Review

1 DOI: 10.1002/prep.201800045
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Engineering of Al/CuO Reactive Multilayer Thin Films for
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Tunable Initiation and Actuation
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Carole Rossi*[a]
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11 Abstract: Sputter-deposited Al/CuO multilayers represent comprehensive review of the materials structural character-
12 the state-of-the-art of energetic nanomaterials for tunable istics. Next, experimental and theoretical works performed
13 ignition and actuation because their theoretical energy on these reactive multilayered materials to date is pre-
14 densities are significantly higher than most conventional sented in terms of methods used, the results acquired on
15 secondary explosives while being less sensitive to un- ignition and combustion properties, and conclusions
16 desired initiation. Both the sensitivity and combustion drawn. Emphasis is placed on several studies elucidating
17 properties (temperature, combustion velocity and products the fundamental processes that underlie propagating com-
18 of reaction) can be manipulated via the layering, reactant bustion reactions. This paper provides a good support for
19 spacing and stoichiometry of the multilayer and, to a lesser engineers to safely propose Al/CuO multilayers structure to
20 extent, via interface engineering. In this article, we first de- regulate the energy release rates and ignition threshold in
21 scribe the technology of deposition of Al/CuO multilayers order to manufacture high performance and tunable ini-
22 focusing on direct current sputter deposition followed by a tiator devices.
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Keywords: Al/CuO · pyroMEMS · multilayer · nanothermite · microinitiator · combustion
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27 1 Introduction niques (e-beam evaporation of magnetron sputtering), as
28 they provide well-defined heterostructures with excellent
29 A reactive multilayer thin film is composed of alternating control over layering, reactant spacing and composition (re-
30 thin layers (tens to hundreds nm thick) of reactants chosen actant ratio). An excellent review paper [17] compre-
31 for their propensity to react together and generate a high hensively discusses the progress of the research in reactive
32 amount of heat after being ignited by an external source of multilayers after two decades of research.
33 energy. Initially for welding, soldering and brazing applica- Among thermite reactive multilayers, the overwhelming
34 tions [1–4] a variety of binary reactive multilayers have been majority of works concerns Al/CuO systems, as they feature
35 investigated (Al/Ni [5, 6], Al/Pt [7], Nb/Si [8]), involving the an exceptionally high energy release with gaseous pro-
36 formation of a product composed of the two reactants. duction (See Table 1). Different uniformly layered Al/CuO
37 Rapidly, thermite multilayers [9–13], composed of alterning thermites have been processed and investigated to probe
38 metal and metal-oxide reactants, have emerged as interest- the role of the oxide nature (oxidation degree), interface
39 ing fully dense energetic thin film. They are capable to layers, and final oxides on initiation and reaction prop-
40 promptly release high amount of heat with emission of agation, as well as the effect of reactant spacing (bilayer
41 light, thus opening opportunities for tunable on-chip igni- thickness) and the sample thickness (number of bilayers).
42 tion [14, 15] and actuation [16]. Themite multilayers feature This paper presents the results obtained on Al/CuO
43 self-sustained propagating reaction after being ignited lo- sputter-deposited multilayers in my research team. Al-
44 cally by an external source of heat. These materials are non- though some of the presented results have been already
45 detonative as they exhibit combustion reactions in which published, it provides some original unpublished material. I
46 the chemical reaction wave moves through the multilayers first describe the technology of deposition focusing on DC
47 at subsonic rates. As the exothermic chemical reactions are sputter deposition followed by a comprehensive review of
48 controlled by the outward migration of oxygen atoms from the materials structural and chemical characteristics (sec-
49 the metal oxide matrix towards the aluminum layers tions 2 and 3). Next, section 4 describes the conditions re-
50 through the final oxide layer, the chemical reaction rate quired for initiating a high-temperature reaction in Al/CuO
51 strongly depends on the reactant spacing and final oxide
52 nature (Al2O3 in the case of Al based thermite) affecting the
[a] C. Rossi
53 oxygen diffusivity. LAAS-CNRS
54 Detailed investigations, both theoretical and ex- University of Toulouse
55 perimental, of thermite multilayer ignition and reaction 7 avenue du colonel Roche, 31031 Toulouse, France
56 propagation have benefited from vacuum deposition tech- *e-mail: rossi@laas.fr

Propellants Explos. Pyrotech. 2018, 43, 1–16 © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1
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 Review C. Rossi

1 Table 1. Theoretical Al/CuO thermite characteristics: heat of reaction, adiabatic temperature, mass of produced gas and oxygen diffusivity of
2 the final oxide.
3
Reactants Adiabatic State of Gas Heat of Oxygen diffusivity
4 temperature reaction production reaction in Al2O3
5 (K) products (g of gas/g) (J/g) (cm2/s)
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7 2Al + 3CuO 2843 Liquid & gas 0.3431 3900 2.33 3 1028
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10 multilayers by uniform heating and local hot point stim- were found to be the key parameters for the formation of
11 ulation. This section underlines the role of the substrate CuO polycrystalline films. To produce Al/CuO multilayers,
12 that has to be taken into consideration by engineers to tai- thin layers of Al and CuO are deposited on top of each oth-
13 lor the multilayer structure to the application requirements. er in an alternating fashion. In this way, the successive dep-
14 Section 5 focusses on the dynamic of self-propagating com- osition of CuO and Al is performed without venting the
15 bustion. This point has been the focus of many ex- chamber. To avoid reaction between Al and CuO, the dis-
16 perimentations and a recent analytical theoretical tool dem- charge plasma is confined to a small volume below each
17 onstrates how the reaction rate varies with the multilayer target and the substrate is placed outside of the plasma
18 design and substrate material. Finally, section 6 proposes such that the growing multilayer avoids bombardment by
19 engineering methods to regulate the energy release, re- high-energy particles such as electrons and negative ions.
20 action rate and onset reaction temperature before over- Often, the substrate is water-cooled to minimize mixing and
21 viewing the major applications, such as high performance reacting of the layers during deposition. Figure 1 illustrates
22 initiator microdevices, or fast microactuators. the process.
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25 2 Manufacturing Al/CuO Thermite Multilayers
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27 Fully dense thermite multilayers can be produced either by
28 mechanical powder processing [18, 19] or by vacuum depo-
29 sition [13, 20] including sputtering and e-beam evaporation.
30 The first method, mechanical powder processing, permits
31 the creation of thick foil (> 100 mm) multilayers. It starts
32 from micron-sized powders, which are manually mixed ac-
33 cording to the desired Al to CuO equivalence ratio. Powders Figure 1. Schematics of Al/CuO multilayered thin film sputtering
34 are later pressed into a tube for swaging. After swaging, the deposition sequences.
35 resulting cylinder was cut and cold rolled several times to
36 reduce the thickness to the desired thickness (~ several
37 100 mm). The multilayer specimens considered in this paper are
38 For thinner foils (below 10 mm in total thickness), vac- grown following the sputtering conditions as published in
39 uum deposition techniques are preferred, as they provide [21] (Table 2). The sputtering chamber contains two targets:
40 excellent control over the layering and average stoi- one is pure Al, the other is pure Cu, and both have a diame-
41 chiometries. Cupric oxide thin films can be synthesized by ter of 10 cm. Al is sputter-deposited under Ar plasma. Dur-
42 using the direct current (DC) or Radio Frequency (RF) re- ing the deposition, the Ar partial pressure is maintained at
43 active magnetron sputtering technique in an oxygen en- 0.13 Pa. CuO is deposited by DC sputtering in an enriched
44 riched environment. Ratios of argon and oxygen gas in the O2 atmosphere. The procedure is to pump down to a base
45 plasma and the substrate temperature during deposition pressure of less than 1.33 3 105 Pa before admitting the
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48 C. Rossi received her M.S and Engineer degree from the National Institute of Applied Sciences in Toulouse (France) in
49 1994, in material science. She received her PhD degree in electrical engineering and physics in 1997 from the same
Institute. After one post-doctoral fellowship at Berkeley Sensors and Actuators Center, she joined the French National
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Center for Scientific Research (CNRS) in 1998 as researcher. Her primary research interest is in the design, fabrication,
51 modeling, and testing of pyrotechnical microsystems (PyroMEMS). In 2005, she enriched her research with the nano-
52 engineering of energetic materials. She is the author of multiple scientific publications and technical patents. She lead
53 a research department from 2010 to 2016 and is currently leading a research team in nanoenergetic materials and
54 pyroMEMS.
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 Engineering of Al/CuO Reactive Multilayer Thin Films for Tunable Initiation and Actuation

