Shenzhen, June 16th, 2018

Dr. Iván Fernández Martínez

Dr. Iván Fernández Martínez, co-founder, managing director ofNano4Energy SL and hipV AB.Physicist, over 16 years insputtering and particularly, inHiPIMS.

Ambiorn Wennberg, co-founderand business manager ofNano4Energy SL and hipV AB.Material Science Engineer. Hisbackground is in metallurgy,vacuum technology.

Alvaro Mendez, degree on Chemistry. PhD on HiPIMS withEU Marie CurieAction.

Sandra Muñoz Piña,degree on Chemistry.PhD on sputteringcoatings with GLAD.

Prof. Fernando Briones, co-founder of Nano4Energy SL.Material Science Engineer. Over 45years experience in R&D. Over 300published papers.

Plasma process development (magnetron, process controller, etc …)

- Gencoa (UK) as strategic partner

High power electronics / HiPIMS power supplies

- Viesca (ES) as strategic partners

Characterization of thin film properties

- Access to european research center facilities.

1st proof ofconcept

First industrial 6kW prototype

(Gen 1)

Generation 21st commercial

version

New Jointventure launched

Generation 3Made for the industry

Complete plasma operation functionality provided by Dr. Fernandez in 2007 and manufactured by Ingeniería Viesca SL.

Frank Papa, founder and president of GP Plasma, LLC. Herepresents Nano4Energy in the USA and China. He has worked atHauzer Techno Coating, Crystallume Inc., Vergason Technologyand Gencoa Ltd.. His background is in sputtering, arc and CVDprocesses and hardware development. He has developed theHiPIMS technology at Hauzer.

Feng Limin / 冯利民, 工程热物理专业；豪泽技术涂层5年销售经理; 上海新弧源涂层技术有限公司6年总经理； representsNano4Energy in China 国内独家代理.

Gerhard Eichenhofer, founder and president of 4APlasma(Germany). Sales manager at hipV AB. He has worked at Solvix,ENI and Advanced Energy. His background is in sputtering, arcand CVD processes and hardware development.

Biggest market for hipV

• Allows DC, HiPIMS and Bias operation (units are fully exchangeable!!).

• Already in production for large coating system builders worldwide.

.- Reliable operation in production is a must (24/7 operation).

2.- Plasma process understanding by the manufacturer. It is a complex process!!.

3.- Demonstrate it is possible to achieve deposition rates comparable to DC sputtering… Advanced solutions such as anodes, Positive V reversal, etc… are required.

4.- PLC communication with the latest protocols (Profibus, Ethercat, ……).

5.- Ability to run stable in reactive sputtering.

6.- Ability to run stable Metal Ion etching. Widely used process to improve adhesion in arc systems.

Vacuum chambers (x3 different sizes)

Magnetrons:

- Circular 2”

- Rectangular 20x7.5cm2

- Gencoa rectangular 40x10cm2

Gases: Ar, O2, N2, He, H, D….SpeedFlo reactive process controller.

Power supplies (up-to-date):

- AC Dual Magnetron 40kHz (AE/10kW)

- DC-Pulsed 150kHz (EN Tech/10kW)

- 3x hipV HIPIMS + Bias (6-20kW)

- RF

Plasma process development (magnetron, process controller, etc …)

- Gencoa (UK) as strategic partner

High power electronics / HiPIMS power supplies

- Viesca (ES) as strategic partners

Characterization of thin film properties

- Access to european research center facilities.

www.gencoa.com 17

V±EE DLC

±

Hugo Huang (黄汉乐)

hugo@gencoa.com

Lane Bao (鲍磊先生）

Shanghai Triplewins

Lane.bao@www-vacuum.com

19

• Higher plasma density → Higher ionization of gases and sputtered material.

• Higher ion assistance to the growing film → Denser and smoother films.

Time (us)

Po

we

r (k

W)

DC mode (10A)

DC-pulsed (10A- kHz range)

10

102

1

103HIPIMS mode (1000A - 100Hz range)

MW power range

Ar

300 400 500 600 700 800 900 1000 1100

0.0

0.5

1.0

0.0

0.5

1.0

wavelength (nm)

No

rma

lize

d in

tensity (

a.u

.)

W (2+) W (1+)Ar

DC

HIPIMS

Optical emission Spectroscopy (OES)

First experiments with HiPIMS in lab. scale magnetrons… 2008!

Evidences of highly ionized tungsten metal plasma

Single phase metastable cubic Ti 1-x AlxN (x<0.64) with low stress (<0.7GPa).

Ti+ irradiation gives rise to two phase cubic TiAlN + hexagonal AlN (brittle, 17GPa)

G. Greczynski et al, SCT 206, 4202 (2012) Reduced damage with low energy assistance

t0

t (us)t0

t (us)

t (us)t0 t1

t1

HiPIMS/DC Magnetron 1 HiPIMS Magnetron 2

Sync to Ti+ assistance (Magnetron 2)

TiAl

t1 Floated at Magnetron 1 operation

Bias HiPIMS

I target = 570A(80us)

V Bias=1000V (300us)

I Bias=170A

Bias pulse is sync and extended to collect the highest amount of ions (bias current) with low risk of arcing.

