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Ink Jetted Metallization Mikko Ruskola Marianne Joutti Anas Al-Azawi Jukka Heikkurinen Sasha Hoshian. Contents. Inkjetting Ink formulation and nanoparticle properties Sintering Electrical characterization Smallest line width. Ink Jetting (1/5). Etch-mask patterning

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slide1

Ink Jetted Metallization

Mikko Ruskola

Marianne Joutti

Anas Al-Azawi

Jukka Heikkurinen

Sasha Hoshian

contents
Contents

Inkjetting

Ink formulation and nanoparticle properties

Sintering

Electrical characterization

Smallest line width

ink jetting 1 5
Ink Jetting (1/5)

Etch-mask patterning

Deposition and patterning simultaneously

Low temperature process

Large area devices

All additive process

Wide variety of ink materials

Source: IDTechEx

ink jetting 2 5
Ink Jetting (2/5)

Continuous InkJet

Droplet charging

Deflection

Ink recirculation

Can degrade inks

Unusually used for functional materials

Annu. Rev. Mater. Res. 2010. 40:395–414

ink jetting 3 5
Ink Jetting (3/5)

Drop-on-Demand

Piezoelectric actuator or

Resistive heater

Vapour bubble near the nozzle

Annu. Rev. Mater. Res. 2010. 40:395–414

ink jetting 4 5
Ink Jetting (4/5)

Piezoelectric DoD

No thermal degradation of ink

Usually for functional materials

Nozzle size -> 20-30um

Droplet volume -> 10-20pl

Droplet generation -> 1-20kHz

Droplet diameter on paper -> 20-50um

Narrowest linewidth -> between 14 and 25um (without surface treatment)

ink jetting 5 5
Ink Jetting (5/5)

Ink Jetting can be divided to

Droplet formation

Aligning droplets and their interaction with the substrate

Sintering or drying on the substrate

Performance

Carrier mobility

Reduction of traps

Materials compatibility

Possible applications

Sensors, actuators, displays, rapid prototyping

slide8

Ink formulationProperties of the ink

  • The most critical parameters for selecting an ink are its
  • fluid properties such as viscosity, density and surface tension.
  • They determine the “jettability” of the material,
  • influence the size and shape of the deposited droplets and
  • indicate the wetting of the substrate and the presence of
  • satellite drops
  • The viscosity of the ink must be low enough to
  • enable the refill of the ink reservoir in about 100 ms and the
  • expulsion of a drop out of the nozzle by the transient pressure
  • pulse. The surface tension must be high enough to prevent
  • unwanted dripping from the nozzle but low enough such that
  • the ejected droplet can break away from the nozzle
  • The best values of these properties depend on used printer but on average for inkjet printing the viscosity should be within the range of 1-25mPa · s and the surface tension would be between 25 and 50mNm21.

Source: Inkjet printing of conductive materials:a review. Gerard Cummins and Marc P.Y. Desmulliez. Circuit World. Volume 38 · Number 4 · 2012 · 193–213

slide10

Ink formulationThe fluid properties part II

Source: Inkjet printing of conductive materials:a review. Gerard Cummins and Marc P.Y. Desmulliez. Circuit World. Volume 38 · Number 4 · 2012 · 193–213

ink formulation different ink types
Ink formulationDifferent ink types
  • Different types of used conductive inks include colloidal suspensions of nanoparticles, organometallic compounds in solution and conductive polymers. Indepent on the conductive component or solvent used these inks will often contain other constituents such as dispersants, adhesion promoters, surfactants, thickeners, stabilizing agents and other additives
  • Depending on the conductive agent these inks can be distributed on following categories
    • Organometallic inks which are not easily clogged and have high conductivities
    • Conductive polymers (PEDOT, polyaniline and Carbon nanotubes etc.)
    • Nanoparticle inks (=> continues in the next slide)

Source: Inkjet printing of conductive materials:a review. Gerard Cummins and Marc P.Y. Desmulliez. Circuit World. Volume 38 · Number 4 · 2012 · 193–213

different ink types nanoparticle inks
Different ink typesNanoparticle inks
  • Nanoparticle inks are a suspension of nanoparticles either in water or an organic solvent such as toluene, ethylene glycol or cyclohexanone. The solvent chosen must be easily evaporable once deposited but not so quickly that it forms a viscous film to the top of nozzle which prevents drop ejection.
  • Nanoparticles are commonly used in inks because they are easy to make ,can be dispersed in high concentrations and have good electrical conductivities.
  • According to G. Cummins and M. Desmulliez, the particle size should be less than 1/100 of the diameter of the nozzle. In addition, “particles should also have a narrow distribution of sizes and be homogeneously distributed throughout the solution to ensure good jetting.”
  • The advantage of these inks is that high surface area to volume ratio of these particles enables sintering at temperatures lower than that of the bulk material. For example, gold nanoparticles with diameters less than 5nm are predicted to melt at 300-500 °C, compared to the melting point of bulk gold (1 064 °C)

