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High-Pressure/High-
Temperature Microreactors Klavs Jensen, Ph.D.
hemically synthesized nanomaterials, such as combined with the high heat and mass transfer rates
Keywords:
microfluidics,
C nanocrystalline quantum dots, are being considered
as the active element in many applications, including
enable reactions to be performed under more controlled
conditions with higher yields than can typically be achieved
high pressure, photovoltaics, displays, and biochem sensing. To realize with conventional reactors. Moreover, manipulation of
synthesis, the promise of these devices, it will be critical to have an reaction parameters, while the reaction proceeds, allows
nanoparticles, efficient, reproducible synthesis technique of the optimization of synthesis conditions. The ability to work at
quantum dots
nanostructures. Currently, nanoparticles are synthesized elevated temperatures and pressures while confining
in a batch mode in small volumes, which is appropriate for potentially toxic, high reactive starting materials will
studying the fundamental properties of nanosized become important for the synthesis of novel
structures and for developing proof of principle device nanostructured materials. ( JALA 2009;14:36773)
structures. However, batch synthesis suffers from control
of size, size distribution, and quality of the nanomaterial
from batch to batch. Moreover, there is an inherent INTRODUCTION
difficulty in scaling up to quantities more reasonable for
device development and optimization. Continuous-flow
reactors based on microfluidics (microreactors) integrated Chemically synthesized nanomaterials are being
with heaters and fluid control elements offer a solution to considered as the active elements in many applica-
these problems and additional advantages. We describe tions, including photovoltaic, energy, displays,1 and
biochem sensing.2 To realize the promise of these
continuous synthesis of nanostructures in microfluidic
devices, it will be critical to have an efcient, repro-
systems consisting of multiple subemillimeter-sized
ducible synthesis technique of the nanostructures.
channels in which fluid flows continuously and chemical Currently, nanoparticles are synthesized in a batch
reactions take place. The small reaction volumes mode in small volumes, which is appropriate for
studying the fundamental properties of nanosized
structures and for developing proof of principle
*Correspondence: Klavs F. Jensen, Ph.D., Department of Chemical device structures. However, batch synthesis suffers
Engineering, Massachusetts Institute of Technology, Room 66- from irreproducibility of size, size distribution, and
350, 77 Massachusetts Avenue, Cambridge, MA 02139, USA;
Phone: 1.617.253.4589; Fax: 1.617.258.8992; E-mail: quality of the nanomaterial from batch to batch, as
kfjensen@mit.edu well as fast screening and optimization of the synthesis
1535-5535/$36.00 conditions. Moreover, there is inherent difculty in
Copyright c
2009 by The Association for Laboratory Automation scaling up to quantities more reasonable for device
doi:10.1016/j.jala.2009.06.005 development and optimization.
Continuous-ow reactors based on microuidics (micro- However, even with ow segmentation, limitations on the
reactors) integrated with heaters and uid control elements number of compatible chemistries and the limited number
oer a solution to these problems as well as additional ad- of available high boiling point solvents have been a major
vantages, including enhancement of mass and heat transfer, obstacle in the rapid adoption of microreactors as a universal
feedback control of temperature and feed streams, reproduc- platform for nanostructure synthesis.
ibility, potential for sensor integration for in situ reaction One avenue of improving synthesis in microreactors is to
monitoring, rapid screening of parameters, and low reagent perform experiments at high pressure (Fig. 1). High pressure
consumption during optimization.3e5 The small reaction vol- allows for wider range of chemistries and processes, because
umes combined with the high heat and mass transfer rates at sufciently high pressure, virtually any common solvent,
enable reactions to be performed under more aggressive con- precursor, and ligand will remain either liquid or become su-
ditions with higher yields than can typically be achieved with percritical (sc) at the temperatures required for nanomaterial
conventional reactors. Moreover, new reaction pathways synthesis. This particular homogeneous domain (supercriti-
deemed too difcult to control in conventional macroscopic cal) of the pressure/temperature phase diagram of compound
equipment can be conducted safely because of the high heat is located above the critical coordinates (Tc and pc) of the
transfer and ease of conning small volumes. This ability to considered uid or mixture. The supercritical regime allows
work at elevated temperatures and pressures while conning tuning the uid properties from liquid-like to gas-like, dis-
potentially toxic, high reactive starting materials could be- playing the high miscibility and fast diffusion rates typical
come important for the synthesis of novel nanostructured of gasses, but with sufciently high densities for solubilizing
materials. a wide range of compounds of low-to-medium polarity,
The development of high-temperature microuidic reac- typical of liquids.
tors for inorganic nanocrystal (NC) synthesis has been dem- The main challenge for adoption and development of high-
onstrated in several studies with the continuous synthesis of pressure/high-temperature (HP/HT) microuidic is the uidic
NCs at atmospheric pressure using a single-phase laminar connections (packaging). Several authors have recently
ow microreactor designs.6 However, one difculty of these reported several ways to connect tubing to chips enabling
synthetic procedures is the requirement for solvents that medium pressure use in microreactors,11 but these packaging
can both dissolve the precursors at ambient conditions and techniques are not suitable for high-temperature processes,
also remain liquid over the entire operating temperature though their use was demonstrated for low temperature pro-
range (25e350 C), signicantly limiting the set of solvents, cesses using supercritical CO2 as medium to perform catalysis
ligands, and precursors that are compatible with continu- and chemical reactions.12 However, nanostructure synthesis
ous-ow systems. Furthermore, solvents that are available, often requires higher temperature conditions, which are not
are typically very viscous, leading to slow mixing, broad res- feasible in those microsystems.
