**1. Introduction**

546 Acoustic Waves – From Microdevices to Helioseismology

[9] United States Patent No. 5,289,715, Vapour Detection Apparatus and Method Using an

[9] G. C. Frye, S. J. Martin, R. W. Cerenosek, K. B. Pfeifer, and J. S. Anderson, Portable acoustic wave sensor systems, in *Proc. IEEE Ultrason. Symp.*, 1991, pp. 311–316. [10] G. C. Frye and S. J. Martin, Dual output acoustic wave sensor for molecular

[11] T.Wessa, S. Kueppers, G. Mann, M. Rapp, and J. Reibel, "On-line monitoring of process HPLC by sensors," *Organ. Process Res. Develop.*, vol. 4, no. 2, pp. 102–106, 2000. [12] D. A. Howe, D.W. Allan, and J. A. Barnes, Properties of Signal Sources and Measurement Methods, *U.S. Dept. Commerce, NIST Tech. Note 1337*, 1990. [13] D. S. Ballantine, Jr. and H.Wohltjen, Elastic properties of thin polymer films

R. Seitz, Eds. Washington, DC: Amer. Chem. Soc., 1989, pp. 222–236. [14] J. W. Grate and E. T. Zellers, The fractional free volume of the sorbed vapor in modeling

responses, *Anal. Chem.*, vol. 72, no. 12, pp. 2861–2868, July 1, 2000.

[17] H. Yasuda, *Plasma Polymerization*. New York: Academic, 1985, p. 11 and 294.

properties and applications, *Vacuum*, vol. 34, pp. 1053–1059, 1984.

*Proc. 2000 IEEE International Frequency Control Symposium*, pp. 58-65. [22] I. D. Avramov, A. Voigt and M. Rapp, "Rayleigh SAW Resonators Using Gold Electrode

*Control Symposium*, 5-7 June 2006, Miami, Florida, USA, pp. 381-388. [24] F. Bender, L. Waechter, A. Voigt and M. Rapp, Deposition of High-Quality Coatings on

*Electronics Letters*, 31-st March 2005, Vol. 41, No. 7, pp. 450-452.

[15] F. L. Dickert and A. Haunschild, Sensor materials for solvent vapor detection-donor-

[16] N. Barie, M. Rapp, and H. J. Ache, UV crosslinked polysiloxanes as new coating

[18] C. Hamann and G. Kampfrath, Glow discharge polymeric film: Preparation, structure,

[19] E. I. Radeva, Thin Plasma-Polymerized Layers of Hexamethyldisiloxane for

[20] G. Kovach, G. W. Lubking, M. J. Vellekoop, and A. Venema, Love waves for (bio) chemical sensing in liquids, in *Proc. IEEE Ultrason. Symp.*, 1992, pp. 281–285. [21] I. D. Avramov, M. Rapp, A. Voigt, U. Stahl and M. Dirschka, Comparative studies on

[23] I. D. Avramov, Design of Rayleigh SAW resonators for applications as gas sensors in

investigated with surface acoustic wave devices, in *Chemical Sensors and Microinstrumentation*, R.W. Murry, R. E. Dessy,W. R. Heinemann, J. Janata, and W.

the viscoelastic contribution to polymer-coated surface acoustic wave vapor sensor

acceptor and host-guest interactions, *Adv. Mater.*, vol. 5, no. 12, pp. 887–895, Dec.

materials for SAW devices with high long-term stability, *Sens. Actuators B, Chem.*,

Acoustoelectronic Humidity Sensors, *Sensors and Actuators,* B, vo1.44, pp.275-278,

polymer coated SAW and STW resonators for chemical gas sensing applications,

Structure for Gas Sensor Applications in Chemically Reactive Environments",

highly reactive chemical environments, *Proc. 2006 IEEE International Frequency* 

SAW Sensors using Electrospray, *IEEE Sensors Conference*, 2003, Paper ID 1022 (on

identification, in *Proc. IEEE Transducers*, 1991, pp. 566-569.

Acoustic Interferometer.

1993.

1997.

CD).

vol. B46, pp. 97–103, 1998.

