Thin Solid Films 384 2001.

90 101

Atomic force microscopy observation of the morphology of tetracyanoquinodimethane TCNQ. deposited from solution onto the atomically smooth native oxide surface of Al 111. lms
M. Higo a,U , X. Lub,1, U. Mazur b , K.W. Hippsb
Department of Applied Chemistry and Chemical Engineering, Faculty of Engineering, Kagoshima Uni ersity, Korimoto, Kagoshima 890-0065, Japan b Materials Science Program and Department of Chemistry, Washington State Uni ersity, Pullman, WA 99164-4630, USA Received 1 March 2000; received in revised form 16 August 2000; accepted 13 October 2000
a

Abstract The morphology of tetracyanoquinodimethane TCNQ. and of benzoic acid deposited from solutions onto atomically smooth native oxide surfaces of Al111. lms was observed by atomic force microscopy AFM.. A surface height analysis bearing analysis . of the AFM images of TCNQ-deposited atomically smooth oxidized Al lms gave a bimodal height distribution of the adsorbed TCNQ on the surfaces. The height distribution showed that TCNQ is adsorbed on the oxide surface as both a uniform lm on a nanometer scale and micrometer-sized particles with the height ranging from 10 to 100 nm above the surface. The large particles are easily identied by AFM as microcrystallites of neutral TCNQ and they have many morphologies. The uniform lm with the nanometer scale height distribution results predominantly from corrosion of the oxide surface by the TCNQ anion formation reaction. The volumes of the large particles and of the thin uniform lm were obtained separately from the analysis of the bearing histogram and bearing area curve. Generally, the volume approx. 2 m3 for a 30 = 30- m2 area. of the thin uniform lm is 4 5 times larger than the volume of one monolayer of TCNQ or TCNQ salt. Benzoic acid treated surfaces, on the other hand, did not show a bimodal distribution nor large particles, and surface roughness is consistent with monolayer formation of aluminum benzoate. Discrepancies in inelastic electron tunneling spectroscopy and X-ray photoelectron spectroscopy results for TCNQ adsorption on alumina were discussed. 2001 Published by Elsevier Science B.V. All rights reserved.
Keywords: Aluminium oxide; Atomic force microscopy; Deposition process; Surface morphology

1. Introduction Scanning probe microscopes are powerful tools for observing the morphology of solid surfaces and species adsorbed on them. These unique devices enable us to investigate material surfaces in situ and non-destructively on an atomic scale. Many studies of surface species using scanning tunneling microscopy STM.
U

Corresponding author. Fax: q81-99-285-8344. E-mail address: higo@apc.kagoshima-u.ac.jp M. Higo.. Present address: Seagate Recording Media, 311 Turquoise Street, Milpitas, CA 95035, USA.
1

and atomic force microscopy AFM. have been introduced in several books and articles w1 3x. These techniques have made, and continue to make, great contributions to modern science and technology. One prerequisite for successful imaging of adsorbed species on and below the nanometer scale is the use of substrates having atomically smooth surfaces. In the case of oxide substrates, it is often difcult or impossible to shape and polish a macroscopic sample to the requisite atness and smoothness. In this paper, we will use the previously characterized surface of a native oxide grown on an Al111. lm as an atomically smooth substrate and report on the adsorption of an organic redox active

0040-6090r01r$ - see front matter 2001 Published by Elsevier Science B.V. All rights reserved. PII: S 0 0 4 0 - 6 0 9 0 0 0 . 0 1 8 0 7 - 1

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molecule, 7,7,8,8-tetracyanoquinodimethane TCNQ., onto that surface. Our motivation for this work was twofold. First, we wanted to observe and characterize the morphology of spin-doped surfaces. Second, we wanted to relate the observed morphology to differences in spectroscopic results obtained by different techniques from the same surface. We chose TCNQdoped alumina in particular because of the differences in the surface species reported TCNQ 0 , TCNQy1 , TCNQy2 , etc.. by different spectroscopic techniques. To this end, TCNQ a low volatility reactive compound. is compared against benzoic acid a volatile reactive reagent.. TCNQ has four cyano groups and all electrons are delocalized. It is a strong electron acceptor and forms a variety of charge-transfer complexes with inorganic and organic donors w4 7x. Copper and silver complexes of TCNQ and its derivatives exhibit unique electrical and optical eld-induced switching and memory phenomena w8 20x. The resistivity of Cu or Ag TCNQ complex lms grown on Cu or Ag and coated with Al switches from a high impedance state to a low impedance state under the application of an external electric eld or laser irradiation. These materials have been proposed for applications in molecular electronic devices such as switches and data storage media. However, the mechanism of the resistivity transition in the switching device and the resulting structure change of the TCNQ complexes are not well understood. Since the resistivities of these molecular semiconductors vary greatly with crystallographic orientation, degree of crystallinity, and surface orientation of the lms w4 7x, a detailed understanding of the morphology, spectroscopy, and chemistry of these materials in bulk, in thin lms, and at interfaces is necessary w21 38x. Morphological studies of TCNQ and its metal complexes on metal surfaces have been done by scanning probe microscopy. Yamaguchi and co-workers w21,26,27x have imaged the surface structures of Ag and Cu TCNQ lms on graphite HOPG. with molecular level resolution by STM. They have also observed a eld-induced charge-transfer reaction driven by the electric eld generated by the microscope tip potential when the bias voltage exceeds the switching threshold of the metal TCNQ complexes. They concluded that the electrical switching phenomenon is a bulk property of the metal TCNQ, as proposed previously w8 18x. Similar observations have been reported for Cu TCNQ lms on HOPG by Matsumoto et al. w22x. Hietschold et al. w23x applied both AFM and STM to image polycrystalline TCNQ lms on a steel substrate used as a pressure sensor. Hoagland et al. w24x used scanning electron microscopy SEM. and STM to determine the morphology of Cu TCNQ lms made using solution phase and vapor phase spontaneous reaction methods. They showed that all the lms display roughness on the

