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Colloids and Surfaces A: Physicochemical and Engineering Aspects 198 200 (2002) 645 650 www.elsevier.

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Electrical properties of thin copper sulde lms produced by the aggregation of nanoparticles formed in LB precursor
Svetlana Erokhina a,*, Victor Erokhin b, Claudio Nicolini a
a

Department of Biophysical M&O Sciences and Technologies, Uni6ersity of Genoa, Corso Europa 30, 16132 Genoa, Italy b Fondazione Elba, Corso Europa 30, 16132 Genoa, Italy Received 30 August 2000; accepted 14 May 2001

Abstract The present work is dedicated to the formation and characterization of copper sulde layers. Nanoparticles of CuS were formed by exposing the deposited LB lms of copper stearate to the H2S atmosphere for at least 12 h. The aggregation of the nanoparticles into thin layers was performed by washing the sample with chloroform after the reaction for removing stearic acid molecules. Electrical properties of CuS layers of different thickness were examined. The dependence of an electrical conductivity upon the frequency was observed. The electrical conductivity is strongly dependent upon the frequency when the thickness of the precursor copper stearate LB lms is less than 30 bilayers. For such thickness the resultant aggregated layer is not continuous one and can be considered as a lm of islands separated one from the other. This fact is responsible for the increase of conductivity with frequency. Linear voltagecurrent characteristics with practically no dependence of the conductivity on frequency were measured for the lms, obtained from more than 30 bilayers of the precursor. Typical resistivity of such layers was less than 1.0 V cm. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Copper sulde; Nanoparticles; LangmuirBlodgett lms; Aggregated layer; Conductivity

1. Introduction The possibility of the nanoparticle formation in Langmuir Blodgett (LB) precursor layers [1] had opened perspective opportunities of studying new quantum phenomena. Particles of different types were formed and studied [2 10]. Further works on the aggregation of such particles into thin lms
* Corresponding author. Tel.: + 39-010-353-7429; fax: + 39-010-353-8346. E-mail address: svetla@ibf.unige.it (S. Erokhina).

by selective removal of the organic molecules [11] resulted in the establishing of the technology of ultrathin inorganic semiconductor layer formation. The technology was shown to be adequate even for the formation of heterostructures, composed of two or more different materials [12]. Molecular structure of the aggregated layers was shown to be similar to that in the bulk of the same material [11]. High thickness resolution and low cost of the technology allow to consider it as very perspective method for the applications,

0927-7757/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 7 - 7 7 5 7 ( 0 1 ) 0 0 9 7 6 - 1

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where ultrathin semiconductor layers must be used, such as electronics and optoelectronics. Detailed electrical characterization of such aggregated layers is a necessary step to understand the best way of their utilization for the construction of working elements. The present work is dedicated to the formation and characterization of copper sulde aggregated layers.

3. Results and discussion BAM images of the sample at different stages of the layer formation are shown in Fig. 1. Initially at and homogeneous lm of copper stearate (Fig. 1(a)) was transformed into a corrugated layer after the particle formation reaction (Fig. 1b). Such behaviour indicates the fact, that the whole layer is involved into the reorganization during the particle formation process. Removal of the fatty acid molecules with chloroform washing results in the formation of at homogeneous layer of aggregated particles (Fig. 1(c)). The scheme of the process is shown in Fig. 2. During the reaction, protons of H2S molecules attach themselves to stearic acid molecule head groups, while Cu2 + ions bind to the sulfur. Growth of the particles is rather random process centers of nucleation can be distributed in the lm in not regular manner. However, dimensions of such particles are within not very wide size distribution function [15]. Formation of the particles results in the complete disturbance of the layer. Organic molecules are also involved into the motion, and the layer surface is signicantly corrugated. After the removal of the corrugated organic matrix the layer begins to be again at and homogeneous, what can be explained taking into consideration small sizes of the particles. Electrical properties of CuS layers of different thickness were examined. Typical V/I characteristics, obtained from the layers of different thickness, are presented in Fig. 3(ac). Characteristics are linear indicating the Ohmic contact of electrodes with aggregated lms. Current values are different for lms of different thickness. This difference is due to not only the increase of the thickness, but also the variation of the conductivity mechanism. The dependence of the specic resistance upon the aggregated layer thickness is presented in Fig. 4. The term specic resistance is, probably, not completely correct in this case. However, the comparison of absolute values of the resistivities can be more difcult to analyze. It seems to be more convenient to compare these values taking into account their thickness dependence and it was called specic resistance. Therefore, the resistivity was normalized to the

