Phil's Patent Picks

Patents with a printed electronics theme

Aqueous Conductive Silver Ink

Posted by Phil C on May 16, 2014

Printed electronics is continuing to grow as more and more applications are developed and commercialised.  One of the key stumbling blocks continues to be the practicalities of printing narrow conductive tracks and the ease of use of the materials and processes involved.  One of the key system components, often taken for granted,  is the ink.  The majority of conductive ink compositions in use today are solvent-based thick film systems designed for low speed screen printing.  Water based conductive inks and coatings offer significant ecological advantages over solvent-based compositions, as the latter release solvents into the atmosphere on drying.  Aqueous conductive inks, however, have so far not offered the high conductivity, or low electrical resistivity, achievable with solvent-based formulas.

Sun Chemical Corp. have just been granted a patent for an aqueous ink with high conductivity and good printing properties.  This invention more specifically relates to an aqueous conductive silver ink suitable for use in RFID and other electronic technologies. The composition is highly conductive and requires reduced drying energy. In addition, it may be applied to low cost substrates via high speed printing processes. The key components of the ink formulation include: (meth)acrylic copolymer or salt thereof; conductive particles; an anionic surface wetting agent; defoamer and water.  The first claim suggests the ink can be up to 80% water depending on the amount of the other ingredients.

The patent is US8709288 and it was issued on 29 April 2014.  The Inventors are Jason Rouse and Dave Klein.

The independent claims from the patent are listed below:

1. A method of forming a conductive pattern on a substrate comprising applying a conductive composition comprising (a) metallic silver conductive particles, (b) water soluble styrene/(meth)acrylic copolymer, (c) an anionic wetting agent, (d) defoamer and (e) 10 to 80% water, the composition providing a sheet resistance of less than 0.83 ohms/sq, on the substrate and drying the composition.
34. A method of forming a conductive pattern on a substrate comprising applying a conductive composition consisting essentially of (a) metallic silver conductive particles, (b) water soluble styrene/(meth)acrylic copolymer, (c) an anionic surfactant, (d) defoamer and (e) 10 to 80% water, the composition providing a sheet resistance of less than 0.83 ohms/sq, on the substrate and drying the composition.
37. A method of forming a conductive pattern on a substrate comprising applying a conductive composition consisting of (a) metallic conductive particles, (b) water soluble styrene/(meth)acrylic copolymer, (c) an anionic surfactant, (d) defoamer, (e) 10 to 80% water, and optionally another solvent, the composition providing a sheet resistance of less than 0.83 ohms/sq, on the substrate and drying the composition.

The differences above are subtle but important, claim 34 describes the composition with an anionic surfactant rather than a wetting agent, and claim 37 describes a more general formulation with any metallic conductive particle and optionally includes another solvent.  Each claim includes the requirement that the composition provides a resistance of less that 0.83 ohms/sq on the substrate.

 

Phil’s Comments:

Good to see that research into inks suitable for printed electronics is providing environmentally acceptable formulations.  Reducing solvents and also reducing the energy requirements for drying are all good directions for the ink design.  We sometimes forget the huge demand put upon the inks we use, for example they need good abrasion and chemical resistance when dried so that they are not easily scratched or wiped off during subsequent uses, they need to have proper rheology and substrate wetting properties to obtain good ink transfer and graphic reproduction. Additionally, the ink should possess good flexibility and thermal stability to withstand the physical deformation to which the substrate may be subjected.  Let’s remember the research that goes into the inks when we next see a printed electronics design in use!

 

Posted in Conductive Ink, Printed Electronics, RFID | Tagged: , , , | Leave a Comment »

“Thinking Ink” – allows printed packaging to interact with smartphones

Posted by Phil C on February 24, 2014

A recent patent lawsuit filed by Touchpac Holdings against TouchBase Technologies Inc. has highlighted the US Patent US8497850 which is owned by Printechnologics GmbH (T+Ink).  Details of the lawsuit were reported by Printed Electronics World in their article on 18 Feb 2014.