order of the lm thickness and that the morphology of the lms varied signicantly with the preparation procedure. Only devices having a thin Al top electrode, and then only after exposure to air, had signicant resistance. They suggested that the switching is an interfacial phenomenon between the rough Cu TCNQ surface and a deposited aluminum electrode. Others have also suggested that the interface between the electrode and metal TCNQ complex plays an important role in switching devices w19,20x. Gu et al. w25x observed many nanometer-sized passageways in the growth direction in the crystalline grains of Cu TCNQ lms prepared by the spontaneous reaction method using AFM. In thin lms prepared on HOPG by an ionized-cluster-beam deposition method, Gao et al. w28x used STM to observe a periodic arrangement and they interpreted as molecular chains of TCNQ. High-resolution X-ray photoelectron spectroscopy XPS. spectra of C1s. and N1s. of TCNQ and Cu-, Ni-, and Li-complexes have been measured by Lindquist and Hemminger w29,30x. The growth of TCNQ lms on Ni111. has been investigated using XPS, Auger electron spectroscopy, and ultra-violet photoelectron spectroscopy by Giergiel and co-workers w31,32x. Patterson et al. w33x have reported the characterization of TCNQ lms on Cu, Au, Pt and SnS 2 . The vibrational spectra of TCNQ adsorbed on a Cu111. single crystal surface at 100 K have been obtained using high-resolution electron energy loss spectroscopy HREELS. by Erley and Ibach w34x. They have found that TCNQ is adsorbed predominantly as the trianion with its plane parallel to the surface for coverage up to a single monolayer. As the coverage increases, the monoanion was dominant in the second layer and nally neutral TCNQ appeared in the multilayer. The vibrational spectra of TCNQ and its derivatives adsorbed on alumina have been recorded and studied by inelastic electron tunneling spectroscopy IETS. w35 38x. Korman and Coleman w36x compared the tunneling spectra of TCNQ adsorbed on alumina with the infrared and Raman spectra of the neutral TCNQ and of the TCNQy1 and concluded that the monoanion of TCNQ is the stable form on alumina. Neutral TCNQ also makes a small contribution to the IETS signal, but this was thought to arise from large clusters of material isolated from the alumina surface by several layers of TCNQ anion. Cooper et al. w37x have compared the tunneling spectrum of TCNQ on alumina with the vibrational structure in the optical reectivity of K TCNQ and found a good correspondence between these results. Hipps and Mazur w38x have measured the tunneling spectra of TCNQ on alumina doped under inert conditions using a glove box deposition system. They have reported that the surface species formed are independent of the presence of air during the adsorption step and concluded that TCNQ is adsorbed as the

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M. Higo et al. r Thin Solid Films 384 (2001) 90 101

monoanion on the alumina surfaces. These tunneling spectra show that the monoanion of TCNQ is the dominant surface species on alumina. However, the XPS study w39x of TCNQ adsorbed on an oxidized Al lm suggested that neutral TCNQ predominates on the alumina surface. This difference in results could be due to the morphology of the adsorbed TCNQ, because TCNQ is adsorbed from monolayer to multilayer coverage on the alumina surfaces, and IETS is sensitive only to areas having sub- to two-monolayer coverage. XPS, on the other hand, probes all the material within a few tens of nanometers of the surface w40x. Thus, knowledge of the morphology of the adsorbed species is critical to interpret the various surface spectroscopic results correctly. These electron spectroscopies have shown that TCNQ interacts with metals and aluminum oxide to produce a surface anionic species. Neutral TCNQ is also present in multilayer lms. Although these electron spectroscopies provide information about the adsorption state of TCNQ, the morphology of the adsorbed TCNQ at low coverage and the degree of surface roughness have not been considered. Morphological observation of TCNQ at low coverage on reactive surfaces are needed in order to understand thoroughly the adsorption chemistry of this important redox active species and to provide a model for the adsorption of other redox active organic adsorbates. Another driving force for morphological studies of spin-doped surfaces is the fact that more controlled adsorption methods such as vapor deposition. on well-dened surfaces are not available for ionic species. Surface oxidized aluminum and magnesium have long served as models for catalytic oxides; models that are much easier to dene than conventional high surface area powders w41 45x. In studies of ionic metal catalysts and catalyst precursors, adsorption on these model surfaces by spin doping is the only viable way to distribute the inorganic species in near monolayer concentrations. To our knowledge, this is the rst study that has actually probed the morphology of a spin-doped species on an atomically smooth surface. As such, it will provide insights into the practice of spin-doping in general. We have reported the preparation and characterization of very smooth Al lms on a nanometer scale over a wide surface area w46,47x. Such atomically smooth lms are important and useful in modern surface science techniques in order to study chemisorption from submonolayer to multilayer coverage. In our preliminary study w48x, we have demonstrated that these atomically smooth Al lms enable us to perform a morphological observation of TCNQ on alumina by AFM. We have observed the morphology of TCNQ deposited from various solutions onto the oxidized Al lms. The analysis of the AFM images showed that