Diamond is one of the most promising materials for SAW applications due to the highest sound velocity and thermal conductivity. Unfortunately single crystals and epitaxial CVDfilms are expensive and beyond that conventional CVD grown microcrystalline diamond films feature large facet structures with high roughness inapplicable for this application. Ultra-Nanocrystalline diamond (UNCD) films grown in a microwave plasma enhanced chemical vapor deposition (MPECVD) system on Si substrates possess a smooth surface making it an ideal material for SAW applications. Moreover, due to its nanocrystalline structure, the film properties of the UNCD material can be tailored in a wide range to adjust them to the specific needs of a SAW filter. For this task a profound understanding of the growth process of UNCD and the dependency of the film performance from the film properties is needed. In addition, a simple and quick method to characterize the properties of the UNCD films is necessary. Laser-induced SAW pulse method, which is fast and accurate, is demonstrated to measure the mechanical and structural properties of the UNCD films. AFM measurements were done to correlate the SAW pulse method results with the surface roughness of the deposited films.

Another advantage of the UNCD films is, that highly C-axis textured aluminum nitride (AlN) films can be grown directly on UNCD films by DC-sputtering. Using this technique a feasibility study for SAW devices has been successfully performed.

### **2. Saw filters**

SAW devices are electromechanical products commonly used in high frequency applications such as filters, oscillators and transformers and are based on the transduction of acoustic waves. SAW filters are now widely used in mobile telephones applications for filtering and provide significant advantages in performance, cost, and size over other filter technologies such as quartz crystals (based on bulk waves), LC filters, and waveguide filters by offering a high degree of frequency selectivity with low insertion loss in compact size (Campbell, 1989). In SAW filters an Interdigital Transducer (IDT) that is attached to a piezoelectric material converts electrical signals to a mechanical wave. The piezoelectric effect and the electric field generated by the IDT are distorting the crystal close to its surface.

Ultrananocrystalline Diamond as Material for Surface Acoustic Wave Devices 549

The nanostructured films differ from the microcrystalline films in grain size and in

Fig. 1. Morphological comparison of microcrystalline diamond film (upper picture) and UNCD film (lower picture). The scale bar in the upper picture corresponds to 1 µm while

The terms nanocrystalline (NCD) and ultrananocrystalline diamond (UNCD) were coined by the Argonne National Laboratory group that performed the pioneering work in this field. These terms were introduced to establish a differentiation to the microcrystalline diamond films that differ not only in film properties but also in the way they are deposited. The technology developed at Argonne National Laboratory started from deposition of hydrogen free plasmas using fullerenes in Ar (Ar/C60) and was thereafter extended to hydrogen diluted plasmas using Ar/CH4 and gas mixtures containing only about 1 % hydrogen (either added intentionally or through the thermal decomposition of CH4) (Gruen, 1999). UNCD is grown from Argon-rich plasma giving it a very fine and uniform structure with grain sizes between 2 and 15 nm (Auciello et. al., 2004). The grain sizes are independent

the scale bar in the lower picture corresponds to 5 µm

roughness of the surface as shown in Fig. 1.

The oscillations of the crystal lattice can than add up by constructive wave interference and superimpose to a surface wave before being converted back to an electrical signal by further electrodes.

The passing frequency of a SAW filter can be calculated by

$$f\_0 = \frac{\nu\_0}{\mathcal{A}}\tag{1}$$

where λ represents the wavelength of the acoustic surface wave (corresponding to twice the distance of the fingers of the IDT) and v0 is the crystal-dependent velocity oft the surface wave. The operation frequency of a SAW device is closely related to the spacing of the interdigital transducer (IDT) that is significantly limited by the photolithograph capability (Springer et al., 1999). Thus one way to achieve higher passing frequencies is to use crystals with a higher speed of sound, such as sapphire (Caliendo, 2003), SiC (Takagaki, 2002) or diamond (Yamanouchi et al., 1989)(Nakahata et al., 1992).

### **3. Diamond as SAW material**

The material with the highest speed of sound is diamond with 18000 m/s. Besides the high speed of sound, diamond features other remarkable properties such as high thermal conductivity and high hardness to name only a few. Due to its extraordinary properties natural and HPHT diamond is used for a long time as a material for tools, especially for grinding or sawing of rocks. Since the 1980s the microcrystalline diamond deposited by thin film technology is increasingly used. One major problem with the microcrystalline diamond films deposited in CVD processes – especially for microelectronics and micromechanical applications with their decreasing structural sizes - is the high surface roughness (Malshe et. al., 1999). Moreover, high surface roughness results in large propagation loss, reducing the applicability of the material. Although Sumitomo Electrics developed SAW filters and resonators with various bandwidth in the 2-5 GHz range it turned out that the polishing of the rather rough CVD diamond surface was too expensive and time consuming due to the chemical inertness and highest hardness of diamond and the SAW filters were never produced in an industrial scale (Fujimori, 1996). Even if one solution to this problem was demonstrated by using the unpolished nucleation side of freestanding CVD diamond (Lamara et. al., 2004) this idea never went into production.

