CN101041898A - Electron attachment assisted formation of electrical conductors - Google Patents

Abstract

The invention provides a method of forming an electric conductor through conducting metals loaded on a substrate, in which, a conductor preparation formed of metallic metallics or a metal precursor and the compound is typically in a printing ink or an oar mode, which is applied on the substrate and can be converted to the electric conductor through fully heating under an ionic reducing gas with negative electricity, and the electric conductor can be sintered sufficiently.

Description

The formation of the auxiliary electrical conductor of electron attachment

The cross reference of related application

The application number that the application has required on February 23rd, 2006 to propose is the right of priority of 60/775906 U.S. Provisional Patent Application.

Background technology

[0001] electronics, indicating meter and energy industry depend on organic and inorganic substrate the coating that forms the electrical conductor that is made of conducting metal and pattern to form circuit.Electrical conductor is used to make the conductor wire that is used for flat-panel monitor; The antenna of cellular phone and radio frequency (RF) sign; Be used to form electrode and the bus and the shield blade of plasma display panel; Be used to make the sensing apparatus that comprises transformer, power converter and phase converter; Be used to make low power consuming or disposable electronics; Be used to form metal layer under the salient point; Being used as scolder replaces; Be connected with providing at assembly with being used at smart card and chip chamber in the radio frequency identification.

[0002] recent development in forming electrical conductor focuses on the addition manner of using the conductive media thing at desired location.Opposite with addition manner, the mode of deleting is applied to a big zone then with electro-conductive material, described electro-conductive material by selectively never desired region remove.The addition manner that makes up circuit has comprised treatment step still less, and they have used material still less, and the common waste relevant with the mode of deleting minimized.They have also eliminated the needs to the vacuum-treat process of high loss simultaneously.

[0003] thick film technology is a kind of method of interpolation property structure electrical conductor.Metallics and thin glass particle by steel seal to or be screen-printed on the substrate and produce and add the property circuit.Early stage thick film technology needs thermal extremes (＞650 ℃) with sintering metal.The only following substrate that can bear this temperature just can be used, as silicon, pottery and glass.Therefore, the selection to substrate is restricted.Simultaneously, relatively costly by the product of thick film technology manufacturing.

[0004] polymer thick film (PTF) technology is the example of another interpolation property structure electrical conductor, and its advantage with respect to thick film technology is to use lower temperature.Metallics be dispersed on the polymer binder and by steel seal to or be screen-printed on polymkeric substance or the paper substrates.The major limitation of this PTF technology is that typical material only has the 10-20% of the specific conductivity of the best high-temperature electric conduction body of being made by thick film technology, and its specific conductivity only is the 30-50% of piece metallic conductor.

[0005] nearest, the printing ink and the soup compound that are made of metal precursor are developed, and it can be applied to be changed into conductor on a large amount of substrates and by heating.Yet, change metal precursor into conducting metal, copper especially, with some low consumption flexible substrate, need high temperature when together using equally as thermoplastic polymkeric substance and paper.Therefore, just need a chilling process if on these substrates, form electrical conductor.

[0006] following patent and document are for making electrical conductor that is made of the conducting metal on the substrate and the representative that is formed the correlation technique of electrical conductor especially by metal precursor.

[0007] US6036889, US6143356, US6153348, US6274412B1, US6379745B1 disclose that gang is commercial can be based on trade mark, PARMOD ^TMThe precursor mixture of realizing.These syntheticss can be on substrates as are used to printed-wiring board (PWB) and flexible circuit printing, and they have and make the metallic conductor with superperformance can be by simple printing and heat-processed rather than the advantage by common multistep photoetching etching process generation.

[0008] printable printing ink or soup compound are by active organic medium (ROM) and tinsel and/or metal-powder formation, and it has admixed a kind of organic carrier.When printing ink or soup compound are heated, owing to thermolysis generates metal, the network structure that tinsel in the new metal of this generation " chemistry welding " mixture and/or metal-powder constitute a conduction together.

[0009] WO03/032084A2 (2003/0180451) discloses the sedimentary low viscosity precursor of the electronic characteristic that is used to conduct electricity, and this feature allows to use direct WriteMode, deposits as ink jet.When making great efforts to be reduced in metal precursor sintering temperature used in printing ink and the soup compound, along with particulate is reduced to nanometer or micron order size, the size of particles of metal-powder is reduced.Typical nanoparticle comprises CuxO (sic), Ag and pyrogenic silica.The oxide compound of indium metal, antimony, platinum and the nickel of also proposal conduction is as the material standed for that forms electrical conductor.

[0010] US6776330 discloses a kind of dried flux processing with soldered metallic surface.The dried flux of this employing is handled and is called as electron attachment, and it provides a kind of reducing gas need for interelectrode target area.A kind of electronegative reducing gas as electronegative hydrogen, is applied to dried flux and handles.

[0011] US2004/0211675 discloses a kind of method that removes metal oxide from substrate surface.This substrate surface has comprised a large amount of solder bumps, wherein comprises that to small part the surface of described a large amount of solder bump is exposed in the gaseous mixture that comprises a kind of electronegative reducing gas and a kind of carrier.

[0012] US2004/0226914 discloses the method that a kind of surface from least a assembly removes metal oxide, comprising: allow a kind of reducing gas pass ion generator and form electronegative reducing gas; Target device is contacted with electronegative reducing gas to reduce oxide compound at least a assembly.

[0013] US2004/0231597 discloses in the dried flux of face of weld is handled and has used electron attachment.The oxide compound of the various components of face of weld is removed by electronegative hydrogen ion in this process.

The invention summary

[0014] the present invention is designed to improve the formation of the electrical conductor that comprises conducting metal on the various types of common substrate that is applied in the electronic industry.In basic skills, the conductor preparation generally is made of at least a composition of selecting from the group of being made up of metallics and a kind of metal precursor and composition thereof, general form with printing ink or soup compound, this conductor preparation is applied on the substrate, change electrical conductor into by abundant heating, and it is carried out sintering through time enough.The improvement of this method is to use the electron attachment process, to help sintering and to change described composition into metal.

[0015] can obtain significant advantage by this method, comprise:

Can comprise on the flexible thermo-sensitivity substrate and make electrical conductor at low temperatures at multiple substrate;

Can under atmospheric pressure make electrical conductor;

Can use atoxic and non-flammable gaseous mixture to make electrical conductor;

Can be beneficial to the shaping of metallic conductor at 200 ℃ and the following metal precursor of on multiple substrate, using as copper or silver.

Can be at 200 ℃ and the following sintering that carries out metallics; With,

Can on porous paper and polymeric substrates or semiconductor surface, obtain conductor wire and have the characteristic of low-resistivity.

Detailed description of the present invention

[0016] recent, for allowing low temperature to form by loading on substrate, the process of the pattern that the high-conductive metal that carries out on substrate such as paper or the polymer thin film especially cheaply constitutes has given enough concerns.Treatment temp is 200 ℃ or has special significance during preferably smaller or equal to 150 ℃, especially for the situation of making the copper pattern of high conductivity on heat sensitive substrates such as thermoplast and paper.

