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Fig. 3. a) Weak electrostatic binding of GOx occurs due to the low amount of positive charges in the PEDOT matrix. b) Strong electrostatic binding of this enzyme occurs due to the presence of the electrostatic interaction between negatively charged GOx and the presence of positively charged PMVP in this matrix.

PEDOT/PMVP coated pores inside a track-etch membrane can occur not withstanding the fact that the active site of the enzyme is hidden deeply inside the insulating protein shell. Further research is ongoing to elucidate this intriguing phenomenon and evaluate its potential for biosensor applications.

Experimental
Synthesis of the PEDOT and PMVP/PEDOT-Coated Track-Etch Membranes: A nucleopore track-etch membrane (diameter = 36 mm, pore size = 0.8 lm) was placed in a stirred solution of 3.5 g (21.5 mmol) ferric chloride in 12 mL of an acetonitrile/water solution (5:1 v/v). Subsequently, 350 mg (2.46 mmol) EDOT dissolved in 0.5 mL of acetonitrile was added at room temperature. After the appropriate time, the track-etch membrane was rinsed with water and the PEDOT on the surface of the membrane was removed by carefully wiping with a tissue. PMVP was added to the ferric chloride solution for the synthesis of the PMVP/PEDOT membranes. Immobilization of GOx: Typically, a track-etch membrane was mounted in an Amicon cell and 10 mL of a glucose oxidase solution (5 mg/mL) with or without DEAE (10 mg/mL) in aqueous PBS (0.1 M, pH 7.4) was placed in the cell and stirred for at least 30 min at a temperature of 4 C. Subsequently, the membrane was dried overnight over CaCl2 in a desiccator at 4 C. The sensors were stored in PBS (pH 7.4) at 4 C. Amperometric Biosensor Measurements: To perform amperometric measurements, the glucose sensors were placed in a flow cell in an aqueous PBS buffer (pH 7.4) and connected to a potentiostat. The potential was set to the desired value. After the background current had diminished sufficiently to a stable value, glucose was added to the buffer solution and the resulting current was monitored. Received: April 27, 2001 Final version: June 19, 2001

[6] a) L. Jiang, C. J. McNeil, J. M. Cooper, J. Chem. Soc., Chem. Commun. 1995, 1293. b) K. Yamada, H. Koizumi, K. Ikeda, Y. Ohkatsu, Chem. Lett. 1997, 201. [7] C. G. J. Koopal, M. C. Feiters, R. J. M. Nolte, B. de Ruiter, R. B. M. Schasfoort, R. Czajka, H. van Kempen, Synth. Met. 1992, 51, 403. [8] a) Z. H. Cai, C. R. Martin, J. Am. Chem. Soc. 1989, 111, 4138. b) C. R. Martin, Acc. Chem. Res. 1995, 28, 61. c) V. P. Menon, J. T. Lei, C. R. Martin, Chem. Mater. 1996, 8, 2382. [9] L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik, J. R. Reynolds, Adv. Mater. 2000, 12, 481. [10] H. Yamato, M. Ohwa, W. Wernet, J. Electroanal. Chem. 1995, 397, 163. [11] I. Winter, C. Reese, J. Hormes, G. Heywang, F. Jonas, Chem. Phys. 1995, 194, 207. [12] a) R. Rajagopalan, A. Aoki, A. Heller, J. Phys. Chem. 1996, 100, 3719. b) J. G. Franchina, W. M. Lackowski, D. L. Dermody, R. M. Crooks, D. E. Bergbreiter, K. Sirkar, R. J. Russell, M. V. Pishko, Anal. Chem. 1999, 71, 3133. c) M. M. Verghese, K. Ramnathan, S. M. Ashraf, B. D. Malthora, J. Appl. Polym. Sci. 1998, 70, 1447. [13] The molar ratio was based on the ratio between EDOT and PMVP dissolved in the water/acetonitrile mixture. [14] Oxygen may become a competing species for the conducting polymer in accepting the electrons from the active site of the enzyme, since under natural conditions glucose oxidase produces hydrogen peroxide in the presence of oxygen. If the working electrode of the track-etch membrane sensor is capable of oxidizing hydrogen peroxide, this process will compete with the direct electron transfer from the enzyme to the electrode. It was shown in a separate experiment that the glucose sensor was insensitive to 500 lM of hydrogen peroxide, a concentration that is significantly higher than those that can be produced by the GOx enzymes in the biosensor. [15] S. Kuwabata, C. R. Martin, Anal. Chem. 1994, 66, 2757. Martin et al. have suggested that the previously described glucose sensors [4,5] based on polypyrrole track-etch membranes operate by direct electrochemical oxidation of glucose at the platinum film that is coated onto one face of the membrane rather than by direct electron transfer. The excellent conducting properties of PEDOT do no longer require the use of platinum as an electrical contact between the membrane and the potentiostat. Hence, a mechanism such as the one proposed by Martin does not apply in the present system.