The patent was granted on 30 July 2013 and describes the technology that T+Ink have developed and called Touchcode.  This is a highly secure printed conductive ink signature embedded in packaging, labels and other objects that a smartphone or other sensing device can detect through capacitive touch.  The patent provides some detail of the system which is defined in independent claim 22:

A system comprising: a. an information carrier comprising a dielectric and/or conductive pattern which encodes information, and wherein the information carrier (1) comprises a substrate (2) with a first dielectric coefficient ∈1 and a second material with a second dielectric coefficient ∈2, the second coefficient ∈2 being different from the first coefficient ∈1, or wherein the information carrier (1) comprises a substrate (2) with a first conductivity σ1 and a second material with a second conductivity σ2, the second conductivity σ2 being different from the first conductivity σ1, b. a detection device having a capacitive touch screen; the detection device decodes the information upon interaction between the information carrier and the touch screen, wherein the interaction is based on a difference in the dielectric coefficient and/or the conductivity of the pattern, wherein the interaction is induced by relative motion between the information carrier and the touch screen.

A more visual explanation can be found on the T+Ink Touchcode website.  As explained on the website, Touchcode is an invisible electronic code printed on paper, cardboard, film or labels. Just put the product on the display of your smartphone/tablet/multitouch device to read the data.  In this way you can add interactivity to just about any product.  The system is similar to QR codes, barcodes or other tags but does not require activating a camera app on the phone or tablet to work.

Posted in Conductive Ink, Printed Electronics | Tagged: , , , | Leave a Comment »

Metal Nanoparticle Conductive inks Patented by Aculon Inc

Posted by Phil C on November 5, 2013

Aculon Inc. were granted a patent on 15 October for “Electroconductive Inks made with Metallic Nanoparticles”.  Aculon are well known for their surface coatings using nanoparticle technology, featuring improved adhesion to a wide range of surfaces and adding functionality for numerous applications including printed electronics.  It is therefore no surprise that conductive inks are described with advantageous adhesion to a variety of substrates including silicon, glass and plastic.

The granted patent is US8558117 and the claims are quite broad but require the inks to have an omega substituted organophosphoric acid, this is the added ingredient which helps to improve the adhesion.

The first 10 claims are shown below:

What is claimed is: 1. An electroconductive ink comprising: (a) a dispersion of metal nanoparticles with a dispersant on the surface of the metal nanoparticles and as a separate component, (b) an omega substituted organophosphorus acid; the metal nanoparticles being present in amounts of 5 to 80 percent by weight and the omega substituted organophosphorus acid being present in amounts of 0.0005 to 5 percent by weight; the percentages by weight being based on total weight of the electroconductive ink.

2. The composition of claim 1 in which the metal is selected from copper, silver, palladium, gold or any combination thereof.

3. The composition of claim 2 in which the metal is silver.

4. The composition of claim 3 in which the dispersant is an organic carboxylic acid.

5. The composition of claim 4 in which the organocarboxylic acid contains from 4 to 36 carbon atoms.

6. The composition of claim 1 in which the metal nanoparticles have a particle size of 1 to 500 nanometers.

7. The composition of claim 1 in which the dispersion contains an organic diluent.

8. The composition of claim 7 in which the organic diluent is selected from hydrocarbons, alcohols, esters and ketones.

9. The composition of claim 1 in which the organo groups of the organophosphorus acid have omega substituted functional groups.

10. The composition of claim 1 in which the omega substituted functional groups are selected from phosphonic acid, carboxylic acid, hydroxyl, thiol and amine including various combinations thereof.

Phil’s Comments:

I have reported on a number of conductive ink patents over the past year or two and a common theme running through them is the need for good adhesion along with their conductivity.  The patents generally differ in the description of the adhesion promoting substances used in the nanoparticle inks and on other improved properties that enhance their application for printed electronics.  Successful conductive ink formulations are essential for printed electronics to become a mainstream technology for building new devices and specialist inks with patented formulations will continue to dominate the scene for a number of years before generic formulations will be cheaply available as we see for conventional inkjet printing.