TCNQ is adsorbed onto the surfaces as both a uniform lm on a nanometer scale and micrometer-sized particles with many morphologies. In the present paper, we report a thorough AFM study of the morphology of TCNQ deposited from various solutions onto atomically smooth native oxide surfaces grown on polycrystalline Al111.. We also discuss the discrepancy in IETS and XPS results on the adsorption state of TCNQ on alumina. 2. Experimental Atomically smooth Al lms with a thickness of 200 300 nm were prepared at a temperature of 350 C and at a pressure of 10y7 torr by vacuum evaporation of Al 99.999%. onto previously cleaved and heated 550 C. mica substrates 8 = 8 mm2 .. The details of the evaporator and the procedures have been previously described w46,47x. Freshly prepared Al lms were cooled to below 90 C in vacuum and their surfaces were oxidized in an oxygen a.c. glow discharge 50 mtorr, 3 min. to form a stable surface oxide. Samples of adsorbed TCNQ on atomically smooth aluminum oxide surfaces were prepared by the spin doping technique as used in the preparation of tunneling junctions for inelastic electron tunneling spectroscopy IETS. w35 38x. TCNQ was spin-doped from various solvents and concentrations at room temperature 22 23 C. and humidity of approximately 30%. One drop of solution was placed on the oxide surface and excess solution was immediately removed by spinning. The spin times were 5, 10 and 25 s. After doping, volatile materials were removed from the samples by vacuum treatment for approximately 5 min at a pressure of 10y6 torr in a bell-jar evaporator Denton Vacuum DV-502A. equipped with a liquid-nitrogentrapped 2.5-inch diffusion-pump. TCNQ Tokyo Kasei Organic Chemicals, ) 98%. was puried by recrystallization from distilled CH 3 CN. Acetonitrile, acetone, and methanol J.T. Baker Inc.. were used without further purication. The AFM images 256 or 512 pixels wide. of the TCNQ-coated atomically smooth Al oxide surfaces were taken with a Digital Instruments NanoScope III operating in contact mode in air. The cantilevers were 200- m long Si 3 N4 with an approximate force constant of 0.06 Nrm. The images were automatically plane-tted to account for sample tilt. 3. Results and discussion 3.1. Undoped and sol ent-doped atomically smooth oxidized Al lms The AFM top views and histograms of the bearing analysis of an atomically smooth oxidized Al lm pre-

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93

Fig. 1. AFM top views top. and histograms bottom. from the bearing analysis of an oxidized Al lm prepared on mica substrate at 20 C left. and a typical atomically smooth oxidized Al111. lm prepared on mica substrates at 350 C right.. Image size: 1 = 1 m2 and 20-nm gray scale. The full width at half maximum W . of the histogram is also shown. The bearing volume V . is dened as the volume above the depth of W indicated by the marker.

pared at 350 C and an oxidized Al lm prepared at 20 C are shown in Fig. 1. The picture size is 1 = 1 m2 and a 20-nm gray scale is used to represent height. The bearing analysis provides a method of plotting and analyzing the histogram of surface height over a sample. A surface area and a volume above a certain depth are calculated using the standard NanoScope III software. The histogram of a rough surface displays a wider distribution than that of a smooth surface. Therefore,

