PLANSEE High Performance Materials

PVD Target Materials for Hard Coating Solutions

Leading PVD coating solutions

PLANSEEs mission is to develop PVD coating solutions that offer our customers real competitive advantages. As the global market leader, we are a reliable partner in the manufacturing of sputtering targets and arcing cathodes. We integrate our development, production and logistics processes within our customers value chains. Our global sales network ensures availability and expert service at the customers site. Continuous investments made to our in-house production allow PLANSEE to offer exceptional levels of flexibility, availability and quality. By establishing industrial and scientific partnerships to develop new technologies, we set new standards for the industry and ensure that coating solutions will continue to be developed for growth markets around the world. Our expertise in powder metallurgy forms the basis of all our activities. The PVD coating solutions we develop together with our customers involve target materials such as: chromium, titanium, aluminum, zirconium, copper, tungsten, molybdenum, composites and alloys thereof and novel ceramic materials. PLANSEE offers all of the target materials from this catalogue in any OEM target design.

Targets that strengthen your products

Hard coatings are designed to significantly increase the life span of a product. Providing wear protection and serving as tribological thin films, their main applications are for tools, components, and as decorative layers. Two main processes are employed to deposit the layers magnetron sputtering and arc evaporation. PLANSEE supplies high-quality sputtering targets and arc cathodes for the entire variety of advanced hard coatings. Our materials provide the flexibility to produce coatings that achieve high oxidation resistance, tailored tribological behavior and outstanding wear resistance.

CONTENTS
Hard Coating Solutions Page

Aluminum-Based Composite Materials Other Metallic Composites Ceramics Pure Elements Services & Accessories

4 10 13 16 18

Data concerning the condition or recommendations for the use of materials and products are given for information only. All data are based on practical experience. Information referring to the existence of specific properties is given to the best of our knowledge, but does not imply any guarantee. Any assurances in this respect must always be obtained specifically in writing. All rights reserved, in particular for translation into foreign languages. Reproduction of any part of this brochure is not permitted without the express consent of PLANSEE.

Right picture on page 3 with the permission of Hauzer Techno Coating. Left picture on page 3 with the permission of Schaeffler Technologies GmbH.

Aluminum-Based Composite Materials

Aluminium-Chromium
PLANSEE offers the full range of compositions of the AlCr system. This can be achieved only by powder metallurgical processes to obtain a suitable quality. We are use different raw materials as well as various methods for densification. AlCrN coatings are widely used for tool coating, where outstanding high temperature wear resistance is needed and highest oxidation resistance is beneficial. Those properties can be even more pronounced by selective alloying with other elements (see also page 9).

(Al, Cr)2O3 coatings have been introduced to the coating market quite recently. These new types of PVD coatings are intended to compete with Al2O3 coatings produced by CVD. As the PVD process is limited in temperature, the formation of pure alpha-aluminumoxide is not possible yet. The addition of Cr to the target material results in a growth of mixed (Al, Cr)2O3 in the preferred corundum structure. PLANSEEs AlCr target materials are of the highest purity, density and homogeneity. The powder metallurgical production routes allow us to introduce other additional elements for creating tailored coatings. From the pictures of microstructure below it can be seen that PLANSEE has a wealth of experience with different compositions in the AlCr binary system. Beyond that, also many ternary and quarternary AlCr targets have been successfully produced.

AlCr 70/30 at%

AlCr 50/50 at%

AlCr 30/70 at%

AlCrB 52/28/20 at%

AlCrC 25/50/25 at%

AlCrSi 50/40/8 at%

Titanium-Aluminum
TiAl-based coatings are used for various applications to improve/generate: - surface hardness - corrosion resistance - oxidation resistance - decorative colors - wear resistance

Our powder metallurgically produced TiAl targets are characterized by several advantageous properties such as high density, uniform elemental distribution, fine-grained microstructure and a low content of residual impurities. Due to the typical microstructure of powder metallurgical TiAl targets, where pure Ti-particles are embedded into a pure Al-matrix, the thermal as well as electrical conductivity is twice as high as for cast -TiAl material. Therefore PLANSEEs TiAl-based targets show improved performance. In the case of arcing cathodes, a simple substitution from cast-type to powder metallurgical TiAl achieved similar tool life, without the need to change process parameters. High quality is guaranteed by many years of experience and the selection of high purity powders sourced from long-standing and reliable partners. Due to the combination of our advanced production expertise and extensive quality assurance processes, PLANSEE products achieve outstanding results.