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Spray on Solar PV

Posted by Phil C on October 18, 2013

New Energy Technologies Inc. have been promoting a new spray-on, see through solar PV coating which can be applied to glass windows.  Earlier this year they were indicating that around 20 new patent filings have been submitted for their proprietary SolarWindow™ technology.  Last year I reported on one of the early patent filings and the article can be viewed here.  Dr Xiaomei Jiang has been leading this effort with New Energy Technologies under a Sponsored Research Agreement at the University of South Florida (USF).

Two more patent applications have emerged this month from Dr Jiang at USF and they continue to reveal further details of the spray on techniques and solar PV architecture.

US20130255757: ORGANIC PHOTOVOLTAIC ARRAY AND METHOD OF MANUFACTURE

Publication date: 03/10/2013

Inventor(s): JIANG XIAOMEI JANE [US]; LEWIS JASON ERIK [US]

Abstract

The fabrication and characterization of large scale inverted organic solar array fabricated using all-spray process is disclosed, consisting of four layers; ITO-Cs2CO3-(P3HT:PCBM)-modified PEDPT:PSS, on a substrate. With PEDPT:PSS as the anode, the encapsulated solar array shows more than 30% transmission in the visible to near IR range. Optimization by thermal annealing was performed based on single-cell or multiple-cell arrays. Solar illumination has been demonstrated to improve solar array efficiency up to 250% with device efficiency of 1.80% under AM1.5 irradiance. The performance enhancement under illumination occurs only with sprayed devices, indicating device enhancement under sunlight, which is beneficial for solar energy applications. The semi-transparent property of the solar module allows for applications on windows and windshields, indoor applications, and soft fabric substances such as tents, military back-packs or combat uniforms, providing a highly portable renewable power supply for deployed military forces.

US20130263916: ALL SPRAY SEE-THROUGH ORGANIC SOLAR ARRAY WITH ENCAPSULATION

Publication date: 10/10/2013

Inventor(s): LEWIS JASON ERIC [US]; JIANG XIAOMEI JANE [US]

Abstract

An inverted organic solar photovoltaic cell is described that may be fabricated onto rigid or flexible substrates using spray-on technology to apply the various layers of the cell. Indium tin oxide with a thin layer of cesium carbonate functions as the cathode for the novel inverted cells. An active layer of poly-3(hexylthiophene) and [6,6]-phenyl C61-butyric acid methylester having a thickness around 200 nm to 600 nm facilitates a high level of light transmittal through the cell. A modified PEDOT:PSS, made by doping a conductive polymer with dimethylsulfoxide (DMSO), functions as the anode. A method of forming the inverted organic solar photovoltaic cell is also described using gas-propelled spraying to achieve thin layers. After the layers are formed, the cell is sealed using a vacuum and temperature-based annealing and encapsulation with UV-cure epoxy.

Phil’s Comments:

These applications are going through the patent office examination process so it is difficult to comment on the claims until we know what will actually be allowed.  The claims do make reference to spraying and the second application indicates that nitrogen is used as a propellant.

The device is an inverted solar cell design and may be fabricated onto both rigid and flexible substrates. Exemplary substrates include cloth, glass, and plastic. For example, the substrate may be a low alkaline earth boro-aluminosilicate glass.

Two figures from the second application are shown below:

FIG. 1 is a diagram that depicts the modified PEDOT:PSS as it is sprayed onto the substrate through a stainless steel shadow mask with an airbrush. Nitrogen is used as the carrier gas at a pressure of 20 psi.

FIG. 13 is a diagram showing the cross sectional view of the device architecture of an inverted solar array showing series connection

Figure 1 Capture2

Posted in Flexible substrates, Photovoltaics (PV) | Tagged: , , | Leave a Comment »

Printed Electronics via Electrophotography

Posted by Phil C on August 8, 2013

There are many different technologies used for printing electronic circuits such as screen printing, flexography, gravure, offset lithography and inkjet – a review of these can be found on the Wikipedia page for Printed Electronics.  One of the printing technologies which is not currently used is electrophotography although there have been various publications including patent applications that have proposed this route.