the width full width at half maximum: W . of the histogram is a good measure of the surface roughness. The bearing volume V . is dened as the volume above the depth of W in the histogram, as shown in Fig. 1. The average values and standard deviations of the root-mean-square roughness Rms., the maximum height between the highest point and lowest point R max . obtained from the roughness analysis w47x, and W and V obtained from the bearing analysis of the AFM images of the atomically smooth oxidized Al lms prepared at 350 C are shown in Table 1. Since the bearing analysis is very sensitive to the curvature of the image plane, a third order polynomial planet was used to account for the sample tilt and a slight curvature that results from coupling between the z and the x y piezoelectric positioners. The roughness analysis is not so sensitive to the image curvature and a rst order plane t was used w47x. The surface of the oxidized Al lm prepared at 20 C is very rough; Rms is 1.63" 0.47 nm and R max is 12.2" 2.8 nm w47x. There are small grains approximately 100 nm in diameter and their tops are rounded. The grains are loosely packed and their boundaries are wide and deep. The lm is typical polycrystalline and the structure is characterized by columns with domed tops. The surface morphology of the lm is caused by self shadowing during the deposition, because the surface diffusion of adatoms is too small to allow migration into the shadowed regions at this temperature w46,47x. The bearing histogram shows that the surface height distributes over a wide range of approximately 10 nm; W is 3.13" 0.70 nm and V is 3.11" 0.67. = 10y3 m3. The AFM top view of the atomically smooth oxidized Al lm prepared at 350 C shows that the grains become bigger and the surfaces are very smooth over a wide area; Rms and R max are 0.55" 0.18 and 5.4" 1.6 nm, respectively w46,47x. These values are due to steps of a few atoms high rather than to roughness in the terraces. The grain size is approximately 300 nm and terraces are atomically smooth. The grains are tightly packed and their boundaries are narrow and well de-

Table 1 Roughness Rms., maximum height between the highest and lowest points R ma x ., full width at half maximum W . of the bearing histogram, and bearing volume V . obtained from the analysis of the AFM images 1 = 1 and 30 = 30 m2 . of undoped and solvent-doped atomically smooth oxidized Al111. lms prepared on mica at 350 C a Image size Solvent Undoped CH3 CN CH3 .2 C O CH3 OH H2 O
a

1 = 1 m2 Rmsrnm 0.55" 0.18 0.63 0.52 0.41 0.55 Rma xrnm 5.4" 1.6 9.0 6.1 2.8 5.2 Wrnm 0.88" 0.42 0.89 0.69 0.87 0.93 V = 10 r m 0.88" 0.42 0.86 0.68 0.89 0.94
3 3

30 = 30 Wrnm 2.5" 0.7 2.4 3.1 2.2 2.2

m2 Vr m3 2.3" 0.7 2.2 2.8 2.0 2.0

Uncertainties of the values of the solvent-doped Al lms are identical to the standard deviations of the undoped Al lms.

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M. Higo et al. r Thin Solid Films 384 (2001) 90 101

ned. Apparently, surface diffusion of the adatoms is sufcient to overcome the self-shadowing effect and it leads to surface recrystallization and atomically smooth surfaces at this temperature. The bearing histogram shows that the surface heights distribute in a relatively narrow range and W and V become smaller 0.88" 0.42 nm and 0.88" 0.42= 10y3 m3 , respectively.. The 30 = 30- m2 images of the undoped atomically smooth oxidized Al lms were also analyzed by bearing analysis and the results are shown in Table 1. The transmission electron diffraction TED. pattern of the Al lm prepared at 350 C has clear sixfold symmetry spots and is a typical pattern produced by the 111. face of a face-centered-cubic fcc. lattice w46,47x. As the aperture size increases, the pattern becomes a ring. The TED patterns show that the lms prepared at 350 C consist of relatively big crystals with 111. faces but that each crystal is oriented randomly about the w111x direction. The dark-eld TEM micrographs show almost the same contrast for all the crystals and indicates that the crystals are exactly oriented about the w111x direction which is perpendicular to the substrate. Thus, the Al lm prepared on mica at 350 C is not epitaxial w46,47x. Al lms prepared on mica at 350 C and then plasma oxidized were used as the substrates for the TCNQ adsorption study reported here. The surfaces of atomically smooth oxidized Al lms doped with pure solvents acetonitrile, acetone, methanol, and water. were characterized by roughness and bearing analysis of 1 = 1- m2 images, and the values of Rms, R max , W and V are shown in Table 1. The AFM top view and histogram of the bearing analysis of an image 30 = 30 m2 and 200-nm gray scale. taken from an atomically smooth oxidized Al lm doped from CH 3 CN are shown in Fig. 2. The values of W and V for 30 = 30- m2 images of the undoped, acetonitrile-, acetone-, methanol- and water-doped oxide surfaces are also shown in Table 1. There were no discernible changes in alumina surface morphology upon solvent doping. Thus, these solvents have no signicant effect on the morphology of the alumina lms, and they are appropriate for morphological studies of spin-doped materials on atomically smooth alumina. 3.2. Morphology of TCNQ on atomically smooth oxidized Al lms deposited from solutions The AFM top view and the bearing histogram of an atomically smooth oxidized Al111. lm doped from the 0.10-mgrml acetonitrile solution using a 10-s spin time is shown in Fig. 2. The image size is 30 = 30 m2 and a 200-nm gray scale is employed. It was found that TCNQ is deposited on the oxidized Al surface as particles in a mixture of morphologies. Images with a size of 100 m wide and taken at other sites on this lm indicate that the particles are uniformly deposited

