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JOURNAL OF MICROELECTROMECHANICAL SYSTEMS 1

A Thermal Ink-Jet Printer Head Prototype With


Full Carbon Based Microbubble Generator
Yunhong Xiang, Lvhui Jiang, Yu Zhu, Changsheng Chen, Yangyang Chen, and Wenli Zhou

Abstract This paper presents the development of a novel CNT-metal, e.g., 0.4eV for CNT(8,0)-Pd [8]. Furthermore,
thermal ink-jet printer head prototype using full carbon- as their phonon spectra are similar due to sp2 bond,
based microbubble generators with carbon nanotubes as the CNT-graphene junction has very low interface thermal
heating elements and graphene as electrodes. Meanwhile, each
microbubble generator is equipped with a carbon nanotube resistance [9].
sensor to real-timely probe the temperature of its surrounding The thermal conductivity of CNT is very high and
micro-environment. With an array of microbubble generators anisotropic, i.e., the tubular is three orders bigger than across
and sensors fabricated on quartz glass, as well as a microfluidic the axis [10], [11]. The one-dimensional tubular structure of
structure constructed by the micromachined silicon, the printer CNTs restricts their heat conduction and it is dominated in
head prototype is formed by an anodic silicon-glass bonding
process with several scattered graphene film flakes as medium. the tubular direction. Its joule heating density can be thus
Droplet ejection with volume as tiny as 0.03 pl corresponding very high and localized when working as a heating element.
to a very high spatial resolution of >2000 dpi driven by two Therefore, we proposed and fabricated a low power and high
microbubble valves is demonstrated by the printing unit in the resolution multiwalled CNT based microbubble generator with
prototype. Increasing the input power cannot only speed up the gold electrode [12], [13], and built a printer head structure with
bubble nucleation and growth, but also improve the utilizing
efficiency of electric heating energy. The experimental detected silicon microfluidic structure micromachined by wet etching
temperature variation in the printing unit reveals its nonlinear method [14].
heat convection property by comparison with the theoretical Graphene has the highest thermal conductivity among
calculation by finite-element analysis. [2017-0048] the existing known materials which is also anisotropic,
Index Terms Thermal ink-jet printing, carbon nanotubes- the in-plane is several hundreds times bigger than the out-of-
graphene hybrid structure, MEMS, microbubble generator, full plane [15]. In this paper, we use graphene to replace the metal
carbon-based device. electrodes of our previous CNTs based microbubble generator.
Combing their excellent electrical and thermal contact,
I. I NTRODUCTION
the joule heating of CNTs-graphene structure is theoretically

