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A Nano Initiator Realized by Integrating Al/CuO-Based Nanoenergetic Materials With a Au/Pt/Cr Microheater
Kaili Zhang, Carole Rossi, Marine Petrantoni, and Nicolas Mauran
AbstractA nano initiator is developed by integrating Al/CuObased nanoenergetic materials with a Au/Pt/Cr thin-lm microheater realized onto a glass substrate. It is fabricated by using standard microsystem techniques that allow batch fabrication and high level of integration and reliability. The nano initiator is characterized by open-air combustion testing with an ignition success rate of 98%. The ejected combustion ame is seen clearly with a potential exceeding 2000 C. The ignition power, ignition delay, and ignition energy are 1.16 W, 0.10.6 ms, and 0.120.70 mJ, respectively. The energy output is calculated to be around 60 mJ. [2008-0035] Index TermsAl/CuO, energetic material, heater, initiator, micro, nano.

I. I NTRODUCTION N ELECTROPYROTECHNIC (or explosive) initiator that is activated by the application of electrical energy is used to initiate an explosive, burning, electrical, or mechanical train. Electropyrotechnic initiators have found numerous civilian and military applications such as triggering the ination of airbags in automobiles [1], [2], micropropulsion systems for microsatellites [3][5], arm re and safe-and-arm devices used in missiles, rockets, and the like apparatus [6], and many other ordnance systems [7]. Traditional electropyrotechnic initiators use a bridgewire to initiate the subsequent reactions, which is not suitable for batch fabrication and high level of integration. Nowadays, electropyrotechnic initiators employ a semiconductor bridge (SCB) instead of a bridgewire [7][9]. Although the performances are greatly improved, there are still some problems remaining such as not very high reliability, not very good intimate contact between the SCB and the attached reactive materials, and smaller output energy compared with input energy. Recently, nanoenergetic materials (nEMs) have received steadily growing interests because of their improved performances in terms of energy release, ignition, and mechanical properties compared with their bulk or micro counterparts [10][18]. However, there are very few studies in the literature to utilize nEMs in order to realize functional devices, although this is very interesting for the practical applications of nEMs.
Manuscript received February 12, 2008. First published June 24, 2008; last published August 1, 2008 (projected). Subject Editor R. Syms. The authors are with the Laboratory for Analysis and Architecture of the Systems, French National Center for Scientic Research (CNRS), 31077 Toulouse Cedex 4, France (e-mail: kaili_zhang@hotmail.com; rossi@laas.fr). Color versions of one or more of the gures in this paper are available online at http://ieeexplore.ieee.org. Digital Object Identier 10.1109/JMEMS.2008.926144

In this paper, an electropyrotechnic nano initiator is developed by integrating Al/CuO-based nEMs with a Au/Pt/Cr thin-lm microheater realized onto a Pyrex 7740 glass substrate due to its much lower thermal conductivity (1.18 W/mK) compared to that of silicon substrate (141.2 W/mK). The nano initiator is able to partially solve the problems mentioned previously. First, the nano initiator is fabricated with standard microsystem techniques that allow mass production and high level of integration and reliability. Second, the exothermic reaction of the nEMs produces high-temperature products, which discharge to a distance of several millimeters or more. The ejected products can ignite the attached reactive materials even if the initiator makes no physical contact to the reactive materials. Third, the nano initiator is able to generate much more output energy than input energy. II. F ABRICATION P ROCESS AND R ESULTS The process ow of the fabrication is shown in Fig. 1. The process starts with a 500-m-thick double-polished 4-in Pyrex 7740 glass substrate. The substrate is cleaned by using acetone and chromic sulfuric acid mixture (RT2), thoroughly rinsed by deionized (DI) water, and blow dried by nitrogen. Then, the substrate is placed into an oven at 200 C for 20 min for further drying. Positive photoresist is spin coated onto the Pyrex glass substrate and patterned using photolithography through a designed mask-1. The resist is exposed twice to generate a reentrant prole. Metal lms of Cr/Pt/Au with thicknesses of 20/120/800 nm are deposited by e-beam evaporation. The Cr lm acts as the adhesion layer between Pt and substrate. The Pt lm serves as the resistor, and the Au lm acts as both the conductor and contact pad. Metal Cr/Pt/Au liftoff is performed in acetone with ultrasonic for 30 min. After solvent and DI water cleaning, the Pyrex glass substrate with Cr/Pt/Au metals is spin coated with resist and patterned using photolithography by a mask-2. After the developed resist is removed, the substrate is put into the Au etchant. The Au in the designed area is removed, and the Pt is exposed as the resistor. The fabricated Au/Pt/Cr microheater on the glass substrate is shown in Fig. 2(a). The zigzag geometry is used for the microheater because it is the most widely employed geometry for microheater-based devices in both commercial products and research. A SiO2 layer with a thickness of 300 nm is deposited onto the glass substrate by plasma-enhanced chemical vapor deposition (PECVD). Resist is spin coated and patterned using a mask-3.

