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[6] K. H. An, K. K. Jeon, J. K. Heo, S. C. Lim, D. J. Bae, Y. H. Lee, can be made using ZnO nanoparticles and a conjugated poly-
J. Electrochem. Soc. 2002, 149, A1058. mer. These cells can be processed from solution and exhibit
[7] L. Valentini, I. Armentano, J. M. Kenny, C. Cantalini, L. Lozzi,
an incident photon to current conversion efficiency up to
S. Santucci, Appl. Phys. Lett. 2003, 82, 961.
[8] J. Li, Y. Lu, Q. Ye, M. Cinke, J. Han, M. Meyyappan, Nano Lett. 40 %. The environmentally friendly and low-cost ZnO offers
2003, 3, 929. a new perspective towards green electricity'.
[9] H. J. Chang, J. D. Lee, S. M. Lee, Y. H. Lee, Appl. Phys. Lett. 2001, In contrast to inorganic semiconductors, photoexcitation of
79, 3868. organic semiconductors results in a strongly bound electron±
[10] C. Zhou, J. Kong, H. Dai, Appl. Phys. Lett. 2000, 76, 1597. hole pair, called an exciton.[9] As an important consequence
[11] R. Martel, V. Derycke, C. Lavoie, J. Appenzeller, K. K. Chan,
for photovoltaic p±n junctions, such bound electron±hole pairs
J. Tersoff, P. Avouris, Phys. Rev. Lett. 2001, 87, 256 805.
[12] S. J. Tans, A. R. M. Verschueren, C. Dekker, Nature 1998, 393, 49. in organic semiconductors are only effectively separated at an
[13] C. Zhou, J. Kong, E. Yenilmez, H. Dai, Science 2000, 290, 1552. interface between a p-type (electron-donating) and n-type
[14] F. Selampinar, L. Toppare, U. Akbulut, T. Yalcin, S. Suzer, Synth. (electron-accepting) material. In general, the exciton lifetime
Met. 1995, 68, 109. and mobility within organic semiconductors are limited by ra-
[15] J. M. Moon, Y. S. Park, K. H. An, G. S. Park, Y. H. Lee, J. Phys.
diative and non-radiative decay; so only excitons generated in
Chem. B 2001, 105, 5677.
[16] E. Ando, S. Onodera, M. Iino, O. Ito, Carbon 2001, 39, 101.
close vicinity of a p±n interface will give rise to charges. In
[17] F. Selampinar, U. Akbulut, L. Toppare, Synth. Met. 1997, 84, 185. bulk-heterojunction solar cells this limitation is circumvented
by intimately mixing the p- and n-type materials, creating
junctions throughout the bulk of the material and ensuring
quantitative charge generation from photogenerated excitons.
High charge-carrier mobilities are advantageous to effectively
Efficient Hybrid Solar Cells from Zinc collect these charges and prevent charge recombination. Hy-
Oxide Nanoparticles and a Conjugated brid nanocomposite mixtures can combine the advantages of
Polymer** both types of materials: the solution processing of organic
semiconductors and the high charge-carrier mobility of inor-
ganic semiconductors. The effectiveness of the use of nano-
By Waldo J. E. Beek, Martijn M. Wienk, and
structured interfaces for photovoltaic applications is most
RenØ A. J. Janssen*
vividly demonstrated by the high efficiencies obtained by
dye-sensitized photoelectrochemical cells.[10,11] However, the
Solution processing of polymer organic photovoltaic de-
use of an electrolyte in this type of cell imposes serious tech-
vices may offer an inexpensive technology for production of
nological complications. Hybrid bulk-heterojunction cells
solar cells but requires low-cost materials that offer a high
allow easier processing, and promising efficiencies have
photovoltaic efficiency. Polymer organic solar cells often use a
already been obtained by combining CdSe nanorods with a
nanostructured interpenetrating network of electron-donor
polythiophene conjugated polymer.[7]
and electron-acceptor materials.[1±3] This bulk-heterojunction
Here we introduce nanocrystalline ZnO (nc-ZnO) as the
morphology enhances the interfacial area were the photogen-
n-type semiconductor in hybrid bulk-heterojunction solar
erated excitons are dissociated into charge carriers and
cells as it is a cheap and environmentally friendly material
enables holes and electrons to be transported and collected.