Material properties PLANSEE produces powder metallurgical TiAl targets and cathodes ensure constant quality in a wide range of material compositions. The unique advantages of powder metallurgically manufactured TiAl arc cathodes and sputter targets include:
Thermal conductivity [W/mK]

- high ductility of Al-based microstructure prevents crack formation in the target during use. This guarantees a high utilization for each target - high thermal conductivity due to Al matrix compound microstructure - high homogeneity due to uniform distribution of Ti grains in Al matrix - highest stability of material quality due to selected raw materials as well as constant manufacturing process

70 60 50 40 30 20 10 0 50 100
TiAl 50 / 50 at% molten quality TiAl 50 / 50 at% PLANSEE pm-standard quality TiAl 50 / 50 at% PLANSEE pm-finegrain quality

150

200

250

300

350

400

450

500

Temperature / C
Thermal conductivity of different TiAl 50/50 at% target qualities

TiAl 25/75 at%

TiAl 50/50 at%

TiAl 75/25 at%

Microstructure of fine grain TiAl 50/50 at%

Microstructure of standard TiAl 50/50 at%

Microstructure of axial deformed TiAl 33/67 at%

Using different raw material powders and densification processes the microstructure of the target material can be influenced to meet special customer requirements. For example, droplet rate and droplet size can be influenced by the grain morphology (see picture above). On the other hand, this effect seems to be related to the PVD equipment type also. Some scientific investigations concerning the effect of target microstructure on deposited coatings have been carried out by PLANSEE. In a study, cast and powder metallurgical TiAl 50/50 at% targets were used in an arc-ionplating system from Oerlikon Balzers (type BAI 1200) to deposit coatings using a standard coating recipe. Both types of targets produced coatings that had similar coating structure and composition. Milling tests showed the average droplet size and distribution can be further improved, using fine grained PM targets.

Microstructure of cast-type TiAl 50/50 at%

Microstructure of PM (fine grain) TiAl 50/50 at%

Cross section of a coated sample using cast-type TiAl 50/50 at% targets deposited in an Oerlikon Balzers BAI 1200 coating unit

Cross section of a coated sample using PM (fine grain) TiAl 50/50 at% targets deposited in an Oerlikon Balzers BAI 1200 coating unit

TiAl 50/50at% can be manufactured either via powder metallurgy (PM) or casting technology. For PM production the target consists of fine Ti particles homogeneously embedded in a ductile Al-matrix. The cast target, on the other hand, consists of different brittle phases of TiAl intermetallics. During the arc evaporation process, a local melting of the target material happens at the arc spot. Therefore the surface of the PM target transforms to a similar structure as is usually seen for cast-type targets. During the conditioning process, before the actual coating cycle, a thin layer (~3-5m) of TiAl intermetallic phases is already formed at the target surface.

PM TiAl 50/50 at% target (arced surface)

Intermetallic layer at the PM target surface

Intermetallic layer at the PM target surface

to demonstrate that cast-type TiAl 50/50 at% can be easily replaced by powder metallurgical material, resulting in similar coating structure and performance. More detailed results of this investigation may be found in the following publication: Impact of the targets microstructure on the microstructure of the cathodic arc evaporated Ti0.5Al0.5N coatings by D. Rafaja et. al., Proceedings 17th INTERNATIONAL PLANSEE SEMINAR, Vol. 2 (2009) Reutte, Austria, HM38/1.

Intensity Intensity(counts) (counts)

PLANSEE investigated this topic very thoroughly,

103 (a)

102

101

(b)

100

(c)

10-1

30

40

50

60

70

80

90

Diffractionangle angle (20) (20) Diffraction

For the remaining wide range of typically-used compositions of the TiAl system (other than the TiAl 50/50 at%), there has never been an alternative to PM targets, as casting technology would not be able to overcome some of its intrinsic disadvantages, like segregation and pore formation. Graphic: Diffraction patterns of the Ti0.5Al0.5N coatings deposited at UB = -80 V from a cast-type cathode (a) and from a coarsegrain and fine-grain cathodes produced using powder metallurgy (b and c, respectively). Thin solid lines indicate the respective background intensity. Positions of the diffraction lines are labelled at the bottom of the figure. The order of phases is as follows: WC (substrate), fcc Ti0.5Al0.5N, fcc AlN, wurtzitic AlN (from top to bottom).

