2(Sn 1.5Te 0.5) O 6.5, Pb 2SrTeO 6, Pb 2ZnTeO 6, Pb 3Zn 3TeAs 2O 14, Pb 2(Zr 1.5Te 0.5) O 6.5, PbTe 5O 11, Pb 3(Te2O 6) Cl 2, Pb 2ZnTeO 6In at least one.Described crystalline compounds be also included in small region memory more than two yuan or two yuan small low-melting alloy crystal (Eutectic) as plumbous tellurium bismuth (Pb-Te-Bi), plumbous tellurium lithium (Pb-Te-Li), as plumbous tellurium silver bismuth (Pb-Te-Ag-Bi) alloy etc.
Change the condition of above case study on implementation, can obtain the similar crystalline compounds of performance.For example, reaction can be carried out after melting in the temperature below 700 ℃ or more than 1200 ℃, can use the mobile protective gas not heating (as N2, CO2, Ar 2deng) flow through its molten mass surface, accelerate cooling rate, or use the protective gas of heating (as N 2, CO 2, Ar 2deng) flowing through its molten mass surface, the cooling rate that slows down, obtains its crystalline compounds.
In a case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2o or Li 2cO 3further evenly mix again, then be placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then from heating furnace, take out, be positioned in air atmosphere, naturally cool to 25 ℃ or cool to 25 ℃ with the furnace, pulverize, after milled processed, obtain multiple two yuan or the two yuan mixtures that contain above the crystalline compounds of lead, tellurium and lithium and oxygen formation.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2o or Li 2cO 3, boron oxide B 2o 3with the oxide of bismuth as Bi 2o 3further evenly mix again, then be placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then from heating furnace, take out, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, after milled processed, obtain multiple two yuan or the two yuan mixtures that contain above the crystalline compounds of lead, tellurium, lithium, boron and bismuth and oxygen formation.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3, titanyl compound is as TiO 2with the oxide of barium as BaO, further evenly mix again, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium and barium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3, titanyl compound is as TiO 2, barium oxide if the oxide of BaO, sodium is as Na 2o, and aluminium oxide is as Al 2o 3further evenly mix again, then be placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃-1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, aluminium, sodium and barium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3, titanyl compound is as TiO 2, barium oxide if the oxide of BaO, tungsten is as WO 3further evenly mix again, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, tungsten and barium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3, titanyl compound is as TiO 2, barium oxide if the oxide of BaO, tungsten is as WO 3, tantalum oxide as Ta 2o 5further evenly mix again, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, tungsten, tantalum and barium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3, titanyl compound is as TiO 2, barium oxide if the oxide of BaO, tungsten is as WO 3, tantalum oxide as Ta 2o 5with the oxide of chromium as Cr 2o 3further evenly mix again, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, tungsten, tantalum, chromium and barium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, silicon oxide as SiO 2, the oxide of boron is as B 2o 3, bismuth oxide as Bi 2o 3, titanyl compound is as TiO 2, barium oxide if the oxide of BaO, tungsten is as WO 3, tantalum oxide as Ta 2o 5with the oxide of chromium as Cr 2o 3further evenly mix again, then be placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, tungsten, tantalum, silicon, chromium and barium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3, titanyl compound is as TiO 2, the oxide of zinc is if the oxide of ZnO, tungsten is as WO 3, tantalum oxide as Ta 2o 5with the oxide of chromium as Cr 2o 3further evenly mix again, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, tungsten, tantalum, zinc and chromium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3, titanyl compound is as TiO 2, the oxide of zinc is if the oxide of ZnO, niobium is as Nb 2o 5, magnesium oxide if the oxide of MgO, tungsten is as WO 3, tantalum oxide as Ta 2o 5with the oxide of chromium as Cr 2o 3further evenly mix again, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, niobium, magnesium, tungsten, tantalum, zinc and chromium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3, titanyl compound is as TiO 2, barium oxide if the oxide of BaO, yttrium is as Y 2o 3, zirconium oxide as ZrO 2with the oxide of chromium as Cr 2o 3further evenly mix again, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, zirconium, yttrium, chromium and barium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3, titanyl compound is as TiO 2, the oxide of barium is if the oxide of BaO, lanthanum is as La 2o 3, scandium oxide as Sc 2o 3with the oxide of chromium as Cr 2o 3further evenly mix again, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, zirconium, lanthanum, chromium, scandium and barium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, silicon oxide as SiO 2, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3with titanyl compound as TiO 2, more further evenly mix, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, silicon.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3with titanyl compound as TiO 2, more further evenly mix, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, silicon oxide as SiO 2, boron oxide as B 2o 3, bismuth oxide as Bi 2o 3, titanyl compound is as TiO 2, aluminium oxide as Al 2o 3, more further evenly mix, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃～1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, silicon and aluminium.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, the oxide of silicon is as SiO 2, the oxide of boron is as B 2o 3, the oxide of bismuth is as Bi 2o 3, and titanyl compound is as TiO 2further evenly mix again, be then placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃-1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium and silicon.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, the oxide of silicon is as SiO 2, the oxide of boron is as B 2o 3, the oxide of bismuth is as Bi 2o 3, titanyl compound is as TiO 2evenly mix as CuO2 is further again with the oxide of copper, then be placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃-1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of titanium, copper and silicon.
In another one case study on implementation, first by the oxide of tellurium as TeO 2with plumbous oxide as Pb 3o 4or PbO mixes, and then adds the oxide of lithium as Li 2cO 3, the oxide of silicon is as SiO 2, the oxide of boron is as B 2o 3, the oxide of bismuth is as Bi 2o 3, titanyl compound is as TiO 2the oxide of ruthenium is as RuO4, evenly mix as CuO2 is further again with the oxide of copper, then be placed in crucible, put into air atmosphere or the oxygen atmosphere of heating furnace at 800 ℃-1200 ℃, under molten condition, it is reacted, then cool to 25 ℃ or take out with the furnace from heating furnace, be positioned in air atmosphere, naturally cool to 25 ℃, pulverize, pulverize, after milled processed, obtain multiple two yuan or two yuan and contain above lead, tellurium, lithium, bismuth, boron, the mixture of the crystalline compounds of ruthenium, titanium, copper and silicon.
Corrosion etching agent of the present invention also vacuum available melting is controlled cooling method preparation, and its preparation process is: the oxide of tellurium is mixed with plumbous oxide, then add respectively lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, in germanium, at least one adds the oxide of element, further evenly mix again, then be placed in crucible, put into vacuum furnace, in the atmosphere in vacuum at 800 ℃～1200 ℃, carry out melting, then, naturally cool to 25 ℃, pulverize again, after milled processed, obtain one or more two yuan or two yuan and contain above plumbous and tellurium and lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium etc. add element and the formed crystalline compounds of oxygen.
As appreciated by those skilled in the art, change the chemical reaction condition of above case study on implementation, can obtain the similar plumbous tellurium of performance is crystalline compounds.For example, its smelting temperature can be below 700 ℃ or more than 1200 ℃; Again for example, after melting completes, except using the cooling method of nature, can also use the mobile protective gas not heating (as N 2, CO 2, Ar 2deng) flow through its molten mass surface, accelerate to be cooled to 25 ℃, or use the protective gas of heating (as N 2, CO 2, Ar 2deng) flowing through its molten mass surface, the cooling rate that slows down, is cooled to 25 ℃.
Corrosion etching agent of the present invention is available chemical vapour deposition preparation also, its preparation process is: tellurium and plumbous gas are imported in the reative cell of oxygen atmosphere continuously, then add respectively lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the gas of at least one in germanium, make it 1000～1300 ℃ of reactions 1～3 hour, naturally cool to after 25 ℃, after milled processed, obtain one or more by plumbous and tellurium and interpolation element lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, the formed crystalline compounds of at least one in germanium and oxygen, its melting temperature is 250 ℃～760 ℃.
Particularly, below by exemplary case study on implementation and contrast property case study on implementation, further illustrating the present invention uses crystalline compounds corrosion etching agent to use merely glass dust to have advantages of in conventional method:
Exemplary case study on implementation 1: first by 14g TeO 2with 8.75g Pb 3o 4oxide powder mixes, and then, adds successively 0.75g Al 2o 3with 1.5g Li 2cO 3oxide powder, further evenly mix again, then be placed in crucible, put into heating furnace, be warming up to 900 ℃, in the air atmosphere at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment naturally coolingly, form block.The block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder of ball milling, within the scope of 0.1～15 μ m, obtains its crystalline compounds.The temperature of the mixture of melting in stove is 900 ℃, and after taking out from stove, temperature drops to 732 ℃.Fig. 5 is cooling time after the mixture of melting takes out from stove and the relation of temperature, record is since 732 ℃, can find out, in the 1st minute, from 732 ℃, be cooled to 593 ℃, average cooling rate is 139 ℃/min, in second minute, from 593 ℃, be cooled to 504 ℃, average cooling rate is 89 ℃/min, in the 3rd minute, from 504 ℃, be cooled to 449 ℃, average cooling rate is 55 ℃/min, in the 4th minute, is cooled to 416.2 ℃ from 449 ℃, and average cooling rate is 32.8 ℃/min, at this moment, molten mass has become crystal.After being cooled to 25 ℃, the block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again.By XRD, the crystalline compounds of preparing in above-mentioned case study on implementation has been carried out to analytical control, result as shown in Figure 6 a.From Fig. 6 a, Li 2teO 3and PbTeO 3the angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, Al 2o 3but the angle of diffraction that characteristic peak is corresponding demonstrates a lower sharp-pointed diffractive features peak, so exemplary case study on implementation 1 has obtained Li 2teO 3and PbTeO 3the mixture of two kinds of crystalline compounds and small Al 2o 3crystal.