1 Table 2. Conditions of Al and CuO layer deposition using DC re- chiometric situation. 1 : 1 Al/CuO bilayer (& = 1) is a stoichio-
2 active magnetron sputtering. metric stack. The thickness ratio provides sufficient moles of
3 O in CuO to fully oxidize all the initial Al layer into Al2O3.
Deposition parameters Al CuO
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5 Target Al Cu
6 Mode DC DC 3 As-deposited Multilayers Properties
7 Argon flow rate (sccm) 60 100
Total pressure (Pa) 0.5 0.5
8 3.1 Nature and Structure of Sputtered Cupric Oxide (CuO)
Target power (W) 800 400
9 Power density (W/cm2) 5 10
10 The distance target-substrate (cm) .5 8.5 As the reaction onset in Al/CuO multilayers materials are
11 Deposition rate (nm/min) ~ 50 ~ 45 mostly controlled by the outward migration of oxygen
12 atoms from the oxide matrix towards the aluminum layers
13 through the interfacial layers, the precise characterization of
14 oxygen alone at such a rate that the desired partial pressure CuO and interfacial layers are the first step to further char-
15 is reached. Next, the Ar is admitted at such rate to build up acterize the ignition and reaction process upon heating.
16 a total pressure to 0.5 Pa. During deposition, the oxygen High magnification TEM micrographs (Figure 4) and
17 partial pressure is maintained at 0.5 Pa. Atomic Force Microscopy (AFM) maps (Figure 3) obtained
18 Note that the chamber is fully pumped out after each after CuO deposition on an oxidized Silicon wafer show the
19 cycle (Al or CuO deposition) to prevent cross contamination columnar growth by the pillar-like structure [22]. Grain sizes
20 and aluminum oxidation by residual oxygen during the 30 in the CuO film grown under sputtering parameters are re-
21 minutes Al deposition. Figure 2 gives Transmission Electron ported in Table 2 and vary between 10 and 20 nm. Films
22 Microscopy (TEM) images of Al/CuO multilayers with three were found to be preferentially oriented in (111) direction
23 different bilayer thicknesses produced using this method. (See X-Ray Diffractometry spectra in Figure 3). The RMS sur-
24 face roughness is found to be 5.2  0.2 nm in a 1 mm 3 1 mm
25 scanning area. This roughness is substantially larger than
26 that of the initial SiO2 surface (RMS ~ 0.3 nm) [22].
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37 Figure 3. AFM maps of 200 nm thick CuO after sputter deposition
38 (substrate is oxidized silicon) and X-ray diffraction scan [22].
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41 There is no evidence for copper (I) oxide (cuprous oxide,
42 Cu2O), which is usually seen at 36.58 and 42.48. Altogether,
43 the above measurements indicate that the CuO films are of
44 Figure 2. Transmission electron micrographs of the cross section of quality similar to films previously reported in the literature,
45 multilayers obtained by reactive DC magnetron sputtering with the mostly developed for solar cell application [23, 24]. The den-
46 parameters reported in Table 1. (a) Seven 400 nm thick 2 : 1 bilayers, sity of the as-deposited 200 nm CuO is estimated by X-ray
(b) six bilayers 300 nm thick 1 : 1 Al/CuO, (c) three layers: Al and CuO
47
are 500 and 1000 nm thick respectively.
reflectrometry at 5.6  0.2 g/cm3, i. e., 90 % of bulk CuO.
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50 3.2 Nature of the Spontaneously Formed Interfacial Layer
51 For the rest of the paper, three main parameters are
52 used to characterize the multilayer: the number of Al/CuO We can distinguish the two distinct interfaces on the TEM
53 bilayers (n), the bilayer thickness (w) and the Al to CuO ratio images of Figure 4 (a) showing that they are different in na-
54 (1:&). In a 1 : 1 Al/CuO bilayer (& = 1), the aluminum thickness ture and thickness. The bottom interface, BIAl/CuO (Figure 4
55 is half the CuO thickness whereas in &:1 Al/CuO, the Al thick- (b) formed upon the deposition of CuO onto Al (Albottom) is a
j
56 ness is 2 of the CuO thickness, corresponding to a non-stoi- flat alumina layer (4.1  0.3 nm in thickness), whereas the