that can be synthesized in high purity and crystallinity at low
Various bulk-heterojunction photovoltaic devices have been
temperatures. ZnO has high electron mobility, even when
made in recent years using polymer composites[1] or conjugat-
measured on films consisting of assembled ZnO nanoparti-
ed polymers with fullerenes.[2,4±6] Moreover, polymers have
cles.[12] ZnO nanoparticles of approximately 5 nm diameter
been blended with CdSe nanoparticles to create hybrid solar
(Fig. 1a) are synthesized by hydrolysis and condensation of
cells.[7,8] These hybrid polymer±inorganic solar cells utilize the
zinc acetate dihydrate by potassium hydroxide in methanol,
high electron mobility of the inorganic phase to overcome
using the method of Pacholski et al.[13] Thus-prepared nano-
charge-transport limitations associated with organic materials.
particles are insoluble in pure methanol, but by adding suit-
Here, we show that efficient bulk-heterojunction solar cells
able amounts of less polar solvents such as dichloromethane,
chloroform, or chlorobenzene, stable solutions are obtained.
± No additional surfactants or ligands are needed to disperse
[*] Prof. R. A. J. Janssen, W. J. E. Beek, Dr. M. M. Wienk the ZnO nanoparticles in these solvent mixtures to reach solu-
Molecular Materials and Nanosystems bilities up to 70 mg mL±1. Moreover, also p-type p-conjugated
Departments of Chemical Engineering & Chemistry and polymers such as poly[2-methoxy-5-(3¢,7¢-dimethyloctyloxy)-
Applied Physics
Eindhoven University of Technology 1,4-phenylenevinylene] (MDMO-PPV, Fig. 1b)[14] can be dis-
PO Box 513, NL-5600 MB Eindhoven (The Netherlands) solved in this mixture, allowing simultaneous casting of both
E-mail: [email protected] the polymer and the nc-ZnO. The highest occupied molecular
[**] This work is supported by the Council for Chemical Sciences of the orbital (HOMO, 5.3 eV) and lowest unoccupied molecular
Netherlands Organization for Scientific Research (CW-NWO) in the
Pionier program and forms part of the research program of the orbital (LUMO, 3.0 eV) levels of MDMO-PPV[15] and the
Dutch Polymer Institute (DPI). valence (7.6 eV) and conduction (4.4 eV) bands of ZnO[16]

Adv. Mater. 2004, 16, No. 12, June 17 DOI: 10.1002/adma.200306659  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1009
COMMUNICATIONS

Figure 1. Layout of the photovoltaic device. a) Transmission electron

microscopy (TEM) photograph of ZnO nanoparticles on a carbon-coated
copper grid, bar indicates 20 nm. b) Structure of MDMO-PPV conjugated
polymer. c) Schematic energy level diagram for the device, with energy Figure 2. Photovoltaic device characterization. a) Incident photon to cur-
levels in eV relative to vacuum. d) Device structure, consisting of rent conversion efficiency (IPCE) as function of the wavelength of mono-
an 80 nm thick MDMO-PPV:nc-ZnO blend, sandwiched between chromatic irradiation, co-plotted with the fraction of photons absorbed
PEDOT:PSS and an aluminum top electrode. by the blend. b) Current density±voltage (J±V) characteristic of a
MDMO-PPV:nc-ZnO (with 67 wt.-% nc-ZnO). The dotted line is mea-
sured in the dark, the solid line under illumination with white light from
a tungsten±halogen lamp estimated at 0.71 sun equivalent intensity by
relative to the vacuum level, schematically shown in Fig-
integration of the quantum efficiency data shown in (a) with the AM1.5
ure 1c, indicate that exciton dissociation of photoexcited solar emission spectrum. The inset shows the same data in a semi-loga-
MDMO-PPV via electron transfer may occur at the interface rithmic plot. c) Evolution of short-circuit current density JSC (squares)
with ZnO, enabling the photogeneration of electrons and with least-squares fit of power-law behavior (solid line), open-circuit volt-
age VOC (open circles), and fill factor FF (triangles) as a function of light
holes.
intensity.