C ARBON nanotubes (CNTs) and graphene are two most


promising nanoelectronic materials in post-silicon era
due to their unique and excellent electrical, optical, thermal,
confined inside with the heat flow limited in tubular and in-
plane, high utilizing efficiency of electric heating energy can
be expected. Meanwhile, the chemical inertness and stability
mechanical properties [1][5]. So far, CNT has been broadly of full carbon material broadens the application fields of this
investigated in many fields such as field effect transistor, kind of mcirobubble generator without specific circumstance
sensor, field emitter, and energy storage. In general, there restriction, e.g., bio-MEMS and micro fluidic chips.
exists a Schottky barrier at normal metal-carbon nanotube Through Ab initio study of the electronic transport
contacts [6], [7], which affects the corresponding device properties of the CNT-graphene contact by a fully
performances. At present, graphene field effect transistor due nonequilibrium Greens functions method combined with the
to its low On/Off ratio has not yet been generally adopted as density functional theory, we found that electron transmission
the circuit building block because that the intrinsic graphene coefficients at high energy (e.g., 1eV) has little dependence
is zero-bandgap and it is difficult to wide open. Nevertheless, on the detail of contact junction such as armchair or zigzag
graphene is still much concerned as an unprecedented edge, edge passivated by hydrogen or not, overlap dimension,
excellent electrode material. Specifically, its lattice has etc., suggesting that the CNT-graphene contact can be used
similar chemical bonding to CNT, making it an ideal electrode at relatively high bias (i.e., 1V) without precise control
material for CNT devices connection. The Schottky barrier of of the edge condition [16]. This gives a broad margin to
CNT-graphene, e.g., 0.09eV for CNT(8,0), is much lower than the corresponding fabrication to construct CNTs-graphene
Manuscript received March 4, 2017; revised April 22, 2017; accepted hybrid structure. Therefore, in this paper, we employ CNTs-
May 6, 2017. This work was supported by the National Natural Science graphene hybrid structure based microbubble generator in
Foundation of China under Grant 61274115. Subject Editor J. Miao. thermal printer head, providing an insight into the formation
(Corresponding Author: Wenli Zhou.)
The authors are with School of Optical and Electronic Information, and integration of full-carbon nano structure for MEMS
Huazhong University of Science and Technology, Wuhan 430074, China application to benefit from the advancement of carbon
(e-mail: wlzhou@hust.edu.cn). electronics. Besides, CNT is employed as a temperature
Color versions of one or more of the figures in this paper are available
online at http://ieeexplore.ieee.org. sensing element and located nearby the microbubble generator
Digital Object Identifier 10.1109/JMEMS.2017.2703131 to real-timely monitor the microchamber environment of each
1057-7157 2017 IEEE. Personal use is permitted, but republication/redistribution requires IEEE permission.
See http://www.ieee.org/publications_standards/publications/rights/index.html for more information.
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2 JOURNAL OF MICROELECTROMECHANICAL SYSTEMS

Fig. 2. Schematic drawing of the micro-bubble generator (a) and temperature


sensor (b).

current and the experimental tested temperature coefficient of


resistance of the carbon nanotubes and graphene hybrid struc-
Fig. 1. (a) Schematic drawing of the thermal ink-jet printer head
ture is positive (see Fig. 3(a)), we still use Pt/Ti electrode in the
(crosssectional view); (b) partial layout design of the printer head. sensor so as to lower its power consumption and disturbance to
the surrounding environment, although the temperature sensor
can be also constructed by the CNTs-graphene hybrid structure
printing unit. Experimental evidences of convection nature like the microbubble generator.
in the surrounding can be collected for precise control of
microbubble generation. So far, our effort is focused on the
B. Fabrication
fabrication and proof-of-concept performance characterization
of the novel printer head prototype. The array of the microbubble generators and sensors are
fabricated on the top-cover quartz glass substrate. The process
II. S TRUCTURE AND FABRICATION OF P RINTER H EAD starts with the sputtering and patterning of Pt/Ti (100/20 nm)
film, as the device electrodes of the temperature sensors and
A. Structure peripheral electrodes for both microbubble generators and
The structure of our thermal ink-jet printer head is schemati- sensors. A very few (1-2) layered graphene film is grown on
cally drawn in Fig. 1 [14]. There are two parallel microbubble copper foil by low pressure chemical vapor deposition (CVD)
generators in the microchamber of each printing unit, with method [17]. It is transferred to glass substrate by a
a narrow channel called chamber neck to link microchamber well-known wet transfer technology using spin-coating of
and main channel. When certain voltages are applied to the polymethyl methacrylate (PMMA) and patterned by oxygen
microbubble generators, a highly localized bubble nucleation reactive ion etching (O2 /50sccm, 80W/60s). Afterwards, mul-
and growth will be generated at each center. The expanding tiwalled CNTs (diameter 10 30 nm, length 4 10m) are
bubble near the chamber neck functions as a valve to isolate aligned between graphene electrodes of microbubble genera-
the liquid supply from the main channel. When these two tors and Pt/Ti electrodes of sensors concurrently using dielec-
growing bubbles are big enough and the balance between the trophoretic (DEP) technique (see a SEM picture in Fig. 3(b)).
surface tension and liquid pressure at the nozzle is broken, A silicon dioxide layer (200 nm) is then sputtered on the
a droplet will be ejected through the nozzle. Then the voltage contacts between graphene electrodes and CNTs to fix their
supply can be stopped to make the bubble collapse and the ink connection. It also helps confine the joule heating in the
refill the microchamber. Afterwards, another cycle of bubble microbubble generator and protects the metal electrode from
generation and droplet ejection can be implemented. corrosion.
The layout and structures of the microbubble generator The microfluidic structures are fabricated on a piece of
and temperature sensor are depicted in Fig. 1(b) and Fig. 2. double side polished silicon wafer. ICP technique is used
Considering that the sensor is usually driven by a constant to etch silicon with a sputtered and wet etched Cr film as
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XIANG et al.: THERMAL INK-JET PRINTER HEAD PROTOTYPE WITH FULL CARBON BASED MICROBUBBLE GENERATOR 3