Contrast property case study on implementation 1: first by 14g TeO 2with 8.75g Pb 3o 4oxide powder mixes, and then, adds successively 0.75g Al 2o 3with 1.5g Li 2cO 3oxide powder, further evenly mix again, then be placed in crucible, put into heating furnace and exist, be warming up to 900 ℃, in the air atmosphere at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, pour in the deionized water of 25 ℃ and quench, obtain block.The block obtaining obtains granule through pulverizing again, granule is formed to powder by ball milling again, the powder D of ball milling 50within the scope of 0.1～15 μ m, obtained glass dust.By XRD, the glass dust of preparing in above-mentioned case study on implementation has been carried out to analytical control, result as shown in Figure 6 b.From Fig. 6 b, the XRD of described glass dust check demonstrates the lower bulge of the very wide intensity of distribution, does not demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 1 and contrast property case study on implementation 1, prepared crystalline compounds has identical chemical composition with glass dust, but, because its preparation method is different, internal structure is different, atomic arrangement is different, has caused their change procedures of physical state in heating process to have obvious difference.Wherein, the former is crystalline compounds Li of the present invention 2teO 3and PbTeO 3, the physical aspects change in heating process is: solid-state-liquid state; The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid state.
Exemplary case study on implementation 2: first by 3.5g TeO 2with 6.6g Pb 3o 4oxide powder mixes, and then, adds 0.45g SiO 2oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 1000 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment and naturally cool to 25 ℃, form block.The block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder of ball milling, within the scope of 0.1～15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparing in above-mentioned case study on implementation has been carried out to analytical control, result as shown in Figure 7a.From Fig. 7 a, PbTeO 3, Pb 11si 3o 17the angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 2 has obtained PbTeO 3and Pb 11si 3o 17the mixture crystal of two kinds of crystalline compounds.
Contrast property case study on implementation 2: first by 3.5g TeO 2with 6.6g Pb 3o 4oxide powder mixes, and then, adds 0.45g SiO 2oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 1000 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, pour in the deionized water of 25 ℃ and quench, obtain block.The block obtaining obtains granule through pulverizing again, granule is formed to powder by ball milling again, the powder D of ball milling 50within the scope of 0.1～15 μ m, obtained glass dust.By XRD, the glass dust of preparing in above-mentioned case study on implementation has been carried out to analytical control, result as shown in Figure 7b.From Fig. 7 b, the XRD of described glass dust check demonstrates the lower bulge of the very wide intensity of distribution, does not demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 2 and contrast property case study on implementation 2, prepared crystalline compounds has identical chemical composition with glass dust, but, because its preparation method is different, internal structure is different, atomic arrangement is different, has caused their change procedures of physical state in heating process to have obvious difference.Wherein, the former is crystalline compounds PbTeO of the present invention 3and Pb 11si 3o 17, the physical aspects change in heating process is: solid-state-liquid state; The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid state.
Exemplary case study on implementation 3: first by 4.9g TeO 2with 6.6g Pb 3o 4oxide powder mixes, and then, adds 0.24g BaO 2oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment and naturally cool to 25 ℃, form block.The block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder of ball milling, within the scope of 0.1～15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparing in above-mentioned case study on implementation has been carried out to analytical control, result as shown in Figure 8 a.From Fig. 8 a, PbTeO 3, BaTeO 5, and BaTe 4o 9the angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 3 has obtained PbTeO 3, BaTeO 5and BaTe 4o 9, the mixture of three kinds of crystalline compounds and BaO crystal.
Contrast property case study on implementation 3: first by 4.9g TeO 2with 6.6g Pb 3o 4oxide powder mixes, and then, adds 0.24g BaO 2oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, pour in the deionized water of 25 ℃ and quench, obtain block.The block obtaining obtains granule through pulverizing again, granule is formed to powder by ball milling again, the powder D of ball milling 50within the scope of 0.1～15 μ m, obtained glass dust.By XRD, the glass dust of preparing in above-mentioned case study on implementation has been carried out to analytical control, result as shown in Figure 8 b.From Fig. 8 b, the XRD of described glass dust check demonstrates the lower bulge of the very wide intensity of distribution, does not demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 3 and contrast property case study on implementation 3, prepared crystalline compounds has identical chemical composition with glass dust, but, because its preparation method is different, internal structure is different, atomic arrangement is different, has caused their change procedures of physical state in heating process to have obvious difference.Wherein, the former is crystalline compounds PbTeO of the present invention 3, Ba 11teO 5and BaTe 4o 9the mixture of three kinds of crystalline compounds, the physical aspects change in heating process is: solid-state-liquid state; The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid state.
Exemplary case study on implementation 4: first by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.44g Bi 2o 3oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 1100 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment and naturally cool to 25 ℃, form block.The block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder of ball milling, within the scope of 0.1～15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Fig. 9 a.From Fig. 9 a, Bi 4teO 8and PbTeO 3the angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 4 has obtained Bi 4teO 8and PbTeO 3the mixture of two kinds of crystalline compounds.
Contrast property case study on implementation 4: first by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.44g Bi 2o 3oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, pour in the deionized water of 25 ℃ and quench, obtain block.The block obtaining obtains granule through pulverizing again, granule is formed to powder by ball milling again, the powder D of ball milling 50within the scope of 0.1～15 μ m, obtained glass dust.By XRD, the glass dust of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Fig. 9 b.From Fig. 9 b, the XRD of described glass dust check demonstrates the lower bulge of the very wide intensity of distribution, does not demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 4 and contrast property case study on implementation 4, prepared crystalline compounds has identical chemical composition with glass dust, but, because its preparation method is different, internal structure is different, atomic arrangement is different, has caused their change procedures of physical state in heating process to have obvious difference.Wherein, the former is crystalline compounds Bi of the present invention 4teO 8and PbTeO 3the mixture of two kinds of crystalline compounds, the physical aspects change in heating process is: solid-state-liquid state; The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid state.
Exemplary case study on implementation 5: first by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.25g Bi 2o 3oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 1100 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment and naturally cool to 25 ℃, form block.The block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder of ball milling, within the scope of 0.1-15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Figure 10 a.From Figure 10 a, Bi 4teO 8, Bi 2teO 5, and PbTeO 3the angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 6 has obtained Bi 4teO 8, Bi 2teO 5, and PbTeO 3the mixture of three kinds of crystalline compounds.
Contrast property case study on implementation 5: first by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.25g Bi 2o 3oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 1100 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, pour in the deionized water of 25 ℃ and quench, obtain block.The block obtaining obtains granule through pulverizing again, and granule is formed to powder by ball milling again, and the powder D50 of ball milling, within the scope of 0.1-15 μ m, has obtained glass dust.By XRD, the glass dust of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Figure 10 b.From Figure 10 b, the XRD of described glass dust check demonstrates the lower bulge of the very wide intensity of distribution, does not demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 5 and contrast property case study on implementation 5, prepared crystalline compounds has identical chemical composition with glass dust, but, because its preparation method is different, internal structure is different, atomic arrangement is different, has caused their change procedures of physical state in heating process to have obvious difference.Wherein, the former is crystalline compounds Bi of the present invention 4teO 8, Bi 2teO 5, and PbTeO 3the mixture of three kinds of crystalline compounds, the physical aspects change in heating process is: solid-state-liquid state.The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid state.
Exemplary case study on implementation 6: first by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.44g Bi 2o 3oxide powder, 0.05g B 2o 3oxide powder and 1.25g Li 2cO 3oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 1100 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment and naturally cool to 25 ℃, form block.The block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder of ball milling, within the scope of 0.1～15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Figure 11 a.From Figure 11 a, Bi 24b 2o 39, Pb 5b 2o 5, Pb 5teO 7and Li 6teO 6the angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 6 has obtained Bi 24b 2o 39, Pb 5b 2o 5, Pb 5teO 7and Li 6teO 6the mixture of four kinds of crystalline compounds.
Contrast property case study on implementation 6: first by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.44g Bi 2o 3oxide powder, 0.05g B 2o 3oxide powder and 1.25g Li 2cO 3oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 1100 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, pour in the deionized water of 25 ℃ and quench, obtain block.The block obtaining obtains granule through pulverizing again, granule is formed to powder by ball milling again, the powder D of ball milling 50within the scope of 0.1～15 μ m, obtained glass dust.By XRD, the glass dust of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Figure 11 b.From Figure 11 b, the XRD of described glass dust check demonstrates the lower bulge of the very wide intensity of distribution, does not demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 6 and contrast property case study on implementation 6, prepared crystalline compounds has identical chemical composition with glass dust, but, because its preparation method is different, internal structure is different, atomic arrangement is different, has caused their change procedures of physical state in heating process to have obvious difference.Wherein, the former is crystalline compounds Bi of the present invention 24b 2o 39, Pb 5b 2o 5, Pb 5teO 7, and Li 6teO 6the mixture of four kinds of crystalline compounds, the physical aspects change in heating process is: solid-state-liquid state; The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid state.
Exemplary case study on implementation 7: first by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.44g Bi 2o 3oxide powder, 0.05g B 2o 3oxide powder and 1.25g TiO 2oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 1100 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment and naturally cool to 25 ℃, form block.The block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder of ball milling, within the scope of 0.1～15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Figure 12 a.From Figure 12 a, Bi 4teO 8, Pb 3bi 2o 6, Pb 2b 2o 5and PbTiO 3the angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 7 has obtained Bi 4teO 8, Pb 3bi 2o 6, Pb 2b 2o 5and PbTiO 3the mixture of four kinds of crystalline compounds.
Contrast property case study on implementation 7: first by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.44g Bi 2o 3oxide powder, 0.05g B 2o 3oxide powder and 1.25g TiO 2oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 1100 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, pour in the deionized water of 25 ℃ and quench, obtain block.The block obtaining obtains granule through pulverizing again, granule is formed to powder by ball milling again, the powder D of ball milling 50within the scope of 0.1～15 μ m, obtained glass dust.By XRD, the glass dust of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Figure 12 b.From Figure 12 b, the XRD of described glass dust check demonstrates the lower bulge of the very wide intensity of distribution, does not demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 7 and contrast property case study on implementation 7, prepared crystalline compounds has identical chemical composition with glass dust, but, because its preparation method is different, internal structure is different, atomic arrangement is different, has caused their change procedures of physical state in heating process to have obvious difference.Wherein, the former is crystalline compounds Bi of the present invention 24b 2o 39, Pb 5b 2o 5, Pb 5teO 7and Li 6teO 6the mixture of four kinds of crystalline compounds, the physical aspects change in heating process is: solid-state-liquid state; The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid state.