[0017] electrical conductor by the addition manner manufacturing makes from the conductor preparation, and this conductor preparation generally comprises a kind of metallics and a kind of combination that can change the metal precursor of conducting metal into.Most cases lower conductor preparation comprises the mixture of metal precursor and/or metallics and liquid vehicle such as a kind of solvent.In the process of the metal pattern that forms high conductivity, need to finish a plurality of reactions.First reaction that forms electrical conductor is that metal precursor is decomposed into metal and organic by-products.Second reaction needed removes any oxide compound that may be present in the metallics surface.The 3rd reaction be remove the organic constituent that comes from the conductor preparation, stop the agglomerant stablizer of early stage metal-powder, as any organic materials of the additive of tackiness agent, surface energy promotor, viscosity intensifier or tackifier or liquid vehicle.The 4th reaction be fused for the finely divided metal that forms thus or sintering to form the conducting metal conductor.

[0018] by being applied on the substrate by the conductor preparation that at least a metallics or at least a metal precursor or its mixture constitute and making metallics or metal precursor change metal into and the improvement of method of shaping electrical conductor of carrying out the shaping of its electrical conductor thus is to have used electron attachment (EA), wherein metallics or metal precursor are exposed on time enough and temperature in the electric activatory reducing gas, are the agglomerating conducting metal to change this metallics or metal precursor.

[0019] term " electrical conductor " is meant the product of method manufacturing required for protection, and it can be applied in the application except that electrical applications, as using as thermal conductor or reflectance coating.

[0020] the conductor preparation that is used on substrate making conductive pattern comprise a kind of metallics that can change sintering metal into or metal precursor or and composition thereof.The conductor preparation equally can be by non-metallic additive, constitutes as indium/tin-oxide (ITO), himself be conduction and link to each other with conducting metal.

[0021] in the conductor preparation, adopted two types composition or metal component basically.One type of metal-powder or metal block that is based on nanometer and/or micron order size, another kind of based on having formula M ^(+a) _yX ^(-b) _wL _zMetallic compound, wherein M is applicable to a kind of metal of making electrical conductor, X is electronegative part, L is a neutral ligand, wherein ay=bw, and a is 1～5, b be 1～3 and z be 0～5.These metal mixtures are called as metal organic decomposition compound (MOD).The conductor preparation of many printing ink and slurry form adopts metal-powder and one or more metal organic decomposition combination of compounds of nanometer or micron-scale.

[0022] suitable metal that can be used as metallics in the conductor preparation comprises: copper, silver, gold, zinc, cadmium, palladium, iridium, ruthenium, osmium, rhodium, platinum, iron, cobalt, nickel, manganese, indium, tin, antimony, lead, bismuth, vanadium, chromium, titanium, tantalum, aluminium, magnesium, calcium, strontium, barium, cadmium, gallium, bismuth or their a kind of combination.More preferably, this metal is selected from the group of being made up of Cu, Ag, Ni and Au, and copper is most preferred because of it is cheap relatively, high conductivity and Gao Nai electromigration.

[0023] as previously mentioned, one type of the conductor preparation is based on " metallics ", and it comprises that mean sizes is not more than about 100 nanometers, as the nanometer powder of about 5 to 80 nanometers.Particularly preferably be and have the nanometer powder that mean sizes is not more than about 75 nanometers, as in the scope of 25 to 75 nanometers.Preferred nanometer powder is formed and is comprised copper, silver, palladium, gold, platinum and nickel.

[0024] term " metallics " comprises term " tinsel " equally, and it mainly has 1 to 10 micron length, and preferably between 1 to 5 micron, its thickness is less than 1 micron.Thin slice can be carried out several functions.They have formed a skeleton structure in printed images, this structure keeps together other compositions and prevent the loss of resolving power when mixture is heated with curing inks.Thin slice can adopt a kind of lamellated interlock natively, the rock that is similar to stone walling is laminated in together, this structure provides the electroconductibility that is parallel on the substrate surface direction, a kind of framework that reaches the necessary metal transmission quantity of pure metal conductor that fixes that is used for being reduced to also is provided, and this is a purpose of the present invention.They also provide the flat surface that other compositions in the component can the bonded low surface energy.This tinsel can be by technology manufacturing known in the art, and by corresponding metal powder and a kind of lubricant are ground, this lubricant is generally lipid acid or soap.

[0025] know, for reaching and keep the dispersity of metallics expectation, necessary stable particle is so that their not polymerizations.Metallics can be realized on the particle stablizing to prevent contacting of metal and metal by using surfactant or stablizer part to be plated on.Suitable surfactant and stablizer part comprise energy ready-formed or carboxylic acid and the carboxylate metal soap made on the spot.

[0026] particle metal also can comprise the spherical powder of micron order size, and it can comprise that single mode, bimodulus, three mould particle size distribution are to improve tamped density.Preferably, each powder mode has a narrow size distribution with the maximization tamped density.For silk screen printing circuit trace/assembly, preferred preparation is made of the metal particle of 60-85% weight, and wherein, nanometer powder accounts for the 20-50% of whole metal particle weight.

[0027] many organic compound types can both be as at aforementioned chemical formula M ^(+a) _yX ^(-b) _wL _zCompound in X ligand and L, they are owned together make they effectively character be that they all have or can form chemical bond to form a kind of coordination type compound via a heteroatoms and metal, perhaps they can form connect carbon metallic bond to form metal organic decomposition compound.Heteroatoms can be oxygen, nitrogen, sulphur, phosphorus, arsenic, selenium and other non-metallic element, preferred oxygen, nitrogen or sulphur.X is from by carboxylate radical, the halogenated carboxylic acid root, the ammonia root, halo ammonia root, amino, imino-, the halo imino-, beta-diketon, halo (beta-diketon), beta-ketimine, halo (beta-ketimine), beta-diimine, halo (beta-diimine), 'beta '-ketoester, halo ('beta '-ketoester), β-ketone ammonia root, halo (β-ketone ammonia root), alkoxyl group, halogenated alkoxy, aminoalkoxy, phenoxy group, halogenated phenoxy, alkyl, fluoro-alkyl, aryl, halogenated aryl, thiazolinyl, haloalkenyl group, halo alkynes, three fluoro methylsulphonic acid roots, beta-ketimine alkene, beta-diimine alkene, the halogen root, inferior ammonia root, hydroxide radical, sulfate radical, inferior sulfate radical, nitrate radical, nitrite anions, carbonate, the electronegative part of selecting in the group that heavy carbonic root and composition thereof is formed, ligand L are from by ammonia, the amine that replaces, diamines, triamine, imines, nitrile, alkene, alkynes, the neutral ligand of selecting in the group of the neutral ligand of phosphine complex compound that carbon monoxide or alkyl or phenyl replace and composition thereof.