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A 4-in double-polished silicon wafer is spin coated with photoresist with a thickness of 10 m and patterned using photolithography with a mask-5. After developing the resist, the exposed silicon wafer is etched through using deep reactive ion etching. The silicon wafer with holes is employed as the shadow mask for the subsequent Al deposition. Al is deposited by thermal evaporation onto the glass substrate with CuO nanowires, as shown in Fig. 2(e). The deposited thickness (on average across the substrate) of Al is set to be 1.12 m in the thermal evaporator. Fig. 2(f) shows the SEM image for the nanowires after Al deposition. The SiO2 layer deposited by PECVD in the previous step is critical to the initiator. As can be seen in Fig. 2(e), if there was no SiO2 layer, the deposited Al (a good conductor) will connect Pt directly, resulting in short circuit. III. O PEN -A IR C OMBUSTION T ESTING Open-air combustion testing of the nano initiator is achieved by inputting a current to the Pt resistor through the Au contact pads. Fig. 3 shows the optical images of two igniting samples. After the ignition, the reaction is accompanied by a bright ash of light, and the ejected products can be clearly seen from the images. The high ame temperature is consistent with the large energy release. The ame temperature in our samples may be compared with the reported adiabatic ame temperature of about 2570 C for the reactions of Al and CuO/Cu2 O [19]. For actual air bags in automobiles, micropropulsion systems, and many ordnance systems, even if there is a gap (no contact) between the initiator and the reactive material, the gap will be very small. The small gap can be readily penetrated by the ejected high-temperature products, as shown in Fig. 3. However, for the bridgewire and SCB based initiators, if a small gap exists between igniter and reactive material, the ignition of the devices may fail due to the requirement of intimate contact between igniter and reactive material [1][6], [8], and [9]. The Cu thin lm is converted into bicrystal CuO nanowires and CuO/Cu2 O thin lm after the thermal annealing at 450 C for 5 h in static air [17]. After Al deposition, nano Al is integrated with CuO nanowires to form a core-shell nanostructure and also deposited onto the CuO/Cu2 O thin lm under the nanowires to form a layered structure. The exothermic reaction of the Al/CuO-based nEM has been characterized by using differential thermal analysis (DTA), as shown in Fig. 4 [17]. There are two major exotherms associated with the thermite reaction. The rst exotherm is observed with an onset temperature of about 500 C, which means that nEM reacts prior to the melting of Al. This suggests that the rst exotherm is caused by the thermite reaction between the CuO nanowires and nano Al. The reaction is based on the solidsolid diffusion mechanism. The second exotherm is found with an onset temperature of around 720 C. After melting, the remaining Al reacts with the CuO/Cu2 O thin lm beneath the CuO nanowires. Therefore, the ignition temperature is estimated to be around 500 C. Fig. 5(a) shows an image of the nano initiator after combustion. Part of the Pt heater covered by nEMs is exposed again because some of the combustion products are ejected from the heater. Fig. 5(b) shows the SEM image of some of the combustion products. Nanoparticles with average sizes of

Fig. 1.

Fabrication process ow.