Exemplary case study on implementation 8: first by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.44g Bi 2o 3oxide powder, 0.05g B 2o 3oxide powder, and 1.25g TiO 2oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 1100 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment and naturally cool to 25 ℃, form block.The block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder of ball milling, within the scope of 0.1-15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Figure 13 a.From Figure 13 a, Ti 2teO 8, Pb2Te 3o 8, Pb 5bi8O 17, and PbBiO 6the angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 8 has obtained Ti 2teO 8, Pb 2te 3o 8, Pb 5bi8O 17, and Pb 3biO 6the mixture of four kinds of crystalline compounds.
Contrast property case study on implementation 8: first by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.44g Bi 2o 3oxide powder, 0.05g B 2o 3oxide powder, and 1.25g TiO 2oxide powder, more further evenly mix, be then placed in crucible, put into the air atmosphere of heating furnace at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, pour in the deionized water of 25 ℃ and quench, obtain block.The block obtaining obtains granule through pulverizing again, and granule is formed to powder by ball milling again, and the powder D50 of ball milling, within the scope of 0.1-15 μ m, has obtained glass dust.By XRD, the glass dust of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Figure 13 b.From Figure 13 b, the XRD of described glass dust check demonstrates the lower bulge of the very wide intensity of distribution, does not demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 8 and contrast property case study on implementation 8, prepared crystalline compounds has identical chemical composition with glass dust, but, because its preparation method is different, internal structure is different, atomic arrangement is different, has caused their change procedures of physical state in heating process to have obvious difference.Wherein, the former is crystalline compounds Ti of the present invention 2teO 8, Pb2Te 3o 8, Pb 5bi8O 17, and PbBiO 6the mixture of four kinds of crystalline compounds, the physical aspects change in heating process is: solid-state-liquid state.The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid state.
Exemplary case study on implementation 9: by 12g TeO 2with 0.625g B 2o 3, 1.25g Bi 2o 3, and 1.5g Li 2cO 3oxide powder evenly mixes, and is then placed in crucible, puts into heating furnace, be warming up to 1100 ℃, in the air atmosphere at 1100 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment naturally coolingly, form block.The block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder of ball milling, within the scope of 0.1-15 μ m, obtains its crystalline compounds.By XRD, the crystalline compounds of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Figure 14 a.From Figure 14 a, Li 2teO 3and Bi 6b 10o 24the angle of diffraction that characteristic peak is corresponding demonstrates sharp-pointed diffractive features peak, so exemplary case study on implementation 9 has obtained Li 2teO 3and Bi 6b 10o 24the mixture of two kinds of crystalline compounds and small Al 2o 3crystal.
Contrast property case study on implementation 9: by 12g TeO 2with 0.625g B 2o 3, 1.25g Bi 2o 3, and 1.5g Li 2cO 3oxide powder evenly mixes, then be placed in crucible, put into heating furnace, be warming up to 1100 ℃, in air atmosphere at 1100 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, pour in the deionized water of 25 ℃ and quench, obtain block.The block obtaining obtains granule through pulverizing again, and granule is formed to powder by ball milling again, and the powder D50 of ball milling, within the scope of 0.1-15 μ m, has obtained glass dust.By XRD, the glass dust of preparing in above-mentioned case study on implementation has been carried out to analytical control, result is as shown in Figure 14 b.From Figure 14 b, the XRD of described glass dust check demonstrates the lower bulge of the very wide intensity of distribution, does not demonstrate sharp-pointed diffractive features peak.
In above-mentioned exemplary case study on implementation 9 and contrast property case study on implementation 9, prepared crystalline compounds has identical chemical composition with glass dust, but, because its preparation method is different, internal structure is different, atomic arrangement is different, has caused their change procedures of physical state in heating process to have obvious difference.Wherein, the former is crystalline compounds Li of the present invention 2teO 3and Bi 6b 10o 24, the physical aspects change in heating process is: solid-state-liquid state.The latter is glass dust, and the physical aspects change in heating process is: solid-state-softening state-liquid state.
Electrode slurry of the present invention contains glass dust and crystalline compounds corrosion etching agent simultaneously.In slurry sintering process, when temperature reaches fusing point, its crystalline compounds corrosion etching agent physical aspect is changed to liquid state by solid-state.Before fusing point, be solid, can be filled between metal powder particle in hole, can not hinder the discharge of organic component, thereby effectively avoid as the glass dust softening blockage problem of bringing in early days; After the fusing of corrosion etching agent, for liquid state, its viscosity is low, can by the space between metal powder, flow into bottom rapidly, the antireflective insulating barrier that can effectively corrode and penetrate crystal silicon solar energy battery front, makes conductive metal powder and crystal silicon solar energy battery form good ohmic contact, can effectively soak conductive metal powder, urge into the combination between metal powder, form the good crystal silicon solar batteries front electrode of electric conductivity.The crystalline compounds corrosion etching agent of its liquid condition, easily sprawls, and more interface can be provided, and increases contact point and the tunnel effect of conduction, and the electrode resistance forming is diminished.Inventor finds under study for action, if the content of the corrosion etching agent in above-described embodiment crystal silicon solar batteries front electrode electrocondution slurry is greater than 10 weight portions, may burn PN junction, causes short circuit; If corrosion etching agent is less than 0.5 weight portion, may be difficult to remove antireflection layer completely, cause the crystal silicon solar batteries performance of preparation to worsen.Therefore, frit is controlled within the scope of 0.5～10wt% with the total weight ratio of corrosion etching agent, and frit is 5/95～95/5 with the weight ratio of corrosion etching agent.
iI. glass dust and corrosion etching agent
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention, contain corrosion etching agent and glass dust, this corrosion etching agent and the weight ratio of glass dust total amount in electrodes conduct slurry are 0.5-10%, and the part by weight of corrosion etching agent and glass dust can be 5/95-95/5.
Corrosion etching agent of the present invention be plumbous, tellurium and/or add element (as in lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium at least one) the formed crystalline compounds of oxide, its melting temperature is 250 ℃～760 ℃.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.Crystalline compounds of the present invention comprises in following crystalline compounds: PbTe 4O 9, PbTeO 3, PbTeO 4, PbTe 3O 7, PbTe 5O 11, Pb 2TeO 4, Pb 2Te 3O 7, Pb 2Te 3O 8, Pb 3TeO 5, Pb 3TeO 6, Pb 4Te 1.5O 7, Pb 5TeO 7, Pb 5TeO 7, PbTe 2O 5, Li 2TeO 3, Bi 6B 10O 24, Na 2B 8O 13, Bi 4TeO 8, Pb 6Bi 4O 18, PbBi 6Te 10, Bi 2TeO 5, PbBi 6TeO 12, BiTe 0.5Pb 0.5SrNb 2O 9, Pb 0.25SrBi 1.5Te 0.25Nb 2O 9, Pb 3Te 2Br 2O 6, Pb 3TeBr 2O 4, Pb 2CaTeO 6, Pb 2TeCoO 6, PbTe 2CuO 6, PbTeCu 3O 7, Pb 3Te 2Fe 2O 12, Pb (Te 0.33Fe 0.67) O 3, Pb 2(Hf 1.5Te 0.5) O 6.5, Pb 2Te (Li 0.5Al 0.5) O 6, Pb 2Te (Li 0.5Bi 0.5) O 6, Pb 2TeLi 0.5Fe 0.5O 6, PbTeLiFeO 6, Pb 2Te (Li 0.5La 0.5) O 6, Pb 2(Ti 1.5Te 0.5) O 6.5, Pb 2(Ti 1.5Te 0.5) O 6.5, Pb 2(Li 0.5Sc 0.5) TeO 6, Pb 2Li 0.5Y 0.5TeO 6, Li 0.5Pb 2Yb 0.5TeO 6, Pb 2MgTeO 6, Pb 11Si 3O 17, Ba (Fe 0.5Mg 0.5) PbTa 0.5Te 0.5O 6,PbBaMgTeO 6, Pb 0.5BaNbTe 2O 9, BaTeO 5, BaTe 4O 9, Pb 2MgTeO 6, Pb 2Mg 0.5Fe 0.5(Ta 0.5Te 0.5) O 6, Pb 2MgSrTeO 6, Pb 2Mg (W 0.9Te 0.1) O 6, Pb 2Mg (W 0.7Te 0.3) O 6, Pb 2Mg (W 0.5Te 0.5) O 6, Pb 2Mg (W 0.4Te 0.6) O 6, Pb 2Mg (W 0.4Te 0.6) O 6, PbMnTeO 6, Pb (Mn 0.5Te 0.5) O 3, Pb 2MnTeO 6, PbMn 2Ni 6Te 3O 18, Pb (Na 0.4Te 0.6) O 3, Pb 2(Na 0.5Bi 0.5) TeO 6, Na 0.5Pb 2Fe 0.5TeO 6, Pb 2(Na 0.5La 0.5) TeO 6, Pb 2Na 0.5Sc 0.5TeO 6, Na 0.5Pb 2Yb 0.5TeO 6, Na 0.5Pb 2Y 0.5TeO 6, Pb 4Te 6Nb 10O 41, Pb 3Ni 4.5Te 2.5O 15, Pb 2NiTeO 6, PbSc 0.5Ti 0.25Te 0.25O 3, Pb 2Sn 1.5Te 0.5O 6.5, Pb 2(Sn 1.5Te 0.5) O 6.5, Pb 2SrTeO 6, Pb 2ZnTeO 6, Pb 3Zn 3TeAs 2O 14, Pb 2(Zr 1.5Te 0.5) O 6.5, PbTe 5O 11, Pb 3(Te2O 6) Cl 2, Pb 2ZnTeO 6In at least one.
Glass dust of the present invention includes lead glass powder and lead-free glass powder: have lead glass powder to comprise Pb-Si-O, Pb-B-O and Pb-Te-O system; Lead-free glass powder comprise Bi-Si-O, Bi-B-O,, Bi-Te-O, P-Zn-Na-O, B-Al-Na-O, B-Zn-Ba-O and V-P-Ba-O system.This glass dust size is not subject to concrete restriction, and in a case study on implementation, its size is less than 10 μ m, and in another case study on implementation, its size is less than 5 μ m.