Another drawback of the microcrystalline diamond films is that the homogeneous deposition of such films on substrates with a high aspect ratio is difficult because the films consist of relatively large crystals.

### **4. Nanocrystalline diamond as SAW material**

The growing interest in nanotechnology and nanostructured materials has encouraged the research of diamond films with reduced grain size. By reducing the grain size those films feature rather unique combinations of properties making them potential materials for emerging technological developments such as Nano/Micro- Electro-mechanical Systems (N/MEMS) (Auciello et. al., 2004) (Hernandez Guillen, 2004), optical coatings, bioelectronics (Yang et. al., 2002), tribological applications (Erdemir et. al., 1999) and also surface acoustic wave (SAW) filters (Bi et. al., 2002).

The oscillations of the crystal lattice can than add up by constructive wave interference and superimpose to a surface wave before being converted back to an electrical signal by further

> <sup>0</sup> *f*<sup>0</sup> = λ

where λ represents the wavelength of the acoustic surface wave (corresponding to twice the distance of the fingers of the IDT) and v0 is the crystal-dependent velocity oft the surface wave. The operation frequency of a SAW device is closely related to the spacing of the interdigital transducer (IDT) that is significantly limited by the photolithograph capability (Springer et al., 1999). Thus one way to achieve higher passing frequencies is to use crystals with a higher speed of sound, such as sapphire (Caliendo, 2003), SiC (Takagaki, 2002) or

The material with the highest speed of sound is diamond with 18000 m/s. Besides the high speed of sound, diamond features other remarkable properties such as high thermal conductivity and high hardness to name only a few. Due to its extraordinary properties natural and HPHT diamond is used for a long time as a material for tools, especially for grinding or sawing of rocks. Since the 1980s the microcrystalline diamond deposited by thin film technology is increasingly used. One major problem with the microcrystalline diamond films deposited in CVD processes – especially for microelectronics and micromechanical applications with their decreasing structural sizes - is the high surface roughness (Malshe et. al., 1999). Moreover, high surface roughness results in large propagation loss, reducing the applicability of the material. Although Sumitomo Electrics developed SAW filters and resonators with various bandwidth in the 2-5 GHz range it turned out that the polishing of the rather rough CVD diamond surface was too expensive and time consuming due to the chemical inertness and highest hardness of diamond and the SAW filters were never produced in an industrial scale (Fujimori, 1996). Even if one solution to this problem was demonstrated by using the unpolished nucleation side of freestanding CVD diamond

Another drawback of the microcrystalline diamond films is that the homogeneous deposition of such films on substrates with a high aspect ratio is difficult because the films

The growing interest in nanotechnology and nanostructured materials has encouraged the research of diamond films with reduced grain size. By reducing the grain size those films feature rather unique combinations of properties making them potential materials for emerging technological developments such as Nano/Micro- Electro-mechanical Systems (N/MEMS) (Auciello et. al., 2004) (Hernandez Guillen, 2004), optical coatings, bioelectronics (Yang et. al., 2002), tribological applications (Erdemir et. al., 1999) and also surface acoustic

*<sup>v</sup>* (1)

The passing frequency of a SAW filter can be calculated by

diamond (Yamanouchi et al., 1989)(Nakahata et al., 1992).

(Lamara et. al., 2004) this idea never went into production.

**4. Nanocrystalline diamond as SAW material** 

**3. Diamond as SAW material** 

consist of relatively large crystals.

wave (SAW) filters (Bi et. al., 2002).

electrodes.

The nanostructured films differ from the microcrystalline films in grain size and in roughness of the surface as shown in Fig. 1.