The effectiveness of this process is demonstrated by photo-
voltaic cells based on MDMO-PPV:nc-ZnO bulk heterojunc-
tions. The devices were made by spin-casting MDMO-
PPV:nc-ZnO solutions (67 wt.-% nc-ZnO) into thin films with tions resembling operation under solar illumination. The
a thickness of ca. 80 nm on a transparent hole-collecting elec- IPCE spectrum closely resembles the absorption spectrum of
trode consisting of a glass substrate, coated with indium tin the MDMO-PPV:nc-ZnO layer on glass, and reaches a value
oxide (ITO) and poly(3,4-ethylenedioxythiophene):poly(styr- of 40 % at the absorption maximum MDMO-PPV. Integration
ene sulfonate) (PEDOT:PSS) (Fig. 1d). The devices (0.1 cm2 of this spectral response with the solar spectrum (AM1.5G,
area) were completed by thermal evaporation of a 100 nm normalized 100 mW cm±2) affords an estimate of the short-cir-
thick aluminum layer and characterized in inert nitrogen cuit current density of JSC = 3.3 mA cm±2 under AM1.5
(< 1 ppm H2O, < 1 ppm O2) atmosphere. The incident photon (1 sun) conditions.
to current conversion efficiency (IPCE, Fig. 2a) has been Current density±voltage (J±V) measurements (Fig. 2b), car-
measured with white-light bias illumination to create condi- ried out in the dark reveal excellent diode behavior, with a

1010  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 12, June 17
 COMMUNICATIONS
rectification ratio of 3 ” 104 at ±2 V. The forward current den-
sity through the MDMO-PPV:nc-ZnO layer is considerably
higher than for pure MDMO-PPV in a similar device config-
uration, demonstrating that the electron current dominates
the current density in forward bias. This supports the presence
of a continuous pathway for electron transport through the
nc-ZnO network. Light-intensity-dependent J±V measure-
ments, using a tungsten±halogen white-light lamp and a set of
neutral density filters, show a sub-linear relationship between
the light intensity (I) and JSC:JSC µ In, with n = 0.93 (Fig. 2c).
This near-linear relationship implies only minor bulk charge-
carrier recombination is occurring in these photovoltaic de-
vices. Upon increasing the illumination power, the open-cir-
cuit voltage (VOC) continuously improves, ultimately reaching
values over 800 mV, while the fill factor (FF) increases up to
values close to 0.6. At the highest light intensities measured,
the FF begins to decrease slowly, due to increasing resistive
losses.
The J±V curve, measured at I = 0.71 sun equivalent[17]
white-light illumination using a tungsten±halogen lamp, is
shown in Figure 2b. Under these conditions
JSC = 2.40 mA cm±2 is obtained, together with VOC = 814 mV
and FF = 0.59, leading to an estimated overall power conver-
Figure 3. Investigation of charge-carrier formation and electron-transfer
sion efficiency (g) of 1.6 % at this light intensity. At 1 sun kinetics. a) Near-steady-state photo-induced absorption (PIA) spectrum
equivalent no dramatic decrease of this efficiency is expected, of a MDMO-PPV:nc-ZnO blend on quartz, measured at 80 K with modu-
in view of the evolution of the photovoltaic parameters with lated (275 Hz) excitation at 2.54 eV (488 nm). The pump power was
increasing light power (Fig. 2c). This is confirmed by a single 25 mW with a beam diameter of 2 mm. b) Time-resolved pump±probe
spectroscopy measured at room temperature, monitoring the intensity of
measurement at 1.7 sun equivalent (JSC = 5.40 mA cm±2; the radical cation band at 0.56 eV (2200 nm), after excitation at 2.43 eV
VOC = 844 mV; FF = 0.53; g = 1.4 %). The lower fill factor is (510 nm) with 200 fs pulses. The inset shows the transient absorption at
partly compensated by an increased open-circuit voltage. short time delays. In these experiments the pump beam (510 nm, flu-
At between 60 wt.-% and 75 wt.-% nc-ZnO, the power con- ence 0.5 mJ mm±2 per pulse, 500 Hz) was linearly polarized at the magic
angle (54.7) with respect to the probe beam (2200 nm, 1 kHz). The dif-
version efficiency is not very sensitive to the MDMO-PPV:nc- ferential transmission was recorded using a cooled InSb detector and
ZnO ratio. More nc-ZnO affords a higher JSC, but this effect lock-in detection at 500 Hz.