One or more in the interpolation element oxides such as the oxide of plumbous, silicon and Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, B, Al, Sn, P, Bi of Pb-Si-O glass dust of the present invention form, above oxide is mixed in proportion, be heated to molten condition, then, the mixture of molten condition is quenched, grind and obtain its glass dust.Described glass dust is noncrystal.In an exemplary embodiment, described Pb-Si-O glass dust is 0.5～10% with the weight ratio of corrosion etching agent in electrocondution slurry.
Pb-Te-O glass dust of the present invention is by the oxide of plumbous, tellurium and add one or more in the oxide of element Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, P, Bi etc. and form, by a kind of or two or more mixing in proportion in lead, the oxide of tellurium and the oxide of above interpolation element, be heated to molten condition, then, the mixture of molten condition is quenched, grind and obtain this glass dust.This glass dust is noncrystal.In an exemplary embodiment, described Pb-Te-O glass dust is 0.5～10% with the weight ratio of corrosion etching agent in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
Pb-B-O glass dust of the present invention is by the oxide of plumbous, boron and add one or more in the oxide of element Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, Al, Sn, P, Te, Bi etc. and form, by a kind of or two or more mixing in proportion in lead, the oxide of boron and the oxide of above interpolation element, be heated to molten condition, then, the mixture of molten condition is quenched, grind and obtain its glass dust.This glass dust is noncrystal.
In an exemplary embodiment, described Pb-B-O glass dust is 0.5～10% with the weight ratio of corrosion etching agent in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
One or more in the oxide of the oxide of bismuth, silicon and Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, B, Al, Sn, P, Te etc. of Bi-Si-O glass dust of the present invention form, by a kind of or two or more mixing in proportion in the oxide of the oxide of bismuth, silicon and above interpolation element, be heated to molten condition, then, the mixture of molten condition is quenched, grind and obtain its glass dust.This glass dust is noncrystal.
In an exemplary embodiment, this Bi-Si-O glass dust is 0.5～10% with the weight ratio of corrosion etching agent in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust can be 5/95～95/5.
Bi-B-O glass dust of the present invention is by the oxide of bismuth, boron and add one or more in the oxide of element Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, Al, Sn, P, Te etc. and form, by a kind of or two or more mixing in proportion in the oxide of the oxide of bismuth, boron and above interpolation element, be heated to molten condition, then, the mixture of molten condition is quenched, grind and obtain this glass dust.This glass dust is noncrystal.
In an exemplary embodiment, described Bi-B-O glass dust is 0.5～10% with the weight ratio of corrosion etching agent in electrocondution slurry.
Bi-Te-O glass dust of the present invention is by the oxide of bismuth and tellurium and add one or more in the oxide of element Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, P etc. and form, by a kind of or two or more mixing in proportion in the oxide of the oxide of bismuth, tellurium and above interpolation element, be heated to molten condition, then, the mixture of molten condition being quenched, grind and obtain its glass dust. described glass dust is noncrystal..In an exemplary embodiment, described Bi-Te-O glass dust is 0.5～10% with the weight ratio of corrosion etching agent in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
P-Zn-Na-O glass dust of the present invention is by the oxide of phosphorus, zinc, sodium and add one or more in the oxide of element Li, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Si, Ag, B, Al, Sn, Te, Bi etc. and form, by a kind of or two or more mixing in proportion in the oxide of the oxide of phosphorus, zinc, sodium and above interpolation element, be heated to molten condition, then, the mixture of molten condition being quenched, grind and obtain its glass dust. described glass dust is noncrystal..In an exemplary embodiment, described P-Zn-Na-O glass dust is 0.5～10% with the weight ratio of corrosion etching agent in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
Na-Al-B-O glass dust of the present invention is by the oxide of sodium sodium, aluminium, boron and add one or more in the oxide of element Li, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, Sn, P, Bi, Te etc. and form, by a kind of or two or more mixing in proportion in the oxide of the oxide of sodium, aluminium, boron and above interpolation element, be heated to molten condition, then, the mixture of molten condition is quenched, grind and obtain its glass dust.Described glass dust is noncrystal.In an exemplary embodiment, described P-Zn-Na-O glass dust is 0.5～10% with the weight ratio of corrosion etching agent in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
B-Zn-Ba-O glass dust of the present invention is by the oxide of boron, zinc, barium and add one or more in the oxide of element Li, Na, K, Mg, Ca, Sr, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Si, Ag, Al, Sn, P, Bi, Te etc. and form, by a kind of or two or more mixing in proportion in the oxide of the oxide of boron, zinc, barium and above interpolation element, be heated to molten condition, then, the mixture of molten condition is quenched, grind and obtain its glass dust.Described glass dust is noncrystal.In an exemplary embodiment, described B-Zn-Ba-O glass dust is 0.5～10% with the weight ratio of corrosion etching agent in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
V-P-Ba-O glass dust of the present invention is by the oxide of vanadium, phosphorus, barium and add one or more in the oxide of element Li, Na, K, Mg, Ca, Sr, Sc, Ti, Zr, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, Bi, Te etc. and form, by a kind of or two or more mixing in proportion in the oxide of the oxide of vanadium, phosphorus, barium and above interpolation element, be heated to molten condition, then, the mixture of molten condition is quenched, grind and obtain its glass dust.Described glass dust is noncrystal.In an exemplary embodiment, described V-P-Ba-O glass dust is 0.5～10% with the weight ratio of corrosion etching agent in electrocondution slurry, and the part by weight of its corrosion etching agent and glass dust is 5/95～95/5.
iII. metal powder
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains metal powder.In a case study on implementation, described metal powder is the coated metal powder of non-silver, comprises at least one in silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, manganese, palladium, rhodium.
In another one case study on implementation, described metal powder is at least one in the coated copper of silver, iron, nickel, aluminium, zinc, titanium, cobalt, chromium, manganese, and wherein the thickness of silver coating is 10～2000nm, and the coated metal powder of this silver is of a size of 0.1-5.0 μ m.
In another one case study on implementation, described metal powder is the mixture of the coated metal powder of the coated metal powder of non-silver and silver, and the coated metal powder of its non-silver is 95/5～5/95 with the part by weight of silver-colored coated metal powder.Particularly, the effect in embodiments of the present invention of above-mentioned metal powder is the composition that forms electrode, plays electric action.In a preferred embodiment, this metal powder fusing point is preferably 350 ℃～2000 ℃, and more preferably 450 ℃～1800 ℃, more preferably 600 ℃～1450 ℃.Inventor finds under study for action, if the fusing point of this metal powder is during lower than 350 ℃, in sintering, the too early melting of metallic particles meeting, can hinder the discharge to organic carrier, thereby can affect the discharge of organic carrier, and in sintering process, can produce significantly and flow, reduce the depth-width ratio of grid line; If fusing point, higher than 2000 ℃, has been difficult to effective sintering in sintering process process, electric metal block space is more, causes path resistance large, performance degradation.
In further preferred embodiment, this metal powder is selected from least one in silver, gold, platinum, palladium, rhodium, or in silver, gold, platinum, palladium or rhodium doped with at least one metal or its alloy of copper, iron, nickel, zinc, titanium, cobalt, chromium, manganese, as copper-manganese, constantan, nichrome.
In preferred embodiment further, this metal powder is any the metal powder of silver-colored clad structure in the coated copper of silver, iron, nickel, aluminium, zinc, titanium, cobalt, chromium, manganese, that is to say the outer surface of any metallic particles in copper, iron, nickel, aluminium, zinc, titanium, cobalt, chromium, manganese continuous be coated with one deck silver metal.In the embodiment of the metal powder of this silver clad structure, the thickness of this silver coating is preferably 1～2000nm, more preferably 2～1000nm.Inventor finds under study for action, if when Ag layer thickness is less than 1nm, Ag content is very few, and the contact resistance of electrode or leakage current can obviously increase; If Ag layer thickness is greater than 10 4nm, can make the particle diameter of conductive metal powder excessive, because Ag is precious metal, causes metal dust high cost simultaneously, thereby increases the cost of crystal silicon solar batteries.Certainly, the silver layer of the metal powder of this silver clad structure can substitute with other precious metals, as gold, platinum etc.The silver-colored coated metallic particles of quilt is yet to be the alloy of the metals such as copper, iron, nickel, aluminium, zinc, titanium, cobalt, chromium, manganese, as copper-manganese, constantan, nichrome.The coated metal powder of silver is realized by plate one deck silver on copper, iron, nickel, aluminium, zinc, titanium, cobalt, chromium, manganese metal powder.
In an exemplary case, particle diameter is placed in to rare weak acid at one or more metallic particles of the copper of 0.1～5.0 μ m, iron, nickel, titanium, cobalt, chromium, zinc, manganese etc. or its alloy and soaks 10～300s, remove out oxidation on metal surface layer, then, use the method for chemical plating, on its metal powder, plate the silver of about 10～2000nm.
In another exemplary case study on implementation, solution composition and the process conditions of chemical plating are as follows: AgNO3:2.4～14.2g/L, ammoniacal liquor: 0.8g/L, formaldehyde: 1～3g/L, hydrazine hydrate: 1～4g/L, composite dispersing agent: 1.0g/L, pH value: 11, bath temperature: 60 ℃, mixing speed: 1000r/min, dry: 50 ℃, 30min.
In another exemplary case, particle diameter is placed in to rare weak acid at one or more metallic particles of the copper of 0.1～5.0 μ m, iron, nickel, titanium, cobalt, chromium, zinc, manganese etc. or its alloy and soaks 10～300s, remove out oxidation on metal surface layer.
Adopt deionized water repeatedly to wash, remove remaining acid.Wet powder is dry in vacuum drying chamber, then, the metallic particles of dry non-oxidation layer is placed in vacuum evaporation equipment, by evaporation, obtain the coated metal powder of silver.