Fig. 1. Morphological comparison of microcrystalline diamond film (upper picture) and UNCD film (lower picture). The scale bar in the upper picture corresponds to 1 µm while the scale bar in the lower picture corresponds to 5 µm

The terms nanocrystalline (NCD) and ultrananocrystalline diamond (UNCD) were coined by the Argonne National Laboratory group that performed the pioneering work in this field. These terms were introduced to establish a differentiation to the microcrystalline diamond films that differ not only in film properties but also in the way they are deposited. The technology developed at Argonne National Laboratory started from deposition of hydrogen free plasmas using fullerenes in Ar (Ar/C60) and was thereafter extended to hydrogen diluted plasmas using Ar/CH4 and gas mixtures containing only about 1 % hydrogen (either added intentionally or through the thermal decomposition of CH4) (Gruen, 1999). UNCD is grown from Argon-rich plasma giving it a very fine and uniform structure with grain sizes between 2 and 15 nm (Auciello et. al., 2004). The grain sizes are independent

Ultrananocrystalline Diamond as Material for Surface Acoustic Wave Devices 551

Ultra-Nanocrystalline diamond (UNCD) films were synthesized by microwave plasma enhanced chemical vapour deposition technique using a 2.45 GHz IPLAS CYRANNUS® I-6" plasma source. The nanocrystalline films were deposited from an Ar/H2/CH4 plasma. As standard substrates in this work (100) oriented double side polished silicon wafers with a thickness of 425 μm were used. The substrates were usually cut from a wafer to a size of

To enhance the nucleation of diamond the substrates were ultrasonically scratched for 30 min with a scratching solution consisting of diamond powder (~ 20 nm grain size), Ti powder (~ 5 nm particle size) and Ethanol in a weight percent ratio of 1:1:100 (wt%). Afterwards the substrates were ultrasonicated for 15 min in Acetone to clean the surface from any residues of the scratching solution (Lin et. al., 2006) (Buck, 2008). After the substrate pre-treatment they were immediately installed into the vacuum chamber placed on top of the molybdenum substrate holder and the recipient was pumped down to high-

The plasma is ignited at ca. 1 mbar pressure with a process gas mixture of hydrogen (≈ 3 %) in argon (≈ 97 %) and a MW-power of 1 kW. After the ignition the pressure was slowly increased up to the deposition pressure (typically 200 mbar) during a 30 min period. This 30 min step is due to two reasons: Firstly the substrate surface is cleaned by the etching effect of the plasma. Secondly the temperature of the substrate is slowly increased in the process of the rising pressure. In doing so the substrate is already close to the targeted deposition temperature before switching to the deposition parameters and introducing the carbon carrier gas into the chamber. During the whole process of increasing the pressure the MW power coupling into the plasma is adjusted to the changing conditions. After reaching the desired deposition pressure the carbon carrier gas was introduced therewith starting the

The nanocrystalline films shown here were deposited at a pressure of 200 mbar from an Ar/H2/CH4 plasma. To investigate the influence of the hydrogen admixture on the properties of the deposited films, the percentage of hydrogen in the process gas was varied

The MW-power was kept constant at 1 kW and the films were deposited for 5 h.

Ar fraction 91,2 % - 97,2 %

Substrate Pretreated Silicon (100)

The deposition parameters were systematically varied to investigate the influence on film structure and film properties with special attention to the speed of sound and the roughness of the films as most important properties for the application as SAW filters. Because of that

Pressure 200 mbar Gasflow 400 sccm H2 fraction 2 % - 8 % CH4 fraction 0,8 %

MW-power 1 kW Deposition time 5 h

about 20 x 20 mm.

deposition process.

between 2 % and 8 % as shown in Table 1.

Table 1. CVD Deposition Parameters

**6. Morphology of the films** 

vacuum.

from film thickness due to the high secondary nucleation of new growth sites during the whole deposition that is not taking place in the standard growth of diamond. This can be shown within the experimental errors when measuring the Young's modulus (GPa) as a function of the deposition time (Shen et. al., 2006).

UNCD consists of pure sp3 crystalline grains that can be separated by atomically abrupt (0.5 nm) grain boundaries or embedded in an amorphous 3D matrix. By reducing the grain size of microcrystalline diamond films the amount of material between the grains is increased. This matrix in the films can contribute to a large fraction of the overall film, sometimes exceeding 10 % of the total volume, giving those films a great proportion of non-diamond or disordered carbon (Auciello et. al., 2004]. But also values down to 5 % sp2-bonded carbon have been reported and determined by UV Raman spectroscopy and synchrotron based near-edge X-ray absorption fine structure measurements (NEXAFS) (Gruen, 1998).