A recent patent alert I received indicated that Eastman Kodak has just been granted a method patent for producing a printed circuit using electrophotography.  The company is just emerging from chapter 11 bankruptcy and one of its stated aims is that it will focus on commercial printing.  This patent therefore fits well with its new strategy.  Although the patent title indicates a printed circuit board the description makes it clear that flexible devices are envisaged such as RFID, sensors and flexible displays.

The patent is US8497057 and was published on 30 July 2013.

Title: Method of Producing Electronic Circuit Boards using Electrophotography

Inventors: Thomas N Tombs; Donald S Rimal

Filed: 14 Sept 2012 and is a division of US 12/341099 filed on 22 Dec 2008

Abstract: The present invention provides a method producing printed electronic circuits using electrophotography.

The granted claims read as follows:

1. A method for producing a printed circuit, the method comprising performing the following steps in order:

charging a primary imaging member;
creating an electrostatic latent image by image-wise exposing the primary imaging member;
image-wise depositing thermoplastic particles onto the primary imaging member;
transferring the thermoplastic particles to an electrically insulating substrate;
a first fixing step of permanently fixing the transferred thermoplastic particles;
depositing conductive particles over the substrate;
a second fixing step of permanently fixing the conductive particles on the fixed thermoplastic particles so that conductive paths are formed between fixed conductive particles; and
removing conductive particles from portions of the substrate other than that coated with the fixed thermoplastic.

2. The method according to claim 1, wherein the conductive particles is permanently fixed by the application of heat.

3. The method according to claim 1, wherein the conductive particles is permanently fixed by the application of pressure.

4. The method according to claim 1, wherein the conductive particles is permanently fixed by the exposure to solvent vapor.

5. The method according to claim 1, wherein the conductive particles is metal.

 

Phil’s Comments

This method patent will shortly be complemented with the original patent which has been granted and is due to be published later this month (info obtained from the USPTO PAIR database).  I will post the details of this one when it is public.  I was interested to see if this was one of the first granted patents for electrophotography and had a quick look through the citations and examiner’s search results.  The USPTO PAIR database is a mine of information when you want to investigate the process by which a US patent is granted and see the comments made by the examiners.

Although a number of documents were found in the search none was considered relevant enough to impact the inventive step of the above claims as they are finally worded.  It should be noted that considerable changes were required to the original 2008 application.

I did a brief search for the keywords electrophotography and printed electronics in titles and abstracts came up with the following:

US7638252: Electrophotographic printing of electronic devices

and

US20070234918 A1:  System and method for making printed electronic circuits using electrophotography

This patent application was never granted and was abandoned.

From the references and citations it is clear that electrophotographic approaches for printed electronics have been documented well before 2008.  However, the Eastman Kodak patent has described a stepwise process which is somewhat different to the prior art and reviewing the prosecution it is clear that considerable detail has been gone over in agreeing the allowed claims over the prior art.

 

 

 

Posted in Printed Electronics | Tagged: , , , | 1 Comment »

Copper Inks for Printed Electronics

Posted by Phil C on April 26, 2013

I recently spotted a patent for copper based metallic inks jointly granted to Applied Nanotech Holdings, Inc. and Ishihara Chemical Co., Ltd.  The conductive inks I have previously reported on have been silver or graphene based, these can be very expensive and so there is always interest in a lower cost alternative.  Copper metal is a standard in the electronics industry and is about one tenth the cost of silver.

Patent summary:

US8404160   –  METALLIC INK

Inventor(s): LI YUNJUN [US]; ROUNDHILL DAVID MAX [US]; LI XUEPING [US]; LAXTON PETER B [US]; ARIMURA HIDETOSHI [US]; YANIV ZVI [US]

Applicant(s): APPLIED NANOTECH HOLDINGS INC [US]; ISHIHARA CHEMICAL CO LTD [JP]

Filing date: 31/03/2009
Issue date: 26/03/2013

Abstract
A metallic ink including a vehicle, a multiplicity of copper nanoparticles, and an alcohol. The conductive metallic ink may be deposited on a substrate by methods including inkjet printing and draw-down printing. The ink may be pre-cured and cured to form a conductor on the substrate.

Claim 1:

1. A conductive metal ink comprising: a vehicle comprising two or more oxygenated organic compounds; copper nanoparticles; and a medium length chain aliphatic alcohol, wherein the ink does not comprise a binder.

