EP2735002A1 - Method for producing thin electrically conductive layers of silver, a silver layer, a silver complex, the solution of said silver complex, and the use of the silver complex in a solution - Google Patents
Method for producing thin electrically conductive layers of silver, a silver layer, a silver complex, the solution of said silver complex, and the use of the silver complex in a solutionInfo
- Publication number
- EP2735002A1 EP2735002A1 EP12733165.0A EP12733165A EP2735002A1 EP 2735002 A1 EP2735002 A1 EP 2735002A1 EP 12733165 A EP12733165 A EP 12733165A EP 2735002 A1 EP2735002 A1 EP 2735002A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver
- solution
- layer
- electrically conductive
- process step
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
- C23C18/143—Radiation by light, e.g. photolysis or pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
Definitions
- the invention relates to a method for producing thin electrically conductive layers of silver on a surface of substrates, electrically conductive layers, a silver complex and a solution of the silver complex and the use of a silver complex solution. It can preferably be used for the production of electrically conductive structural elements, such as electrodes or conductor tracks, which may also be optically transparent, as is the case, for example, with thin-film solar cells or light-emitting diodes.
- Metal layers which are preferably made of silver, can hitherto be produced in the required thickness only with known vacuum coating technology, in the required homogeneity while maintaining sufficient optical transparency, which also increases the production costs.
- this object is achieved by a method having the features of claim 1.
- An electrically conductive silver layer is defined by claim 8.
- Claim 11 relates to a silver complex and claim 12 relates to a solution of the silver complex.
- a use is specified in claim 15.
- the procedure is that, in a first process step, silver nitrate (AgNO 3 ) and 2-pyrrolidone are dissolved in a solvent, preferably water or an ethanol / water mixture. It is also possible, for example, to use water / acetone or water / THF as solvent.
- a solvent preferably water or an ethanol / water mixture. It is also possible, for example, to use water / acetone or water / THF as solvent.
- the solution obtained can be subjected directly to a second process step.
- the solution is kept at room temperature with exclusion of light for several days is, and there is an evaporation of liquid.
- a second process step the solution is applied to a surface of the substrate to be coated and then subsequently in a third process layer a chemical reduction, which leads to the separation of silver from the other contained chemical components, by irradiation with electromagnetic radiation from the wavelength spectrum of the UV light over a period of at least 15 min, preferably 20 min performed.
- a heat treatment is carried out at a temperature of at most 500 ° C., preferably at 250 ° C., more preferably 220 ° C. over a period of at least 30 min, preferably 60 min, and one at least almost exclusively of silver formed layer on the surface of the substrate. Remains of other chemical elements and compounds with a content of ⁇ 2% can remain in the layer.
- the maximum temperature depends on the temperature permissible for a substrate to be coated and, if appropriate, the melting temperature of silver.
- the substrate material should not be adversely affected by the temperature used and at least neither deform nor chemically react. Diffusion processes with components contained in the substrate material should also be avoided.
- silver nitrate and 2-pyrrolidone [Ag (pyl) 2] N03 - (C8H14AglN305) are formed as a complex, which can crystallize.
- the monoclinic space group C2 / c (No. 15) with four formula units forms a cell unit.
- the asymmetric unit contains the 2-pyrrolidone molecules, a half silver atom, a half nitrate anion occupying certain positions of a double axis, one of which passes through the Nl-04 bond, as shown in the graph of FIG.
- the silver atom has a disordered irregular Ag0 6 geometry consisting of two oxygen atoms of a pyrrolidone molecule and four oxygen atoms of the nitrate anion.
- the distances between the silver atom and the oxygen atoms are in the range 2.358 to 2.683 angstroms.
- Nitrate anions have a linker function and connect the structure in 1-D polymer chains in one direction.
- the silver atoms are linear
- the 1-D polymer chains in the 2D network are linked by intermolecular NH ... O bonds.
- a pyrollidone derivative as crystallization inhibitor preferably tert-butylpyrrolidone, may be used at least 2% by mass to a maximum of 20% by mass of the solution are added. This addition may take place before, during or after the first process step.
- a crystallization inhibitor By using a crystallization inhibitor, a homogeneous and uniform silver layer can be obtained.
- a ratio of water to ethanol of 1 to 4 is selected smaller amounts of water.
- any influence of electromagnetic radiation should be avoided and the solution enclosed in a hermetically sealed optically nontransparent container.
- the surface of the substrate should be cleaned.
- a suitable liquid which can be selected taking into account the substrate material, are used.
- this may be "piran ha solution ", ie an aqueous solution of peroxomonosulphuric acid, which can be cleaned with ultrasound assistance.
- the order of the solution after the first process step on the surface of the substrate can be done by a dip, spin coating or a printing process. It should only be ensured that a constant layer thickness can be achieved in order to achieve homogeneous electrical and / or optical properties of the formed layer over the coated surface.
- nanoimprint lithography or microcontact printing can be used as the printing method. It is thus also possible to produce geometrically differently structured layers on substrate surfaces. This is also possible with screen printing technology.
- a substrate can also be immersed in the prepared solution and pulled out again (dipcoating) before the third and fourth process steps are carried out.
- the formation of the layers can also be done by spin coating.
- the layers formed by the invention should not exceed a maximum layer thickness of 200 nm. Layer thicknesses in the range 50 nm to 100 nm are to be preferred in order to be able to comply with a sufficient electrical conductivity.