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 Review C. Rossi

1 The asymmetry of the bottom Al/CuO and top CuO/Al

2 interfaces observed in the TEM images is confirmed in the
3 energy dispersive X-ray (EDX) analyses, giving the chemical
4 profile across both interfaces (Figure 6).
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Figure 4. Transmission electron micrograph of the cross section of
14 the Al/CuO/Al trilayer after sputter deposition (a), with a zoom
15 around the BIAl/CuO interface (b). The (c) image is a high angle an-
16 nular dark field image corresponding to the rough TICuO/Al interface. Figure 6. Energy dispersive X-ray spectroscopy composition meas-
17 ured across interfaces: (a) BIAl/CuO formed upon the deposition of
18 CuO onto Al, (b) TICuO/Al created upon the deposition of Al onto
19 top interface (TICuO/Al) interface created upon the deposition CuO.
20 of Al (Altop) onto CuO is overall ill-defined (see dark-field im-
21 age in Figure 4 (c)) over a thickness of 15  5 nm.
22 The top interface composition was analyzed using elec- In BIAl/CuO, we detect both the O (25 %) and Al (75 %) sig-
23 tron energy-loss spectroscopy (EELS) : it is scanned starting nal over ~ 6 nm: this confirms the formation of an amor-
24 in the CuO layer, moving through the interface into the Al phous Al2O3 when O2 plasma is generated inside the cham-
25 layer. The background subtracted EELS spectra of the O K- ber just before starting the Cu sputtering; in other words,
26 edge, Al K-edge and Cu L-edge acquired every 1 nm the virgin Al surface is briefly bombarded with O atoms or
27 through the top interfacial layer (TICuO/Al) are given in Fig- O2 prior the CuO sputtering, which permits to grow a thin
28 ure 5. We detect CuOx, CuxAlyOz and AlOx signal over 15  alumina layer [20]. In TICuO/Al, we detect Al (13 %), Cu (43 %)
29 5 nm thick, which clearly indicates atomic intermixing dur- and O (42 %) signal over 15  5 nm thick, which clearly in-
30 ing material deposition [25]. dicates atomic intermixing. EDX profile confirms that this
31 Previsous detailed theoretical investigation in [26] sug- top interface is much thicker and less abrupt than the bot-
32 gested that CuO is partially reduced in the vicinity of the tom one. Figure 6 also reveals a slight oxygen intensity
33 interface and a pre-mixed layer with a thickness of several along the aluminum bottom layer, but in the EELS spectra,
34 nm exists between the Al and CuO layers. no presence of alumina was observed along the layer and
35 no aluminum is detected in the CuO [25]. Further analysis
36 (not reported in this paper) of the oxygen elemental dis-
37 tribution image by EELS indicated that the oxygen apparent
38 in the Al layer is primarily a result of surface oxidation after
39 TEM lamella preparation. Thus, the concentration of oxygen
40 incorporated in the sputtered deposited Al layers is either
41 below the limit of detection of the analysis or simply not
42 present.
43 To conclude on this section, the large interfacial thick-
44 ness compared to native Al oxidation seen in sputtered Al/
45 CuO multilayers may be attributed to the influence of two
46 factors : i) in the case of BIAl/CuO, the energetic oxygen ions
47 from the reactive plasma which bombard the virgin alumi-
48 num surface may have the thermal energy required to dif-
49 fuse deeper. ii) In the case of TICuO/Al, the aluminum oxide
50 Figure 5. Spatial resolved EELS spectra of OK edge at 530 eV, CuL layer may grow due to its proximity to CuOx [27]. This effect
edge at 935 eV and AlK edge at 1560 eV across the TICuO/Al inter-
51 was observed in powder mixtures of Al and Cu2O. P.S Wang
face. Patterns are plotted every 2 nm. The blue, red and black pat-
52 terns correspond to the region on the aluminum, interface and CuO et al. [28] found that the thickness of the oxide layer on Al
53 layer respectively. The acquisition time is chosen as 2 s for each powders increased when they were compacted with Cu2O
54 spectrum in order to obtain a high signal-to-noise ratio. One acquis- powder.
55 ition is taken each 1 nm, and a small electron probe was scanned
56 across a large area (100 3 100 nm2).

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 Engineering of Al/CuO Reactive Multilayer Thin Films for Tunable Initiation and Actuation

1 4 Ignition thin film is hot-wire by a local metallic thin film resistance.

2 Our team has developped a simple hot-wire initiator con-
3 Applying an external source of energy (ignition power 3 ig- sisting of a Ti thin film resistance on a Pyrex substrate or
4 nition time), locally on the multilayer results in an increase Kapton film from the DuPont Corporation. The fabrication
5 of the temperature in the multilayer section directly in con- process summarized in Figure 7, as well as the ignition ex-
6 tact with the heated surface. This can be done by electro- perimental set up and procedures were already published
7 static discharge [29–31], mechanical impact [32], laser irradi- in [38].
8 ation [7, 33], electrical heating (spark) [34, 35] and, thermal
9 hot points [36]. A good understanding of the point of igni-
10 tion, depending on the ignition technique, multilayer stoi-
11 chiometry (affecting its chemistry) and dimensional fea-
12 tures, is critical for applications. Indeed, the determination
13 of ignition threshold values for each multilayer system and
14 environment is of importance to ensure a safe use of these
15 materials. Understanding the ignition threshold values vs
16 multilayers characteristics and stoichiometry also permits
17 tailoring the reactive material ignition sensitivity to the ap-
18 plication requirements. In the following sections, the results
19 obtained on Al/CuO multilayers thermal ignition are re-
20 viewed giving data on how the ignition sensitivity is af-
21 fected by the Al/CuO bilayer thicknesses and substrate type
22 (on which the multilayer is deposited). Later, in section 6,
23 the role of the interfacial layer and final oxide are also dem-
24 onstrated to influence the ignition mechanisms and re-
25 action onset. Figure 7. Schematics of the hot-wire ignition MEMS devices proc-
26 ess; (a) on Pyrex substrate and, (b) on Kapton substrate.
27
28 4.1 Threshold Under Uniform Heating
29 Experimentally, the ignition time corresponds to the de-
30 First, we utilize a hot-plate to instantaneously and uniformly lay between the time of application of the electrical power
31 heat the multilayers of different bilayer thickness (w). This and the emission of the light captured by a photodiode.
32 method already used in [37] involves placing the multilayer For any heating surface areas, the ignition time rapidly
33 specimen in contact with the hot surface and observing the decreases when the ignition power density increases until
34 reaction (spark emission or not). Samples that fail to ignite an asymptotic value, defining the minimum ignition response
35 when heated do not emit a burst of light. Ignition threshold time, which is a characteristic of the multilayered material
36 temperatures are determined by incrementing the hot plate itself. In [38], authors investigated both experimentally and
37 surface temperature (in 5 8C) between experiments. Note theoretically, the main parameters influencing the minimun
38 that, for each test, the hot-plate is held at a constant tem- ignition response time such as the heating surface area, the
39 perature and fresh multilayer specimens are dropped onto multilayers characteristics (bilayer thickness, film thickness
40 its surface. Reproducible threshold temperatures have been and stoichiometry). For a given electrical power, they
41 obtained. The ignition temperature are between 475 8C and showed that the minimum ignition response time is highly
42 525 8C. Bilayer thicknesses smaller than 100 nm have the affected by the substrate thermal conductivity, the heating
43 lowest ignition temperature and thick bilayers (w = 400 nm) surface area, defined through the resistance design, and
44 have the highest (525 8C). It is interesting to see that the nanothermite film layering.
45 nanoscale Al/CuO multilayers ignite at temperatures below As an illustration, Figure 8 provides the ignition time vs
46 the melting point of Al. This confirms that ignition can oc- the ignition power for a thin reactive film made of five
47 cur by solid-state diffusion. The importance of the large in- 300 nm thick 1 : 1 Al/CuO bilayers, deposited on a thin Ti fil-
48 terfacial area (thin bilayer thickness) and intimate contact ament evaporated on either a Kapton membrane or directly
49 between layers is confirmed in combustion test described onto the Pyrex substrate. The simulation results (solid line)
50 in section 5. are detailed in [38]. Below a certain electrical power, no ig-
51 nition occurs, regardless the duration of application of the
52 power. This is simply explained by the fact that, below this
53 4.2 Threshold Under Local Point Ignition ignition power threshold, the electrical energy supplied to
54 the microheater is not sufficient to compensate for the en-
55 When integrated on a device/substrate, the widest and sim- ergy lost by conduction through the substrate, by radiation
56 plest ignition method for igniting an Al/CuO multilayered