idence time distributions (RTDs), and as a consequence, In this contribution, we present our strategy to develop
broad NC size distributions. Segmentation of the reacting high pressure microuidic devices, which can be further in-
phase with an immiscible phase7 can address some of these terfaced with online characterization techniques coupled to
limitations by narrowing the RTD and improving reactant optimization software, allowing for fast screening and opti-
mixing.8,9 Application of segmented ow for continuous syn- mization of processes, especially for inorganic nanostructure
thesis of inorganic NCs has been previously demonstrated synthesis. Proofs of concept are illustrated with the synthesis
for liquidegas,4 and liquideliquid10 segmented ows. of semiconductor NCs in various solvents.
Figure 1. Pressure/temperature diagram with typical batch process conditions and potential novel on chip processes using high-pressure/
high-temperature microfluidic systems.
Figure 2. Top: High-pressure microreactors for nanomaterial synthesis: (a) 45-mL microreactor, (b) 100-mL microreactor, and (c) modular
high-pressure fluidic connections. Bottom: High-pressure experimental setup, including a high-pressure high-temperature microreactor,
a compression-cooling aluminum interface, two high-pressure syringe pumps, and a back-pressure regulator.
MICROFABRICATION AND EXPERIMENTAL SETUP temperature characteristics, and it has good chemical compat-
ibility characteristics. Oxidation of silicon through
To overcome the above-mentioned HP/HT limitations, we high-temperature wet oxidation process in a furnace leads to
have developed high-pressure high-temperature continuous- the formation of a glass layer on the surface so that an oxidized
ow silicon-Pyrex microreactors (Fig. 2) for the synthesis of silicon microreactor becomes functionally equivalent to a glass
nanomaterials. Well-established wet etching (with potassium reactor. This allows for further surface functionalization with
hydroxide) and dry etching (deep reactive ion etching) proce- the wide available silane chemistry for controlling the wettabil-
dures enable fabrication of microchannels with controlled ity of the walls from hydrophilic to hydrophobic.13
sidewall shape and channel dimensions from tens to hundreds After forming channels in the silicon and oxidizing the
of micrometers.3 Silicon has excellent mechanical strength and surface, the patterned substrate was anodically bonded to
Figure 3. (a) Example of characterization techniques that can be used with the high-pressure/high-temperature (HP/HT) microreactors.
(b) General scheme of an online HP/HT optimization setup.
Pyrex for easy optical access. The microreactors (Fig. 2a, b) with length 0.1e1 m, leading to volume ranging from w1
consisted of an injection zone maintained at room tempera- to 100 mL.
ture and in a reaction zone under temperature. The two From this initial conguration, characterization techniques
zones were separated by a thermally isolating halo etch that can be further integrated, allowing control of reaction param-
allowed for a temperature gradient of 25 C/mm. The pack- eters as well as collecting time- and space-resolved informa-
aging was realized using high-pressure modular compression tion. Potential characterization techniques include physical
uidic connections by compressing the microreactor between measurements (thermocouples and piezo electric pressure
two stainless steel parts using viton O-rings. In this congu- monitoring) and chemical measurements via integration of
ration, the setup enabled reaching high pressure (upto 300 optic bers for in situ spectroscopy ultraviolet-visible (UV-
bar) and temperature (upto 450 C in the heated section) vis), infrared (IR), Raman14 (Fig. 3). Conventional online
(Fig. 2c). Typical dimensions for the microchannels were characterization techniques, well developed for microuidic
100e400 mm for the width and 100e300 mm for the depth, applications,15 could be used as well, such as microparticle
Figure 6. TEM images of CdSe quantum dots synthesized from sc-hexane at T 250 C and 80 bar for a residence time of 30 s, with
[Cd] [Se] 3.8 103 M. The average size is 3.8 0.2 nm.
optimization of processes, making this tool powerful for de- (b). Tiggelaar, R. M.; Benito-Lopez, F.; Hermes, D. C.; Rathgen, H.;
veloping high-quality nanoparticles for a wide range of Egberink, R. J. M.; Mugele, F. G.; Reinhoudt, D. N.; van den Berg,
promising applications, including displays, medical imaging, A.; Werboom, W.; Gardeniers, H. J. G. E. Fabrication, mechanical
and solar cells. testing and application of high-pressure glass microreactor chips.
Chem. Eng. J. 2003, 131, 163e170
ACKNOWLEDGMENTS (c). Murphy, E. R.; Inoue, T.; Sahoo, H. R.; Zaborenko, N.; Jensen, K.
This research was funded in part by the NSF and the US army through the F. Solder-based chip-to-tube and chip-to-chip packaging for micro-
Institute for Soldier Nanotechnology. J. Park was supported by the Korean uidic devices. Lab Chip 2003, 7, 1309e1314
research Foundation Grant funded by the Korean Government (KRF-2006- (d). Trachsel, F.; Hutter, C.; Rudolf von Rohr, P. Transparent silicon/
214-D00038). glass microreactor for high-pressure and high-temperature reac-
tions. Chem. Eng. J. 2003, 135S, S309eS316.
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