Fig. 3. (a) DC resistances of microbubble generator and temperature sensor


versus temperature. (b) A SEM picture of carbon nanotubes deposited between
the graphene electrodes by DEP technique.

mask, deeper trench thicker Cr. The geometric structures with


the same depth are formed at one ICP step. We developed a
specific process for the shallow etching after a deep etching
to obtain the intact edge profile along the trench, i.e., filling
Fig. 4. The schematic fabrication process of microfluidic structure on Si (a);
the deep trench with polydimethylsiloxane (PDMS) to planar the microscopic pictures of a fabricated microfluidic structure by process (a):
the surface after the Cr mask layer deposition. (b)(d) are top view; (c) a 3D view, the nozzle is 911m in diameter,
In detail, as shown in Fig. 4(a), the micromaching of silicon microchamber window is (48m52m)(28m32m), 25m in depth;
the nozzle and main channel are 95m deep; (e) a fabricated microstructure
starts with the ICP etching of the nozzle and main channel without PDMS planarization procedure. Schematic diagram of anodic bonding
(95m depth, step (1)-(2)); Then the planarization process method to form the closed printer head structure (f). A closeup top view of a
is inserted before both ICP steps to form the microchamber bonded printing unit (g), the red dot lines stand for the profiles of microbubble
generators with graphene electrodes.
(25m depth, step (3)) and the chamber neck (12m
depth, step (4)-(5)) in sequence; It should be noted that the
PDMS is removed by oxygen reactive ion etching after each
ICP step. Afterwards, a very deep well (360m depth, surface cannot be sealed when bonding to form the printer
step (6)) on the backside of silicon is formed by the last head.
ICP step. Fig. 4 (b)(c)(d) shows a satisfactory microfluidic Graphene was reported to function as a interlayer to enhance
structure (nozzle diameter 9-11m, the circular edge of the the adhesion between Si and glass substrate in anodic bond-
nozzle window is not very smooth because of the patterning ing [18]. With several graphene film flakes scattered on the
resolution 1m of UV aligner but its sidewall roughness is blank surface of the Si microfluidic structure as medium (as
only 10 nm by AFM inspection; microchamber window schematically shown in Fig. 4(f)), our printer head prototype is
(48m52m) (28m32m)). Fig. 4 (e) shows a successfully obtained (see a bonded printing unit in Fig. 4(g))
incomplete edge profile without PDMS planarization proce- where the optimal bonding parameters are 350, 900V in our
dure, its chamber neck is seriously shorten and the uneven experimental results.
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4 JOURNAL OF MICROELECTROMECHANICAL SYSTEMS

Fig. 6. Estimated electrical energy required for bubble nucleation with


different input power for individual bubble generation.
Fig. 5. A printer head prototype to test.