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 Review C. Rossi

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10 Figure 8. Ignition times as a function of the ignition power density
11 and comparison with simulations (details in [38]).Curves and points
correspond to five 300 nm thick 1 : 1 Al/CuO bilayers deposited on a
12
thin Ti filament evaporated on Kapton (left) and Pyrex (right).
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Figure 9. The minimum ignition power density as a function of film
16 from the exposed surface, and by convection in the air. The thickness (number of bilayers, n). The multilayers are composed of n
17 multilayer cannot reach its ignition temperature. 300 nm thick 1 : 1 Al/CuO bilayers and are deposited on Kapton. Tak-
18 This threshold highly depends on the heating surface en from [39].
19 area. Considering five 300 nm thick 1 : 1 Al/CuO bilayers de-
20 posited on Kapton, the ignition power threshold is 575 and
21 215 mW for a heating surface area of 1 and 0.8 mm2, re- that varying the number of bilayers in the film does not
22 spectively. The same thermite film (five 300 nm thick 1 : 1 Al/ modify the ignition time and thereby the design of the
23 CuO bilayers) deposited on Pyrex has an ignition power heater or the choice of the substrate type (Figure 9).
24 threshold of 1424 and 579 mW for heating surface area of 1 As summary, in addition to the stoichiometry and layers’
25 and 0.8 mm2, respectively. Results are summarized in Ta- thickness [38], both the hot point surface area and sub-
26 ble 3. strate thermal conductivity, have a great impact on the igni-
27 tion threshold. They have to be carefully chosen to fullfil
28 the application requirements.
Table 3. Values of ignition power threshold and minimum ignition
29
time for multilayers made of five 300 nm thick 1 : 1 Al/CuO bilayers
30 deposited on Pyrex or Kapton substrates and heated through 2 dif-
31 ferent surface areas (1 and 0.8 mm2). 5 Exothermic and Self-Sustained Combustion
32
33 Substrate type Pyrex Kapton Pyrex Kapton 5.1 Effect of Multilayer Strcuture on Combustion Velocity
34 Heating surface area (mm )2
0.8 1
35 Ignition power threshold 579 215 1424 575 We have to distinguish between the slow heating rate com-
36 (mW) bustion often characterized by calorimetric measurements
37 Minimum Ignition time (ms) 140  3 75  2 967  30 241  10 [35] and sustained combustion reactions. The latter is char-
38 acterized by a high-temperature front that propagates rap-
39 idly through the multilayers. As it is highly luminescent, the
40 Additionally, the results summarized in Figure 9 illustrate combustion front’s velocity is commonly characterized with
41 that the substrate type, on which the multilayer is de- a standard high speed camera under ambient pressure. For
42 posited, considerably affects the ignition time and therefore this particular paper, a 6 cm long by 1.6 mm width line of
43 the self-sustained combustion capability. When the sub- Al/CuO multilayers is deposited on low conductive sub-
44 strate thermal conductivity (ls Þ increases by three orders of strate, such as polyethyleneterephtalate or Kapton. Three
45 magnitude (from 0.1 to 100 W m1 8C1), the ignition power electrical resistances are also patterned underneath the
46 threshold increases by two orders of magnitude. We also nanothermite line according to the design shown in the
47 demonstrated that the ignition of five 300 nm thick 1 : 1 Al/ Figure 10. One resistance at the beginning of the line is the
48 CuO bilayers was successful on Kapton (ls = 0.1 W m1 8C1) heater to bring the multilayer to its ignition point, and two
49 and glass (ls = 1.4 W m1 8C1) but failed on a silicon sub- others at the end of the line and separated by 0.8 cm serve
50 strate (ls = 140 W m1 8C1). to capture the combustion front travel. A current of 40 mA
51 Ignition and subsequent sustained combustion cannot is supplied to the second and third resistance and voltage
52 be obtained when the thin reactive multilayers are de- through a dummy 1 kW resistance is recorded on the oscil-
53 posited on highly conductive substrates, i. e., with ls loscope to detect the combustion front passage. The prop-
54 > 10 W m1 8C1. This finding means that silicon, metallic or agation of the combustion front is therefore recorded using
55 ceramic substrates are prohibited as support for thin multi- both the high speed camera (a SA3 photron with max
56 layers (total thickness below 10 mm). We also demonstrated 120 000 fps) and by measuring the travel time between the

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 Engineering of Al/CuO Reactive Multilayer Thin Films for Tunable Initiation and Actuation