Fig. 2. AFM top view top. and bearing histogram bottom. of TCNQ on an atomically smooth oxidized Al111. lm spin-doped from the 0.10-mgrml CH 3 CN solution. AFM top view and bearing histogram of the CH 3 CN-doped atomically smooth oxidized Al111. lm is also shown. The Al lms were prepared on mica substrates at 350 C. Spin time: 10 s. Image size: 30 = 30 m2 and 200-nm gray scale. The bearing histogram of the TCNQ-deposited oxidized Al lm shows a bimodal height distribution of TCNQ particles. The bearing volumes of large and small TCNQ particles are separated from that of total TCNQ particles at a depth of y5.0 nm in the histogram.

on the surface. The bearing histogram indicates a bimodal height distribution of the surface resulting from spin-doping TCNQ onto alumina. The main peak near 0 nm relative depth in Fig. 2 is associated with both the initial surface roughness and slight roughening or small particles of surface reaction products. The broad peak maximizing near y30 nm reects the presence of the large particles of TCNQ seen in the AFM image. The width of the main peak, W, will be used to characterize both distributions. The bearing volume corresponding to depths more negative than yW is associated with the large particles on the surface. The bearing volume associated with the 2W region from yW to qW will be attributed to the initial surface roughness and small nanoscopic. particle formation. For convenience of nomenclature, we will speak of the small particle distribution, when in fact much of the width may be due to roughening rather than particle deposition vide infra.. In the particular case of Fig. 2, the surface height of the small particle distribution is spread over a

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wider range Ws 5.0 nm. than in the case of the undoped oxide surface Ws 2.5 nm. or the solventdoped oxide Ws 2.4 nm.. The heights of large particles distribute in a range of 10 60 nm and the average height is approximately 30 nm. The lateral size of these large particles ranges from 1 to 10 m in length. The bearing volume above the depth of W 5.0 nm. gives the volume 8.8 m3 . of all TCNQ particles and any roughness of the oxide, including the initial roughness. The volume increase 6.5 m3 . associated with TCNQ adsorption can be obtained by subtracting the volume 2.3 m3 . of the undoped oxide from the bearing volume 8.8 m3 .. If the histogram is separated at the depth of y5.0 nm, we can calculate the volumes of large and small deposited TCNQ particles to be 3.9 and 2.6 m3, respectively. The AFM top views of atomically smooth oxidized Al111. lms doped from 0.50-mgrml a,b,c. and 0.20mgrml d,e,f. acetonitrile solutions are shown in Fig. 3. The spin times were 5 s a,d., 10 s b,e., and 25 s c,f.. All of these images are 30 = 30 m2 with a 200-nm gray scale. There are many of the large particles present on these surfaces. Images with a size of 100 m wide and taken at other sites on these lms indicate that the particles are uniformly distributed and their morphology changes slowly with spin time and solution concentration. The size of large particles ranges from 0.1 to 1 m in length. The bearing analysis of these images shows that the heights of the large particles deposited from the 0.50- and 0.20-mgrml solution distribute in height ranges of 10 100 and 10 50 nm, respectively. The average values and standard deviations of the widths W . of the small particle peaks in the bearing histograms of these lms are shown in Table 2. The average peak width 11.2 nm. in the bearing histograms of small particles of the TCNQdoped alumina lms from the 0.50-mgrml solution is larger than that 4.8 nm. of the lms from the 0.20mgrml solution, suggesting growth in the particles with increasing solution concentration. The average volumes of the large, small, and total particles calculated using the widths and the bearing histograms are also shown

in Table 2. After the AFM measurement, the sample doped from the 0.50-mgrml solution with the 25-s spin time c. was returned to the vacuum chamber and pumped at a pressure of 10y6 torr for 5 min and measured again by AFM. The morphology of the particles, the bearing histogram of the image, and the volume of TCNQ particles had not changed, showing that the TCNQ particles are stable on the surfaces. The AFM top views of atomically smooth oxidized Al111. lms doped from 0.10-mgrml a,b,c. and 0.05mgrml d,e,f. acetonitrile solutions are shown in Fig. 4. The spin times were 5 s a,d., 10 s b,e., and 25 s c,f.. All of these images are 30 = 30 m2 with a 200-nm gray scale. The average values of the peak widths W . in the bearing histograms of the small particles, and the volumes V . of the large, small, and total particles are shown in Table 2. In the case of the lms doped from the 0.10-mgrml solution, we note that two additional images of different lms were also used for the calculation. All of the values of the TCNQ-doped lms from the 0.50-mgrml solution are larger than those of lms formed from lower concentration solutions. On the other hand, there is little statistical difference in the particle distributions obtained over the 0.05 0.20mgrml solution range. This suggests that the spin doping of TCNQ from acetonitrile solutions produces a stable surface distribution so long as the concentration lies in the range extending from 0.20 mgrml down to below 0.05 mgrml. All of these images have the common feature of being composed of short thread-like segments of TCNQ crystallites. The heights of the large particles deposited from these solutions distribute in a range of 10 50 nm and are of the order of 10 m in length. These same lament structures can also be seen in Fig. 2 a different sample prepared under conditions similar to Fig. 4b. However, the laments in Fig. 2 are shorter and there are also some circular structures present. Thus, we have the curious situation that the statistical measures reported in Table 2 are very stable over the 0.05 0.20-mgrml concentration range, but the detailed appearance of the macroscopic structures is not. This suggests to us that there is some uncontrolled