generator #2, i.e., power of 443W, 452W and 462W,


III. P ERFORMANCE OF P RINTING U NIT the nucleation happened at 8.8s, 1.2s and 0.9s.
To balance between the power consumption and the speed
A. Experimental Method
of bubble generation, it is necessary to have a look at
The printer head prototype is mounted to a printed the conversion efficiency from electrical energy to bubble
circuit board (PCB) with wires connecting the electrodes of generation and growth. Suppose all the electrical energy is
microbubble generators and temperature sensors to the voltage consumed by microbubble nucleation, then it can be calculated
source for their performance characterization (see Fig. 5). by the product of the input power and application time before
A testing system is developed with functions of voltage pulse bubble nucleation. As shown in Fig. 6, the lower power input,
generation, data acquisition and video capturing with a graph- the higher electric energy is consumed by bubble nucleation.
ical user interface based on Labview software. To avoid water Moreover, for every input power increase of 10W, the electric
electrolysis, we use sine wave pulses to drive the microbubble energy required for bubble generation is decreased by 57mJ.
generators at present. For each printing unit, the system This means that the energy conversion efficiency is increased
can output individual programmable sine pulse to each by 5%10%, speculating that the normalized energy stands
microbubble generator, and collect its surrounding temperature for or at least is proportional to the utilizing efficiency of
by the resistance acquisition of CNT sensor simultaneously. electric heating energy. Accordingly, the higher input power,
The procedure of microbubble generation and ink droplet the lower heat loss before the bubble nucleation. Increasing the
ejection are captured at 50 frame/s by two CCD cameras input power can not only speed up the bubble nucleation and
oriented in-plane and vertically, respectively and concurrently. growth, but also improve the utilizing efficiency of electric
The timing starts at the moment of input voltage applying. heating energy. Meanwhile, for this specific printing unit,
The bubble nucleation is timed when a visible light spot when the input power is over 450W, the electric energy
(corresponding to a bubble with a diameter of 2m) appears required for bubble generation is lower than 0.5mJ and the
on the video (this causes a timing error 20 ms at 50 frame/s). efficiency is over 70%. This indicates that the highest effi-
ciency is to drive the microbubble generators at their maximum
B. Performance of Microbubbles Generation voltage without electrical broken, e.g., 20V for single CNT
and single layer graphene structure in our experimental results,
Before the initiation of droplet ejection by microbubble
which is still limited by the power source if in consideration
generation, we test the performance of each microbubble
of integration.
generator separately.
The initial resistances of two microbubble generators in a
printing unit are usually different, e.g., the one #1 located C. Behavior of Droplet Ejection
near the chamber neck is 65k and the other #2 is 104k. Fig. 7(a)(b)(c)(d) shows the procedure of the microbubble
Subjected to voltage pulses of 7.2 V and 9.4 V at 1 kHz, their growth and droplet ejection sequences captured in the video
bubble nucleation happen at 11.1s and 18.6s, with power con- under 7.3V and 9.6V/1kHz at 1# and 2# respectively and
sumption calculated to be 398W and 425W, respectively. simultaneously (their minimum power for microbubble
Their duration for bubble to reach the diameter of 20m is 3.1s nucleation might change a little bit after several cycling).
and 3.9s. With higher input voltage, i.e., higher input power, The bubble growth rates are plotted in Fig. 7(e). At 4.2s,
bubble nucleation appears earlier. Under voltage of 7.3V, 7.6V the microbubble nucleation appeared at #1 (near the chamber
and 7.8V on microbubble generator #1, i.e., power of 410W, neck, see Fig. 7(a)), 0.9s later, it happened to #2 (see Fig. 7(b)).
444W and 468W, the nucleation happened at 7.2s, 0.8s and Then these two microbubbles grew bigger quickly in the
0.65s. Under voltage of 9.6V, 9.7V and 9.8V on microbubble following seconds (see Fig.7(c)). At 7.1s, their diameters
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XIANG et al.: THERMAL INK-JET PRINTER HEAD PROTOTYPE WITH FULL CARBON BASED MICROBUBBLE GENERATOR 5