[0028] chemical formula M ^(+a) _yX ^(-b) _wL _zThe special case of metal precursor comprise neodecanoic acid metallic soap and 2-ethyl acetic acid metallic soap.The mantoquita of formic acid, formic acid, neodecanoic acid and 2 ethyl hexanoic acid and silver salt are the representatives of carboxylate salt.The fine octanoate metal of 2 ethyl hexanoic acid metal amine salt and iodobenzene amine salt is to use the example of nitrogen growth, and uncle-lauryl mercaptan metal-salt is to use sulfur derivatives as metal, as the example of the part of copper.It is the examples for compounds with X and L part that ((4-N-methyl-imino)-3-amylene-2-ketone acid root) trimethyl-ethylene silane closes copper.Other concrete examples comprise venus crystals, trifluoracetic acid copper, cupric nitrate, methanolizing copper, ketoimine copper, cupric thiosulfate, five fluorine propionic acid copper, cupric octoate and corresponding to the silver-colored derivative of these copper compounds, as Silver Trifluoroacetate, silver thiosulfate or the like.

[0029] comprises that in soup compound or ink formulations solvent or liquid vehicle are very common.The effect of solvent is the dissolution of metals precursor, and the effect of liquid vehicle is to adjust viscosity.In some preferred implementation, solvent also can be simultaneously as carrier.Solvent and carrier should have suitable vapor pressure, to such an extent as to it should the too high work-ing life that can not keep them in sintering, to such an extent as to be not difficult for being removed after also should too low function when them not finishing.Solvent and carrier should not reduce or the performance of negative impact substrate, and should have low impurity, low steam toxicity, the low organic detritus proneness of leaving over.In addition, preferably, this solvent provides the high resolution of metal precursor.The α Terpineol 350 is an example of carrier, with the viscosity that reduces copper and silver-colored composition to quicken silk screen printing.The α Terpineol 350 that contains OH group and the single degree of unsaturation of ring participates in the middle of the formation of ink formulations equally.By selective solvent and carrier additives, can make the scope that can print composition for from liquid ink with 10 centipoises to soup compound with 40000 to 60000 centipoises.

[0030] preferably, the metal precursor that adopts in printing ink or soup compound and other are used agent, if adopt, have high purity and the high dissolubility in solvent.Equally preferably, metal precursor has the low propensity of chemical stability and toxigenicity volatile matter equally with other under envrionment conditions with agent.They should have the low propensity of leaving over organic detritus and produce the hypotoxicity volatile matter when curing.In addition, these metal precursor compound preferably have high metal yield and low reduction temperature.

[0031] metal precursor can be solid or liquid, also can make an addition in advance in the conductor preparation or pines for on-the-spot the shaping adding.This metal precursor also can spread on the special metallic surface that is used for the conductor preparation in advance.

[0032] special case that is used to make the above-mentioned representational printing ink of electrical conductor or soup compound is included in the PARMOD by the Parelec company limited of New Jersey Rocky Hill ^TMThe moiety of the type that trade mark is bought down.The details about commercial available printing ink or soup compound preparation that comprise the conducting metal preparation that can buy in order to generate conductive metal film and special copper film are open in US6036889, US6143356, US6153348, US6274412B1, US6379745B1 and WO03/032084 (2003/018045), the theme of these reference is introduced into by reference simultaneously, and metal comprises printing ink and the conductor precursor that above provides in more in addition the description.

[0033] knows electron attachment (EA) and can be used to accelerate forming of the electrical conductor that constitutes by the metal that loads on the substrate.More specifically, known that electron attachment can allow to form electrical conductor by carrying out the conductor preparation to the transformation of metal under than lower in the past possible temperature.

[0034] be applied on substrate, the principle that particularly on paper and polymeric substrates, forms the electron attachment of electrical conductor be set up an electric activatory reducing gas and expose this metal-powder or the metal precursor preparation in wherein.The electricity activation that should believe reducing gas has caused an electronegative ionic reducing gas, also can exist in electric activatory reducing gas positively charged or do not have electric charge chemical species.In a step that adopts electron attachment, the gaseous mixture of a kind of vector gas such as nitrogen and a kind of reducing gas such as hydrogen is introduced in to have in negative electrode and anodic heating compartment, baking box or the stove, and wherein substrate is connected to anode to form a destination apparatus.A pulsed dc voltage is applied between negative electrode and the anode, to produce low-energy electronics at cathode side.These electronics float to anode under electric field action, and in the drift process, part molecule reducing gas is as H ₂, because electron attachment has formed negative ion.They also float to anode.At anode, the ionic hydrogen of on-load and metal precursor and granular metal interact.This effect, stoichiometric calculation ground or has catalytically not only reduced the oxide on surface of some metallics, also help the chemical bond between metal and other elements, from metal precursor, discharge metal, thus, be somebody's turn to do " fresh " or newly-generated metal and quickened fusing or sintering again.In this process, select vector gas to make the electron affinity of its electron affinity less than reducing gas, therefore can infer that it can not be affected.N ₂Be the optimal selection of vector gas, because of its electron affinity is 0, low consumption, and do not have safety and environmental problem.

[0035] uses low-energy electron electricity activating and reducing gas, for example can be by following realization: from photoemissivity, electron beam technology, radiation activated source technology and the snowslide technology of light-sensitive cathode from the reducing gas of hydrogen molecule, the initiating electron of its cascade floats on the electrode that current potential raises one by one in the electrod-array, discharges extra electron from each follow-up electrode.The photoemissivity of low-energy electron can take place behind the light that for example photosensitive source is exposed to UV-light or other suitable wavelengths freely.In above-mentioned technology, electronics does not adopt volts DS emission (that is, photoemissivity), bias voltage must be set between negative electrode and the anode arrive anode with the electronics of traction generation and final electronegative ion.

[0036] reducing gas of using in electron attachment generally has two classes: 1) this gas is a kind of reducing gas and 2 in essence) this gas can generate active reducing substance.First kind gas comprise any can be in the conducting metal preparation as the gas of metallic reducing agent.The example that is essentially reducing gas comprises H ₂, CO, SiH ₄, Si ₂H ₆, formic acid, alcohol as methyl alcohol, ethanol etc.The second class reducing gas comprises it not being reductibility in essence, but can produce active substance by adhering to of the dissociating property of electronics on gas molecule, as forming H respectively ^-, C ^-, and S ^-Any gas of the gas that comprises H, C, S.The examples of gases of the type comprises: ammonia, low-grade alkylamine, hydrazine, hydrogen sulfide and C ₁To C ₁₀Hydrocarbon.

[0037] except the mixture that comprises one or more above-mentioned electron attachment reducing gass, this electron attachment gaseous mixture can further comprise one or more vector gas.This vector gas can be used to, and as, dilution reducing gas, collision stability is provided and will be transmitted electronically on the reducing gas.This vector gas that is applied in the gaseous mixture can be any gas that electron affinity is lower than the reducing gas in the gaseous mixture.In some preferred implementation, this vector gas is a rare gas element.The example of suitable rare gas element includes, but not limited to N ₂, Ar, He, Ne, kr and Xe.

[0038] in the enforcement of the electron attachment method that forms electrical conductor, the concentration of the reducing gas that comprises in gaseous mixture can be in the scope of approximate 0.1 to 100% volume.In preferred embodiment, this gaseous mixture comprises as the hydrogen of reducing gas with as the nitrogen of vector gas, and gaseous mixture comprises the hydrogen of 1 to 4% volume.The amount of preferred hydrogen is equal to or less than 4% volume, because electron attachment gaseous mixture right and wrong are flammable.