After removing the developed resist, the SiO2 layer that is not covered by the resist is etched by a buffer HF solution. The SiO2 layer is used to protect the microheater and to prevent the potential short circuit in the following process. A 30-nm-thick Ti thin lm is then deposited onto the glass substrate, followed by a 50-nm Cu thin-lm deposition by thermal evaporation, where the Ti lm serves as the adhesion layer between Cu and Au/Pt/Cr/glass, and the 50-nm Cu lm acts as the electrical conducting layer for the subsequent electroplating. The Cu lm with a thickness of 1 m is then deposited by electroplating. The substrate with Cu/Ti lms is spin coated with resist and patterned using photolithography by a mask-4. After the developed resist is removed, the substrate is rst put into a solution with 10-ml H2 O2 , 10-ml HCl, and 80-ml H2 O to etch the exposed Cu lm, and then, it is put into a buffer HF solution to remove the uncovered Ti lm. After this stage, the substrate with the microheater, SiO2 layer, and patterned Cu lm is shown in Fig. 2(b). The glass substrate is then cleaned for 20 s in a solution containing 10-ml HCl (37%) and 120-ml DI water to remove the natural copper oxide formed on the Cu lm surface. After being rinsed with DI water and blow dried by N2 , the substrate is placed onto a clean silicon wafer that is put onto a quartz boat. The quartz boat is positioned into a quartz tube that is mounted inside a horizontal tube furnace. The substrate is then heated in the furnace under static air at 450 C for 5 h. After the heat treatment, the color of the lm is changed into black, as shown in Fig. 2(c). During the thermal treatment, CuO nanowires grow from the Cu thin lm, as can be seen from a scanning electron microscopy (SEM) image in Fig. 2(d).

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Fig. 2. Optic and SEM images of the fabrication results. (a) Au/Pt/Cr microheater. (b) Patterned SiO2 and Cu lms. (c) and (d) CuO nanowires. (e) and (f) Al/CuO nEMs.

Fig. 3. Optic images of the combustion ame.

1050 nm are formed after the combustion due to the highly energetic impact of the combustion wave and the high local temperature generated. The combustion reaction between nano Al and CuO nanowires may also be called nanoexplosion process, which has been used to synthesize a wide range of multimetal oxide ceramic and metalceramic composite nanopowders, with precise stoichiometries and uniform morphologies [20].

Fig. 4. DTA plot of the Al/CuO-based nEM. Reproduced with permission from [17]. Copyright 2007 American Institute of Physics.

IV. O PEN -A IR I GNITION P OWER , I GNITION D ELAY , I GNITION E NERGY , AND E NERGY O UTPUT Ignition power, ignition delay, ignition energy, and energy release are important parameters for the practical applications of the Al/CuO-based nEM initiator. A setup is built to determine

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Fig. 5.

Optic and SEM images of the combustion products.

Fig. 6.

Current variation with time.

these parameters. Basically, the setup inputs a voltage to the Pt heater through the Au contact pads with a current limitation of 0.35 A. The voltage and current variations with time are recorded simultaneously by a digital oscilloscope. The duration of the voltage-source power supply is set as 0.1 s. All the devices are controlled by a computer through user interface software. Figs. 6 and 7 show the current and voltage variations as a function of time for one typical sample, respectively. After the voltage supply is triggered, the current reaches 0.35 A rapidly, whereas the voltage increases and keeps a relatively constant value of 3.3 V due to the current limitation. At 0.2 ms, the thermite reaction between nano Al and CuO nanowires starts. The released heat causes the increase of the Pt resistance, which results in the decrease of the current. At 0.24 ms, the reaction of Al/CuO/Cu2 O occurs, resulting in a further sharp decrease of the current due to the highly energetic impact of the combustion wave and the extremely high local temperature generated. Consequently, the ignition power, ignition delay, and ignition energy can be conveniently derived from the curves in Figs. 6 and 7. Fifty samples from the rst fabrication batch were tested under the same conditions, and one of them was not ignited. Therefore, the ignition success rate is estimated as 98%. The ignition power, ignition delay, and ignition energy are determined as 1.16 0.13 W, 0.10.6 ms, and 0.120.70 mJ, respectively. More precise control of the micro-/nanofabrication process is