There are a further 23 claims giving more details of the components mentioned in claim 1.

Two figures from the patent give a flow chart for two processes which can be used:

Direct printing:

ink1

Patterning after the ink deposition:

ink2

Phil’s Comments

This is a key patent for copper inks and has a broad first claim which had to be modified from the original application by the addition of the restriction that the ink does not contain a binder and I suspect this was to get around some of the prior art identified by the patent examiner.

Six very detailed examples are given which illustrate the invention and provide further details of the printing process, the curing or sintering that is applied to produce the conductive tracks on a range of materials including flexible substrates.

Posted in Conductive Ink, Printed Electronics | Tagged: , , , , | 1 Comment »

Silver Nanoparticle Inks for Printed Electronics

Posted by Phil C on January 26, 2013

Xerox are continuing to add to their patent portfolio of silver nanoparticle inks for printed electronics.  A new patent was granted on 4th Dec 2012 adding to the one already granted on 17th April 2012.  These two patents are summarised below:

US8158032  (B2)  –  SILVER NANOPARTICLE INK COMPOSITION FOR HIGHLY CONDUCTIVE FEATURES WITH ENHANCED MECHANICAL PROPERTIES

Abstract: A conductive ink composition comprising organic-stabilized silver nanoparticles and a solvent, and a polyvinyl alcohol derivative resin of Formula (1) wherein R1 is a chemical bond or a divalent hydrocarbon linkage having from about 1 to about 20 carbons; R2 and R3 are independently an alkyl, an aromatic or substituted aromatic group having from about 1 to about 20 carbon atoms; x, y and z represent the proportion of the corresponding repeat units respectively expressed as a weight percent, wherein each repeat unit is randomly distributed along polymer chain, and the sum of x, y and z is about 100 weight percent, and wherein the polyvinyl alcohol derivative resin is present in an amount of from 0.1 to about 5 weight percent of the ink composition.

US8324294  (B2)  –  SOLVENT-BASED INKS COMPRISING SILVER NANOPARTICLES

Abstract: High performing nanoparticle compositions suitable for printing, such as by inkjet printing, are provided herein. In particular, there is provided a conductive ink formulation comprising silver nanoparticles which has optimal performance, such as, reduced coffee ring effect, improved adhesion to substrates, and extended printhead de-cap time or latency time. The ink formulation comprises two or more solvents and a resin.

Phil’s Comments

The key technology improvements over the general prior art are for the development of inks which do not dry out and clog the printhead along with improvements in the adhesion of the ink to the substrate, reduction of the coffee ring effect and reduction of particle aggregation which leads to black dots in the printed lines.

The improved adhesion is as a result of the incorporation of a resin in the ink based on a polyvinyl alcohol derivative.  The earlier patent goes into some detail over the formulae for these resins.

The extended drying times to prevent printhead clogging are the result of incorporation of two or more ink vehicles (solvents) with vapour pressure properties as described in the second patent.  Typical compositions are based on aliphatic hydrocarbons comprising at least one cyclohexane ring, cyclic terpene, cyclic terpinene, terpineol, methyl naphthalene, and mixtures thereof.  Typical drying times are in excess of 5 hours and one claim states up to about 1 week.

The nanoparticles are stabilised with organo-amines, the first patent gives more detail on these structures,  a preferred compound is dodecylamine.

 

As always please leave a comment if you require further details or are interested in patent landscapes related to these conductive inks.

Posted in Conductive Ink, Printed Electronics | Tagged: , , , , | Leave a Comment »

Printed Electronics using Graphene based Inks

Posted by Phil C on October 19, 2012

When I spotted a recent granted patent with the title Printed Electronics, it was an obvious candidate for a Phil’s Patent Pick.  US8278757 was published on 2nd October 2012 and jointly assigned to Vorbeck Materials Corp. and Univ. of Princeton.  It was originally filed on 9th January 2009 and has a priority date of 5th February 2008.