Table 2 Full width at half maximum W . of the bearing histogram and volume V . of large, small, and total TCNQ particles obtained from the AFM images 30 = 30 m2 . of TCNQ-doped atomically smooth oxidized Al111. lms from various concentrations of acetonitrile solutions a 0.05 mgrml Wrnm Vr m Large Small Total
3

0.10 mgrml Wrnm Vr m Large Small Total

3

0.20 mgrml Wrnm Vr m Large Small Total

3

0.50 mgrml Wrnm Vr m3 Large Small Total 4.2" 1.2 8.8" 6.1 13.0" 5.0

4.4" 1.0

1.0" 0.7 1.8" 0.9 2.8" 1.5

4.3" 0.8

1.6" 1.3 1.8" 0.8 3.4" 2.0

4.8" 0.3

1.7" 0.1 2.3" 0.4 4.0" 0.3

11.2" 6.5

Uncertainties of the values are standard deviations.

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Fig. 3. AFM top views of TCNQ on atomically smooth oxidized Al111. lms spin-doped from CH 3 CN solutions. Concentration: 0.50 mgrml a,b,c. and 0.20 mgrml d,e,f.. Spin time: 5 s a,d., 10 s b,e., and 25 s c,f.. Image size: 30 = 30 m2 and 200-nm gray scale.

parameter that determines the shapes of the large particles but it does not determine the distribution between small and large particles. One such possibility

is the time between wetting the surface and commencing the spin. Because of the way our system is congured, this time interval can lay between 1 and 5 s.

Fig. 4. AFM top views of TCNQ on atomically smooth oxidized Al111. lms spin-doped from CH 3 CN solutions. Concentration: 0.10 mgrml a,b,c. and 0.05 mgrml d,e,f.. Spin time: 5 s a,d., 10 s b,e., and 25 s c,f.. Image size: 30 = 30 m2 and 200-nm gray scale.

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Fig. 5. Full width at half maximum W . of the bearing histogram . and volume V . of large `., small ^., and total I. TCNQ particles obtained from the AFM images 30 = 30 m2 . of TCNQdoped atomically smooth oxidized Al111. lms from various concentrations of acetonitrile solutions.

The average values of the peak widths W . in the bearing histograms of the small particles, and the volumes V . of the large, small, and total particles of the TCNQ-doped lms in Table 2 are also plotted against the solution concentrations and the result is shown in Fig. 5. The peak widths W . in the bearing histograms of the small particles are almost constant approx. 5 nm. in the 0.05 0.20-mgrml concentration range, resulting from the increase of 2 3 nm in the width. The volumes V . of the large and small particles of the TCNQ are almost equal approx. 2 m3 . and also increase slightly with the solution concentrations in the range of 0.05 0.20 mgrml. If TCNQ is adsorbed uniformly on the alumina surfaces, the volume approx. 2 m3 . of the small particles on the 30 = 30- m2 surface gives the height of approximately 2 nm. This is

consistent with the result obtained from the peak width W . of the bearing histogram. Fig. 6 shows the AFM top views of atomically smooth oxidized Al111. lms doped from 0.10-mgrml acetone a,b,c. and 0.10-mgrml methanol d,e,f. solutions. The spin times were 5 s a,d., 10 s b,e., and 25 s c,f.. All of these images are 30 = 30 mm2 with a 200-nm gray scale. There are many TCNQ particles with different sizes and shapes circles, curved strings, branches, etc... The size of the particles has a range of 1 10 m in length. The heights of the large particles distribute in a range of 10 100 nm. The average values and standard deviations of the peak widths W . in the bearing histograms of the smaller features in these surfaces and the volumes V . of the particles are shown in Table 3. The corresponding results from oxidized Al lms doped with 0.10-mgrml acetonitrile solution are also shown in this table. The small particle peak widths 4.4 nm. from the acetone solution are almost equal to those 4.3 nm. from the acetonitrile solution, however, the widths 17.4 nm. from the methanol solution are larger, suggesting that the nanometer scale particle formation is more favorable when TCNQ is deposited from methanol solution. All of the volumes of the deposited particles from the methanol solution are also signicantly larger than those of the particles from the other solvents. After the samples were prepared using the 0.10mgrml acetonitrile, acetone, and methanol solution and the 10-s spin time as described above, the surfaces were rinsed with one drop of the same solvent used for the spin doping. These samples were then placed in a vacuum chamber and pumped at a pressure of 10y6 torr for 5 min to remove any residual solvent and to replicate the treatment of samples studied by IETS. The AFM top views of the TCNQ-deposited oxidized Al111. lms from these solutions following the solvent rinse are shown in Fig. 7. All of these images are 30 = 30 mm2 with a 200-nm gray scale. The peak widths W . in the bearing histograms of the smaller features in these surfaces and the volumes V . of the particles are shown in Table 4. It is clear that the deposited TCNQ particles are broken, spread, and con-