still too big and it will be decreased a little bit in our modified
layout design. Meanwhile, increase the input voltage to speed
up the bubble generation might also increase the chance of
bubble merging. The effort to speed up the bubble nucleation,
growth and droplet ejection will be done in the future after
our image capture system is upgraded.
So far, the total power consumption is still compara-
ble to our previous CNT-metal based microbubble genera-
tor, we speculate that the total thermal conductivity of the
fabricated CNT-grpahene hybrid structure is affected by its
inner interface thermal transport, i.e., lateral CNT separation
and interlayer distance between graphene sheets , e.g., very
dense packing of long CNTs and graphene could significantly
increase the out-of-plane thermal conductivity[9], [21]. The
thermal management can be later tuned with widely spaced
short CNTs with single layer graphene in the hybrid structure.
The smallest droplet ejected in our current experimental
has a diameter about 45m, i.e., a volume of 0.03pl at
minimum, indicating a very high spatial/printing resolution of
>2000/4000 dpi, with reference to Tsengs work [20].

D. Detection of Microenvironment
In general, CNT has a negative temperature coefficient
of resistance [22], our CNTs are measured to be -0.14%.
As shown in Fig. 1(b), each microchamber has two CNT
temperature sensors located at the outsider of two bubble
generators. During the microbubble generation and droplet
ejection, our lab-built measurement system collects the real-
time resistances of CNT sensors and the temperature in
microchamber can be figured out.
Fig.8(a) plots the real-timely measured resistance and
Fig. 7. CCD image sequences of micro-bubble growth (a)-(c) and the calculated temperature variations of sensor #1 (closer to the
trajectory of the corresponding droplet ejected with nozzle position shifted (d). chamber neck, the other sensor #2 is broken unfortunately)
(e) The bubble growth rate in the tested printing unit. during a printing unit testing. When the first bubble nucleated
on the microbubble generator #1 (near the chamber neck,
initial resistance 65 k) at 4.2s, the sensor resistance
reached 30m and 25m (at 1# and 2#), and a droplet was decreased to 704.3k with a R of 235.7k (under
ejection from the nozzle (see Fig. 7(d)) was captured. It is constant current of 200nA, initial resistance 940k at 25),
found that, under the same conditions, the bubble nucleation corresponding to 204.1 at that moment. When the second
time of #1 and #2 are 2.9s and 3.5s shorter respectively than bubble nucleated on the microbubble generator #2 (initial
they worked separately. Apparently, when two generators resistance 104 k) at 5.1s, the sensor resistance reached its
work at the same time, their efficiency to heat the equivalent lowest value of 692.4k with the R of 247.6 k, accordingly
volume of ink are higher than they work alone, the rates of the temperature was the highest 213.1. Afterwards,
bubble nucleation and bubble growth are accelerated. the resistance and the temperature almost kept constant with
Fig. 7(e) depicts the relationship between the bubble diam- slight fluctuation of 10 k and 10 till the droplet ejection.
eter and the duration time of input voltage. The bubbles grow Compared with the transient simulation of temperature
fast at the beginning, and their rates are decreased due to more at the center of microbubble generator and sensor by finite
convection and higher pressure in microchamber that makes it element analysis (FEA) using ANSYS (the strong and
need more input power to maintain the bubble growth rates. weak convection coefficients are 104 W/m2 K and 103 W/m2 K,
Previous research has shown that the bubble valve structure respectively.) as shown in Fig. 8, we can find that the real time
and bubble merging to cut off the droplet can efficiently temperature curve is very similar to the transient FEA calcu-
eliminate the satellite droplet [19], [20]. In our current exper- lation under strong convection at temperature above 100, and
imental results, a satellite droplet appeared and disappeared it is the converse around 100 or less. Therefore, we can infer
0.01s later because that the merging of two microbubbles did that the heat transfer of the microenvironment in a printing
not happen before droplet ejection although they did in an open unit during microbubble generation and droplet ejection is a
water circumstance testing before bonding to form the closed weak convection before the phase change from water to vapor,
structure. It is conjectured that the distance of two heaters is and strong convection after that and till bubble generation.
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6 JOURNAL OF MICROELECTROMECHANICAL SYSTEMS

be lowered by decreasing their distance in theory, but too


small distance may crosslink CNTs between the microbubble
generator and temperature sensor. Certainly, the actual error
might be variable as the organization of CNTs may be scat-
tered in the fabricated printing units and their electro-thermal
properties would somehow fluctuating as well. Nevertheless,
the temperature probing provides evidences for the future
precise control strategy of printing and structure modification
of printer head design.
We are now considering a feedback control based on the
real-time temperature monitoring of microenvironment. To fit
the temperature response of printing unit corresponding to the
microbubble growth might be an approach. The resistance of
temperature sensor near the droplet ejection time might be set
as the threshold to stop the applying of the input voltage until
the microbubble disappear, waiting for next heating cycle.