The patent has quite broad claims and describes printed electronics devices made using a conductive ink comprising functionalized graphene sheets and a binder.  I don’t always reproduce the claims but in this case they are fairly simple to follow:

1. A printed electronic device, comprising a substrate comprising at least one surface, wherein a layer of an electrically conductive ink has been applied to a portion of the surface, and wherein the ink comprises functionalized graphene sheets and at least one binder.

2. The device of claim 1, wherein the substrate comprises paper and/or cardboard.

3. The device of claim 1, wherein the substrate comprises at least one polyolefin.

4. The device of claim 1, wherein the substrate comprises at least one polyimide.

5. The device of claim 1, wherein the ink further comprises at least one dispersant.

6. The device of claim 1, wherein the binder is a polymeric binder.

7. The device of claim 6, wherein the binder is one or more of poly(ethylene oxide), poly(propylene oxide), and ethylene oxide/propylene oxide copolymers.

8. The device of claim 1, wherein the ink further comprises at least one metal component.

9. The device of claim 8, wherein the metal is silver and/or copper.

10. The device of claim 1, wherein the ink further comprises at least one electrically conductive polymer.

11. The device of claim 1, wherein the ink further comprises at least one carbonaceous material other than the functionalized graphene sheets.

12. The device of claim 1, wherein the functionalized graphene sheets have a surface area of from about 300 to about 2630 m²/g.

13. The device of claim 1, wherein the functionalized graphene sheets have a surface area of from about 400 to about 2400 m²/g.

14. The device of claim 1, wherein the functionalized graphene sheets have a carbon to oxygen ratio of about 60:40 to 20:1.

15. The device of claim 1, further comprising one or more components selected from the group consisting of processors, memory chips, batteries, resistors, diodes, capacitors, and transistors.

16. The device of claim 1 in the form of an integrated circuit.

17. The device of claim 1 in the form of a printed circuit board.

18. The device of claim 1 in the form of a light-emitting diode display.

19. The device of claim 1 in the form of a radiofrequency identification device and/or a radiofrequency device antenna.

20. The radiofrequency identification device and/or radiofrequency device antenna of claim 19 in the form of a radiofrequency identification device and/or antenna for use with ultra-high frequencies.

21. A method for forming a printed electronic device, comprising the step of applying an electrically conductive ink to a substrate, wherein the ink comprises functionalized graphene sheets and at least one binder.

22. The method of claim 21, wherein the substrate is selected from one or more of paper, cardboard, polyolefin, and polyimide.

23. The method of claim 21, wherein the electrically conductive ink further comprises a carrier.

24. The method of claim 21, wherein the electrically conductive ink further comprises a dispersant.

25. The method of claim 21, wherein the functionalized graphene sheets have a surface area of from about 300 to about 2630 m²/g.

Phil’s Comments

It is worth looking at the examples in the patent.  The printing methods and samples generated for testing are pretty crude and suggest that only simple circuits have been generated such as RFID antennas.  The type of ink suggests that printing processes will be of the gravure or flexo type rather than ink-jet.  However, the wording of the allowed claims suggests that just about any printed electronic device containing a layer that includes graphene sheets with a functional group in a binder would infringe this patent.  The majority of the claims are all about the device and not the material.  The last five claims are about the method.  Vorbeck sell the graphene based inks and with this patent they will require anyone using the inks to enter into some form of agreement with them to make the devices.  It will be interesting to see how this works in practice and whether the patent will stand the test of time.

Posted in Conductive Ink, Flexible substrates, Printed Electronics | Tagged: , , | Leave a Comment »

Inorganic Nanoparticle Inks for Printed Electronics

Posted by Phil C on October 1, 2012

Silicon ink has sometimes been described as a “Dream Material” for printed electronics.  Conductive or semi-conductive inks that can be printed directly onto a variety of substrates to create transistors or other electronic devices have been talked about and promoted for a number of years but few companies have succeeded in commercializing products for the mass market.  Silicon ink has been promoted as an enhancer for the production of solar cells to squeeze an extra few percent efficiency from the panel.  One Silicon-valley company NanoGram Corp. acquired last year by the Teijin Group has developed a silicon ink using a laser pyrolysis method to create stable nanoparticles in a dispersion that can be printed by various means including spin coating and inkjet processes.