Heat sink solutions for Al-based targets

In addition to the possibilities to adapt the microstructure of target materials, PLANSEE has developed and patented a method to produce advanced Al-based targets with an integrated heat sink (WO 0240735). As can be seen from the pictures, the highly thermal conductive Al- heat sink material is interconnected with the functional target material, without any additional bonding interface. There are some outstanding features of this target type with integrated heat sink: - improved thermal conductivity leads to reduced number of droplets generated - clamping areas (e.g. bayonet) have high strength to protect against target breakage - some brittle compositions (Cr-rich or Ti-rich compositions) may only be feasible applying heat sink type design - cost-saving effect when noble or other expensive materials are incorporated into the target material

TiAl 50/50 at% arc cathode with Al heat sink for improved thermal conductivity

Close-up: interface between TiAl 50/50 at% and Al heat sink

Close-up: interface between TiAl 50/50 at% and Al heat sink

Microstructure (BSE) of the interface (Al = dark color / Ti = light color)

Selective alloying for tailored coatings

PLANSEE products deliver outstanding benefits that are realized through powder metallurgical (PM) production routes. The nearly unlimited flexibility in production of binary, ternary and quaternary target compositions opens new horizons for advanced PVD coatings. The fully in-house production, using a wide range of PM manufacturing technologies, allows PLANSEE to offer target compositions tailored for advanced hard coatings with optimized mechanical and tribological properties. Further topics that might be addressed are: enhancing of thermal and chemical stability, adding of functional properties like self-lubrication, self-hardening and self-healing. To adjust the coating characteristics to the dedicated application, PLANSEE offers its scientific expertise in alloying of targets and cathodes with elements that influence the coating properties as follows: - Grain size and morphology - Hardness adaption - High temperature oxidation resistance - Friction coefficient - Thermal stability - Thermal conductivity - Electrical conductivity - Antibacterial properties - Color effects