is counteracted a by a lower VOC, due to a growing contribu-
tion of photoconduction through the nc-ZnO. Eventually, a
suitable electron-blocking layer between the photoactive probe spectroscopy (Fig. 3b) by monitoring the intensity of
layer and the ITO/PEDOT:PSS electrode may prevent this the low-energy radical cation absorption band at 2200 nm
photo-shunt, allowing higher nc-ZnO contents and current (0.56 eV). Upon excitation at 510 nm (2.43 eV) with 200 fs
densities without the concurrent drop in VOC. Using less than pulses, the PIA signal rises within one picosecond, demon-
60 wt.-% of nc-ZnO leads to a large decrease of current den- strating an ultra-fast electron transfer. The efficiency of
sity, which can no longer be compensated by the increased charge generation has been further investigated by photolu-
voltages of over 900 mV. With over 75 wt.-% nc-ZnO the film minescence (PL) measurements. As shown in Figure 4a, up to
quality becomes very poor, probably due to large ZnO aggre- 85 % of the emission of the MDMO-PPV is quenched by the
gates. Consequently, both JSC and VOC drop significantly. addition of 75 wt.-% of nc-ZnO, due to the fast deactivation
The photoinduced charge separation has been studied in of the excited state by the electron-transfer reaction. This im-
detail by photoinduced absorption (PIA) spectroscopy. Exci- plies a high, but not quantitative, charge-generation efficiency.
tation of the MDMO-PPV:nc-ZnO mixture at 488 nm Since transient spectroscopy demonstrated an ultra-fast elec-
(2.54 eV) affords a PIA spectrum (Fig. 3a) with a photo- tron transfer, the residual PL is attributed to excitons that are
bleaching band of the neutral MDMO-PPV at 2.2 eV and the created too far away from the MDMO-PPV:nc-ZnO interface.
characteristic absorption bands of the polymer radical cation Addition of ZnO nanoparticles exceeding 75 wt.-% does not
around 0.4 eV and 1.3 eV.[18] The intensity ratio of these lead to better PL quenching, probably a result of increased
bands is different from usual, and we attribute the higher in- ZnO aggregation, leading to even coarser phase segregation.
tensity of the 0.4 eV band to electrons injected into the ZnO, The morphology of the MDMO-PPV:nc-ZnO (75 wt.-%)
which also give rise to an absorption in this region.[19] The ki- blend was examined with transmission electron microscopy
netics of charge generation has been studied with pump± (TEM). Freestanding films (50 nm) of the blends were pre-

Adv. Mater. 2004, 16, No. 12, June 17 http://www.advmat.de  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1011
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Experimental
Materials used were MDMO-PPV, PEDOT:PSS (Baytron P VPAI
4083), and Al (Engelhard-Clal). MDMO-PPV has
Mw = ~1 ” 106 g mol±1 and a polydispersity of about 7 as determined by
size-exclusion chromatography (SEC), calibrated against polystyrene.
ZnO particles were prepared following published procedures [13].