In fact the overall volume and structure of the film matrix significantly determine the properties of nanocrystalline diamond films giving another degree of freedom for the material. The well-aimed use of an amorphous matrix for nanocrystalline diamond grains leads to an enormous field of new materials, because a whole class of carbon based materials (diamondlike carbon, DLC) can be used as matrix that may contain carbon solely (a-C) or carbon and hydrogen (a-C:H) as well as other components like metals (Me-C:H); additionally other dopants like silicon, oxygen, halogens or nitrogen may be added with considerable effect on the film properties. By combining soft matrix properties with the hard diamond crystals on the nanoscale it is possible to combine hard with elastic properties and get a material that is hard and tough at the same time. With tailoring the mechanical stress in the films or the coefficient of thermal expansion it was possible to tailor yet other very important mechanical properties for the application of UNCD films by adjusting the overall matrix fraction to the film volume (in the case of a 3D matrix surrounding the nanocrystals) (Woehrl & Buck, 2007) (Woehrl et. al., 2009).

Thus, when comprehensively characterizing UNCD films, one also has to analyze the matrix properties. Since the carbon atoms in the matrix have no crystalline configuration and are indeed amorphous, conventional techniques known from the analysis of amorphous carbon films can be used.

## **5. Deposition of UNCD films**

It is well accepted that the initial nucleation is one decisive factor for the subsequent CVD diamond film growth. While a low nucleation density can lead to van-der-Drift growth – known as the "survival of the largest" – high initial nucleation leads to shorter coalescence time and lower surface roughness. Due to the fact that substrate pre-treatment can significantly increase initial nucleation, the pre-treatment is an important process step already predetermining the film properties (Liu & Dandy, 1995). Three effective seeding methods are known: Mechanical scratching of the substrate surface (see e.g. (Buck & Deuerler, 1998)), enhancing the nucleation by applying a bias voltage to the substrate in the early stages of deposition (Yugo, 1991), and ultrasonically activating the substrate in a suspension containing diamond powder (Lin et. al., 2006)(Sharma et. al., 2010). Nucleation densities of 1010 cm-2 or more were achieved with either of these methods. The latter method was used for the substrates in this work mainly because of the good reproducibility and uniformity even with larger substrates. Details on the pre-treatment and the deposition parameters used for the UNCD films deposited in this work are given below.

from film thickness due to the high secondary nucleation of new growth sites during the whole deposition that is not taking place in the standard growth of diamond. This can be shown within the experimental errors when measuring the Young's modulus (GPa) as a

UNCD consists of pure sp3 crystalline grains that can be separated by atomically abrupt (0.5 nm) grain boundaries or embedded in an amorphous 3D matrix. By reducing the grain size of microcrystalline diamond films the amount of material between the grains is increased. This matrix in the films can contribute to a large fraction of the overall film, sometimes exceeding 10 % of the total volume, giving those films a great proportion of non-diamond or disordered carbon (Auciello et. al., 2004]. But also values down to 5 % sp2-bonded carbon have been reported and determined by UV Raman spectroscopy and synchrotron based

In fact the overall volume and structure of the film matrix significantly determine the properties of nanocrystalline diamond films giving another degree of freedom for the material. The well-aimed use of an amorphous matrix for nanocrystalline diamond grains leads to an enormous field of new materials, because a whole class of carbon based materials (diamondlike carbon, DLC) can be used as matrix that may contain carbon solely (a-C) or carbon and hydrogen (a-C:H) as well as other components like metals (Me-C:H); additionally other dopants like silicon, oxygen, halogens or nitrogen may be added with considerable effect on the film properties. By combining soft matrix properties with the hard diamond crystals on the nanoscale it is possible to combine hard with elastic properties and get a material that is hard and tough at the same time. With tailoring the mechanical stress in the films or the coefficient of thermal expansion it was possible to tailor yet other very important mechanical properties for the application of UNCD films by adjusting the overall matrix fraction to the film volume (in the case of a 3D matrix surrounding the nanocrystals)

Thus, when comprehensively characterizing UNCD films, one also has to analyze the matrix properties. Since the carbon atoms in the matrix have no crystalline configuration and are indeed amorphous, conventional techniques known from the analysis of amorphous carbon