[0039] substrate that can be used to form electrical conductor comprises common high temperature substrate, as, glass or silicon and oxide compound thereof also can comprise low-temperature substrate such as paper and polymer substrate simultaneously.The suitable polymers substrate comprises polyethylene terephthalate, Kapton  polyimide, polynaphthenic acid glycol ester, polyethersulfone, polyetherimide, polycarbonate, polynorbornene, polyacrylic ester, polyetherketone or the like.Preferably some more cryogenic substrate such as polyethylene, polypropylene and poly-(vinylchlorid) in some applications.

[0040] for adhering to the key request that changes various conductor preparations into metallic conductor, applying electronic is in sintering, to get rid of electric charge remains on the dielectric properties on the X-Y plane simultaneously when sintering finishes requirement.The conductive substrates of ground connection and porous substrate are the mode examples that obtains The above results.In first kind of mode, can coat one deck insulating substrate on the surface, make coating heating or when being in noble potential by the conduction that changes into of electrical isolation.Selectively, can be on insulating substrate with semiconductive coatings applications, or this substrate is partly led in essence.By this mode, the electrical property of the conductor of generation can be held.In the second way, can adopt substrate such as porous polyethersulfone (PES) and porous paper, it can pass through electric current along the Z axle.In the third mode, this printing characteristic can be temporarily by being electrically connected to ground or anode with ground connection.The hole dimension of porous substrate can be from 10 nanometers to 1 millimeter, preferably from 100 nanometers to 10 micron, are more preferably from 100 nanometers to 1 micron.The temperature range of the formation electrical conductor by the auxiliary transformation of electron attachment is generally at 25 ℃ to 350 ℃, and preferred 25 ℃ to 200 ℃, more preferably from 100 ℃ to 150 ℃.This volts DS can be included in approximately-1kv is to-50kv, its preferred range greatly about-2kv to-10kv.The negative electrode or other equipment (photoemissivity or radioactive source) that produce electronics should be near anodes.Distance the upper surface from negative electrode to processed substrate is approximately 0.5 to 10 centimetre, and preferable range is 1 to 2 centimetre.Place two interelectrode voltages to can be constant or pulse.The preferred voltage pulse is to be used for reducing electric arc.The range of frequency of voltage pulse is 0 to 100kHz, preferred 5 to 20kHz.

[0041] in order to adapt to open and successive production line, this electron attachment working pressure is preferably environment atmospheric pressure.Yet, in order to improve the efficient that produces ionic reducing gas by electron attachment, is more prone in high atmospheric pressure, operate aforesaid method, as reaches 60 normal atmosphere, but general air pressure is 10 to 50psia.

[0041] using the conductor preparation, when forming conductor wire or feature, can adopt any common technology that said preparation be may be used on the substrate by a kind of metallics or metal precursor or both printing ink or soup compound.Silk screen printing and steel seal are suitable for inflexible and flexible substrate.Photogravure, impression printing and offset printing are suitable for the high yield on flexible substrate.Ink jet printing and xeroprinting provide the image to printing to carry out direct computer-controlled advantage.These methods allow circuit directly to be passed through the printing of computer aided design (CAD) (CAD) file, and they have reduced the needs to speciality tool.If want, each circuit can be according to code or phototype and difference.By computer-controlled partitioning device with the obtainable same result of lower productive rate.This equipment is by mobile syringe needle from the teeth outwards and distribute by what pump or pressure injector provided and be printed as assign to manufacturing place or line.Other method includes but not limited to rotary screen printing, flexographic printing, electric record printing, laser-groove-fill out method, the planography of pen nanometer and shifts from the heat of pre-coating band.

[0043] although is not bound by theory, but provide embodiment based on the above-mentioned low-temperature metal sintering process under the auxiliary situation of electron attachment, as, copper or silver-colored sintering, illustrate as follows: in sintering, will be incorporated in the stove smaller or equal to the hydrogen of 4 volume % and the gaseous mixture of nitrogen.This stove is along comprising heating zone and cooling zone on the different zones of tunnel shaft and comprising from a moving belt of the end to end of stove.At the stove inner top negative electrode of an emitting electrons has been installed, on the ground connection moving belt, has been provided with a rigidity or flexible substrate, conductive copper (or other metals or metal mixture) preparation has been printed on this substrate.When having applied suitable voltage on negative electrode, low-energy electron is shifted to printed substrates from the negative electrode generation and by electric field driven.Hydrogen molecule bumps against with these electronics subsequently, forms neutral and electronegative hydrogen atom.Electronegative atom state hydrogen ion is shifted to substrate along electric field, has caused the preferential absorption of active substance on substrate surface.Metal discharges from metal precursor, and the lip-deep any oxide compound of metal particle all is reduced, and this mixture melt is to form the agglomerating electrical conductor on substrate simultaneously.On substrate surface, the unbound electron that penetrates from negative electrode or generate as the byproduct of the chemical reaction on substrate discharges over the ground along substrate Z axle or the ground connection coating that passes substrate.

[0044], wishes to have an energy and on substrate surface, evenly produce low-energy electron and comprising H for applying electronic in low temperature copper sintering adheres to ₂And N ₂The barometric point of atmosphere surrounding under have the negative electrode of long life.The negative electrode that is made of the salver with distributed emission tip is preferred.In order to maximize electric field, each emission tip is made by the Ni/Cr lead of 0.025 inch of diameter, and the tip of giving prominence to 1.5 centimetres 10 degree angles from the salver surface is provided.For between transmitting terminal and the treat surface 1 centimetre give set a distance, based on the electric field between the minimized adjacent tip disturb and the surface coverage of maximized electron emission between compromise, between its tip apart from being preferably about 1 centimetre.

[0045] following embodiment is used to illustrate various embodiment of the present invention, but is not limited to its scope.

Embodiment 1

The electrical conductor that adopts metal powder mixture to make

[0046] this embodiment has demonstrated at H ₂At N ₂In account for 4% volume atmosphere as adopting copper powder to form electrical conductor in the reducing gas according to electron attachment.

[0047] be mixed in the copper soup compound at a collection of α of comprising-terpinol and copper nanoparticle end in the glove box with 1: 2 weight ratio and by experiment the shredder of chamber scale grind.The soup compound of this grinding is screen printed to aluminium foil (in electron attachment with soup compound ground connection) then.This paper tinsel is placed in the metal anode top and ground connection.Negative electrode with minute hand is placed on the paper tinsel.Spacing between radial spine tip and paper tinsel is about 1 centimetre.Behind the voltage that has applied about 3.5kv, obtained to have the electron emission of the electric current of 0.25mA/ end.By N ₂In account for the H of 4% volume ₂In be heated to 120 ℃ and kept 10 minutes and with the printed traces sintering.This can carry out being with or without under the situation of electron attachment in the maintenance stage.This agglomerating copper tracing wire is transferred on the electrical insulation tape then with measuring resistance.The result shows that the copper pattern that uses electron attachment to form has low conductivity and presented distinct coppery, has shown a kind of typical anaerobic and the copper film that partially sinters.By contrast, the color of copper pattern is a dun when not adopting electron attachment, and similar to the mould of printing before, its specific conductivity is 0, has indicated the lip-deep non-sintered surface oxide compound at nanometer powder.The final copper pattern that under the situation of not adding copper compound particle is connected to each other and obtains all is brittle in two kinds of situations.