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8 Figure 10. Schematic and photo of the combustion front velocity
9 measurement set up used at LAAS.
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12 two last resistances far from the ignition point to prevent to Figure 12. Sustained combustion velocity in air of free-standing
multilayers as a function of bilayer thickness (total thickness t =
13 capture the ignition temperature effect.
2 mm).
14 To study the influence of the bilayer thickness and stoi-
15 chiometry (&) on the self-propagation combustion velocity,
16 several samples of 1 : 1 and 1 : 2 multilayers having different
17 bilayer thickness were deposited on Kapton substrate. Fig- reaction stops suddenly for extremely small bilayer thick-
18 ure 11, plotting their combustion velocity, shows that the nesses (clearly seen on Figure 12), which is due to the pres-
19 sustained combustion velocity decreases when bilayer ence of interfacial layers, as described in section 2 which re-
20 thickness increases. The combustion velocity is faster for duces the amount of stored energy i. e., reaction enthalpy,
21 fuel rich specimen (& = 2). The maximum velocity (10 ms1) DH, according to the relationship [17]:
22 is obtained for bilayers made of Al/CuO bilayers being each
23 100 nm in thickness. d
DH ¼ DHth ð1  Þ ð1Þ
24 0:5w
25
26
DHth is the theoretical enthalpy
27 d is the mean interfacial layer thickness and w is the bi-
28 layer thickness.
29 Additionally, the stoichiometry of multilayers influences
30 both the reaction enthalpyðDHÞ, and the film thermal prop-
31 erties highly impact the combustion velocity (See Table 4).
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33
Table 4. Al/CuO theoretical enthalpy and thermal conductivity of
34
multilayers as a function of their stoichiometry (&).
35
36 & DHth (J/g) Thermal conductivity (Wm1 K1)
37 Figure 11. Sustained combustion velocity in air of different multi-
layers as a function of bilayer thickness (kept constant the number 1 3900 74.2
38
of bilayers). 2 3400 115.6
39
4 2700 153.7
40
41
42 As comparison, the combustion velocities of free-
43 standing 1 : 1 multilayers with different bilayer thicknesses
44 are plotted on Figure 12. In that case, the maximum veloc- 5.2 Sustained Combustion Model
45 ity reaches 80 ms1 for a bilayer thickness equal to 150 nm
46 and drops down 1.5 ms1 for the thickest bilayer (w = 2 mm). Most of combustion models of reactive multilayers gen-
47 Note that combustion velocities of multilayers deposited on erally consider the Al/Ni binary system and rely on a phe-
48 a substrate, even if it is low conductive as Kapton, are 40 nomenological description of the intermixing process cou-
49 times slower than free-standing ones. pled with thermal conduction [40–44]. Thus, the layered
50 The results plotted in Figure 11 and 12 demonstrate sev- structure is often modeled as a concentration profile, and
51 eral key trends discussed previously by [10, 39]. The sus- the reactive heat equation is solved. The evolution of the
52 tained combustion velocity increases for thinner bilayers. film composition (concentration) is described in terms of a
53 Heat release rates are increased with large interfacial area as mass transport process, governed by a temperature-de-
54 reactant atoms are required to diffuse shorter distances to pendent (Arrhenius law) diffusion coefficient. The pre-ex-
55 mix when the bilayer thickness is reduced. Thus, the chem- ponent and activation energy parameters of the Arrhenius
56 ical energy reservoir is released more rapidly. However, the law are, as usual, fitted to experimental measurements of

Propellants Explos. Pyrotech. 2018, 43, 1–16 © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.pep.wiley-vch.de 7
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 Review C. Rossi

1 self-propagating reaction front. This modelling scheme has dHð x; t Þ d2 T ð x; t Þ   DH P s T 4 ð x; t Þ  T 4a
2 been applied to Al/CuO multilayers [39, 45, 46]. In [39], the ¼ lt þ þ 
dt dx 2 w wt wt
3 model considers that the Al/CuO reaction follows three
4 chemical phase transitions (see Figure 13): the CuO first de- hc ðT ð x; t Þ  T a Þ ls
5 composes into Cu2O at a low temperature, and the free oxy-   ðT ð x; t Þ  T a Þ
wt wt  ws
6 gen atoms diffuse across the Al2O3 layers to oxidize the Al
ð3Þ
7 layer close to the interface. This first step induces an in-
8 crease of the Al2O3 thickness. Then, the remaining Cu2O de- dHðx;tÞ
Where dt expresses the variation of enthalpy (in J.m3)
9 composes into Cu and O, enabling further oxidation of pure
d2 Tðx;tÞ
10 aluminum to form Al2O3. These transitions are uniquely driv- as a function of time. The term lt dx2 describes the heat
11 en and sequenced by the parameters governing oxygen dif- diffusion along the propagation direction as a function of
12 fusion (Eq. 2) in Flux (Ø) approximation: mean thermal conductivity of the multilayer, lt :The term
DH
13 w represents the heat released by the highly exothermic
P
14 aluminum oxidation (DH in J mol1). wt is the ignition power
15 density applied on the multilayer having a total thickness
16 wt .
17 The last three terms in Eq. 3 correspond to heat losses
18 by radiation, convection and conduction through the sub-
19 strate, respectively. s is the Stephan-Boltzmann constant, hc
20 the convection coefficient and ls the substrate thermal con-
21 ductivity. w, wt and ws are the bilayer, multilayer and sub-
22 strate thicknesses, respectively. Overall, the enthalpies and
23 temperatures associated with the above physico-chemical
24 processes, including the melting and boiling of various spe-
25 cies, are extracted from the literature (see Table 5).
26 In the case of thin reactive film, the 2D model illustrated
27 in Figure 13 (a) can be split into 1D mass transport along
28 the z-axis and 1D thermal transport along the x-axis, since
29 Figure 13. Schematic views of modeled Al/CuO multilayers: ignition the thermal diffusivities are one decade larger than species
is obtained by the application of a power density at one extremity
30 diffusivities. This means that the temperature stabilizes over
of the film. Then, the reaction front propagates (a) from the left to
31 the right side of the film. (b) A magnified view of the reaction zone the layer thickness while atomic species are still diffusing.
32 showing the oxygen diffusing through interfacial layers, and (c) a On the other hand, the multilayered thin film exhibits very
33 detailed view of the composition of one bilayer. Taken from [39]. high aspect ratios (> 104). The chemical species diffusion
34 along the propagation direction is neglected, justifying the
35 use of a 1D mass diffusion model along the z-axis.
36 The thermal conductivity, density, and heat capacity of
37    the layers are considered to be independent of the temper-
38 DCu2 O CCuO=Cu2 O  CCu2 O Al2 O3 ature and composition of the multilayer film. The average
;¼
39 wCu2 O thermal conductivity lt is deduced from equation (Eq. 4).
40     ð2Þ
41 DAl2 O3 CCu2 O Al2 O3  CAl2 O3 Al w Al þ w CuO w Al w CuO
¼ ¼ þ ð4Þ
42 wAl2 O3 lt lAl lCuO
43
44 Where Dj is the oxygen diffusivity in the material j, the All temperature profiles are represented beyond the re-
45 variables Ci/j, Cj/k, Ck/l, …. Are the oxygen concentration at in- action front, since the thermite film disintegrates at the re-
46 terfaces between materials i and j, j and k, k and l. wi, wj, wk, action front where the temperature reaches 1797 8C. The in-
47 wl …correspond to the thicknesses of materials i, j, k and l. stantaneous reaction front velocity profile, the blue dashed
48 In our particular case of Al/CuO multilayers, i, j, k, l stands line in Figure 14, is 3 m s1 in the steady-state regime. In the
49 for Al, CuO, Cu2O, Al2O3 unsteady zone, immediately in contact with the heated
50 zone, the pre-heating due to the thermal diffusion prior to
51 In addition, the physical phase transitions, such as melt- ignition leads to a slight increase of the reaction front ve-
52 ing and vaporization, as well as thermal losses, are im- locity (3.5 m s1).
53 plemented into the following heat equation. Modeling results plotted on Figure 15 also show that
54 the composition of the multilayer greatly influences the sus-
55 tained combustion, since the Al/CuO ratio i. e., stoi-
56 chiometry, directly impacts the reaction enthalpy and the