2. Materials and methods Stearic acid and copper sulphide were obtained from Sigma. Monolayers of stearic acid were formed at the subphase, containing 10 4 M CuSO4 in water, puried with Milli-Q system till the resistance of 18.2 MV cm. LB lms were deposited onto solid substrates with LB trough (MDT, Russia) [13] by vertical dipping at 28.5 mN m 1 surface pressure. Glass plates were used as solid substrates. Nanoparticles of CuS were formed according to the following reaction by exposing the deposited LB lms of copper stearate to the H2S atmosphere for at least 12 h [1]: [CH3(CH2)16COO]2 Cu + H2S 2CH3 (CH2)16 COOH +CuS The aggregation of the nanoparticles into thin layers was performed by washing the sample with chloroform after the reaction for removing completely stearic acid molecules [11]. Morphology of the lms was studied by Brewster angle microscopy (BAM) (BAM 2, Nanolm Technology GmbH, Germany) [14]. Electrical contacts to the layers were realized by indium. Voltage/current (V/I) characteristics were measured with electrometer Keithly 6517. Frequency dependences of the conductivity were measured with signal generator (Hewlett Packard 33120A) and 20 MHz oscilloscope (HM 203-5). Aggregated lm thickness was estimated according to [11].

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thickness of the layer. Up to 30 bilayers of the initial precursor the specic conductivity increases for several orders of magnitude. Such behaviour allowed to conclude, that very thin layer is not uniform, but is composed of islands of aggregated particles with insulating gaps between them. Increasing the number of layers results in the

reduction of the relative amount of insulating gaps between aggregated particle areas, and, therefore, increases the conductivity. The dependence of the electrical conductivity upon the frequency was observed in order to verify the hypothesis of the island conductivity. The electrical conductivity was strongly dependent upon

Fig. 1. BAM images of the sample at different stages of the layer formation. Image sizes are 0.3 mm per 0.2 mm. (a) Initial precursor LB lm of copper stearate. (b) The layer after the particle formation reaction. (c) Aggregated CuS lm after the organic molecule removal.

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Fig. 1. (Continued)

the frequency when the thickness of the precursor copper stearate LB lms is less than 30 bilayers. Fig. 5 represents the frequency dependence of the resistivity of the aggregated lms obtained from 7 to 40 bilayer precursor lm. These measurements conrmed that for rather thin precursor lm the resultant aggregated layer is not continuous one and can be considered as a lm of islands separated one from the other. No dependence of the conductivity on frequency was measured for the lms, obtained from more than 30 bilayers of the precursor. Thickness of this layer (about 21 nm) is in a good correspondence to the value of the exus in the specic conductivity dependence (Fig. 4). It means that such thickness of the initial precursor provides the rather uniform homogeneous nature of the aggregated layer and the increase of the specic conductivity for the further increase of the thickness of the precursor is not so signicant as in the case of thinner layers. Specic resistance value for such layers is less than 1.0 V cm. Photoconductivity was not observed in such layers when the illumination was performed in the wavelength range 2001000 nm. The fact can be connected to very narrow bandgap of CuS.

Fig. 2. Scheme of the layer formation process. (A) LB precursor of copper stearate. (B) The lm after the particle formation. (C) Aggregated CuS layer.

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Fig. 5. Frequency dependence of the resistivity of the aggregated CuS lms obtained from 7 and 40 bilayer precursor.

4. Conclusions Thin layers of CuS were formed by aggregation of nanoparticles formed in LB precursor layer of copper stearate. Very thin layers are not uniform and can be represented as conductive aggregated islands with insulating gaps between them. When the thickness of the initial precursor layer is more than 30 bilayers, the aggregated layer becomes uniform. Typical specic resistance of such layers was less than 1.0 V cm. Such low value of the specic resistance together with small thickness of the layers (21 nm) allows to consider this material as very perspective for applications in electronics.

Fig. 3. V/I characteristics of CuS aggregated layers obtained from 15 (a), 35 (b) and 50 (c) layers of the precursor.

Acknowledgements The work was supported by CNR 5% project Nanotecnologie e Dispositivi Molecolari per lelettronica Dispositivi a singolo elettrone.

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Fig. 4. Dependence of the specic resistance of the aggregated CuS layers on the number of initial copper stearate precursor bilayers.

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