Embodiment 2

From the copper ketimine compound, form the influence of the electron attachment of copper conductor

[0048] in order to show the effect of electron attachment in forming electrical conductor, carried out following experiment.The copper soup compound that will comprise weight ratio separately and be the copper powder of the copper powder of liquid Cu (II) ketoimine, micron-scale of 0.128,0.698 and 0.181 chemical formula Cu (MeC (O) CHC (Net) Me) 2 and nano particle is mixed in N ₂In the glove box that purge is crossed and adopt three-roll grinder to grind.The soup compound silk screen printing that to grind then is on aluminum substrates.Then with this printed traces at H ₂Account for the N of 4% volume ₂In be sintered to 200 ℃ and kept 10 minutes at 200 ℃, a kind of employing electron attachment during keeping, another kind does not adopt electron attachment.This coalesced copper trace is sent on the electrical insulation tape then with measuring resistance.

[0049] finds to adopt electron attachment agglomerating sample to have low conductivity, do not adopt the sample of electron attachment then non-conductive fully.The same discovery, adopted the color of the sample Sintering Model that electron attachment is shaped obviously more bright-coloured than the color of the sample that does not adopt electron attachment, the effect that shows electron attachment is to help to discharge the copper metal from copper precursors, has reduced the oxide on surface of copper powder, and has carried out the sintering of copper.Therefore, auxiliary being formed on aspect copper sintering and the specific conductivity of the electron attachment of electrical conductor will form significantly better than the electrical conductor that does not adopt electron attachment in the time of 200 ℃.

Embodiment 3

In the influence that forms electron attachment the conductor from the copper ketoimine

[0050] in order to prove that quantitatively electron attachment is at low temperatures at H ₂Account for the N of 4% volume ₂Middle quickening has been carried out following experiment as the influence in the reduction of Cu (II) ketoimine of only metal precursor.Prepared two increments this, every part has all comprised liquid Cu (II) ketoimine among several embodiment 2 on aluminium foil.Use electron attachment that sample 3-1 is heated to 200 ℃ and kept 10 minutes,, do not use electron attachment for sample 3-2.

[0051] after adopting and not adopting the electron attachment heat treated, the scene is originally analyzed two increments by oxidation in air purge TGA/DSC device.By this mode, when any organic residue is heated in TGA equipment with oxidation by air.Change its volatile oxidn (CO by measuring into by the oxide compound that comprises carbon, hydrogen, nitrogen compound ₂, H ₂O, NO _xDeng) the kidney weight loss of gained afterwards, thereby estimation is in the relative mass of the organic residue of implementing to leave over after the thermal treatment.Similarly, the quantity of volatile oxidn also can be measured by FTIR.

[0052] result shows, the organic residue among the sample 3-1 does not wherein have applying electronic to adhere to far below sample 3-2.Therefore, from precursor, discharge the needed temperature of copper metal, therefore reduce the sintering temperature of copper metal simultaneously by using electron attachment to reduce.

Embodiment 4

In the influence that forms electron attachment the copper conductor from neodecanoic acid copper

[0053] in order to show, carried out following experiment in the influence of using only a kind of copper precursor compound electron attachment in the generation electrical conductor.Two increments this, every part comprises several liquors that comprise the toluene of the neodecanoic acid copper (II) that accounts for 60% weight and 40% weight, every part all has fresh blueness, is applied on the aluminium foil.Adopt then and the H that does not adopt electron attachment 4% ₂/ N ₂In two increments originally are heated to 200 ℃ and kept 10 minutes.

[0054] after having adopted electron attachment, after heating cycle, drop is transformed into the film with brown coppery, has shown from neodecanoic acid copper to be transformed into copper.Yet when not adopting electron attachment, this liquor has become the solid phase of very dark color, shows that neodecanoic acid copper is not transformed into the copper metal.

Embodiment 5

In the influence that forms electron attachment the conductor from Tubercuprose

[0055] carried out following experiment to show when adopting electron attachment at H ₂Account for the N of 4% volume ₂The middle formation of using the copper conductor of Tubercuprose (a kind of copper precursors).The saturated solution (12.5g/100cc) of Tubercuprose in water is dripped on the aluminium foil, under the condition of electron attachment and no electron attachment at H ₂Account for 4% N ₂In be heated to 150 ℃, and kept 10 minutes.

[0056] finds when applying electronic adheres to, to have formed the coppery film.Adopted XPS analysis at the film that forms, determined that this film is the copper with organic and inorganic residue of oxide on surface and trace.When not adopting electron attachment for 150 ℃, this processing sample has a green/blueness, indicates the Tubercuprose that is not changed and fails metal precursor is reduced and the formation copper conductor.

Embodiment 6

Form conductor from copper powder mixture with organic surface functionality.

[0057],, neodecanoic acid, copper micron powder and copper nano powder prepare a collection of copper soup compound by being mixed in the glove box of nitrogen purge with weight ratio 0.128,0.698 and 0.181 separately in order to show the advantage of electron attachment on the electrical property that improves the sintering copper film.After mixing, said preparation is ground at laboratory scale shredder.This polished soup compound prints then to aluminium foil (in order temporarily to avoid any discharge problem when adopting electron attachment).Adopt or do not adopt electron attachment, will be at sample sintering in given atmosphere surrounding of each the print copper precursor formulation on the aluminium foil, and kept 10 minutes at peak temperature.This coalesced copper trace is transferred on the electrical insulation tape then to measure its resistance.The result is provided in the table 1.

Table 1

The comparison of the electrical property of agglomerating copper soup compound

Gas	Electron attachment	Peak temperature	Resistivity
				N 2	Not	350	28.9
N 2	Not	200	∞
				The H of 4% volume 2/N 2	Not	200	67.8
The H of 4% volume 2/N 2	Be	200	15.5

[0058] as shown in table 1, when at H ₂Account for the N of 4% volume ₂In when adopting electron attachment, the peak firing temperature of conductive copper is reduced to 200 ℃ from 350 ℃, the electrical conductor of Huo Deing has significantly lower resistivity when not adopting electron attachment simultaneously.The physical strength of the sintering trace when in addition, finding equally that applying electronic adheres to is the sintering trace when not adopting electron attachment obviously.

Can affirm that [0059] in sintering process, the neodecanoic acid that is added and the oxide on surface of copper powder interact, and have produced the copper precursors of transient state.When sintering temperature higher relatively (as 350 ℃), the on-the-spot copper precursors that forms can be thermal decomposited the sintering that generates copper and realize powdered mixture.When at H ₂Account for the N of 4% volume ₂In sintering during, when adopting electron attachment, H ₂Can obtain very big promotion 200 ℃ the time to the reduction of copper precursors.