It is well accepted that the initial nucleation is one decisive factor for the subsequent CVD diamond film growth. While a low nucleation density can lead to van-der-Drift growth – known as the "survival of the largest" – high initial nucleation leads to shorter coalescence time and lower surface roughness. Due to the fact that substrate pre-treatment can significantly increase initial nucleation, the pre-treatment is an important process step already predetermining the film properties (Liu & Dandy, 1995). Three effective seeding methods are known: Mechanical scratching of the substrate surface (see e.g. (Buck & Deuerler, 1998)), enhancing the nucleation by applying a bias voltage to the substrate in the early stages of deposition (Yugo, 1991), and ultrasonically activating the substrate in a suspension containing diamond powder (Lin et. al., 2006)(Sharma et. al., 2010). Nucleation densities of 1010 cm-2 or more were achieved with either of these methods. The latter method was used for the substrates in this work mainly because of the good reproducibility and uniformity even with larger substrates. Details on the pre-treatment and the deposition

parameters used for the UNCD films deposited in this work are given below.

near-edge X-ray absorption fine structure measurements (NEXAFS) (Gruen, 1998).

function of the deposition time (Shen et. al., 2006).

(Woehrl & Buck, 2007) (Woehrl et. al., 2009).

**5. Deposition of UNCD films** 

films can be used.

Ultra-Nanocrystalline diamond (UNCD) films were synthesized by microwave plasma enhanced chemical vapour deposition technique using a 2.45 GHz IPLAS CYRANNUS® I-6" plasma source. The nanocrystalline films were deposited from an Ar/H2/CH4 plasma.

As standard substrates in this work (100) oriented double side polished silicon wafers with a thickness of 425 μm were used. The substrates were usually cut from a wafer to a size of about 20 x 20 mm.

To enhance the nucleation of diamond the substrates were ultrasonically scratched for 30 min with a scratching solution consisting of diamond powder (~ 20 nm grain size), Ti powder (~ 5 nm particle size) and Ethanol in a weight percent ratio of 1:1:100 (wt%). Afterwards the substrates were ultrasonicated for 15 min in Acetone to clean the surface from any residues of the scratching solution (Lin et. al., 2006) (Buck, 2008). After the substrate pre-treatment they were immediately installed into the vacuum chamber placed on top of the molybdenum substrate holder and the recipient was pumped down to highvacuum.

The plasma is ignited at ca. 1 mbar pressure with a process gas mixture of hydrogen (≈ 3 %) in argon (≈ 97 %) and a MW-power of 1 kW. After the ignition the pressure was slowly increased up to the deposition pressure (typically 200 mbar) during a 30 min period. This 30 min step is due to two reasons: Firstly the substrate surface is cleaned by the etching effect of the plasma. Secondly the temperature of the substrate is slowly increased in the process of the rising pressure. In doing so the substrate is already close to the targeted deposition temperature before switching to the deposition parameters and introducing the carbon carrier gas into the chamber. During the whole process of increasing the pressure the MW power coupling into the plasma is adjusted to the changing conditions. After reaching the desired deposition pressure the carbon carrier gas was introduced therewith starting the deposition process.

The nanocrystalline films shown here were deposited at a pressure of 200 mbar from an Ar/H2/CH4 plasma. To investigate the influence of the hydrogen admixture on the properties of the deposited films, the percentage of hydrogen in the process gas was varied between 2 % and 8 % as shown in Table 1.


The MW-power was kept constant at 1 kW and the films were deposited for 5 h.

Table 1. CVD Deposition Parameters

### **6. Morphology of the films**

The deposition parameters were systematically varied to investigate the influence on film structure and film properties with special attention to the speed of sound and the roughness of the films as most important properties for the application as SAW filters. Because of that

Ultrananocrystalline Diamond as Material for Surface Acoustic Wave Devices 553

diffraction limit. The AFM consists of a cantilever with a sharp tip with a radius of curvature in the order of nanometers at its end that is used to scan the sample surface. When the tip is brought close to the surface, atomic forces between the tip and the sample lead to a deflection of the cantilever. The deflection of the cantilever is then measured by a laser that is reflected from the cantilever onto an array of photodiodes. In comparison to the scanning electron microscope (SEM) that is measuring a two- dimensional image of a sample not necessarily corresponding to the morphological features, the AFM provides a true threedimensional topographical image of the surface giving information about the roughness of the investigated surface. While specimens measured in SEM needs to be conducting and are therefore often coated with a thin metal film (e.g. gold) irreversibly alter the film properties, AFM measurements do not require such special treatments. While the SEM can easily measure an area in the order of square millimeters with a depth of field on the order of millimeters the AFM is usually restricted to a maximum scanning area of around 150 μm2 with a depth of field in the order of micrometers. Another characteristic that has to be considered for high resolution AFM is the fact that the quality of an image is limited by the

radius of curvature of the probe tip and can lead to image artifacts. (Sarid, 1991)