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 Engineering of Al/CuO Reactive Multilayer Thin Films for Tunable Initiation and Actuation

1 Table 5. Physical and thermodynamic parameters of the different species and materials present during the multilayer combustion.
2
Al CuO Cu2O Cu Al2O3
3
3
4 Density (kg m ) 2698 6313 5983 8960 3970
5 Molar mass (g mol1) 26.98 79.54 143.08 63.54 101.96
6 Molar enthalpy of formation (kJ mol1) 0 157.3 168.6 0 1675.7
7 Thermal conductivity (W m1 K1) 237 0.847 1 401 10
Heat of fusion (kJ mol1) 10.79 17.47 17.47 13 111
8
Melting point (8C) 660 1326 1232 1085 2054
9 Boiling point (8C) 2470 1997 1797 2562 2977
10 – – 1.16 3 106[47] 1.16 3 106[47] 9 3 105
Diffusion coefficients of oxygen in species i Di : prefactor (m s2)
11 (Fitted from [48])
12 E i : activation energy (kJ mol1) – – 67.3 [47] 67.3[47] 140
13 (Fitted from [48])
14
15
16 film thermal conductivity. Indeed enriching the multilayer in
17 aluminum induces an important increase of the multilayer
18 global conductivity leading to the dissipation of the thermal
19 energy.
20 The originality of this modelling approach, is that the
21 authors treat the physico-chemical mechanisms activated
22 by the temperature in Al/CuO multilayer by a diffusion-re-
23 action modeling scheme, which has been successfully used
24 for treating the thermal oxidation of silicon [49]. This brings
25 multiple advantages: i. it is easy to implement and allows
26 for efficient computational calculations. ii. The transport of
27 oxygen, treated as fluxes, does not assume a particular
28 mode of migration (e. g., capillarity through grain bounda-
29 ries, Fickian process, and electromigration), and enables a
Figure 14. Temperature profiles at selected times and the instanta-
30 neous reaction front velocity. The multilayer is composed of five simple parametrization, i. e., the determination of oxygen
31 300 nm 1 : 1 Al/CuO bilayers deposited on a Kapton substrate. Igni- diffusivity in each reactant layer. iii. The same is true for the
32 tion power is 40 W/mm2 applied on 100 mm 3 100 mm surface area Al oxidation occurring at both interfaces.
33 (at left end). Taken from [39].
34
35 6 Tailoring the Reaction Outputs
36
37 Regulating either the fraction of material that reacts, or the
38 time during which the combustion occurs, enables us to tai-
39 lor the energy (DH) and power ðDH  v) outputs re-
40 spectively. Three ways are explored in the literature to tailor
41 the thermite multilayers reaction onset and reaction rate re-
42 lease: i) changing the reactant spacing and stoichiometry to
43 affect the enthalpy of reaction, ii) interface layer engineer-
44 ing to produce a more or less porous barrier for oxygen dif-
45 fusion prior the reaction ignition, or iii) changing the re-
46 actant nature, which induces either a modification of the
47 final oxide, directly impacting the oxygen diffusion, or a
48 modification of the reaction products (suboxides), impact-
Figure 15. Combustion velocity and reaction front temperature as a
49 ing the kinetic and reaction gaseous products.
function of Al to CuO reactant ratios (stoichiometry). The multi-
50 layers are composed of five 300 nm thick j:1 Al/CuO bilayer de-
51 posited on a polymer substrate, with ls = 0.1 W m1 8C1. For each,
52 heating power density is of 40 W mm2 on 100 mm 3 100 mm surface 6.1 Reaction Steps and Calorimetric Response
53 area. Taken from [39].
54 A recent study based on TEM observations and EELS analy-
55 ses presented in [50] quantified the Al2O3 growth during the
56 reaction progression in Al/CuO multilayers. It permitted to