In the embodiment of above-mentioned each metal powder, first the size of this metal powder particle should can meet the requirement of printing, if do not stopped up Printing screen etc.Therefore, preferably, this metal powder grain diameter is preferably distributed within the scope of 0.1～5.0 μ m μ m, if be greater than the 5 μ m μ m problems such as Printing screen and electrode broken string that easily result in blockage, if be less than 0.1 μ m μ m, can make the viscosity of slurry significantly improve, to such an extent as to can not normally print.In addition, the metal powder particle of this preferable particle size can also effectively reduce electrode area occupied, thereby improves the conversion efficiency of solar cell to light, the thick end that can also effectively reduce electrode simultaneously, save materials, and reduce production costs.
iV. organic carrier;
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains organic carrier, and described organic carrier comprises organic solvent, polymer, wetting dispersing agent, thixotropic agent and other function additive etc.The weight ratio of described organic carrier in electrodes conduct slurry is 5～25.With described organic carrier assembly, be divided into 100 listed as parts by weight, wherein organic solvent accounts for 50～95 weight portions; Polymer accounts for 1～40 weight portion; Wetting dispersing agent accounts for 0.1～10 weight portion; Thixotropic agent and other function additive account for 1～20 weight portion.
In an exemplary case study on implementation, this organic solvent can be selected from alcohol (as terpinol, fourth card) at least one, in alcohol ester (as lauryl alcohol ester), terpenes etc. in the solvent of high boiling range, its polymer can be selected from least one in ethyl cellulose, polymethacrylates, alkyd resins etc.; Wetting dispersing agent is for helping inorganic particle in the dispersion of organic carrier, without specific (special) requirements; Thixotropic agent is the thixotropy in printing process for increasing slurry, to guarantee electrode pattern clarity and good depth-width ratio, can select organic thixotropic agent such as rilanit special derivative or polyamide wax; Other function additives can be selected to add as required, as add microwax etc. to reduce surface tension, add DBP etc. to improve the pliability of slurry, add PVB etc. to improve adhesive force.
v. electrocondution slurry preparation method
The invention provides a kind of technique simple, condition is easily controlled, and the crystal silicon solar batteries front electrode electrocondution slurry preparation method that production cost is low, comprises the steps:
Prepare described corrosion etching agent; Take the oxide of plumbous and tellurium and etching agent is corroded in oxide the preparation of relevant interpolation element, prepare corrode etching agent method as described above.
Prepare described glass dust; Take relevant oxide and prepare glass dust, preparing the method for glass dust as described above.
Prepare described organic carrier; Take relevant organic material and prepare organic carrier, preparing the method for organic carrier as described above.Formula according to crystal silicon solar batteries front electrode electrocondution slurry described in claim 1 takes described corrosion etching agent, glass dust, metal powder and organic carrier;
Described corrosion etching agent, glass dust, metal powder and organic carrier are mixed, grind, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
First, take metal powder, comprise the coated metal powder of non-silver and the coated metal powder of silver, secondly, take oxide and prepare glass dust, above-described corrosion etching agent, glass dust and metal powder are pre-mixed.Then, take organic substance and prepare organic carrier.Finally, then the corrosion etching agent, glass dust and the metal powder that are pre-mixed are mixed with organic carrier, milled processed obtains electrodes conduct slurry.
Below, we further narrate case prepared by several electrodes conduct slurries.
In one embodiment, first the corrosion etching agent, glass dust and the metal powder that take are pre-mixed, then its mixture is mixed with the organic carrier taking, then, milled processed obtains described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, first the corrosion etching agent, glass dust and the organic carrier that take are pre-mixed, then in mixture, add the metal powder taking, further mix, then, milled processed obtains described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, first the metal powder taking and organic carrier are pre-mixed, then in mixture, add corrosion etching agent, glass dust further to mix, then, milled processed obtains described crystal silicon solar batteries front electrode electrocondution slurry.
In another embodiment, first the metal powder taking and part organic carrier are pre-mixed, again corrosion etching agent, glass dust and part organic carrier are pre-mixed, then, by two kinds, be pre-mixed thing again and mix, milled processed obtains described crystal silicon solar batteries front electrode electrocondution slurry.
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention, contains corrosion etching agent and glass dust.Its corrosion etching agent and the weight ratio of glass dust total amount in electrodes conduct slurry are 0.5～10%, and the part by weight of its corrosion etching agent and glass dust can be 5/95～95/5.Corrosion etching agent of the present invention is plumbous, tellurium and/or adds in element lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium at least one and the formed crystalline compounds of oxygen, and its melting temperature is 250 ℃～760 ℃.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.Corrosion etching agent of the present invention comprises that plumbous tellurium is crystalline compounds PbTe below 4O 9, PbTeO 3, PbTeO 4, PbTe 3O 7, PbTe 5O 11, Pb 2TeO 4, Pb 2Te 3O 7, Pb 2Te 3O 8, Pb 3TeO 5, Pb 3TeO 6, Pb 4Te 1.5O 7, Pb 5TeO 7, Pb 5TeO 7, PbTe 2O 5, Li 2TeO 3, Bi 6B 10O 24, Na 2B 8O 13, Bi 4TeO 8, Pb 6Bi 4O 18, PbBi 6Te 10, Bi 2TeO 5, PbBi 6TeO 12, BiTe 0.5Pb 0.5SrNb 2O 9, Pb 0.25SrBi 1.5Te 0.25Nb 2O 9, Pb 3Te 2Br 2O 6, Pb 3TeBr 2O 4, Pb 2CaTeO 6, Pb 2TeCoO 6, PbTe 2CuO 6, PbTeCu 3O 7, Pb 3Te 2Fe 2O 12, Pb (Te 0.33Fe 0.67) O 3, Pb 2(Hf 1.5Te 0.5) O 6.5, Pb 2Te (Li 0.5Al 0.5) O 6, Pb 2Te (Li 0.5Bi 0.5) O 6, Pb 2TeLi 0.5Fe 0.5O 6, PbTeLiFeO 6, Pb 2Te (Li 0.5La 0.5) O 6, Pb 2(Ti 1.5Te 0.5) O 6.5, Pb 2(Ti 1.5Te 0.5) O 6.5, Pb 2(Li 0.5Sc 0.5) TeO 6, Pb 2Li 0.5Y 0.5TeO 6, Li 0.5Pb 2Yb 0.5TeO 6, Pb 2MgTeO 6, Pb 11Si 3O 17, Ba (Fe 0.5Mg 0.5) PbTa 0.5Te 0.5O 6, PbBaMgTeO 6, Pb 0.5BaNbTe 2O 9, BaTeO 5, BaTe 4O 9, Pb 2MgTeO 6, Pb 2Mg 0.5Fe 0.5(Ta 0.5Te 0.5) O 6, Pb 2MgSrTeO 6, Pb 2Mg (W 0.9Te 0.1) O 6, Pb 2Mg (W 0.7Te 0.3) O 6, Pb 2Mg (W 0.5Te 0.5) O 6, Pb 2Mg (W 0.4Te 0.6) O 6, Pb 2Mg (W 0.4Te 0.6) O 6, PbMnTeO 6, Pb (Mn 0.5Te 0.5) O 3, Pb 2MnTeO 6, PbMn 2Ni 6Te 3O 18, Pb (Na 0.4Te 0.6) O 3, Pb 2(Na 0.5Bi 0.5) TeO 6, Na 0.5Pb 2Fe 0.5TeO 6, Pb 2(Na 0.5La 0.5) TeO 6, Pb 2Na 0.5Sc 0.5TeO 6, Na 0.5Pb 2Yb 0.5TeO 6, Na 0.5Pb 2Y 0.5TeO 6, Pb 4Te 6Nb 10O 41, Pb 3Ni 4.5Te 2.5O 15, Pb 2NiTeO 6, PbSc 0.5Ti 0.25Te 0.25O 3, Pb 2Sn 1.5Te 0.5O 6.5, Pb 2(Sn 1.5Te 0.5) O 6.5, Pb 2SrTeO 6, Pb 2ZnTeO 6, Pb 3Zn 3TeAs 2O 14, Pb 2(Zr 1.5Te 0.5) O 6.5, PbTe 5O 11, Pb 3(Te2O 6) Cl 2, Pb 2ZnTeO 6In at least one., its melting temperature is 250 ℃～760 ℃.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.
Glass dust of the present invention includes lead glass powder and lead-free glass powder.There is lead glass powder to comprise Pb-Si-O, Pb-B-O and Pb-Te-O; Lead-free glass powder comprise Bi-Si-O Bi-B-O,, Bi-Te-O, P-Zn-Na-O, B-Al-Na-O, B-Zn-Ba-O and V-P-Ba-O.
In a case study on implementation, metal powder of the present invention is the coated metal powder of non-silver, comprises at least one metal in silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, manganese, palladium, rhodium or the alloy of described metal.
In another one case study on implementation, metal powder of the present invention is any or its two or more mixture in the coated copper of silver, iron, nickel, aluminium, zinc, titanium, cobalt, chromium, manganese, and wherein, the thickness of described silver coating is 2～2000nm.The coated metal powder of described silver is of a size of 0.1～5.0 μ m.
In another one case study on implementation, metal powder of the present invention is the mixture of the coated metal powder of the coated metal powder of non-silver and silver, and the coated metal powder of its non-silver is 95/5～5/95 with the part by weight of silver-colored coated metal powder.
Crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains glass dust and corrosion etching agent, in use, when temperature reaches the fusing point of corrosion etching agent, corrosion etching agent is converted into liquid state by solid, can be deposited on rapidly antireflection layer surface, fully react with it in the short period of time, by its physical aspect, there is solid-state with liquid changing and can solve the blockage problem that glass dust softens state rapidly, glass dust is in soft state, for the discharge of organic carrier provides space.This mushy stage coordinates, not only can effectively corrode and penetrate the antireflective insulating barrier in crystal silicon solar energy battery front, and can make organic carrier easily discharge, also can effectively soak conductive metal powder simultaneously, urge into the combination between metal powder, make conductive metal powder and crystal silicon solar energy battery form good ohmic contact, form the good crystal silicon solar batteries front electrode of electric conductivity, make it finer and close, improve weld strength and bulk conductivity.