For device preparation, cleaned ITO-covered glass substrates (de-
vice area 0.1 cm2) were covered with a ~70 nm PEDOT:PSS layer by
spin-coating. Composite layers of MDMO-PPV and ZnO were spin-
coated from chlorobenzene/methanol (v/v = 95:5) solutions and the
samples were transferred to a N2 atmosphere glove box (1 ppm O2
and < 1 ppm H2O). Finally, ~100 nm thick Al layers were deposited
by thermal evaporation in vacuum (5 ” 10±6 mbar). Film-thickness
measurements were performed with a Tencor P10 surface profiler.
Device measurements were performed in a N2 atmosphere at room
temperature. In forward bias the ITO electrode was positively biased.
J±V characteristics were measured with a Keithley 2400 source meter.
For white light illumination a tungsten±halogen lamp was used, fil-
tered by a Schott KG01 and GG420 filter resulting in a spectral range
of 400±900 nm with its maximum at ~650 nm. Incident light power
was varied over 5 orders of magnitude with a series of metal-coated
neutral density filters. Incident photon to current conversion efficien-
cies (IPCE) were measured on a homebuilt setup, using a Xenon lamp
and a Spex minimate monochromator. The monochromatic light was
focussed on a diaphragm (2 mm in diameter) to create a small light
spot for solar cell illumination. Light power intensity at 500 nm was
0.74 mW cm±2 as determined with a calibrated Melles±Griot silicon
diode. Currents were recorded using a Keithley 2400 source meter.
Absorption spectra were recorded on a Perkin±Elmer Lambda 900
spectrophotometer. Fluorescence spectra were recorded on an Edin-
burgh Instruments FS920 double-monochromator spectrometer with
a Peltier-cooled red-sensitive photomultiplier.
Near-steady-state photoinduced absorption (PIA) spectra were re-
corded between 0.25 and 3 eV by exciting an MDMO-PPV:nc-ZnO
Figure 4. Investigation of charge separation efficiency. a) Photolumines- film on quartz in an Oxford Optistat continuous flow cryostat at 80 K
cence (PL) of MDMO-PPV:nc-ZnO blends as a function of the weight with a mechanically modulated (275 Hz) Ar-ion laser (Spectra Physics
fraction of nc-ZnO, after excitation at 505 nm. b) TEM photograph of a 2025) pump beam tuned to 488 nm (25 mW, beam diameter of 2 mm)
MDMO-PPV:nc-ZnO blend (with 75 wt.-% nc-ZnO), bar indicates and monitoring the resulting change in transmission (DT) of a tung-
200 nm. Dark regions indicate nc-ZnO-rich domains and lighter regions sten±halogen white-light probe beam after dispersion by a triple-grat-
indicate polymer-rich domains. ing monochromator, using Si, InGaAs, and (cooled) InSb detectors.
The femtosecond laser system used for pump±probe experiments
consisted of an amplified Ti/sapphire laser (Spectra Physics Hurri-
cane), providing 150 fs pulses at 800 nm with an energy of 750 lJ and
pared by a floating technique. The transmission micrograph of a repetition rate of 1 kHz. The pump pulses (510 nm) were created
an MDMO-PPV:nc-ZnO blend thin film in Figure 4b shows via optical parametric amplification (OPA) of the 800 nm and fre-
contrast between domains containing more ZnO (darker) and quency doubling. The probe beam (2200 nm) was generated in a sepa-
domains containing more MDMO-PPV (lighter). On a micro- rate OPA. The pump beam was linearly polarized at the magic angle
(54.7) with respect to the probe beam, to cancel out orientation ef-
meter length-scale, the films are very homogeneous, illustrat- fects in the measured dynamics. The temporal evolution of the differ-
ing the intimate mixing of the ZnO and the MDMO-PPV. The ential transmission was recorded using a cooled InSb detector by a
majority of the polymer domains appear smaller than a few standard lock-in technique at 500 Hz.
tens of nanometers, which has been shown to be the exciton Films for TEM were prepared by floatation onto the surface of
deionized water and picked up by a 400 mesh copper grid. The TEM
diffusion length in a similar PPV polymer.[20] The small num-
observations were conducted on a JEOL JEM-2000FX transmission
ber of larger polymer domains can account for the incomplete electron microscope operating at an acceleration voltage of 80 kV for
PL quenching; the residual PL stems from these domains the MDMO-PPV:nc-ZnO blends and 180 kV for the nc-ZnO nano-
where not all excitons reach an interface with a ZnO particle. particles.