 Fig. 3. AFM measurements of UNCD samples deposited with 2,5 % H2 (left) and 6 % H2

Fig. 2 shows UNCD films deposited with different admixtures of hydrogen to the process gas. It is clearly seen that the hydrogen is influencing the morphology of the deposited films. In fact the crystals are larger and the surface is rougher at hydrogen admixtures of 7%

Fig. 3 shows an AFM measurement of 5 μm thick UNCD films on a Si substrates. The measured area on the sample was 25 μm2. The RMS-roughness (root-mean-squared roughness) of the surface is measured to be Rq= 21.1 nm for the sample deposited at 2.5 %

SEM as well as AFM measurements show that higher hydrogen admixture in the process

The RMS-roughness measurements as a function of the hydrogen admixture are shown in

H2 (left picture) and Rq= 51.3 nm for the sample deposited at 6 % H2 (right picture).

(right). Both images cover a 5 x 5 µm area

Fig. 4.

compared to the films deposited at lower admixtures.

gas lead to larger diamond crystals and rougher surfaces.

the main focus was on deposition parameters that influence the diamond grain size and matrix. It is expected that both are directly influencing the elastic modulus of the films and thus the speed of sound. One important parameter that is influencing the crystal size is the admixture of hydrogen in the process gas. The higher the hydrogen fraction the bigger the crystals grow. (Woehrl & Buck, 2007)

In previous publications it was suggested that different species for the nucleation on the one hand and the growth of diamond grains on the other hand exist. The ratios of these species determine the macroscopic structure of the growing films by influencing the rate of secondary nucleation and therefore the matrix density and the grain size of the growing crystals. A higher amount of the nucleation species leads to smaller crystals and more material between the grains. A higher amount of growth species allows the grains to grow faster (thus a higher growth rate) suppressing the secondary nucleation. In the literature, C2 was suggested to be the nucleation species (Gruen, 1999) as strong emission of the C2 dimer could be found in the plasmas used for the deposition of fine-grained UNCD films. On the other hand the CH3 radical is generally believed to be the growth species of diamond films (May & Mankelevich, 2008). Without taking part in the discussion concerning specific details of growth and nucleation species, previously published data can be interpreted in a way that these two competitive processes determine the structure of the deposited films.

The atomic force microscope (AFM) is a scanning probe type microscope that offers a resolution of less than a nanometer that is by a factor of 1000 better than the optical

the main focus was on deposition parameters that influence the diamond grain size and matrix. It is expected that both are directly influencing the elastic modulus of the films and thus the speed of sound. One important parameter that is influencing the crystal size is the admixture of hydrogen in the process gas. The higher the hydrogen fraction the bigger the

In previous publications it was suggested that different species for the nucleation on the one hand and the growth of diamond grains on the other hand exist. The ratios of these species determine the macroscopic structure of the growing films by influencing the rate of secondary nucleation and therefore the matrix density and the grain size of the growing crystals. A higher amount of the nucleation species leads to smaller crystals and more material between the grains. A higher amount of growth species allows the grains to grow faster (thus a higher growth rate) suppressing the secondary nucleation. In the literature, C2 was suggested to be the nucleation species (Gruen, 1999) as strong emission of the C2 dimer could be found in the plasmas used for the deposition of fine-grained UNCD films. On the other hand the CH3 radical is generally believed to be the growth species of diamond films (May & Mankelevich, 2008). Without taking part in the discussion concerning specific details of growth and nucleation species, previously published data can be interpreted in a way that these two competitive processes determine the structure of the deposited films.