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with exemplary case study on implementation, the present invention is further elaborated.Should be appreciated that specific embodiment described herein is only to explain to be not intended to limit the present invention the present invention.
In an exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Pb-Si-Al-B-O system glass dust and corrosion etching agent.Described in it, corrode etching agent and the weight ratio of glass dust total amount in electrodes conduct slurry is 2wt%, the part by weight that corrodes etching agent and glass dust described in it can be 3: 7.Corrosion etching agent of the present invention is one or more by a kind of or the two or more and formed crystalline compounds of oxygen of plumbous and tellurium and interpolation element lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium etc., and its melting temperature is between 250 ℃ and 760 ℃.Described corrosion etching agent is crystalline compounds, and its performance and preparation method are as described above.Described Pb-Si-Al-B-O system glass dust comprises lower percentage by weight component:
PbO 65～85%
SiO 2 10～20%
Al 2O 3 0.1～10%
B 2O 3 0.1～10%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metals such as Li, Na, K, Mg, Ca, Sr, Ba, Ti, Zr, Sc, Zn, Bi maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Bi-Si-B-Zn-O system glass dust and corrosion etching agent.Described in it, corrode etching agent and the weight ratio of glass dust total amount in electrodes conduct slurry is 5wt%, the part by weight that corrodes etching agent and glass dust described in it can be 3:7. corrosion etching agent of the present invention for one or more are by plumbous and tellurium and interpolation element lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, a kind of or the two or more and formed crystalline compounds of oxygen of germanium etc., its melting temperature is between 250 ℃ and 760 ℃.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.Described Bi-Si-B-Zn-O system glass dust comprises lower percentage by weight component:
Bi 2O 3 65～85%
SiO 2 10～20%
B 2O 3 0.1～10%
ZnO 0.1～10%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of any metals such as Li, Na, K, Mg, Ca, Sr, Ba, Ti, Al, Zr, Sc, W, Co, Cu, Fe, Ni, Sn, Mn, Ag maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Zn-B-P-Na-O system glass dust and corrosion etching agent.Described in it, corrode etching agent and the weight ratio of glass dust total amount in electrodes conduct slurry is 8wt%, the part by weight that corrodes etching agent and glass dust described in it can be 3:7. corrosion etching agent of the present invention for one or more are by plumbous and tellurium and interpolation element lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, a kind of or the two or more and formed crystalline compounds of oxygen of germanium etc., its melting temperature is between 250 ℃ and 760 ℃.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.Described Zn-B-P-Na-O system glass dust comprises lower percentage by weight component:
B 2O 3 0.1～10%
ZnO 30～50%
P 2O 5 30～50%
Na 2O 0.1～10%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metals such as Li, K, Mg, Ca, Sr, Ba, Ti, Al, Zr, Sc, Ni, Co, Cu, Fe, Sn, Mn, Ag, Bi, Ga maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Ba-B-Zn-O system glass dust and corrosion etching agent.Its corrosion etching agent and the weight ratio of glass dust total amount in electrodes conduct slurry are 1.5wt%, the part by weight of its corrosion etching agent and glass dust can be 9:1. corrosion etching agent of the present invention for one or more are by plumbous and tellurium and interpolation element lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, a kind of or the two or more and formed crystalline compounds of oxygen of germanium etc., its melting temperature is between 250 ℃ and 760 ℃.Described corrosion etching agent is crystalline compounds, and its performance and preparation method are as described above.Described Ba-B-Zn-O system glass dust comprises lower percentage by weight component:
BaO 10～35%
B 2O 3 30～60%
ZnO 25～35%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metals such as Li, Na, K, Mg, Ca, Sr, Ba, Ti, Zr, Sc, Zn, Co, Cu, Fe, Sn, Mn, Ag maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Pb-Te-Li-O system glass dust and corrosion etching agent.Its corrosion etching agent and the weight ratio of glass dust total amount in electrodes conduct slurry are 3wt%, and the part by weight of its corrosion etching agent and glass dust can be 5:5.Corrosion etching agent of the present invention is one or more by a kind of or the two or more and formed crystalline compounds of oxygen of plumbous and tellurium and interpolation element lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium etc., and its melting temperature is between 250 ℃ and 760 ℃.Described corrosion etching agent is crystalline compounds, and its performance and preparation method are as described above.Described Pb-Te-Li-O system glass dust comprises lower percentage by weight component:
PbO 20～50%
TeO 2 40～70%
Li 2O 0.1～10%
Other oxides 3～15%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metals such as Na, K, Mg, Ca, Sr, Ba, Ti, Si, B, Al, Zr, Sc, Zn, Co, Cu, Fe, Sn, Mn, Ag maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Na-Al-B-O system glass dust and corrosion etching agent.Its corrosion etching agent and the weight ratio of glass dust total amount in electrodes conduct slurry are 10wt%, the part by weight of its corrosion etching agent and glass dust can be 9:1. corrosion etching agent of the present invention for one or more are by plumbous and tellurium and interpolation element lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, a kind of or the two or more and formed crystalline compounds of oxygen of germanium etc., its melting temperature is between 250 ℃ and 760 ℃.Described corrosion etching agent is all crystalline compounds, and its performance and preparation method are as described above.Described Na-Al-B-O system glass dust comprises lower percentage by weight component:
Na 2O 5～20%
Al 2O 3 5～40%
B 2O 3 35～75%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metals such as Li, K, Mg, Ca, Zn, Sr, Ba, Ti, Zr, Sc, Si, Ni, Co, Cu, Fe, Sn, Mn, Ag maybe can be decomposed into its oxide.
In another exemplary case study on implementation, crystal silicon solar batteries front electrode electrocondution slurry of the present invention contains Sb-V-Ba-P-O system glass dust and corrosion etching agent.Its corrosion etching agent and the weight ratio of glass dust total amount in electrodes conduct slurry are 5wt%, part by weight of its corrosion etching agent and glass dust can be that 8:2. corrodes etching agent described in it and the weight ratio of glass dust total amount in electrodes conduct slurry is 8wt%, the part by weight that corrodes etching agent and glass dust described in it can be 3: 7. corrosion etching agent of the present invention is for one or more are by plumbous and tellurium and interpolation element lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, a kind of or the two or more and formed crystalline compounds of oxygen of germanium etc., its melting temperature is between 250 ℃ and 760 ℃.Described corrosion etching agent is crystalline compounds, and its performance and preparation method are as described above.Described Sb-V-Ba-P-O system glass dust comprises lower percentage by weight component:
V 2O 5 45～60%
Sb 2O 3 5～25%
BaO 5～25%
P 2O 5 15～30%
Other oxides 0～5%,
Wherein, other oxides can be other compounds that the oxide of arbitrary middle metals such as Li, Na, K, Mg, Ca, Si, Zn, Sr, Ti, Zr, Sc, Cr, Co, Cu, Fe, Sn, Mn, Ag maybe can be decomposed into its oxide.
Embodiment 1
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to total weight, and it comprises 3 parts of corrosion etching agents, 85 parts of metal powders, 2 parts of glass dust, 10 parts of organic carriers.Wherein, corrosion etching agent is Li 2teO 3and Bi 6b 10o 24the mixture of crystalline compounds; Metal powder is silver powder; Glass dust is Pb-Si-Al-B-O system glass dust.Organic carrier is 100 parts of calculating according to total weight, and it comprises that terpinol organic solvent is 70 parts, 14 parts of ECN7NFs, 10 parts of wetting dispersing agents, 5.5 parts of thixotropic agent, 0.5 part of microwax.
The preparation process of corrosion etching agent is: first by 12g TeO 2with 8g Pb 3o 4oxide powder mixes, and then, adds successively 0.625gB 2o 3, 1.25g Bi 2o 3with 1.25g Li 2cO 3oxide powder, more further evenly mix, be then placed in crucible, put into heating furnace, be warming up to 900 ℃, in the air atmosphere at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment naturally coolingly, form block, the block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, and the powder of ball milling is within the scope of 0.1～7 μ m, obtains its crystalline compounds.
Metal powder is silver powder, its particle size D 50be 1～3 μ m; Glass dust is Pb-Si-Al-B-O, and its percentage by weight consists of: PbO79wt%, SiO 217wt%, Al 2o 33wt%, B 2o 31wt%, mixes above-mentioned each component by mixer, heat after packing container in Muffle furnace, and peak temperature is 1000 ℃, makes it complete melting become uniform liquid at peak value insulation 60min.Pour molten mass into water-cooled and quench and make glass, then through ball milling or after grinding diameter of particle be less than 5 μ m.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are taken according to above-mentioned formula, corrosion etching agent, glass dust are mixed with organic carrier, add again metal powder to mix, finally by three-roll grinder, be ground to particle diameter and be less than 5 μ m, obtain crystal silicon solar batteries front electrode electrocondution slurry.
Embodiment 2
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to total weight, and it comprises the corrosion etching agent of 4 parts, the metal powder of 83 parts, the glass dust of 1.6 parts, the organic carrier of 11.4 parts.Wherein, corrosion etching agent is Bi 4teO 8, Bi 2teO 5, PbTeO 3the mixture of crystalline compounds, metal powder is silver coated nickel powder; Glass dust is Bi-Si-B-Zn-O system glass dust.Organic carrier is 100 parts of calculating according to total weight, and it comprises that lauryl alcohol ester organic solvent is 50 parts, 40 parts of polymethacrylate polymers, 5 parts of wetting dispersing agents, 4 parts of thixotropic agent, DBP1 part.
The preparation process of corrosion etching agent is: by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.25g Bi 2o 3further evenly mix again, be then placed in crucible, put into heating furnace, be warming up to 900 ℃, in air atmosphere at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment naturally cooling, form block, the block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder D of ball milling is within the scope of 0.1～7 μ m, obtains its crystalline compounds.