Embodiment 7

Adopt the influence of the exposure duration of electron attachment

[0060] in order to study the influence of exposure duration of electron attachment when copper agent is sintered to electrical conductor, carried out following experiment.In embodiment 6, by being 0.128,0.698 and 0.181 to be mixed in the glove box that purging with nitrogen gas crosses and to have prepared a collection of copper soup compound with weight ratio respectively with neodecanoic acid, copper micron powder and each composition of copper nano powder.After mixing, adopt laboratory scale shredder that this mixture is ground.The soup compound of this grinding is screen printed on a slice silicon wafer subsequently temporarily avoiding the discharge problem in applying electronic adheres to, thereby allows the direct measurement to the resistance of sintering conductor.

[0061] sample with two parts of print copper soup compounies on silicon is comprising 4% volume H ₂N ₂Reducing gas in sintering.For first increment sintering originally, adhere at applying electronic from 150 ℃ to 200 ℃ heat-processed, the electron attachment time is discontinuous during this period.For this sintering of second increment, adhere to and kept 2 minutes at 200 ℃ at applying electronic from 150 ℃ to 200 ℃ heat-processed.

This resistance of [0062] two increment is found to be identical, show in heat-processed, to have obtained the auxiliary chemical reduction of electron attachment, and for extra electron attachment be radiated at 200 ℃ the time hold-time be unnecessary.

Embodiment 8

Adopt porous paper substrate dissipation electric charge

[0063] whether the purpose of this embodiment be to determine can be with porous paper as substrate when applying electronic adheres to the sintering that quickens copper agent.

[0064] can buy the porous paper with good soup compound impressionability from Stora Enso, this porous paper can be used as a kind of flexible substrate especially.This paper can bear 200 ℃ and non-oxidation and damage in air.This paper is placed on the top of metal anode.Negative electrode with minute hand is placed on the paper.Gap between emission needle tip and paper is approximately 1 centimetre.Behind the voltage that applies about 3.5kv, obtained to have the electron emission of the electric current at 0.25mA/ tip.In the time of 200 ℃, has 4% volume H ₂N ₂In implemented 5 minutes electron attachment.After being exposed to electron attachment, do not find on paper that obvious color changes, and shows in the electronic discharge process not owing to overheated or overcurrent produce cause thermal damage.

[0065] result shows that simultaneously porous paper can allow to pass the Z axle from the paper electric charge that dissipates, and therefore allows to adopt dielectric substrate when electron attachment.

Embodiment 9

The sintering of the copper powder conductor preparation on porous paper

[0066] this embodiment has shown at H ₂Account for the N of 4% volume ₂In to adopt electron attachment (EA) be the benefit of electrical conductor with the copper powder assist formation on paper.

[0067] a collection of copper soup compound that will comprise α-terpinol and copper nanoparticle end at 1: 2 with weight ratio be mixed in the glove box and by experiment the shredder of chamber scale grind.The soup compound of this grinding is screen printed to then on the surface coated porous paper and (is made by Stora Enso).By at H ₂Account for the N of 4% volume ₂In be heated to 120 ℃ and kept 5 minutes and with this printed traces sintering.In one of two sintering situations, adhere to and continue 5 minutes hold-time at applying electronic from 100 ℃ to 120 ℃ heat-processed.Under another sintering situation, there is not applying electronic to adhere to.

[0068] result shows, the conductive pattern that does not adopt electron attachment to form presents the dun similar to the pattern that is printed before, is indicated as a kind of non-agglomerating film.On the contrary, adopt the color of the copper pattern that electron attachment forms to present bright-coloured coppery, show that oxide compound at powder surface is removed and this membrane portions is sintered.Because the conductor preparation does not comprise copper precursors, thereby the generation that does not have fresh copper is with melting copper powder in sintering, and the specific conductivity of the sintered membrane when this adopts electron attachment is very poor.

Embodiment 10

The sintering of the conductor preparation that on porous paper, constitutes by copper powder and copper precursors

[0069] this embodiment has shown at H ₂Account for the N of 4% volume ₂In adopt electron attachment (EA) to assist on paper the conductor preparation agglomerating benefit that will constitute by copper powder and copper precursors.

[0070] a collection of copper soup compound that will comprise α-terpinol, micron copper powder and the Tubercuprose of following weight percent 11%, 71% and 18% be mixed in the glove box and by experiment the shredder of chamber scale grind.The soup compound of this grinding is screen printed to then on the surface coated porous paper and (is made by Stora Enso).By at H ₂Account for the N of 4% volume ₂In be heated to 150 ℃ and kept 5 minutes and with this printed traces sintering.In one of two sintering situations, adhere to and continue 5 minutes hold-time at applying electronic from 100 ℃ to 150 ℃ heat-processed.Under another sintering situation, there is not applying electronic to adhere to.

[0071] result shows that the conductive pattern that does not adopt electron attachment to form presents the dun similar to the pattern that is printed before, is indicated as a non-sintered membrane.On the contrary, adopt the color of the copper pattern of electron attachment shaping to present bright-coloured coppery, show the formation of sintered membrane.By measuring the resistance and the thickness of sintered membrane, the resistivity of sintered membrane be about 232 micro-ohms-centimetre.Though resistivity is higher relatively, this experiment shows can be at H in the time of 150 ℃ ₂Account for the N of 4% volume ₂The middle electron attachment that adopts forms conductive pattern on porous paper.

Embodiment 11

The sintering of the conductor preparation that on porous paper, constitutes by copper sheet and copper precursors

[0072] this embodiment has shown at H ₂Account for the N of 4% volume ₂In adopt electron attachment (EA) to assist on paper the conductor preparation agglomerating benefit that will constitute by copper sheet and copper precursors.

[0073] prepared a collection of copper soup compound that comprises with α-terpinol, copper sheet and the Tubercuprose of following weight percent 11%, 71% and 18%.For better mixing, at first, then copper sheet is joined in the mixture, once more mixing/grinding Tubercuprose and α-terpinol mixing and grinding.This soup compound is screen printed on the surface coated porous paper and (is made by Stora Enso) then.By at H ₂Account for the N of 4% volume ₂In be heated to 150 ℃ and kept 5 minutes and with this printed traces sintering.In one of two sintering situations, adhere to and continue 5 minutes hold-time at applying electronic from 100 ℃ to 150 ℃ heat-processed.Under another sintering situation, there is not applying electronic to adhere to.

[0074] result shows, the conductive pattern that does not adopt electron attachment to form presents the dun similar to the pattern that is printed before, is indicated as a kind of non-sintered membrane.On the contrary, adopt the color of the copper pattern of electron attachment formation to present bright-coloured coppery, show the formation of reduction and sintered membrane.By measuring the resistance and the thickness of sintered membrane, the resistivity of sintered membrane be about 97 micro-ohms-centimetre, significantly better than the embodiment (embodiment 10) that in soup compound, uses the micron copper powder.When this experiment is further illustrated in 150 ℃ at H ₂Account for the N of 4% volume ₂Middle employing electron attachment (EA) is assisted and formed conductive pattern on porous paper, and specific conductivity can be enhanced when adopting copper sheet to replace the micron copper powder simultaneously.