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 Review C. Rossi

1 unravel the several mechanisms describing the multi-steps

2 reaction and summarized in Figure 16. As the temperature
3 increases above ~ 200 8C, the copper oxide releases oxy-
4 gens, which diffuse across the interfacial layers to oxidize
5 the neighboring aluminum and form amorphous alumina
6 (Figure 16 (b)). In consequence, the amorphous alumina
7 film thickens in both interfaces (Figure 16 (c)). Because
8 amorphous alumina density is higher than that of naturally
9 grown interface (mixture of Al, O and Cu), the structure of
10 the interface is mechanically degraded at ~ 350 8C leading
11 to the accelerated redox reaction. The resulting increase in
Figure 17. DSC traces of five 2 : 1 Al/CuO multilayers with bilayer
12 amorphous alumina layer thickness provides a barrier to the thickness w = 400 nm, collected at 5, 10 and 20 8C min1.
13 oxygen diffusion that slows down Al oxidation, thus re-
14 ducing the heat release corresponding to the drop of the
15 first exotherm in the DSC (Differential Scanning Calorimetry)
16 traces (Figure 17 &). At a temperature close to 500 8C, fol- 6.2 Interfaces Engineering Impacting the Onset
17 lowing a conventional aluminum oxidation mechanism, the
18 amorphous alumina transforms into g Al2O3 (Figure 16 (d.)) As already said, with scaling Al and CuO thickness down to
19 which explains the sharp decrease in the second main exo- the nanoscale, it is logical to consider that the thickness and
20 thermic DSC peak at 550 8C (Figure 17 *). Next, Al oxida- nature of the interface play a dominant role regarding at
21 tion continues through the g Al2O3 after the aluminum least the onset reaction temperature and material sensi-
22 melts (Figure 17 ~). tivity. In [51] the authors modified the interfacial Al/CuO lay-
23 ers by alternating the deposition processes between sput-
24 tering and atomic layer deposition (ALD). Two samples were
25 prepared: one with Al deposited directly onto the CuO fol-
26 lowing the process presented in section 2, and in the other
27 interfacial 0.5 nm thick Al2O3 was deposited by atomic layer
28 deposition prior the deposition of Al. DSC traces showed
29 that the main exothermic peak occurred at similar temper-
30 atures for both materials. However, small weak exothermic
31 peaks were noticed in the DSC trace of the material pre-
32 pared without the ALD-deposited Al2O3 thin layer. For multi-
33 layers without the ALD-deposited Al2O3 interface, the exo-
34 thermic reactions were noted to begin at a lower
35 temperature of approximately 350–400 8C. The exothermic
36 reservoir is therefore consumed into weak peaks. Un-
37 fortunately, the reactions were insufficient for quantitative
38 characterization. It is noteworthy that the thickness of the
39 ALD-deposited Al2O3 layers (0.5 and 2.4 nm) does not
40 change the onset reaction temperature. It seems that it is
41 the nature of the initial few monolayers (0.5 nm) of alumina
42 on CuO that provides the barrier capacity against the inter-
43 Figure 16. Schematics of the main mechanisms describing the Al + diffusion of elements at low temperature.
44 CuO reaction in sputter-deposited multilayers under slow heating Similarly, in [52], Marin et al demonstrated that the ALD-
45 rate from ambient to 500 8C. deposition of a thin ZnO layer on the CuO prior to Al depo-
46 sition leads to a substantial increase in the efficiency of the
47 overall reaction. The multilayers with an ALD-deposited ZnO
48 Figure 17 gives DSC traces of the Al rich (& = 2) Al/CuO interface generate 98 % of their theoretical enthalpy within
49 multilayers (w = 400 nm) collected at 5, 10 and 20 8C min1. a single reaction at 900 8C, whereas conventional Al/CuO
50 We observe three distinct exothermic events. A first broad multilayers produce only 74 % of their theoretical enthalpy,
51 exothermal event was observed between 350 and 500 8C distributed over two distinct main reaction steps (at 550
52 followed by a strong exothermal peak at 500–650 8C. A last and 850 8C). Again, the exothermic reactions begin at a low-
53 exotherm at high temperature can be detected between er temperature, 350–400 8C, where weak exotherms can be
54 750 and 850 8C. seen on the DSC trace. The spontaneous formation of a thin
55 zinc aluminate (ZnAl2O4) interfacial layer upon deposition of
56 Al on ZnO acts as effective barrier layer against aluminum

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 Engineering of Al/CuO Reactive Multilayer Thin Films for Tunable Initiation and Actuation

1 oxidation at low temperature and has the effect of remov-

2 ing the weak exotherms at 350–400 8C.
3 In [53], the authors incorporated a Cu nanolayer at the
4 interfaces of the Al/CuO multilayers and demonstrated that
5 the control of its thickness enabled the reduction of the on-
6 set reaction temperature of the first main exotherm (&)
7 and improved reactivity. Indeed, the incorporation of 10 nm
8 Cu at both Al/CuO and CuO/Al interfaces lowers the onset
9 temperature from 550 to 475 8C due to the lower-temper-
10 ature formation of the AlCu intermetallic phases and alloy-
11 ing. These results showed that Cu intermixing is in-
12 dependent of total Cu thickness. When a thin layer of Cu is
13 sputter-deposited onto CuO or Al at room temperature (no
14 annealing), Cu spontaneously diffuses into the neighboring
15 Al layers. Figures 18 (a) and (b) illustrate Guinier-Preston 32
Figure 19. Al/CuO enthalpies (DH) as a function of interfacial cop-
16 zones in both Al layers, easily identified by the striped areas: per thickness.Taken from [21].
17 these well-ordered periodic structures have a periodicity of
18 1.92  0.05 nm, in agreement with Guinier’s description.
19 These Guinier Preston structures may nucleate at preexist-
20 ing grain boundaries or more localized defects, such as dis- species (Al, Zr, and Mg) with CuO in alternating layered geo-
21 locations or vacancies. However, whatever the nucleation metries by magnetron sputtering. Keeping the fuel to CuO
22 mechanism, their formation at room temperature demon- equivalence & equal at 1, the effects of varying metallic re-
23 strates the propensity for copper and aluminum to intermix actants were studied with respect to their onset reaction
24 and to form q-Al2Cu alloy at relatively low processing tem- temperature and the enthalpy of the reaction characterized
25 peratures and coexisting with the Al solid solution phase by DSC. It was found that the onset reaction temperature of
26 [21]. It has been demonstrated that 26 % wt Cu at Al/CuO the major DSC peak is the lowest for the Zr/CuO system
27 interfaces constitutes the optimum amount to reduce onset (350 8C), intermediate for the Mg/CuO system (530 8C), and
28 without penalizing the overall reaction enthalpy (See Fig- highest for the Al/CuO multilayer (500 8C). For all, the multi-
29 ure 19). An increase of ~ 20 % in combustion velocity was layers were heated at 5 8C/min and DSC were done on 3 lay-
30 measured. Above 26 % wt Cu at Al/CuO interfaces, there is a ers Al/CuO/Al, Zr/CuO/Zr and Mg/CuO/Mg. Therefore, these
31 rapid decrease of the total reaction enthalpy, reducing the results cannot be directly compared with the onset reaction
32 combustion efficiency. temperatures obtained in different DSC scanning con-
33 ditions. Interestingly, this study shows the correlation be-
34 tween oxygen mass transport in the final oxide (MgO, Al2O3
35 and ZrO2) and the release of energy in the multilayers.
36 Clearly, the onset reaction temperature can be correlated
37 with the oxygen diffusivity in the final oxide. At 600 8C, oxy-
38 gen diffusivity is 2.41 3 1011, 1.31 3 1026, 2.33 3 1028 cm2/s,
39 for ZrO2, MgO and Al2O3, respectively.
40 Combustion properties, such as reaction front temper-
41 ature and gaseous products, can be tuned easily by tuning
42 the reactive oxide nature, i. e., replacing the CuO with an al-
43 ternative thermite oxidant [54–56]. Further, adiabatic tem-
44 Figure 18. Transmission electron micrograph of the cross section of peratures vary with the choice of oxidant oxide (see Table 6)
45 Al/Cu-20 nm/CuO/Cu-20 nm/Al with the visualization of Guinier but the quantity of gas released is also highly dependent
46 Preston zones in (a) Al bottom layer and (b) Al top layer. Taken from on oxidant nature. Upon heating, the Al/CuO system re-
47 [21]. leases high amounts of gaseous oxygen at a temperature
48 well below the onset reaction temperature (~ 250 8C),
49 whereas Al/Bi2O3 ignites in the condensed phase below any
50 oxygen release. However, Al/Bi2O3 is the most gas produc-
51 6.3 Playing with Reactants Nature to Tune Reaction Rate ing nanothermite. In contrast, Al/WO3 does not release gas:
52 and Reaction Products the reaction and combustion occur in condensed phase.
53 Sanders et al. [57] and Glavier et al. [56] investigated the
54 CuO is one of the most used thermite oxidants. However, it pressure generated by Al coupled with the different oxidant
55 can be combined with different metals that are also able to types and showed that Al/Bi2O3 generates the highest max-
56 be oxidized. Mily et al. in [12] deposited different metallic