Table 3 Full width at half maximum W . of the bearing histogram and volume V . of large, small, and total TCNQ particles obtained from the AFM images 30 = 30 m2 . of TCNQ-doped atomically smooth oxidized Al111. lms from 0.10-mgrml acetonitrile, acetone, and methanol solutions a CH3 CN Wrnm Vr m3 Large Small Total 1.6" 1.3 1.8" 0.8 3.4" 2.0 CH3 .2 C O Wrnm Vr m3 Large Small Total 1.6" 0.6 1.9" 1.1 3.6" 1.3 CH3 OH Wrnm Vr m3 Large Small Total 9.6" 6.6 14.4" 5.0 24.0" 11.4

4.3" 0.8

4.4" 1.2

17.4 " 4.3

Uncertainties of the values are standard deviations.

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Fig. 6. AFM top views of TCNQ on atomically smooth oxidized Al111. lms spin-doped from 0.10-mgrml CH 3 . 2 C O a,b,c. and 0.10-mgrml CH 3 OH d,e,f. solutions. Spin time: 5 s a,d., 10 s b,e., and 25 s c,f.. Image size: 30 = 30 m2 and 200-nm gray scale.

nected by the dissolution. However, the peak widths in the bearing histograms and the volumes of the particles did not change appreciably in the case of acetonitrile and acetone, showing that the initial amount of TCNQ still remains on the surfaces. This reinforces our earlier observation that while the detailed appearance of the surface distribution of large particles can vary dramatically with changes in the doping procedure, the relative distribution of small to large particles is quite stable in the 0.05 0.20-mgrml range in the case of acetonitrile and acetone solutions. In order to contrast the morphology of deposited TCNQ on another substrate, the AFM observation of TCNQ-doped mica sheet was carried out. The AFM top views of mica sheet doped from the 0.10-mgrml

acetonitrile solution using the 10-s spin time are shown in Fig. 8. The picture sizes are 30 m wide a., 10 m wide b., and 3 m wide c., and a 300-nm gray scale was used for all. The AFM images of TCNQ-doped mica sheets indicate smaller and fewer particles on the surfaces. The morphology of the particles is simple oval and in clear contrast with that on the alumina lms. The size of the particles is of the order of 0.1 m in length and the height has a range of 5 50 nm. The particles are uniformly present on the surfaces and the peak width approx. 1.1 nm. in the bearing histogram on the 30 = 30- m2 area of the mica substrate has no change upon the doping. No change in this peak width suggests no small nanometer. particles of TCNQ on the mica surface. The total volume of the deposited

Table 4 Full width at half maximum W . of the bearing histogram and volume V . of large, small, and total TCNQ particles obtained from the AFM images 30 = 30 m2 . of TCNQ-doped atomically smooth oxidized Al111. lms from 0.10-mgrml acetonitrile, acetone, and methanol solutions, and following a rinse with the appropriate solvents a CH3 CN Wrnm Vr m3 Large Small Total 1.0 2.0 3.1
a

CH3 .2 C O Wrnm Vr m3 Large Small Total 0.6 2.2 2.8

CH3 OH Wrnm Vr m3 Large Small Total 2.6 12.5 15.1

4.6

4.7

15.2

Uncertainties of the values are identical with those of the TCNQ-doped lms in Table 3.

M. Higo et al. r Thin Solid Films 384 (2001) 90 101

99

Fig. 7. AFM top views of TCNQ on atomically smooth oxidized Al111. lms spin-doped from 0.10-mgrml CH 3 CN a., CH 3 . 2 C O b., and CH 3 OH c. solutions following a rinse with the same solvents and evacuation at 10y6 torr for 5 min. Spin time: 10 s. Image size: 30 = 30 m2 and 200-nm gray scale.

particles on the 30- m wide surface is calculated to be of the order of 0.1 m3. The AFM observation of benzoic acid-doped atomically smooth oxidized Al lm from the 0.50-mgrml aqueous solution was carried out. It is well known that benzoic acid is adsorbed uniformly as benzonate anion on alumina surfaces by IETS w49,50x. The spin doping following removal of excess benzoic acid by the vacuum treatment gives a monolayer of adsorbed benzonate anion on the surface w49,50x. The AFM images of the benzoic acid-doped oxidized Al lm were identical with those of the undoped and solvent-doped oxidized Al lms, showing that benzoic acid is adsorbed as a very thin uniform layer on the surface. The values of Rms and R max on the 1- m wide surface are 0.61 and 5.4 nm, respectively. Those of W and V on the 30- m wide surface are 2.6 nm and 2.4 m3 , respectively. These values agree well with those of the undoped and solvent-doped oxidized Al lms. Thus, it is concluded that benzoic acid is adsorbed uniformly as a monolayer on the atomically smooth oxidized Al lm and the height of the adsorbed species is too low to be detected by AFM. This is in clear contrast to the results obtained in the case of TCNQ adsorption. It has been found that when TCNQ is deposited from several organic solutions onto alumina, a bimodal