2.34 4275 2300

5
Boron

10.81 3

2.62 4470* 4100*

12.01 4 2

1.251* 77.35 63.14

14.01

3 5 4 2

5.8 3682 2175

23

50.94

5 4 3 2

8.55 5017 2740

41

92.91 5 3

16.6 5731 3287

73

180.95 5

B
8

Carbon

C
16

Nitrogen

N
14

Vanadium

V
24

Niobium

Nb
[Kr]4d45s

Tantalum

Ta
74

1s2sp1

1s22s2p2

1s22s2p3

[Ar]3d34s

[Xe]4f145d36s

1.429 90.18 50.35

16.00 -2

2.07 717.75 388.36

32.06

2 4 6

2.33 3540 1685

26.09 4

7.19 2945 2130

52.00 6 3 2

10.2 4912 2890

42

93.94

6 5 4 3 2

19.3 5828 3680

183.85

6 5 4 3 2

Oxygen

Sutfur

Silicon

Si

Chromium

Cr
[Ar]3d54s

Molybdenum

Mo
[Kr]4d55s

Tungsten

1s22s2p4

[Ne]3s2p4

[Ne]3s2p

[Xe]4f145d46s

11.85 1746 577

81

204.37 3 1

6.49 4682 2125

40

91.22 4

13.1 4876 2500

72

178.49 4

1.74 1363 922

12

24.31 2

8.90 3187 1726

28
Nickel

58.70 3 2

8.90 3201 1768

27
Cobalt

58.93 3 2

Thallium

Ti
21

Zirconium

Zr
39

Hafnium

Hf
58

Magnesium

Mg
[Ne]3s

Ni
47

Co
[Ar]3d74s 1 12.2 4423 2523

[Xe]4f145d106s2p1

[Kr]4d5s

[Xe]4f145d6s

[Ar]3d84s

3.0 3104 1812

44.96 3

4.5 3611 1799

88.91 3

6.78 3699 1071

140.12 3 4

8.96 2836 1357.6

29

63.55 2 1

10.5 2436 1234

107.87

44

101.07

8 6 4 3 2

Scandium

Sc
[Ar]3d4s

Yttrium

Ce
[Xe]4f5d6s

Cerium

Cu
[Ar]3d104s1

Copper

Ag
[Kr]4d105s1

Silver

Ruthenium

Ru
[Kr]4d75s1

[Kr]4d5s

Other Metallic Composites

PLANSEE has a wide range of in-house production capabilities. The technologies available for the processing of powder metallurgical materials allow PLANSEE to manufacture the products in a highly efficient manner. Therefore we are able to adapt the manufacturing technology to match either small (R&D) batch size or mass production levels. Particularly in the field of metallic composites and ceramics, powder metallurgical technologies can generate a wide range of compositions.

Overview
The following sputtering targets and arcing cathodes are offered by PLANSEE in a wide range of compositions: - Titanium composites and alloys: Ti-Si, Ti-Cr, Ti-B, Ti-Zr - Chromium composites and alloys: Cr-Si, Cr-B - Zirconium composites and alloys: Zr-Si, Zr-B - Molybdenum composites and alloys: Mo-Cu, Mo-Ag

Metallic composites and ceramic targets

Mo-Cu targets bonded on Cu backing plate

Ti-B targets as a multiple piece (clamped) version

Cr-B targets as a multiple piece (clamped) version

CrSi clamped on Mo backing plate

Ti/TiN composites having various Ti content

10

Titanium-Silicon
For applications like dry, high-speed cutting of high performance materials, PLANSEE recommends the use of TiSiN coatings. Due to the high hardness and highest oxidation resistance of TiSiN nanocomposites, these coatings significantly extend the life time of tools. PLANSEE offers a range of TiSi targets in standard compositions that are produced using powder metallurgical technology. Upon your request, PLANSEE also produces individual compositions with Si contents up to 25 at%.

Product benefits: - Uniform element distribution in the target due to advanced powder metallurgical production route - Fine grained microstructure optimized for sputtering targets as well as for arcing cathodes - High strength and ductility due to the microstructural composition: TiSi/Ti5Si3 grains embedded in Ti matrix - Guaranteed high density of > 98% of the theoretical density - High target/cathode purity due to high purity powder ingredients - Due to PLANSEEs licensing agreement, customers who are using our TiSi targets are free to produce TiSiN coatings which are covered under Japanese Patent JP-3765475 (of Hitachi Metals Ltd.)

Product portfolio: - TiSi 90/10 at%, TiSi 85/15 at%, TiSi 80/20 at% and TiSi 75/25 at%

Typical microstructure of PLANSEE powder metallurgical TiSi 80/20 at% material

Wide range of dimensions of PLANSEE TiSi targets and cathodes

11

Molybdenum-Copper
Advanced PVD coatings already play an important role in automotive applications for reducing the friction losses and, as a consequence, increasing the fuel efficiency. Nano-composite coatings based on hard metal nitrides surrounded by a soft (not nitride-forming) metal, exhibit high hardness, low friction and high wear resistance. For reasons of coating process stability, MoCu sputtering targets with a high volume fraction of molybdenum are best suited to deposit such coatings. During the reactive PVD process the molybdenum will form its nitride while copper is inert in nitrogen atmosphere and therefore will deposit as a metal. For arc ion plating, specially designed MoCu cathodes are available on request.

Product benefits: - Fine-grained microstructure with uniform distribution of molybdenum grains in a copper matrix - High density (>98%) in a wide composition range - High target purity due to high purity powder ingredients

Product portfolio: - Mo-Cu according to customer request with Mo content from 40 to 90 at%

Microstructure of MoCu (Mo-rich)

Fracture surface of MoCu (Mo-rich)

12

Ceramics
Using the advantages of powder metallurgy, mixtures of different ceramic compounds are also available as sputtering targets and cathodes for arc evaporation. By adjusting the microstructure with additions of carbon, a new spectrum of compositions is available. These are mainly dedicated for advanced hard coatings in the field of tools and tribological coatings for components. Examples are WC/C, TiC/C, SiC/C, TiB2/C.