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 Review C. Rossi

1 Table 6. Theoretical characteristics of some Al based thermite characteristics: heat of reaction, adiabatic temperature, mass of produced gas.
2
Thermite Adiabatic temperature State of reaction products Gas production Heat of reaction
3
(K) (g of gas/g of initial thermite) (J/g)
4
5 Al/CuO 2843 Liquid & gas 0.3431 3900
6 Al/Bi2O3 3253 Liquid & gas 0.8941 2115
7 Al/MoO3 3253 Liquid & gas 0.2473 4700
Al/WO3 3253 Liquid & Liquid 0.1463 2910
8
Some gaseous oxide species
9
10
11
12 imum pressure, followed by Al/CuO, and Al/WO3 and Al/ sponse times ranging from 2 to 260 ms. Next, Glavier et al.
13 MoO3. [16] used this igniter to cut and propel a thin metallic foil
14 As a summary, to generate pressure, the best oxide and ignite RDX in a detonation. Authors showed that a
15 combined with Al is not necessarily the most energetic stainless steel flyer of 40 mg can be properly cut and pro-
16 thermite: we have to favor the oxide whose metal evapo- pelled at velocities calculated from 665 to 1083 m s1 as a
17 rates easily and where the reaction temperature enables function of the RDX extent of compaction and ignition
18 alumina decomposition [55]. charge. The impact of the flyer can directly initiate the deto-
19 nation of an RDX explosive, which is very promising to re-
20 move primary explosives in detonators. A schematic view
21 7 Brief Overview of Applications and photo of one miniature detonator is given in Figure 21.
22
23 To date, igniters and exploding foil initiators are the widest
24 investigated applications: igniters can be observed in nu-
25 merous civilian and military applications such as triggering
26 the inflation of airbags, micro-propulsion systems, and arm
27 and fire devices used in missiles, rockets and any other ord-
28 nance systems. Traditionally, igniter technology consists of a
29 metallic hot wire (Ni/Cr, …) or bridge wire in contact with a
30 highly reactive material in the category of primary or secon- Figure 21. Schematic and photo of one miniature detonator in-
31 dary energetic material. The current passing through the tegrating Al/CuO multilayers as initiator. Taken from [16].
32 wire locally heats the material in contact until its ignition.
33 Al/CuO multilayers can efficiently replace the hot wire and
34 highly reactive material. Taton et al. [14] first reported the More recently, Nicollet et al. [38] derived the Al/CuO
35 design, realization and characterization of hot-wire ignition multilayer igniter concept for several substrates and sim-
36 integrating Al/CuO multilayers (see photograph of Fig- plified the fabrication process to adapt it to airbag ini-
37 ure 20) for application in pyrotechnical systems for space tiation. Additionally, our team has demonstrated miniature
38 applications. The reactive Al/CuO multilayered thin film re- one-shot circuit breakers [58] based on the combustion of a
39 sides on a 100-mm-thick epoxy/polyethyleneterephtalate nanothermite (see Figure 22). Each device is simply made
40 (PET) membrane to insulate the reactive layer from the bulk from two assembled Printed Board Circuits (PCBs) to define
41 substrate. When current is supplied, Al/CuO reacts and the a hermetic cavity in which an Al/CuO multilayer initiator
42 products of reaction produce sparks that can ignite any sec- chip ignites – in less than 100 ms – a few milligrams of
43 ondary energetic composition, such as RDX. The authors nanothermite to cut a thick copper connection. We demon-
44 demonstrate a 100 % success of ignition over 0.25–4 A firing strated the good operation (100 % of success rate) with a
45 current range corresponding to 80–244 mJ and with re- response time of 0.57 ms, which is much lower than the re-
46 sponse time of classical mechanical circuit breakers (> ms).
47
48
49 8 Conclusion
50
51 Sputter-deposited Al/CuO multilayers, composed of alter-
52 nating nanolayers of Al and CuO with total thicknesses in
53 the range of 1 mm to tens of mm, have recently emerged as
54 Figure 20. Schematic and photo of the reactive electro-thermal ini- new fully dense 2D energetic materials that present an op-
55 tiator on Expoxy/PET membrane. Chip dimension is 4 mm 3 2 mm. portunity for tunable ignition and actuation, as they feature
56 Taken from [14]. theoretical energy densities significantly higher than most

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 Engineering of Al/CuO Reactive Multilayer Thin Films for Tunable Initiation and Actuation

1 chairet, Iman Abdallah, Jeremy Cure and Guillaume Lahiner. I would

2 like to express my gratitude to my technical staff, in particular Vér-
onique Conédéra and Ludovic Salvagnac for helping me in PVD
3
process.
4
5
6 References
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49
[15] P. Zhu, R. Q. Shen, Y. H. Ye, S. Fu, D. L. Li, Characterization of Al/
50 Acknowledgements CuO nanoenergetic multilayer films integrated with semi-
51 conductor bridge for initiator applications, J. Appl. Phys. 2013,
52 I thank my colleagues Dr. Alain Estève, Prof. Mehdi Djafari-Rouhani 113.
53 and Dr. Daniel Estève who provide frequently their expertise and
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advices that greatly benefit the research in Al/CuO multilayers. I
54 also thank my phD students and post-docs who conducted all the C. Rossi, Nanothermite/RDX-Based Miniature Device for Impact
55 technical work. Among them: Marine Pétrantoni, Guillaume Taton, Ignition of High Explosives, Propellants Explos. Pyrotech. 2017,
56 Andrea Nicollet, Ludovic Glavier, James Zapata, Jean Laurent Pou- 42, 307–316.

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