Metal powder is the method for using chemical plating, plates the silver of about 200nm on nickel powder, and the particle size of nickel powder is 0.5～3 μ m.The percentage by weight component of glass dust is: Bi 2o 367wt%, SiO 218wt%, B 2o 33wt%, ZnO7wt%, other oxides BaO3.5wt%, CuO1.5wt%, above-mentioned each component is mixed by knife-edge mixer, after packing container into, in Muffle furnace, heat, peak temperature can be established 1200 ℃, makes it complete melting become uniform liquid at peak value insulation 60min.Pour molten mass into water-cooled and quench and make glass, then through ball milling or after grinding diameter of particle be less than 5 μ m.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are taken according to above-mentioned formula, metal powder is mixed with organic carrier, add again corrosion etching agent and glass dust to mix, finally by three-roll grinder, be ground to particle diameter and be less than 5 μ m, obtain crystal silicon solar batteries front electrode electrocondution slurry.
Embodiment 3
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to total weight, and it comprises the corrosion etching agent of 2 parts, the metal powder of 86 parts, the glass dust of 0.5 part, the organic carrier of 11.5 parts.Wherein, corrosion etching agent is Bi 24b 2o 39, Pb 5b 2o 5, Pb 5teO 7and Li 6teO 6the mixture of crystalline compounds, metal powder is silver-colored copper-clad; Glass dust is Zn-B-P-Li-O system glass dust.Organic carrier is 100 parts of calculating according to total weight, and it comprises that terpinol organic solvent is 65 parts, 20 parts of alkyd polymers, 0.1 part of wetting dispersing agent, 12.5 parts of thixotropic agent, PVB2.4 part.
The preparation process of corrosion etching agent is: by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds successively 0.05gB 2o 3, 1.44g Bi 2o 3, and 1.25g Li 2cO 3, more further evenly mix, be then placed in crucible, put into heating furnace, be warming up to 900 ℃, in the air atmosphere at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment naturally coolingly, form block, the block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, and the powder of ball milling, within the scope of 0.1～7 μ m, obtains its crystalline compounds.
Metal powder is at silver-coated copper powder, uses the method for chemical plating, plates the silver of about 200nm on copper powder, and the particle size of copper powder is 0.5～3 μ m μ m.The percentage by weight of glass dust is: B 2o 336%, ZnO2%, P 2o 536%, Li 2o1%, MgO4%, MnO 21%, each component in described glass dust is mixed by gravity mixer, in Muffle furnace, heat after packing container into, peak temperature can be established 1200 ℃, makes it complete melting become uniform liquid at peak value insulation 60min.Pour molten mass into corrosion resistant plate and make glass, then must be less than 5 μ m by diameter of particle through ball milling or after grinding.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are taken according to above-mentioned formula, metal powder, glass dust are mixed with corrosion etching agent, add again organic carrier to mix, finally by three-roll grinder, be ground to particle diameter and be less than 5 μ m, obtain crystal silicon solar batteries front electrode electrocondution slurry.
Embodiment 4
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to total weight, and it comprises the corrosion etching agent of 0.5 part, the metal powder of 88.5 parts, the glass dust of 1 part, the organic carrier of 10 parts.Wherein, corrosion etching agent is PbTeO 3, Li 2teO 3, and Al 2o 3crystalline compounds mixture, metal powder is titanium valve; Glass dust is B-Zn-Ba-O system glass dust.Organic carrier is 100 parts of calculating according to total weight, and it comprises that fourth card organic solvent is 60 parts, 15 parts of ECN7NFs, 5 parts of wetting dispersing agents, 15 parts of thixotropic agent, PVB5 part.
The preparation process of corrosion etching agent is: by 14g TeO 2with 8.75g Pb 3o 4oxide powder mixes, and then, adds successively 0.75gAl 2o 3with 1.5g Li 2cO 3, more further evenly mix, be then placed in crucible, put into heating furnace, be warming up to 900 ℃, in the air atmosphere at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment naturally coolingly, form block, the block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, and the powder of ball milling, within the scope of 0.1～7 μ m, obtains its crystalline compounds.
Metal powder is titanium valve, and its particle particle size is 0.5～10 μ m; The percentage by weight of glass dust consists of: B 2o 355%, ZnO30%, BaO12%, Li 2o3%, mixes each component in described glass dust by gravity mixer, heat after packing container in Muffle furnace, and peak temperature can be established 1200 ℃, makes it complete melting become uniform liquid at peak value insulation 60min.Pour molten mass into corrosion resistant plate and make glass, then must be less than 5 μ m by diameter of particle through ball milling or after grinding.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are taken according to above-mentioned formula, metal powder, glass dust, corrosion etching agent are added in organic carrier and mixed, by three-roll grinder, be ground to particle diameter again and be less than 5 μ m, obtain crystal silicon solar batteries front electrode electrocondution slurry.
Embodiment 5
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to total weight, and it comprises the corrosion etching agent of 1.5 parts, the metal powder of 90 parts, the glass dust of 0.5 part, the organic carrier of 8 parts.Wherein, corrosion etching agent is PbTeO 3and Pb 11si 3o 17compound, metal powder is silver powder; Glass dust is Sb-V-Ba-P-O system glass dust.Organic carrier is 100 parts of calculating according to total weight, and it comprises that lauryl alcohol ester organic solvent is 95 parts, 1 part of ECN7NF, 3 parts of wetting dispersing agents, 1 part of thixotropic agent.
The preparation process of corrosion etching agent is: by 3.5g TeO 2with 6.6g Pb 3o 4oxide powder mixes, and then, adds 0.45g SiO 2further evenly mix again, be then placed in crucible, put into heating furnace, be warming up to 900 ℃, in air atmosphere at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment naturally cooling, form block, the block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder of ball milling, within the scope of 0.1～7 μ m, obtains its crystalline compounds.
The percentage by weight component of glass dust is: Sb 2o 35%, V 2o 545%, BaO20%, P 2o 530%.Each component in described glass dust is mixed by gravity mixer, heat after packing container in Muffle furnace, peak temperature can be established 1000 ℃, makes it complete melting become uniform liquid at peak value insulation 60min.Pour molten mass into corrosion resistant plate and make glass, then must be less than 5 μ m by diameter of particle through ball milling or after grinding.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are taken according to above-mentioned formula, metal powder, glass dust, corrosion etching agent are added in organic carrier and mixed, by three-roll grinder, be ground to particle diameter again and be less than 5 μ m, obtain crystal silicon solar batteries front electrode electrocondution slurry.
Embodiment 6
Crystal silicon solar batteries front electrode electrocondution slurry and preparation method thereof.
This crystal silicon solar batteries front electrode electrocondution slurry is 100 parts of calculating according to total weight, and it comprises the corrosion etching agent of 2 parts, the metal powder of 87.5 parts, the glass dust of 0.5 part, the organic carrier of 10 parts.Wherein, corrosion etching agent is Bi 4teO 8and PbTeO 3compound, metal powder is silver powder; Glass dust is Pb-Te-Li-O system glass dust.Organic carrier is 100 parts of calculating according to total weight, and it comprises that lauryl alcohol ester organic solvent is 70 parts, 15 parts of ECN7NFs, 2 parts of wetting dispersing agents, 10 parts of thixotropic agent, PVB3 part.
The preparation process of corrosion etching agent is: by 4.9g TeO 2with 7.56g Pb 3o 4oxide powder mixes, and then, adds 1.44g Bi 2o 3further evenly mix again, be then placed in crucible, put into heating furnace, be warming up to 900 ℃, in air atmosphere at 900 ℃, under molten condition, make it react 60min, then the mixture of melting is taken out from stove, be placed under atmospheric environment naturally cooling, form block, the block obtaining is pulverized and obtained granule, granule is formed to powder by ball milling again, the powder of ball milling, within the scope of 0.1～7 μ m, obtains its crystalline compounds.
The percentage by weight component of glass dust is: PbO38%, TeO 258%, Li 2cO 31.5% and B 2o 32.5% mixes each component in above-mentioned glass dust by gravity mixer, heat after packing container in Muffle furnace, and peak temperature can be established 900 ℃, makes it complete melting become uniform liquid at peak value insulation 60min.Pour molten mass into corrosion resistant plate and make glass, then must be less than 5 μ m by diameter of particle through ball milling or after grinding.
After above-described corrosion etching agent, metal powder and glass dust and organic carrier are taken according to above-mentioned formula, metal powder, glass dust, corrosion etching agent are added in organic carrier and mixed, by three-roll grinder, be ground to particle diameter again and be less than 5 μ m, obtain crystal silicon solar batteries front electrode electrocondution slurry.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any modifications of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.

Claims (20)

1. a crystal silicon solar batteries front electrode electrocondution slurry, is 100 parts of calculating according to total weight, comprises the component of following formula rate:
0.5～10 part, corrosion etching agent and glass dust,
Wherein, described corrosion etching agent is the crystalline compounds that lead, tellurium and/or the oxide that adds element form, and melting temperature is 250 ℃～760 ℃; Described glass dust is amorphization compound;
70～93 parts of metal powders;
5～25 parts of organic carriers.
2. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, is characterized in that, the weight ratio of described corrosion etching agent and glass dust is 5/95～95/5.
3. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, it is characterized in that, described interpolation element is at least one of lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, bromine, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, germanium etc.
4. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, is characterized in that, described crystalline compounds is PbTe 4O 9, PbTeO 3, PbTeO 4, PbTe 3O 7, PbTe 5O 11, Pb 2TeO 4, Pb 2Te 3O 7, Pb 2Te 3O 8, Pb 3TeO 5, Pb 3TeO 6, Pb 4Te 1.5O 7, Pb 5TeO 7, Pb 5TeO 7, PbTe 2O 5, Li 2TeO 3, Bi 6B 10O 24, Na 2B 8O 13, Bi 4TeO 8, Pb 6Bi 4O 18, PbBi 6Te 10, Bi 2TeO 5, PbBi 6TeO 12, BiTe 0.5Pb 0.5SrNb 2O 9, Pb 0.25SrBi 1.5Te 0.25Nb 2O 9, Pb 3Te 2Br 2O 6, Pb 3TeBr 2O 4, Pb 2CaTeO 6, Pb 2TeCoO 6, PbTe 2CuO 6, PbTeCu 3O 7, Pb 3Te 2Fe 2O 12, Pb (Te 0.33Fe 0.67) O 3, Pb 2(Hf 1.5Te 0.5) O 6.5, Pb 2Te (Li 0.5Al 0.5) O 6, Pb 2Te (Li 0.5Bi 0.5) O 6, Pb 2TeLi 0.5Fe 0.5O 6, PbTeLiFeO 6, Pb 2Te (Li 0.5La 0.5) O 6, Pb 2(Ti 1.5Te 0.5) O 6.5, Pb 2(Ti 1.5Te 0.5) O 6.5, Pb 2(Li 0.5Sc 0.5) TeO 6, Pb 2Li 0.5Y 0.5TeO 6, Li 0.5Pb 2Yb 0.5TeO 6, Pb 2MgTeO 6, Pb 11Si 3O 17, Ba (Fe 0.5Mg 0.5) PbTa 0.5Te 0.5O 6, PbBaMgTeO 6, Pb 0.5BaNbTe 2O 9, BaTeO 5, BaTe 4O 9, Pb 2MgTeO 6, Pb 2Mg 0.5Fe 0.5(Ta 0.5Te 0.5) O 6, Pb 2MgSrTeO 6, Pb 2Mg (W 0.9Te 0.1) O 6, Pb 2Mg (W 0.7Te 0.3) O 6, Pb 2Mg (W 0.5Te 0.5) O 6, Pb 2Mg (W 0.4Te 0.6) O 6, Pb 2Mg (W 0.4Te 0.6) O 6, PbMnTeO 6, Pb (Mn 0.5Te 0.5) O 3, Pb 2MnTeO 6, PbMn 2Ni 6Te 3O 18, Pb (Na 0.4Te 0.6) O 3, Pb 2(Na 0.5Bi 0.5) TeO 6, Na 0.5Pb 2Fe 0.5TeO 6, Pb 2(Na 0.5La 0.5) TeO 6, Pb 2Na 0.5Sc 0.5TeO 6, Na 0.5Pb 2Yb 0.5TeO 6, Na 0.5Pb 2Y 0.5TeO 6, Pb 4Te 6Nb 10O 41, Pb 3Ni 4.5Te 2.5O 15, Pb 2NiTeO 6, PbSc 0.5Ti 0.25Te 0.25O 3, Pb 2Sn 1.5Te 0.5O 6.5, Pb 2(Sn 1.5Te 0.5) O 6.5, Pb 2SrTeO 6, Pb 2ZnTeO 6, Pb 3Zn 3TeAs 2O 14, Pb 2(Zr 1.5Te 0.5) O 6.5, PbTe 5O 11, Pb 3(Te2O 6) Cl 2, Pb 2ZnTeO 6In at least one.
5. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, it is characterized in that, described glass dust is at least one in Pb-Si-O, Bi-Si-O, Pb-B-O, Bi-B-O, Pb-Te-O, Bi-Te-O, P-Zn-Na-O, B-Al-Na-O, B-Zn-Ba-O, V-P-Ba-O system glass dust, wherein, at least one in the oxide that described glass dust contains Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, P or Bi.
6. according to the crystal silicon solar batteries front electrode electrocondution slurry described in claim 1～5, it is characterized in that, described corrosion etching agent be spherical, class is spherical, at least one in sheet, graininess, colloid particle, is of a size of 0.1～10.0 μ m.
7. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, is characterized in that: described metal powder is at least one in silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminium, manganese, palladium, rhodium.
8. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, it is characterized in that: described metal powder is at least one in the coated copper of silver, iron, nickel, zinc, titanium, cobalt, chromium, aluminium, manganese, wherein, the thickness of silver coating is 10～2000nm.
9. crystal silicon solar batteries front electrode electrocondution slurry according to claim 1, it is characterized in that: described metal powder is the mixture of the coated metal powder of the coated metal powder of non-silver and silver, wherein, the coated metal powder of described non-silver is 5/95～95/5 with the weight ratio of silver-colored coated metal powder, the coated metal powder of non-silver is silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminium, manganese, palladium, the coated metal powder of at least one silver in rhodium is copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminium, at least one in manganese, the thickness of described silver coating is 10～2000nm.
10. a preparation method for crystal silicon solar batteries front electrode electrocondution slurry, comprises the steps:
Prepare described corrosion etching agent;
Prepare described glass dust;
Prepare described organic carrier;
Formula according to crystal silicon solar batteries front electrode electrocondution slurry described in claim 1 takes described corrosion etching agent, glass dust, metal powder and organic carrier;
Described corrosion etching agent, glass dust, metal powder and organic carrier are mixed, grind, obtain described crystal silicon solar batteries front electrode electrocondution slurry.
The preparation method of 11. crystal silicon solar batteries front electrode electrocondution slurries according to claim 10, it is characterized in that, the preparation method of described corrosion etching agent is: by 0.1～6mol/l temperature, be the telluric acid solution of 60-90 ℃, tellurous acid solution, tellurate solution, the lead acetate solution of tellurite solution and 0.1～10mol/l mixes, making tellurium in mixed solution and plumbous mol ratio is 0.1/10～10/0.1, then add lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, scandium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, in germanium, at least one adds the salting liquid of element, at 50 ℃～250 ℃, stir 2～5 hours, mixing speed is 1000～1500r/min, Separation of Solid and Liquid, washing, until filtrate PH is 5～7, collect solid, dry, pulverize, grind, obtain described corrosion etching agent crystalline compounds.
The preparation method of 12. crystal silicon solar batteries front electrode electrocondution slurries according to claim 10, it is characterized in that, the preparation method of described corrosion etching agent is: by steam and/or lithium plumbous and tellurium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, bromine, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, in germanium, the steam of at least one interpolation element imports in the reative cell that contains oxygen atmosphere, 1000～3000 ℃ of reactions 1～4 hour, cooling, pulverize, grind, obtain described corrosion etching agent crystalline compounds.
The preparation method of 13. crystal silicon solar batteries front electrode electrocondution slurries according to claim 10, it is characterized in that, the preparation method of described corrosion etching agent is: by the oxide of tellurium and plumbous oxide and/or lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, bromine, calcium, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, in germanium, at least one adds the oxide mixing of element, in irreducibility atmosphere, be heated to 700～1200 ℃, frit reaction 30～120 minutes, naturally cooling, pulverize, grind, obtain described corrosion etching agent crystalline compounds.
The preparation method of 14. crystal silicon solar batteries front electrode electrocondution slurries according to claim 10, it is characterized in that, the preparation method of described corrosion etching agent is: by the oxide of tellurium and with plumbous oxide/or lithium, bismuth, boron, titanium, zinc, aluminium, silver, chromium, scandium, copper, niobium, vanadium, sodium, tantalum, strontium, calcium, bromine, cobalt, hafnium, lanthanum, yttrium, ytterbium, iron, silicon, barium, magnesium, manganese, tungsten, nickel, tin, zinc, arsenic, zirconium, potassium, phosphorus, indium, gallium, in germanium, at least one adds the oxide mixing of element, in the atmosphere of vacuum, be heated to 700～1200 ℃, frit reaction 30～120 minutes, naturally cooling, pulverize, grind, obtain described corrosion etching agent crystalline compounds.
The preparation method of 15. crystal silicon solar batteries front electrode electrocondution slurries according to claim 10, it is characterized in that, described glass dust is Pb-Si-O, Bi-Si-O, Pb-B-O, Bi-B-O, Pb-Te-O, Bi-Te-O, P-Zn-Na-O, B-Al-Na-O, B-Zn-Ba-O, at least one in V-P-Ba-O system glass dust, wherein, described glass dust contains Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, at least one in the oxide of P or Bi, be of a size of 0.1～10.0 μ m.
The preparation method of 16. crystal silicon solar batteries front electrode electrocondution slurries according to claim 10, it is characterized in that, described glass dust comprises Pb-Te-O glass dust, and at least one in the oxide of lead, tellurium and the oxide of interpolation element Li, Na, K, Mg, Ca, Sr, Ba, Sc, Ti, Zr, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag, Si, B, Al, Sn, P or Bi of described Pb-Te-O glass dust forms; Described Pb-Te-O glass dust is that at least one in plumbous, the oxide of tellurium and the oxide of above-mentioned interpolation element mixed in proportion, is heated to molten condition, then the mixture of molten condition is quenched, and grinds and obtains described glass dust.
The preparation method of 17. crystal silicon solar batteries front electrode electrocondution slurries according to claim 10, is characterized in that: described metal powder is at least one in silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminium, manganese, palladium, rhodium.
18. crystal silicon solar batteries front electrode electrocondution slurry preparation methods according to claim 10, it is characterized in that: described metal powder is at least one in the coated copper of silver, iron, nickel, zinc, titanium, cobalt, chromium, aluminium, manganese, wherein, the thickness of silver coating is 10～2000nm.
19. crystal silicon solar batteries front electrode electrocondution slurry preparation methods according to claim 10, it is characterized in that: described metal powder is the mixture of the coated metal powder of the coated metal powder of non-silver and silver, the coated metal powder of described non-silver is 5/95-95/5 with the weight ratio of silver-colored coated metal powder; Wherein, the coated metal powder of non-silver is at least one in silver, gold, platinum, copper, iron, nickel, zinc, titanium, cobalt, chromium, manganese, palladium, rhodium, the coated metal powder of silver is at least one in copper, iron, nickel, zinc, titanium, cobalt, chromium, aluminium, manganese, and the thickness of silver coating is 10～2000nm.
The manufacture method of 20. 1 kinds of crystal silicon solar batteries front electrodes, comprises the steps:
The crystal silicon semiconductor element that provides a kind of upper face to there is dielectric film, wherein, described dielectric film is at least one superimposed layer in silicon nitride, titanium oxide, aluminium oxide, silica;
The electrocondution slurry that the preparation method of 1～9 arbitrary described crystal silicon solar batteries front electrode electrocondution slurry or 10～18 arbitrary described crystal silicon solar batteries front electrode electrocondution slurries is obtained is printed on described dielectric film;
Sintering, the step of described sintering is: the described electrocondution slurry being printed on dielectric film is dried at 180 ℃～260 ℃, be heated to 700 ℃～950 ℃ sintering;
Cooling, obtain described crystal silicon solar batteries front electrode.
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