Fig. 7. Voltage variation with time.

needed to improve the ignition repeatability and uniformity. The heat release of the thermite reaction of the Al/CuO-based nEMs has been roughly determined as 2950 J/g by using DTA (see Fig. 4) and differential scanning calorimetry experiments in [17]. For one nano initiator, the Cu surface area is 1.2 1.2 mm, and the deposited Cu and Al thicknesses are 1 and 1.12 m, respectively. Therefore, the mass of the Al/CuO-based energetic materials is estimated to be 2.043 105 g. As a result, the energy output is roughly determined as 60 mJ. The energy output can be further increased without changing the ignition energy by several ways such as increasing the mass of the deposited materials, annealing Cu for longer time or under a N2 /O2 gas ow to obtain pure CuO, and tuning the Al deposition to reach a stoichiometric reaction [17], [21]. V. C ONCLUSION Al/CuO-based nEMs are integrated with a Au/Pt/Cr thinlm microheater realized onto a Pyrex 7740 glass substrate to achieve a nano initiator. The nano initiator is fabricated by using standard microsystem technologies and simple nanofabrication, which are suitable for batch fabrication and high level of integration. Combustion of the nEMs is accompanied by a bright ash of light, which is due to the high reaction temperature with

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a potential of more than 2000 C. The ejected high-temperature products can ensure the successful ignition of the attached reactive materials even if the contact between the nano initiator and the reactive materials is not very intimate. The ignition power, ignition delay, and ignition energy are determined as 1.16 0.13 W, 0.10.6 ms, and 0.120.70 mJ, respectively. The ignition success rate of the nano initiator is estimated as 98%. The released energy is roughly estimated to be 60 mJ with further potential improvement without increasing the energy input. The nano initiator is supposed to have many interesting applications in both civilian and military areas such as air bags in automobiles, micropropulsion systems, and many ordnance systems. R EFERENCES
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Kaili Zhang received the B.S. degree in mechanical engineering from Dong Hua University, Shanghai, China, in 1997, and the Ph.D. degree in microsystems from the National University of Singapore, Singapore, in 2006. Since 2006, he has been with the Laboratory for Analysis and Architecture of the Systems, French National Center for Scientic Research (CNRS), Toulouse, France, where he has been working on nanosystems as a Postdoctoral Researcher. His current research interests include nanoenergetic materials, nanometals, nanometal oxides, nanocatalysis, micropropulsion, microigniters, solar cells, fuel cells, and hydrogen storage.

Carole Rossi received the engineer degree in physics and the Ph.D. degree in electrical engineering from the National Institute for Applied Science, Toulouse, France, in 1994 and 1997, respectively. After her postdoctoral research at the University of California, Berkeley, under the supervision of Prof. Pister, she joined the French National Center for Scientic Research (CNRS), Toulouse, to develop her research at the Laboratory for Analysis and Architecture of the Systems (LAAS). She is currently leading the power MEMS research area at LAAS, with her team proposing new concepts for actuation and energy on a chip. Her research interests include nanoenergetics, micropyrotechnical systems, and power MEMS for electrical generation.

Marine Petrantoni received the Engineer degree from the Department of Materials, PolytechGrenoble, an engineering school that is part of Joseph Fourier University, Grenoble, France, in 2006. She is currently working toward the Ph.D. degree in the Laboratory for Analysis and Architecture of the Systems (LAAS), MEMS Department, Toulouse, France. LAAS is a national laboratory under the French National Center for Scientic Research (CNRS). Her Ph.D. topic concerns the integration of nanoenergetic materials via microelectronic technologies.

Nicolas Mauran was born in Muret, France, in 1974. He received the Engineer degree in instrumentation from the Conservatoire National des Arts et Mtiers, Toulouse, France, in 2003. He has been with the Laboratory for Analysis and Architecture of the Systems, French National Center for Scientic Research (CNRS) since 1996, where he is currently responsible for the Semiconductor Electrical Characterization Center, Toulouse.