A recent patent from NanoGram US8263423 was granted on 11 Sept 2012 and completes a trio of US patents granted for their silicon ink approach.  The other patents are US7993947 and US7892872.  These patents all claim a priority date of 3 Jan 2007 for the US provisional application first filed.  The text of all three patents is more or less the same but differs in the claims, each one covering a different aspect of the invention.  The basic technology is described in the first section “Field of the Invention”:

The invention relates to dispersions/inks of silica/germania particles, such as doped silica particles. The invention further relates to inks that are suitable for ink jet printing. Additionally, the invention relates to the use of doped silica/germania particles for the doping of semiconductor substrates, such as through the drive in of dopants with heat and/or light from a silica/germania deposit formed through inkjet printing onto the semiconductor surface.

The three patents break down the invention into i) the dispersion and method for making the dispersion; ii) the method for depositing the dispersion onto a substrate (inkjet printing); and iii) the method for forming solar cells and optical components.

The following paragraph from the text was selected to describe the dispersion approach:

The dispersions comprise a liquid and the dispersed silica particles, which may or may not be surface modified. In general, silica particles formed by laser pyrolysis can be well dispersed in water or alcohols at moderate concentrations with no surface modification, although higher concentration dispersions generally can be formed with surface modification. Suitable alcohols include, for example, small aliphatic alcohols, such as methanol, ethanol, propylene glycol, butanediol, mixtures thereof and the like. Upon surface modification, the silica particles can be dispersed in a broader range of solvents and solvent blends through the matching of the chemical properties of the surface modifying agent with the liquid. Thus, following surface modification, the particles can be well dispersed in a range of less polar solvents, such as ethyl lactate, n-methylpyrrolidinone, gamma-butyl lactone, and the like.

The following paragraph was selected to illustrate the printing approach:

While various coating and printing approaches are suitable, inkjet printing offers desirable features with respect to speed, resolution and versatility with respect to real time selection of deposition patterning while maintaining speed and resolution. However, practical deposition using inkjet printing with inorganic particles requires dispersion properties that have not been available prior to development of both the techniques to form high quality silica nanoparticle along with the improved ability to form high quality dispersions from these particles. Thus, the particles produced using laser pyrolysis combined with the improved surface modification approaches and dispersion techniques provides for the formation of inks that are amenable to inkjet deposition.

The following paragraphs were selected to describe the solar cell modifications:

To deliver dopant into the semiconductor from the silica deposit, the material is heated. For example, the structure can be placed into an oven or the like with the temperature set to soften the particles such that the dopants can diffuse into the substrate. The time and temperature can be adjusted to yield a desired dopant migration into the substrate…

Following the drive in of the dopant, it may or may not be desirable to remove the silica. For photovoltaic applications it is generally desirable to remove the silica to expose the doped semiconductor for the application of conductive electrical contacts. To remove the silica, the oxide can be etched, for example, using conventional approaches, such as using wet (chemical) etching or plasma etching.

Of course, you would need to review the claims to see exactly what has been allowed by the examiner and to understand the scope of the granted patent.

Phil’s Comments

It is quite common to see a provisional patent application emerge as several patents described as continuations of the first or earlier patent.  These can also appear as divisional patents and arise because the patent examiner or inventor has noted that the original application contains more than one invention.  These days the examiners are more strict in ensuring that the method and the material inventions are separated out.  In this case the distinction between the dispersion, the printing method and the application to solar cells or optical displays has been identified and separated into the three patents reviewed here.

I have not seen any recent evidence that the Teijin group have announced any products based on this approach and about 1 year has elapsed since they were actively promoting the technology.  It has been a tough year for solar cell manufacturers and a number of promising companies exploring plastic electronics approaches have filed for bankruptcy (e.g. Konarka and Novasolar).  It remains to be seen whether the silicon ink approach will be adopted as a means to increase efficiency and lower cost of conventional solar cells.