Source: Inkjet printing of conductive materials:a review. Gerard Cummins and Marc P.Y. Desmulliez. Circuit World. Volume 38 · Number 4 · 2012 · 193–213

slide13

Sintering

Metallic nano-particle inks are widely applied in realizing conductive structures in printed electronics

Typically Au or Ag nano-particles (d = 2-50 nm) encapsulated with protective shell and dispersed in a liquid

  • Sintering temperature is 100 – 300 deg. C
  • Thermal oven sintering has several drawbacks:
  • Time consuming ( up to 60 min )
  • Low cost sintering substrates are prone to shrinkage
  • Undesired gas emission from the heated substrate
  • The entire substrate has to be sintered ( no option for selectivity )
slide14

Laser Sintering

Au nano-particles 2 – 3 nanometer in diameter are protected by SAM and dispersed in the solvent

  • Local laser heating is advantageous because
  • Reduced heat affected zone and more efficient energy is induced
  • Laser sintered gold lines showed much greater uniformity and higher resolution ( few microns ) than those sintered by heater ( ~ 100 µm )
slide15

Laser Sintering

OFET is fabricated by inkjet printing by inkjet printing and selective laser sintering

slide16

Microwave Sintering

SEM inspection of silver tracks after sintering. The sintered lines consist of clusters with diameter ~ 500 nm

Ink used is dispersion of silver nano-particles in Tetradecane

The substrate is polymer PI ( Tg = 385o C)

Unsintered non-conductive silver lines are treated in microwave reactor operating in constant power mode ( 300 W)

slide17

Electrical Sintering

  • A method for sintering nano particles by applying voltage over printed structure.
  • Advantages of electrical sintering:
  • Reduced substrate heating
  • In-situ monitoring of the sintering quality
  • Short sintering time
  • The conductivity can be determined and can reach high values
electrical characterization metallization
Electrical characterizationMetallization
  • Fabrication of different electrical components

(Interconnectors, Transistors, Capacitors, …)

  • Electrical parameters

(Resistance, Impedance, Current, Voltage, mobility, …)

electrical characterization metallization2
Electrical characterizationMetallization

Interconnectors

time-domainfrequency-domain

TDR/TDT(Time Domain Reflectrometer s-parameter

/Time Domain Transmission)

  • characteristic impedance,
  • propagation delay,
  • dielectric constant,
  • Impedance profile,
  • series resistance of the samples
electrical characterization metallization3
Electrical characterizationMetallization

TDR TDT

Equivalent

Circuit at DC

electrical characterization metallization4
Electrical characterizationMetallization
  • OTFTs current-voltage characteristics
  • 1. the Ids vs Vds curve, named output characteristic, where the gate voltage is kept constant.
  • 2. the Ids vs Vgs curve, named transfer characteristic, where the drain voltage is
  • kept constant.
  • Two Keithley 2600 source meters
electrical characterization metallization5
Electrical characterizationMetallization

Output characteristics of an inkjet

printed OTFT with L=50 µm and W=2 mm

electrical characterization metallization6
Electrical characterizationMetallization

transfer plot of OTFTs

with gravure-printed semiconductor and dielectric layers

slide25

Ultra fine lines using Ink jet printing

  • Direct wire printing with width of few microns is possible with NanoPaste(tm)
  • NanoPaste consists of 5 nm silver particles
  • Ink drop size is only 2 pl which is 16 μm in diameter
  • No surface pretreatment or hydrophobic/hydrofilic patterning is needed

Source: Inkjet printing of conductive materials:a review. Gerard Cummins and Marc P.Y. Desmulliez. Circuit World. Volume 38 · Number 4 · 2012 · 193–213

slide26

Ultra fine lines using Ink jet printing

Source: ”Super-fine ink-jet printing: toward the minimal manufacturing system” Kazuhiro Murata et al. 2005DOI 10.1007/s00542-005-0023-9

slide27

Ultra fine lines using Ink jet printing

  • If hydrofilic/-phobic pretreatment is possible a line width of 500 nm can be achieved
  • This has been demonstrated* using poly(3,4-ethylenedioxythiophene) ink SiO2 substrate that is modified with fluorinated SAM

*Source: Nature Materials ”Dewetting of conducting polymer inkjet droplets on patterned surfaces” J. Z. Wang et al. 2004.

conclusions
Conclusions
  • Piezoelectric D-o-D for functional inks
  • Ink properties can be estimated by dimensioless fluid numbers
  • Three sintering techniques are introduced enabling formation of uniform high resolution metallic lines in a fast way
  • Most important way of resistance measurement is four-point probe for electrical characterization
  • Line width of inkjetted wires can be less than 1 micron with masking