- the tert-butylpyrrolidone can be prepared from 20 ml of tetrahydrofuran (THF), triethylamine and tert-butylamine, which are purged with argon and mixed together at a temperature of 0 ° C. 4-chlorobutyryl chloride is added to the mixture and intensive stirring is carried out at this temperature. Subsequently, triethylamine hydrochloride is filtered out and a double washing with THF is carried out. The resulting filtrate is concentrated under reduced pressure and the resulting starting material is mixed with acetate and then washed once with HCL and twice with brine. The organic phase formed can be dried on a substrate with MgSO 4 and the solvent at reduced
- the tert-buty-4-chlorobutanamide then obtained is dissolved in THF and added to a solution of potassium tert-butylate with THF. After prolonged stirring in an ice bath, this mixture from the container can be placed in another container and mixed therein with ethyl acetate and then washed twice with brine. The resulting organic phase can be dried again with MgS0 4 and the solvent removed under reduced pressure. After distillation at reduced pressure and a temperature of 75 ° C, the tert-butylpyrrolidone can be obtained as a colorless liquid.
- sufficiently conductive thin silver layers can be produced which, at a thickness of 100 nm, have electrical sheet resistances ⁇ 10 ⁇ / ⁇ , which is a sheet resistance, which is expressed by the " ⁇ ".
- FIG. 1 shows in schematic form the link function of FIG
- the resulting reaction product [Ag (pyl) 2 ] NO 3 crystallizes out during storage at normal room temperature and the water as solvent evaporates slowly.
- additional water with ethanol preferably after several days storage of the solution previously prepared in a first process step, so that a ratio of water to ethanol of 1: 4 is maintained and a 0.8 M solution is obtained is.
- the substrate was previously cleaned with a solution formed from one part of 30% H 2 O 2 and three parts of concentrated H 2 S0 4 over a period of 30 minutes and then thoroughly washed with deionized water and then dried.
- an approximately 100 nm thick layer could be obtained on the substrate, which had an electrical resistance of ⁇ 10 ⁇ / ⁇ .
- a layer thickness of 60 nm of the silver layer could be achieved. It can be printed line structures with a width of 20 ⁇ . However, it is possible to print smaller, filigree structures down to the "nanometer range”.
- the solution obtained in the first process step can be added to suppress the crystallization of the [Ag (pyl) 2 ] NO 3 complex 10% by mass of the pyrrolidone derivative tert-butylpyrrolidone. As a result, a disorder in the polymer chain can be achieved, which prevents the crystallization, which facilitates the application of the solution to the substrate surface.
Landscapes
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemically Coating (AREA)
- Laminated Bodies (AREA)
- Electrodes Of Semiconductors (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102011108089.2A DE102011108089B4 (en) | 2011-07-18 | 2011-07-18 | Process for the preparation of thin electrically conductive layers of silver, a silver complex, its solution and a use of the silver complex in a solution |
PCT/EP2012/063504 WO2013010858A1 (en) | 2011-07-18 | 2012-07-10 | Method for producing thin electrically conductive layers of silver, a silver layer, a silver complex, the solution of said silver complex, and the use of the silver complex in a solution |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2735002A1 true EP2735002A1 (en) | 2014-05-28 |
EP2735002B1 EP2735002B1 (en) | 2018-09-12 |
Family
ID=46466583
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12733165.0A Not-in-force EP2735002B1 (en) | 2011-07-18 | 2012-07-10 | Method for producing thin electrically conductive layers of silver, a silver layer, a silver complex, the solution of said silver complex, and the use of the silver complex in a solution |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2735002B1 (en) |
DE (1) | DE102011108089B4 (en) |
WO (1) | WO2013010858A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102016125667A1 (en) * | 2016-12-23 | 2018-06-28 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Composition for photochemical deposition of metals |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10241661A (en) * | 1997-02-21 | 1998-09-11 | Matsushita Electric Ind Co Ltd | Electrode containing organic disulfide compound and manufacture thereof |
JP2000144440A (en) * | 1998-11-18 | 2000-05-26 | Nippon Kojundo Kagaku Kk | Electroless silver plating solution for electronic parts |
ITBO20020165A1 (en) * | 2002-03-29 | 2003-09-29 | Consiglio Nazionale Ricerche | ORGANIC ELECTROLUMINESCENT DEVICE WITH CHROMOPHOR DROGANTS |
KR101215119B1 (en) * | 2004-03-01 | 2012-12-24 | 스미토모덴키고교가부시키가이샤 | Metallic colloidal solution and inkjet-use metallic ink |
WO2006005111A1 (en) * | 2004-07-08 | 2006-01-19 | Swinburne University Of Technology | Fibre sensor production |
US20060189113A1 (en) * | 2005-01-14 | 2006-08-24 | Cabot Corporation | Metal nanoparticle compositions |
RU2323276C2 (en) * | 2006-03-23 | 2008-04-27 | Закрытое акционерное общество "Драгцветмет" (ЗАО "Драгцветмет") | Silver-plating electrolyte |
WO2007149885A2 (en) * | 2006-06-19 | 2007-12-27 | Cabot Corporation | Security features and processes for forming same |
DE102009034822A1 (en) * | 2009-07-27 | 2011-02-03 | Osram Opto Semiconductors Gmbh | Electronic component as well as electrical contact |
-
2011
- 2011-07-18 DE DE102011108089.2A patent/DE102011108089B4/en not_active Expired - Fee Related
-
2012
- 2012-07-10 WO PCT/EP2012/063504 patent/WO2013010858A1/en active Application Filing
- 2012-07-10 EP EP12733165.0A patent/EP2735002B1/en not_active Not-in-force
Also Published As
Publication number | Publication date |
---|---|
EP2735002B1 (en) | 2018-09-12 |
DE102011108089B4 (en) | 2015-11-12 |
DE102011108089A1 (en) | 2013-01-24 |
WO2013010858A1 (en) | 2013-01-24 |
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