In summary, we are able to make ZnO nanoparticles, which Received: December 19, 2003
are dispersed in relatively apolar solvent mixtures and can Final version: March 2, 2004
therefore easily be blended with MDMO-PPV. Upon excita-
tion, ultra-fast charge transfer occurs, which is utilized to ±
[1] J. J. M. Halls, C. A.Walsh, N. C. Greenham, E. A. Marseglia, R. H.
make efficient hybrid photovoltaic cells with a high fill factor
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1012  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 12, June 17
 COMMUNICATIONS
[4] S. E. Shaheen, C. J. Brabec, N. S. Sariciftci, F. Padinger, T. From- The range of material systems to which DPN and related tech-
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[5] P. Schilinsky, C. Waldauf, C. J. Brabec, Appl. Phys. Lett. 2002, 81,
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3885.
[6] M. M. Wienk, J. M. Kroon, W. J. H. Verhees, J. Knol, J. C. Hummelen, terning of proteins[5] and DNA[6] on gold surfaces, and metal
P. A. van Hal, R. A. J. Janssen, Angew. Chem. Int. Ed. 2003, 42, 3371. salts,[7,8] metal oxides,[9] silazanes,[10,11] alkoxysilanes,[11,12] or-
[7] W. U. Huynh, J. J. Dittmer, A. P. Alivisatos, Science 2002, 295, 2425. ganic dyes,[13] dendrimers,[14] and polymers[15] on silicon oxide
[8] B. Sun, E. Marx, N. C. Greenham, Nano Lett. 2003, 3, 961. surfaces. Herein we describe a new functional ink based on
[9] B. Schweitzer, H. Bässler, Synth. Met. 2000, 109, 1. trichlorosilane chemistry that is amenable to deposition by
[10] B. O'Regan, M. Grätzel, Nature 1991, 353, 737.
DPN onto silicon oxide. Additionally, we show this produces
[11] A. Hagfeldt, M. Grätzel, Acc. Chem. Res. 2000, 33, 269.
[12] A. L. Roest, J. J. Kelly, D. Vanmaekelbergh, E. A. Meulenkamp, a versatile template that can direct subsequent deposition or
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[13] C. Pacholski, A. Kornowski, H. Weller, Angew. Chem. Int. Ed. 2002, Lithography on insulating substrates at ever-shrinking
41, 1188. scales is critical to the future development of electronic and
[14] H. C. F. Martens, P. W. M. Blom, H. F. M. Schoo, Phys. Rev. B 2000,
sensor devices. DPN has been shown to provide a facile meth-
61, 7489.
[15] I. H. Campbell, T. W. Hagler, D. L. Smith, J. P. Ferraris, Phys. Rev.
od for the serial patterning of silicon oxide surfaces. Ivanisevic
Lett. 1996, 76, 1900. and Mirkin[10] described the deposition of hexamethyldisila-
[16] A. Hagfeldt, M. Grätzel, Chem. Rev. 1995, 95, 49. zane (HMDS) on Si and GaAs native oxide surfaces using
[17] The intensity was determined by comparing the measured JSC with DPN; however, HMDS is not amenable to further chemical
the JSC at 1 sun intensity, which was obtained from the convolution functionalization after patterning. In order to pattern mole-
of the spectral response with the solar AM1.5 spectrum, and correct-
cules on silicon oxide with DPN, Mirkin and co-workers have
ing for the small nonlinearity of the light intensity dependence using
I = I(1 sun) ” [JSC/JSC(1 sun)]1/n) with n = 0.93. also created etch-resists based on self-assembled mono-
[18] X. Wei, Z. V. Vardeny, N. S. Sariciftci, A. J. Heeger, Phys. Rev. B layers.[16,17] In this approach, a thin sacrificial layer of gold is
1996, 53, 2187. deposited on a silicon oxide substrate, followed by patterning
[19] M. Shim, P. Guyot-Sionnest, J. Am. Chem. Soc. 2001, 123, 11 651. of a thiol on the gold by DPN. A final chemical etching step
[20] T. J. Savenije, J. M. Warman, A. Goossens, Chem. Phys. Lett. 1998, removes the unpatterned gold areas. More recent papers by
287, 148.