Fig. 2. Morphology of UNCD films deposited with different hydrogen admixtures. The scale

The atomic force microscope (AFM) is a scanning probe type microscope that offers a resolution of less than a nanometer that is by a factor of 1000 better than the optical

bars in all three pictures correspond to 2 µm

crystals grow. (Woehrl & Buck, 2007)

diffraction limit. The AFM consists of a cantilever with a sharp tip with a radius of curvature in the order of nanometers at its end that is used to scan the sample surface. When the tip is brought close to the surface, atomic forces between the tip and the sample lead to a deflection of the cantilever. The deflection of the cantilever is then measured by a laser that is reflected from the cantilever onto an array of photodiodes. In comparison to the scanning electron microscope (SEM) that is measuring a two- dimensional image of a sample not necessarily corresponding to the morphological features, the AFM provides a true threedimensional topographical image of the surface giving information about the roughness of the investigated surface. While specimens measured in SEM needs to be conducting and are therefore often coated with a thin metal film (e.g. gold) irreversibly alter the film properties, AFM measurements do not require such special treatments. While the SEM can easily measure an area in the order of square millimeters with a depth of field on the order of millimeters the AFM is usually restricted to a maximum scanning area of around 150 μm2 with a depth of field in the order of micrometers. Another characteristic that has to be considered for high resolution AFM is the fact that the quality of an image is limited by the radius of curvature of the probe tip and can lead to image artifacts. (Sarid, 1991)

Fig. 3. AFM measurements of UNCD samples deposited with 2,5 % H2 (left) and 6 % H2 (right). Both images cover a 5 x 5 µm area

Fig. 2 shows UNCD films deposited with different admixtures of hydrogen to the process gas. It is clearly seen that the hydrogen is influencing the morphology of the deposited films. In fact the crystals are larger and the surface is rougher at hydrogen admixtures of 7% compared to the films deposited at lower admixtures.

Fig. 3 shows an AFM measurement of 5 μm thick UNCD films on a Si substrates. The measured area on the sample was 25 μm2. The RMS-roughness (root-mean-squared roughness) of the surface is measured to be Rq= 21.1 nm for the sample deposited at 2.5 % H2 (left picture) and Rq= 51.3 nm for the sample deposited at 6 % H2 (right picture).

SEM as well as AFM measurements show that higher hydrogen admixture in the process gas lead to larger diamond crystals and rougher surfaces.

The RMS-roughness measurements as a function of the hydrogen admixture are shown in Fig. 4.

Ultrananocrystalline Diamond as Material for Surface Acoustic Wave Devices 555

High-resolution SEM pictures were taken to investigate the influence of hydrogen and nitrogen admixture on the morphology of the films. Fig. 5 shows a film deposited with 2.5 % hydrogen and 2.5 % nitrogen in the plasma. The diamond grains appear to be very fine. Increasing the nitrogen admixture to 7.5 % and keeping the hydrogen admixture at 2.5 % changes the shape of the diamond grains. They appear to be needle-shaped as shown in Fig. 6. These measurements show that the nitrogen admixture can influence the shape of the

Fig. 6. High resolution SEM measurement of a UNCD film deposited with 2.5 % hydrogen

It is expected that the change in the crystal shape will have a strong influence on the propagation speed of sound in the material giving yet another degree of freedom when

The low surface roughness of UNCD films on the one hand and the high speed of sound in single crystalline diamond on the other hand are making UNCD a very promising material for SAW application. Yet the decisive question is whether the abundance of grain boundaries in the films or the amorphous matrix surrounding the grains will change this picture by e. g. damping the excellent propagation characteristics of surface acoustics waves. The laser-induced SAW pulse method is capable of measuring the SAW-related (i.e. mechanical and structural) properties of thin films (Weihnacht et. al, 1997) (Schenk et. al., 2001) and was used in this work. The applicability of this method for investigating the film properties of polycrystalline diamond films was demonstrated in previous publications (Lehmann et. al., 2001). This method allows measuring all necessary material constants and the wave excitation and propagation parameters decisive for the performance of the SAW material. The biggest advantage of this method is, that it is not necessary to prepare a piezoelectric layer or patterning an interdigital transducer (IDT) structure on the surface, and that rather thin films can also be measured without being disturbed by effects from the Si substrate. The method is a fast and accurate way to measure acoustic wave propagation

and 7.5 % nitrogen admixture. The scale bar shown corresponds to 200 nm

designing the material for specific applications.

**8. SAW pulse technique** 

diamond grains.

Fig. 4. RMS-roughness measurements as a function of hydrogen admixture in process gas