Overview
The following materials are available as sputtering targets. The properties of the materials can also be adapted to meet the conditions of the arc process: - Carbides: WC (binder-free), TiC, B4C, SiC and others on request - Borides: TiB2, CrB2, WB, W2B, ZrB2, NbB2 and others on request - Nitrides like TiN

Multiple-piece SiC targets bonded on Mo backing plate

Multiple-piece B4C target bonded on Cu backing plate

Multiple-piece SiC/C targets bonded on Cu backing plate

TiN target clamped on Mo backing plate

NbB2 bonded on Cu backing plate

TiC/C bonded on Mo backing plate

13

Titanium Diboride (TiB2)

PLANSEE TiB2 is the material of choice when it comes to advanced coatings for high speed machining of aluminium alloys and a variety of other non-ferrous alloys. Due to its low affinity to aluminum, this coating helps to eliminate the build-up on the cutting edges of the tool during operation which is a major cause of failure. PLANSEE offers single as well as multiple-piece construction targets, bonded on copper or molybdenum backing plates. Thanks to its fine grain size and advanced production processes, PLANSEE TiB2 targets have outstanding properties regarding density and fracture toughness.

Product benefits: - Fine grained microstructure optimized for sputtering with high power density - High strength and thermal shock resistance due to the high temperature and high pressure densification process - Guaranteed high density of > 98% of the theoretical density (corresponds to a specified 4.40 - 4.50 g/cm3) - High target purity (> 99.8 wt% TiB2 content) due to high purity powder ingredients - Unique microstructure developed for arcing cathodes

Product portfolio: - Multiple-piece targets bonded on backing plate (Cu, Mo) - Single piece targets up to 250 x 300 mm - TiB2 cathodes with microstructure and cathode design adjusted for arc ion plating PVD processes

Typical microstructure of PLANSEE TiB2 material (SEM of fracture surface)

Multiple-piece TiB2 targets bonded on Cu backing plate

14

Binder-free Tungsten Carbide (WC)

PLANSEEs binder-free WC is the right material for deposition of Diamond Like Carbon (DLC) coatings. It is applied for high quality and high purity WC/a-C:H coatings for automotive components as well as tool applications. Carbon-based nanostructured composite thin film coatings such as WC/a-C:H have attracted large industrial attention because of their excellent tribological properties. They show a high wear resistance and a low friction coefficient at the same time. PLANSEE offers single-piece as well as multiple-piece constructions for sputtering targets, bonded on copper or molybdenum backing plates. Thanks to the fine grain size and advanced production process, PLANSEEs binder-free WC targets have outstanding properties regarding density and fracture toughness. Another good reason to use PLANSEEs WC is the absence of nickel and cobalt, as inhaling these materials raises the risk of cancer. The elimination of these elements normally used as a binder for WC products reduces these risks. For Arc Ion Plating (AIP) process PLANSEE also offers advanced WC cathodes. Our unique cathode design has a copper heat sink as well as an arc protection ring which leads to stable cathode evaporation.

Product benefits: - Fine-grained microstructure optimized for sputtering with high power density - Binder-free material with guaranteed Ni and Co content below 100 ppm - High strength and thermal shock resistance - Guaranteed high density of > 98% compared to the theoretical density (> 15.50 g/cm3) - High target purity (> 99.9 wt% WC content) due to high purity powder ingredients - Unique microstructure and cathode design developed for arcing cathodes

Product portfolio: - Multiple-piece targets bonded on backing plates (Cu, Mo) - Single piece targets up to 250 x 300 mm - WC cathodes with microstructure and cathode design adjusted for arc ion plating PVD processes

Multiple-piece WC targets bonded on Cu backing plate

WC arc cathodes on Cu with Mo or ceramic arc protection ring

15

Pure Elements
Titanium
Unalloyed commercially pure Titanium is available in four different Grades, 1, 2, 3 and 4, which are selected based on the corrosion resistance, ductility and strength requirements of the specific application. Grade 1 has the highest formability, while Grade 4 has the highest strength and moderate formability. For PVD coating applications the most widespread quality in use is Titanium Grade 2. To offer short lead times to our customers, PLANSEE stocks a large and varied inventory of Titanium Grade 2 mill-products such as plate, sheet, billet and bar. PLANSEEs experienced operators are able to deal with complex operations like titanium machining and processing.