distribution in surface height results. The large size distribution is composed of particles with varying shapes and sizes in the range of 0.1 10 m in length and 10 100 nm in height. The volume of the deposited large particles on the 30 = 30- m2 surface ranges from 1 to 10 m3. Since the volatility of TCNQ is relatively low, it seems that the morphology changes in the large TCNQ particles is mainly related to the doping conditions, for example, solubility of TCNQ in the solvent, vapor pressure and boiling point of the solvent, and so on. In the present study, we have easily observed the morphology of relatively large particles of TCNQ deposited on the oxidized Al surfaces. The second region of the bimodal distribution typically has a width of approximately 5 nm and the volume of the small particles on the 30- m wide surface ranges from 2 to 14 m3. The small particle region of the distribution is probably the result of both reactive etching of the alumina substrate and the formation of nanometer sized crystallites of surface reaction products of TCNQ. The known reaction of TCNQ with alumina or aluminum to produce TCNQy1 w35 38x, represents a corrosion mechanism that may lead to roughening of the surface. Another possible contribution to the small particle distribution is also related to the aluminum TCNQ reaction. Nanocrystals of aluminum salts of

Fig. 8. AFM top views of the TCNQ on mica sheet spin-doped from the 0.10-mgrml CH 3 CN solution. Spin time: 10 s. Image size: 30 = 30 a., 10 = 10 m2 b., and 3 = 3 m2 c., and 300-nm gray scale.

m2

100

M. Higo et al. r Thin Solid Films 384 (2001) 90 101

TCNQy1 may form as the reaction products precipitate from solution during the last stages of the spin doping process. To date, we have not been able to separate these two effects. The vibrational spectra of adsorbed TCNQ on alumina surfaces of AlrAl 2 O 3rTCNQrPb tunneling junctions have been measured by IETS w35 38x. The tunneling junctions were prepared by vacuum evaporation following an oxidation of Al at room temperature, giving rough surfaces as shown in Fig. 1. The tunneling spectra show that surface reaction products TCNQ anion. are the dominant species on the alumina. On the other hand, the XPS spectrum of TCNQ adsorbed on oxidized Al lms suggested the predominance of neutral TCNQ on those surfaces w39x. This discrepancy in the IETS and XPS results can be understood from the morphology of the adsorbed TCNQ and the sensitivities of both the spectroscopies. The present study shows that TCNQ is adsorbed onto the oxidized Al lms as both a uniform lm on a nanometer scale and micrometer sized particles. We can obtain the volumes of the deposited TCNQ in the thin uniform lms and the large particles separately through the bearing analysis. We believe that TCNQ is predominantly in the anionic state in the thin lms, while it exists in the neutral state in the large particles. Tunneling barriers thicker than approximately 3 nm have negligible transmission probability and thus do not contribute to the IETS w40x. The tunneling spectrum is mainly coming from the very thin uniform lms. Only the thin edges of some of the larger particles have any impact on the IETS. XPS, on the other hand, probes all the material within the analytical depth a few tens of nanometers. of the surface. The XPS signal is heavily weighted towards the larger particles. In the limit of decreasing concentration, it is expected that the particles would disappear and the XPS results would parallel those of IETS. The present study clearly shows that the morphology of TCNQ on the oxide surface must be considered in order to interpret the results of any spectroscopic study of the adsorbed state of TCNQ wherein the spectroscopic tool probes a surface area greater than a few m2 e.g. single point Auger electron spectroscopy, X-ray photoelectron spectroscopy, laser Raman, etc... Furthermore, this conclusion can be generalized to any spin-doped adsorbate. 4. Conclusions We have reported the thorough AFM morphology observation of TCNQ deposited from solutions onto the atomically smooth native oxide surfaces of the polycrystalline Al111. lms. It was found that TCNQ is deposited on the surfaces as both a uniform lm on a nanometer scale and micrometer-sized particles with

various morphologies. The thin uniform lm results from both corrosion of the surface by the TCNQ anion formation reaction and the formation of nanometersized crystallites of the surface reaction products of TCNQ. The large particles are neutral TCNQ and the size and morphology changed with variation in the solvent, spin time, and the concentration. The discrepancy in the IETS and XPS results can be explained by the spectroscopic sensitivities of each technique and the morphology of the adsorbed TCNQ on the alumina surfaces. The morphology of benzoic acid doped alumina was also studied. In this case, a monolayer of aluminum benzoate is formed and any unreacted benzoic acid is removed from the surface during the evacuation step. For this system, there is no signicant change in the surface morphology upon adsorption. Acknowledgements The data analyses were done with an AFM in Research and Development Center in Kagoshima University. M.H. thanks Prof. S. Kamata in the Faculty of Engineering of Kagoshima University for his encouragement. The present study was supported by the fellowship from the Ministry of Education of Japan, and partially supported by the Kagoshima Science Scholarship Foundation, and the Light Metal Educational Foundation. We gratefully acknowledge the support of the US National Science Foundation in the form of grants CHE-9709273, and CHE-9819318. References
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