Embodiment 12

The sintering of the conductor preparation that on silicon wafer, constitutes by copper powder and crystalline copper precursor

[0075] this embodiment has shown at H ₂Account for the N of 4% volume ₂In adopt electron attachment (EA) to assist on silicon wafer the conductor preparation agglomerating benefit that will constitute by copper powder and crystalline copper precursor.(this copper precursors has finely divided solid form)

[0076] a collection of copper soup compound that will comprise α-terpinol with following weight percent 11%, 71% and 18%, micron copper powder and Tubercuprose be mixed in the glove box and by experiment the shredder of chamber scale grind.The soup compound of this grinding is screen printed on the silicon wafer then.By at H ₂Account for the N of 4% volume ₂In be heated to 150 ℃ and kept 5 minutes and with this printed traces sintering.In one of two sintering situations, adhere to and continue 5 minutes hold-time at applying electronic from 100 ℃ to 150 ℃ heat-processed.Under another sintering situation, there is not applying electronic to adhere to.

[0077] result shows, the conductive pattern that does not adopt electron attachment to form presents the dun similar to the pattern that is printed before, is indicated as a kind of non-sintered membrane.On the contrary, adopt the color of the copper pattern of electron attachment formation to present bright-coloured coppery, show the shaping of sintered membrane.By measuring the resistance and the thickness of sintered membrane, the resistivity of sintered membrane be about 29 micro-ohms-centimetre.This experiment shows, can be at H in the time of 150 ℃ ₂Account for the N of 4% volume ₂The middle electron attachment that adopts forms conductive pattern on semiconducter substrate.

Embodiment 13

The sintering of the conductor preparation that on silicon wafer, constitutes by copper powder and dissolved copper precursors

[0078] with embodiment 12 contrasts, this example has shown at H ₂Account for the N of 4% volume ₂In adopt electron attachment (EA) to assist on silicon wafer the conductor preparation agglomerating benefit that will constitute by copper powder and dissolved copper precursors.

[0079] preparation comprises the solution that weight ratio is 1 to 1 ammonium hydroxide (30% weight in water) and Tubercuprose, and wherein the Tubercuprose powder is dissolved fully.The copper soup compound of the micron powder of a kind of solution that comprises 12% weight and 88% weight is mixed in the glove box, and the shredder of chamber scale grinds by experiment.The soup compound that will grind is screen-printed on the silicon wafer then.By at H ₂Account for the N of 4% volume ₂In be heated to 150 ℃ and kept 5 minutes and should print the soup compound sintering.In one of two sintering situations, pining for from 100 ℃ to 150 ℃ add that applying electronic adheres to and continuing 5 minutes hold-time.Under another sintering situation, there is not applying electronic to adhere to.

[0080] result shows, the conductive pattern that does not adopt electron attachment to form presents dun and has infinitely-great resistivity.On the contrary, adopt the color of the copper pattern of electron attachment formation to present bright-coloured coppery, show the formation of sintered membrane.The resistivity of sintered membrane be 7 micro-ohms-centimetre.This experiment further shows, can be at H in the time of 150 ℃ ₂Account for the N of 4% volume ₂The middle electron attachment that adopts forms conductive pattern.

Embodiment 14

In the influence that forms electron attachment the silver conductor from neodecanoic acid silver

【0081】

Adopting and do not adopting under the electron attachment condition, at H ₂Account for the N of 4% volume ₂Reducing gas in the neodecanoic acid silver powder is placed aluminium foil and is heated to 150 ℃, kept 10 minutes.

[0082] can find, when adopting electron attachment, form the silver color film.In the sample that does not adopt electron attachment, this sample gray/blueness.Clearly, this neodecanoic acid silver is pined for fusing and the time is solidified again and be not transformed into silver in cooling adding.

Embodiment 15

In the influence that forms electron attachment (EA) the silver conductor from the silver-colored soup compound that can buy

[0083] a kind of silver-colored soup compound of buying is from Parelec, and Inc buys, and is printed on the Kapton polyimide film, this silver soup compound in air or in the nitrogen agglomerating recommended temperature be 150 ℃ and continue 5 to 10 minutes.By with this printed traces at H ₂Account for the N of 4% volume ₂In be heated to 120 ℃ and kept 5 minutes and with its sintering.In one of two sintering situations, adhere to and continue 5 minutes hold-time at applying electronic from 100 ℃ to 150 ℃ heat-processed.Under another sintering situation, there is not applying electronic to adhere to.

[0084] result shows, the pattern that does not adopt electron attachment to form is non-conductive.On the contrary, adopted the resistivity of the pattern of electron attachment be 18 micro-ohms-centimetre.This experimental results show that still can be at H when temperature is hanged down to 120 ℃ ₂Account for the N of 4% volume ₂The middle electron attachment that adopts is assisted the silver-colored conductive pattern of formation on Kapton.

Embodiment 16

The sintering of the ITO film that on silicon wafer, constitutes by indium/tin-oxide (ITO) powder and copper precursors

[0085] this embodiment has shown at H ₂Account for the N of 4% volume ₂In adopt electron attachment to assist on silicon wafer indium/tin-oxide (ITO) film agglomerating benefit that will constitute by ito powder and metal precursor.

[0086] a collection of copper soup compound that will comprise α-terpinol, ito powder and the Tubercuprose of following weight percent 11%, 71% and 18% be mixed in the glove box and by experiment the shredder of chamber scale grind.The soup compound of this grinding is screen printed on the silicon wafer then.By with this printed traces at H ₂Account for the N of 4% volume ₂In be heated to 150 ℃ and kept 5 minutes and with its sintering.In one of two sintering situations, pining for the hold-time that electron attachment is used and continued 5 minutes from 100 ℃ to 150 ℃ add.Under another sintering situation, there is not applying electronic to adhere to.

[0087] result shows, does not adopt pattern that electron attachment forms not by sintering effectively.By contrast, when adopting electron attachment, formed sintered membrane.This experiment shows, can be at H in the time of 150 ℃ ₂Account for the N of 4% volume ₂The middle electron attachment that adopts is assisted formation agglomerating ITO film on semiconducter substrate.

[0088] in a word, this embodiment shows, thereby when using electron attachment to change metal into and allow to produce sintering with the oxide on surface that reduces metal-powder with metal precursor, can on multiple substrate, provide electrical conductor, comprise the thermally sensitized substrate, as, the paper under the low temperature.This embodiment has shown that further those conducting films can be under far below the temperature of original application be formed by the powder of commercialization and the metal precursor that uses usually in the forming of electrical conductor, and does not increase the treatment time.

Claims (28)

1, on substrate, form the method for electrical conductor, may further comprise the steps:

The conductor preparation that at least a one-tenth branch that will select from the group of being made up of metallics, metal precursor and composition thereof constitutes is applied on the substrate;

This conductor preparation is exposed in the electric activatory reducing gas;

Described composition is changed into metal and forms described electrical conductor.