Pena et al.[11] and Jung et al.[12] have explored the ability of
DPN to write alkoxysilanes with functional end-groups that
allow for further chemical modification. Pena et al. demon-
strated the DPN of several trimethoxy and dimethoxy silanes
Dip-Pen Nanolithography of Chemical with amine and mercaptan end-groups in registry with prede-
Templates on Silicon Oxide** fined photolithographically produced features. Similarly, Jung
et al. deposited mercaptopropyltrimethoxysilane on glass via
DPN and demonstrated further chemical modification of the
By Steven E. Kooi, Lane A. Baker, Paul E. Sheehan,
mercaptan functionality with a biotin-labeled malemide.
and Lloyd J. Whitman*
In our studies, we have chosen 10-undecenyltrichlorosilane
(UTCS) as the DPN ink' for several reasons. The choice of
In the search for new methods to pattern materials on the
UTCS, or trichlorosilanes in general, allows the direct pat-
nanoscale, DPN[1] has emerged as a flexible and relatively
terning of molecules on silicon oxide without the need for a
simple technique. In DPN, a material or ink' is coated onto
solvent or elevated temperatures. Our approach results in the
an atomic force microscope (AFM) cantilever tip, generally
direct covalent attachment through only the headgroup of the
by vapour-phase or solution-phase deposition. The ink is sub-
silane, leaving the olefin-terminated tail (in the case of UTCS)
sequently deposited from the AFM tip onto an appropriate
available as a flexible starting point for further chemical mod-
substrate. Typically, there is a clear chemical or electrochemi-
ification. Possible modifications include the covalent or non-
cal driving force for transfer of the ink to the surface; for ex-
covalent growth of nanoparticles, conducting polymers, metal
ample, the chemisorption of alkanethiols onto a gold surface.
films, or biomolecules.
± Although some authors have proposed that trichlorosilanes
[*] Dr. L. J. Whitman, Dr. S. E. Kooi,[+] Dr. L. A. Baker, and alkoxysilanes would be unsuitable inks' for DPN[10] (due
Dr. P. E. Sheehan to possible decomposition or polymerization in the water me-
Naval Research Laboratory niscus that forms between the tip and surface), Pena et al.[11]
Washington, DC 20375 (USA)
E-mail: [email protected] and Jung et al.[12] have both found that deposition is possible
[+] Present address: Institute for Soldier Nanotechnologies, in the case of alkoxysilanes. Given careful tip preparation, we
Massachusetts Institute of Technology, Cambridge, MA 02139, USA. have found that trichlorosilanes can also be written under ap-
[**] We would like to thank Dr. Thomas Clark for insightful discussions propriate conditions. Specifically, to achieve reproducible re-
and Dr. John N. Russell, Jr., for use of an FTIR spectrometer. SEK sults, the silicon nitride AFM tips must be made hydrophobic
and LAB acknowledge the support of NRC/NRL Postdoctoral Re-
search Associateships. The support of this work by the AFOSR and prior to inking by first coating the tips with a silane layer. To
the ONR is gratefully acknowledged. remove any ambiguity as to the silane molecule deposited

Adv. Mater. 2004, 16, No. 12, June 17 DOI: 10.1002/adma.200306468  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1013