IV. C ONCLUSION
So far, our work demonstrates a successful application
of full-carbon device in MEMS. A novel thermal ink-jet
printer head prototype with carbon nanotubes-graphene hybrid
structure based microbubble generator and carbon nanotubes
based temperature sensor is fabricated and characterized. Very
tiny droplet with volume of 0.03pl corresponding to very
high resolution spatial/printing resolution of >2000/4000 dpi
is obtained by driving two microbubble generators in a printing
unit with nozzle diameter less than 10m. The real-time
temperature probing of microbubble generation and droplet
ejection reveals the dynamic behavior of heat convection in
the printing unit, providing evidence for precise control of
thermal ink-jet printing. Further scaling down the nozzle and
microchamber of printing unit can reduce its power consump-
tion and improve the resolution. We are seeking a feedback
Fig. 8. (a) Experimentally measured resistance and calculated temperature control of the microbubble generator to benefit its application
of the sensor during bubble generation and droplet ejection of a printing unit, in our printer head and other MEMS devices and systems.
with comparison to a transient (a) and steady (b) temperature simulation of
the temperature sensor and nearby microbubble generator (MG) by ANSYS.
The strong and weak convection coefficient underwater is 104 W/m2 K and ACKNOWLEDGMENT
103 W/m2 K, respectively.
The authors would thank Analytical and Testing Center
in Huazhong University of Science & Technology, Micro/
Nanofabrication Platform in Wuhan National Laboratory for
Moreover, there exists a lagging of temperature rising at the Optoelectronics.
beginning, which means the coefficient at lower temperature
is actually smaller than that in the FEA calculation. Overall,
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Yunhong Xiang received the B.Eng. degree in


physics and materials science from Anhui Univer-
sity, China, in 2013, and the M.Eng. degree in
microelectronics and solid-state electronics from the Wenli Zhou received the bachelors degree in
Huazhong University of Science and Technology, in measurement technology and instrumentation, and
2016. His thesis is focused on the design and fabrica- the masters degree in semiconductor devices and
tion of a thermal printer head based on carbon hybrid microelectronics from the Huazhong University of
nanostructure. He is currently an Hardware Engineer Science and Technology (HUST), China, in 1990
with China Mobile Communications Corporation. and 1995, respectively, and the Ph.D. degree in
2004. She joined as a Faculty Member with the
Department of Electronic Science and Technology,
HUST, in 1995, and is involved in the teaching and
Lvhui Jiang received the B.Eng. degree in elec- research of microelectronics. From 2000 to 2005,
tronic science and technology from the Huazhong she was a Ph.D. Student and Post-Doctoral Fellow
University of Science and Technology, China, involved in research with MEMS/NEMS in the Department of Automation
in 2013; the M.Eng. degree in microelectronics and and Computer-Aided Engineering, Chinese University of Hong Kong. She is
solid-state electronics with research on the fabri- currently a Professor with the School of Optical and Electronic Information,
cation and characteristic of microbubble genera- HUST. She also did research on the interface technology of novel merged
tor based on carbon hybrid nanostructure in 2016. network by using FPGA and embeded systems. She was a Visiting Scholar
He is currently a Process Engineer with Huawei in the Laboratory of Microsystem, Department of Mechanical and Aerospace
Technologies Co. Ltd. Engineering, UCLA, from 2014 to 2015. She is the author of one book chapter,
over 60 papers, and over 20 patents. Her current research interests are focused
on MEMS/NEMS, carbon devices, and integration.

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