Time (us)t0

Magnetron Discharge (metal ion generator )

Sample Bias (Ion assistance)

Time (us)

1.2

t0 ti

V Bias (0-150V)

t delay (0-50us)

10kW

G. Greczynski et al, JVST A 32, 041515 (2014)H. Fager et al, JAP 121, 171902 (2017)

I bias = 500A

I target = 1500A

V target=1000V

V Bias = 500V

15us delay

Ti plasmaTi+

Biased component

Ti2+

Ti4+

Time (us)

10kW

t0

Magnetron Discharge (metal ion generation)

Sample Bias (Ion assistance)

Time (us)Vo

ltag

e (

kV)1.2

t0

V Bias (0-1200V)

Implantationzone

CrN coating

HSS substrate

AP. Ehiasarian et al, JAP 101, (2007)

300 400 500

0

30

60

90

Inte

nsity (

a.u

.)

Wavelength (nm)

Cr (1+)

Cr (2+)

Cr (0)

Cr (1+)

Cr (0)

Cr (0)

300 400 5000

30

60

90

Inte

nsity (

a.u

.)

Wavelenght (nm)

Ti (1+)

Ti (1+)Ti (1+)

Ti (2+)

Ti (1+)/Ar(1+)

Cr (1A/cm2)

Ti : Metal etching with low bias values→ reduces arcing issues!!

Ti (3A/cm2)

I. Fernandez-Martinez et al, accepted in SCT (doi:10.1016/j.surfcoat.2018.04.090)

Cr : Higher population of neutrals (not affected by Bias)

Cr+1, Cr+2 Ti+1….Ti+4

Ei= E0 + Qe (Vplasma- Vsurface)

Substrate Bias

Net deposition(no etching)

Efective etching

Cr Ti

DLC

HSS

WCM2 HSS

WC

Ti

Cr,Ti modified area

Local epitaxy between HSS substrate and Ti bonding layer at RT

Titanium on HSS :

Implantation depth : 6nm

Chromium on HSS :

Implantation depth : 7nm

I. Fernandez-Martinez et al, accepted in SCT (doi:10.1016/j.surfcoat.2018.04.090)

50N

97N

88N66N

110N 135N

Critical loads above 100N!!

I. Fernandez-Martinez et al, accepted in SCT (doi:10.1016/j.surfcoat.2018.04.090)

HiPIMS MIE

Ti bonding layer

The implementation of magnetically guided anodes (or AC Dual) can boost the film ion incorporation.

Hip-V is a floated HiPIMS power supply!!

• New N4E development. Patent aplication number GB1713385.1

.- New N4E proprietary technology launched at 2016. 2.- Demonstrated >25% increase in deposition rate for Me-N and ta-C in different industrial machines (for example in PVT and Tekniker batch coaters).3.- Generate enhanced coating ion assistance → denser coating structure.4.- Reduced arc appearance in reactive sputtering.

Dep .rate [µm/hr] 0.51 0.42

Hardness [GPa] 21 17

Positive Pulsing YES NONO V+ YES V+

25% increase in ion incorporation!!

(deposition rate and hardness)

Setpoint [%] 45 45

Hardness [GPa] 22.0 13

POSITIVE YES NO

TiN

TaN

More energetic ions → higher sp3 hybridization

Hardness = 36GPa

Young’s Modulus = 248GPa

Triboindenter TI950 from Hysitron equipped with a

diamond Berkovich indenter.

WCM2 Steel SubstrateCr

High energy ions generated in the switching electric field.

16 20 24

-1200

-600

0

+45V

+80V

+110V

+160V

+215V

+325V

+430V

Time (s)

Ta

rge

t vo

lta

ge

(V

)

www.gencoa.com 49

Courtesy of Duralar Technologies

Centurion System from Duralar Technologies

Table diameter = 950 mm

Rotatable Magnetrons – 152 mm Diameter

1200 mm Length

Average Power to Cathode = 5kW

Coating thickness approximately 1μm

Room Temperature

Work done in cooperation with Von Ardenne

North America

Reflectivity improvement with high Ipeak & V+

Process stabilization is more complex than standart DC or Pulsed-DC

Normal operation at 10kW average power, peak power in the MW range

1000A

650V

200A

900V

Pure Ar Ar + N2

Long experience in reactive control process using Gencoa -SpeedFlo

Regulation modes : Ipk, V or Optical monitoring. Proven technology!!

Electrical signalsI peak, Voltage…

Actuator

Constant Power

Optical signalTi, Cr, N2..etc..

45% 35% 25%

Nitrogen flow at setpoint

45% ~ 4.5 sccm35% ~ 5.5 sccm25% ~ 7.0 sccm

50 100 150

20

40

60

80

Nitro

ge

n flo

w (

sccm

)

PM

T S

en

so

r sig

na

l (%

)

0

2

4

6

8

10

Time (sec)

Ti (400mm2) Ar + Nitrogen3kW 120us – 500Hz Ipeak : 220 – 500A peak

Ipk regulation mode for the most complex process : Al in Ar + Oxygen!!

Plasma process development (magnetron, process controller, etc …)

- Gencoa (UK) as strategic partner

High power electronics / HiPIMS power supplies

- Viesca (ES) as strategic partners

Characterization of thin film properties

- Access to European research center facilities.

ta-C on microtools. Al machining!!.

Raman in microtools for sp2/sp3 ratio in sharp edges

DLC

3 meters coating machine 4 x 20 kW power module(HIPIMS + Bias)

1um/hr!! for CrN and ZrN

23-25GPa250 C

3-fold rotation

2 x magnetrons

5kW average each

-60V bias

650 mm diameter x

650 mm height

Thank you for your attention!