2, the method described in claim 1, wherein electric activatory reducing gas produces by following steps:

The conductor preparation is placed between first electrode and second electrode; And

Between described first and second electrodes, set up direct current (DC) voltage to form electric activatory reducing gas.

3, the method for claim 1, wherein said electric activatory reducing gas is electronegative ionic reducing gas.

4, method as claimed in claim 3, wherein said reducing gas is selected from the group that is made of hydrogen, ammonia, carbon monoxide and composition thereof.

5, method as claimed in claim 4, wherein said gaseous mixture are hydrogen and a kind of vector gas of 0.1% to 100% volume.

6, method as claimed in claim 5, wherein said gaseous mixture are hydrogen and a kind of vector gas of 1% to 4% volume.

7, method as claimed in claim 6, wherein said vector gas is selected from the group of being made up of nitrogen, helium, argon, neon, krypton, xenon and composition thereof.

8, method as claimed in claim 3, wherein said conductor preparation is made of described composition and indium/tin-oxide.

9, the method for claim 1, wherein said conductor preparation by from by metallics, have chemical formula M ^(+a) _yX ^(-b) _wL _zMetal precursor and described particle and group that the mixture that metal precursor is constituted is formed in select at least aly become branch to constitute, wherein M is applicable to a kind of metal of making electrical conductor, X is electronegative part, L is a neutral ligand, ay=bw wherein, and a is 1～5, b be 1～3 and z be 0～5.

10, method as claimed in claim 9, wherein the metal that is adopted in described composition is selected from the group of being made up of copper, silver, gold, zinc, cadmium, palladium, iridium, ruthenium, osmium, rhodium, platinum, iron, cobalt, nickel, manganese, indium, tin, antimony, lead, bismuth, vanadium, chromium, titanium, tantalum, aluminium, magnesium, calcium, strontium, barium, cadmium, gallium, bismuth and composition thereof.

11, method as claimed in claim 9, wherein the metal that is adopted in described composition is selected from the group of being made up of palladium, iridium, platinum, cobalt, nickel, manganese, indium, tin, antimony, lead, bismuth, aluminium and composition thereof.

12, method as claimed in claim 10, wherein the metal that is adopted in described composition is selected from the group of being made up of copper, silver, platinum, gold and composition thereof.

13, method as claimed in claim 10, wherein X ligand is from by carboxylate radical, the halogenated carboxylic acid root, the ammonia root, halo ammonia root, amino, imino-, the halo imino-, beta-diketon, halo (beta-diketon), beta-ketimine, halo (beta-ketimine), beta-diimine, halo (beta-diimine), 'beta '-ketoester, halo ('beta '-ketoester), β-ketone ammonia root, halo (β-ketone ammonia root), alkoxyl group, halogenated alkoxy, aminoalkoxy, phenoxy group, halogenated phenoxy, alkyl, fluoro-alkyl, aryl, halogenated aryl, thiazolinyl, haloalkenyl group, halo alkynes, three fluoro methylsulphonic acid roots, beta-keto acid root-alkene, beta-ketimine alkene, beta-diimine alkene, the halogen root, inferior ammonia root, hydroxide radical, sulfate radical, inferior sulfate radical, nitrate radical, nitrite anions, carbonate, select in the group that heavy carbonic root and composition thereof is formed, ligand L is from by ammonia, the amine that replaces, diamines, triamine, imines, nitrile, alkene, alkynes, select in the group that phosphine complex compound that carbon monoxide or alkyl or phenyl replace and composition thereof is formed.

14, method as claimed in claim 13, wherein X ligand is selected from the group of being made up of carboxylate radical, beta-diketon, beta-ketimine, beta-diimine, 'beta '-ketoester and composition thereof, and z is 0.

15, method as claimed in claim 13, wherein said conductor preparation (a) chemical formula M that serves as reasons ^(+a) _yX ^(-b) _wL _zMetal precursor; (b) has first metal-powder of from 1 to 10 micron particle size; (c) has second metal-powder of the particle size of from 5 to 80 nanometers; (d) mixture that a kind of organic liquid constituted.

16, method as claimed in claim 15, wherein the described metal that adopts in described composition is selected from the group that is made of copper, silver and composition thereof.

17, method as claimed in claim 16, wherein said substrate is from by selecting the group that porous paper and porous polymer constituted, and wherein porous polymer is selected from the group that is made of polyethylene terephthalate, polyimide, polynaphthenic acid glycol ester, polysulfones, polyetherimide and composition thereof.

18, method as claimed in claim 17 has coated semiconductor material wherein for described substrate surface.

19, form film and change described composition the method for sintering metal into from a kind of conductor preparation that is made of at least a composition, described composition is selected from the group of being made up of metallics, metal precursor and composition thereof, and this method comprises:

This conductor preparation is exposed in the electronegative ionic reducing gas, described composition is changed into the metal that metal and sintering form thus.

20, process as claimed in claim 19, wherein the described composition in the conductor preparation is from by metallics; Chemical formula M ^(+a) _yX ^(-b) _wL _zMetal precursor; And composition thereof select in the group formed, wherein M selects from the group that is made of copper, silver and composition thereof, X is electronegative part, L is a neutral ligand, wherein ay=bw, and a is 1～5, b be 1～3 and z be 0～5.

21, method as claimed in claim 20, wherein the conductor preparation is made of at least a metal precursor, and described metal precursor is selected from the group that is made of corresponding silver-colored derivative of Tubercuprose, venus crystals, trifluoracetic acid copper, cupric nitrate, methanolizing copper, neodecanoic acid copper, ketoimine copper, 2 ethyl hexanoic acid copper, cupric thiosulfate, five fluorine propionic acid copper, cupric octoate and these copper compounds and composition thereof.

22, method as claimed in claim 21 is 25 ℃ to 350 ℃ in the described temperature that adopts in the process of described electronegative reducing gas that is exposed to wherein.

23, method as claimed in claim 22 is 25 ℃ to 200 ℃ in the described temperature that adopts in the process of described electronegative reducing gas that is exposed to wherein.

24, method as claimed in claim 23 is 100 ℃ to 150 ℃ in the described temperature that adopts in the process of described electronegative reducing gas that is exposed to wherein.

25, method as claimed in claim 24 is 10 to 50psia at the described air pressure that adopts in the process of described electronegative reducing gas that is exposed to wherein.

26. method as claimed in claim 21, wherein said preparation is made of indium/tin-oxide.

27, the method for electrical conductor shaping comprises step:

(a) will be applied on the substrate by the preparation that at least a one-tenth branch of selecting from the group of being made up of metallics, metal precursor and composition thereof constitutes, the described metal in described metallics or the metal precursor is selected from the group of being made up of copper, silver and composition thereof;

(b) said preparation is contacted with the electric activatory reducing gas that is made of rare gas element and hydrogen, wherein said hydrogen accounts for 1% to 4% volume in described reducing gas; With

(c) described composition is changed into the metal that metal and sintering form thus.

28, method as claimed in claim 27, wherein said metal precursor is selected from the group that is made of Tubercuprose, neodecanoic acid copper, neodecanoic acid silver and composition thereof.