Typical microsturcture of Ti Grade 2

Monolithic Ti target

Zirconium
Commercially pure zirconium naturally contains 1-5 percent of hafnium, as it is extremely difficult to separate these two elements from each other. Unalloyed Zirconium is specified as Alloy 702. Zirconium targets are often used for decorative applications as ZrN layers. These are more brass-like in color and offer a higher corrosion resistance than TiN coatings. PLANSEE offers Zirconium targets in every standard dimension.

Typical microstructure of Zirconium Alloy 702

Zirconium arc cathodes and sputtering targets

16

Chromium
Many years of experience in powder metallurgy allow PLANSEE to meet the highest requirements with respect to purity, grain structure, density and target geometry. Careful selection of raw materials and the use of the most up-to-date processing technology guarantee the consistently high quality of PLANSEE Cr sputtering targets. According to customers needs PLANSEE employs aluminothermic High Purity (HP) powder or electrolytic Ultra High Purity (UHP) powder.

Material specifications Element Metallic impurities Fe Si others Content of impurities for UHP Cr (99.95 % metallic purity) in g/g 300 100 150 Content of impuities for HP Cr (99.8 % metallic purity) in g/g 1300 400 400

Non metallic impurities

O N C

300 200 100

1000 200 300

Microstructure of UHP Chromium

Cr sputtering target

Cr sputtering target bonded on Cu backing plate

Cr rotatable targets

17

Services & Accessories

Backing plates and bonding
Depending on the target material, the use of a molybdenum backing plates can be advantageous. Molybdenum has a higher Youngs Modulus compared to copper, making it a stiffer backing plate. It also has a lower expansion coefficient which better matches most ceramic materials, reducing the risk of crack formation. PLANSEE also supplies pure copper backing plates which have the advantage of highest heat conductivity. MoCu and WCu composite materials may also be used as a heat sink material for certain dimensions. By varying the content of copper, the material of the heat sink is adapted more specifically to match the thermal expansion coefficient of the target material. Therefore such material combinations have minimized risk of crack formation.

Material Mo Cu MoCu (30 - 50 wt% Cu) WCu (20 - 30 wt% Cu) Ti

Thermal conductivity 0-100 C (W/mK) 138 401 190 - 240 225 - 240 22

Coefficient of thermal expansion x10-6/K 5.3 16.5 7.5 - 9.9 8.3 - 10.3 8.6

Youngs Modulus (GPa) 320 130 225 - 170 280 - 220 110

WC Cr TiB2

120 94 64

4.3 7.0 7.4

680 280 560

PLANSEE offers in-house bonding capabilities. In most cases we use an indium bond, but also some high temperature soldering is available on request. Please ask for further information.

Graphite foils
PLANSEE offers all items which are necessary for the different types of coatings as well as all items required for mounting our targets including: - Standards like graphite-foils - Non-magnetic screws - Non-magnetic washers - Specially designed clamping bars and holders used for PLANSEE clamping systems
Graphite-foils, mounting screws and washers

18

R&D Services
Based on a long history of target development, PLANSEE shares a broad knowledge of target compositions and target designs with its customers. Coating parameters and fixing instructions for the usage of PLANSEE targets have been documented. Also an extensive database is available with recommendations on certain chemical compositions for creating tailored coatings. According to the intrinsic properties of the target material systems, PLANSEE has established a huge variety of in-house manufacturing methods. We individually choose the opimal production route to ensure that our customers receive only fully dense and homogeneous targets, for R&D as well as for standard materials. The PLANSEE R&D team assists you to solve any coating problems and to jointly engineer coating solutions for future demands. Based on the scientific content and depth of the problem, cooperation can be established bi-laterally or include support from scientific partners (universities, institutes). PLANSEE serves all customers with its global network of experts. Main production plant for the Hard Coating Target Materials is PLANSEE Composite Materials GmbH, located in Lechbruck, Germany. This PLANSEE site has its expertise in the production of different metal and ceramic-based composite materials for almost 40 years.

19

Close to the customer - our global network

PLANSEE manufactures and markets its products worldwide. Production sites in Europe, USA, India, Japan, and China as well as our global network of sales subsidiaries and sales partners, enable outstanding customer service and product quality delivered by local teams. Stronger than any alliance and more diversified than single producers, PLANSEE is the most reliable source for high performance components made of refractory metals.

For more information and local contacts please visit our website:

www.plansee.com

We reserve the right to make technical changes for improvement of the product.