Posted in Photovoltaics (PV), Printed Electronics | Tagged: , , , , , , | Leave a Comment »

A Combination Patent for Electrowetting and Quantum Dot Technologies

Posted by Phil C on September 20, 2012

As followers of this blog will know I keep a look out for new and interesting patents that become granted in the field of printed and plastic electronics.  This field is forever expanding as new technologies are discovered that can be created by printing functional materials.

Recently I came across a patent granted to QD Vision Inc. that is basically a combination patent of quantum dot technology and electrowetting display technology to provide a low cost, low power display that can be read under a wide variety of conditions.  Under good ambient light is relies on its reflective electrowetting display technology but as light levels are detected to drop below a critical level a UV backlight switches on (either via a sensor or manually) to activate a quantum dot (QD) light emitting display.  The electrowetting colour cells and the quantum dots are chosen so that the colours match and provide a seemless transition between the two types of display technology.

The patent is US8264777 and was published as a granted patent on 11th September 2012.   As always it is the claims that define the invention but there is a lot of technical description that can be read from the main specification as well.

Claim1:

1. An electrowetting display, comprising: a plurality of transparent layers defining a cavity; a combination of a first fluid and a second fluid positioned in the cavity; first circuitry configured to be coupled to a first voltage source for selectively repositioning the second fluid in relation to the first fluid; a first plurality of quantum dots positioned within the second fluid; a light source disposed contiguous to the plurality of layers; and second circuitry configured to be coupled to a second voltage source for selectively causing the light source to emit photons to strike the first plurality of quantum dots.

This helps us to realise that the quantum dots are included in the second fluid (the one that moves as part of the electrowetting action) and defines the way the technologies have been combined together.

In the patent FIGS. 2-5 are schematic partial cross sections illustrating four operational states for an exemplary embodiment.

Patent image

Display structure

Patent Image

Display Structure

The images show the electrowetting display in the two main states where the second liquid is either evenly spread over the whole surface (wetting) or at the side (non-wetting).  FIGS. 2-5 are schematic diagrams of four states of a single level and a single pixel in which an electrowetting display 200, 202, 204, 206, respectively, includes QDs 208 disposed within an oil 210. Each of the FIGS. 2-5 comprise a reflective surface 211 deposited on a substrate 212. A ultraviolet (UV) light source 209 is disposed on a side of the reflective surface 211 opposed to the substrate 214 and is coupled to a voltage source 226 through switch 228 for selectively activating the UV light source 209. A transparent electrode 214 is formed over the light source 209. A transparent hydrophobic insulator 216 is formed on the electrode 214 for supporting the combination of oil 210 and water 218. A transparent electrode 220 is formed above and for containing the water 218 and oil 210 in a cavity 219. A (low frequency or DC) voltage source 222 is coupled between the electrodes 214 and 220, and is selectively applied by closing the first switch 224.

When ambient lighting is sufficient, the ambient light entering the electrowetting displays 200, 202, 204, 206 is reflected by the reflective surface 211 back out, either through the oil, or not through the oil when the oil has been moved to the side. Note that when the oil contains a color pigment, the light reflected back out will be of that color. The QDs 208 may be activated, e.g., when ambient light is insufficient, to provide additional light exiting the electrowetting displays 200, 202, 204, 206. The QDs 208 will provide a light having a color depending on the diameter of the QDs 208. Preferably, when a colored oil is used, the QDs 208 will provide light of the same frequency (color).

Phil’s Comments:

Combination patents are great ways for expanding a patent portfolio and also for ensuring that other companies don’t block you from exploiting your technology by generating their own combination patents.  The key concern is always whether the combination is obvious to anyone skilled in the art.  In this case there seems to be enough novelty in the way the technologies have been combined that the patent has been granted.  The fact that the original application claims have not been significantly amended suggests that it went through the patent process quite smoothly.

This patent was identified in a printed electronics search because various lithography processes, e.g., photolithography, electron beam lithography, and imprint lithography, ink jet printing, may be used to fabricate the light emitting device, and a printing process is preferred. In the printing process, the Freestanding Quantum Dots (FSQD) ink in liquid form is printed in desired locations on the substrate.

Posted in Displays, Printed Electronics | Tagged: , , , | 2 Comments »

 
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