Luminescence Properties of Nanocrystalline Y2O3:Eu**

By Gareth Wakefield,* Edward Holland, Peter J. Dobson, and John L. Hutchison Recent advances in field emission display (FED) technology have placed a requirement on the development of a corresponding screen technology.[1] FED technology requires that a phosphor screen be developed to operate under a lower electron accelerating voltage, typically 15 kV, than a conventional cathode ray tube (CRT) screen.[2] There is, therefore, a need to develop phosphors that display a higher efficiency than the materials conventionally used in CRT screens under

[1] a) D. W. Schmidtke, A. Heller, Anal. Chem. 1998, 70, 2149. b) E. J. Calvo, R. Etchenique C. Danilowicz, L. Diaz, Anal. Chem. 1996, 68, 4186. c) E. Katz, A. Riklin, V. Heleg-Shabtai, I. Willner, A. F. Bckmann, Anal. Chim. Acta 1999, 385, 45. d) P. N. Bartlett, Y. Astier, Chem. Commun. 2000, 105. e) L. Habermuller, M. Mosbach, W. Schuhmann, Fresenius J. Anal. Chem. 2000, 366, 560. [2] a) R. Wilson, A. P. F. Turner, Biosens. Bioelectron. 1992, 7, 165. b) H. J. Hecht, H. M. Kalisz, J. Hendle, R. D. Schnid, D. Schomburg, J. Mol. Biol. 1992, 229, 153. [3] M. Gerritsen, A. Kros, J. A. Lutterman, R. J. M. Nolte, J. A. Jansen, J. Invest. Surgery 1998, 11, 163. [4] C. G. J. Koopal, B. de Ruiter, R. J. M. Nolte, J. Chem. Soc., Chem. Commun. 1991, 1691. [5] C. G. J. Koopal, M. C. Feiters, B. de Ruiter, R. B. M. Schasfoort, R. J. M. Nolte, Biosens. Bioelectron. 1992, 7, 461.

[*] Dr. G. Wakefield Oxonica Ltd, Unit 7, Begbroke Science and Business Park Sandy Lane, Yarnton, Kidlington, Oxford OX5 1PF (UK) E-mail: gareth.wakefield@oxonica.com Dr. E. Holland, Dr. P. J. Dobson Department of Engineering Science, University of Oxford Parks Road, Oxford OX1 3PJ (UK) Dr. J. L. Hutchison Department of Materials Science, University of Oxford Parks Road, Oxford OX1 3PH (UK)

[**] The authors thank Dr. Shengcheng Luo of the Department of Mechanical and Aerospace Engineering, University of California, San Diego for the cathodoluminescence measurements.

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low to medium electron accelerating voltages. It is also advantageous that the phosphor particle size is as small as possible as this potentially leads to higher screen resolution, lower screen loading, and a higher screen density. When fine-grained luminescent material is required, the conventional fabrication route is via a grinding or milling technique. A high-temperature solid state reaction is used to form large grains, which are subsequently reduced in size.[3] This has the serious drawback that grinding techniques introduce defects into the surface of the phosphor crystal. Defects have serious implications for luminescent materials as they provide non-radiative recombination routes for electrons and holes. In order for the material to be as efficient as possible, the number of electron/hole recombinations via optically active centers must be maximized, i.e., the crystal structure is as important as the choice of host lattice and light-emitting center. As the crystal is reduced in size during grinding the proportion of surface-damaged region to undamaged bulk increases. Typically, as particles are ground below about 3 lm there is a substantial drop-off in luminescence efficiency.[4] One phosphor compound that is commonly used as a red emitting material is Y2O3:Eu. This material has been utilized for some time due to its efficient luminescence under ultraviolet (UV) and electron beam excitation.[5] There have been a number of attempts to synthesize fine-grained variations of this material by a variety of methods, including thin film chemical vapor deposition,[6] combustion synthesis,[7] and colloidal reactions.[8] We have used a colloid-based route to synthesize Y2O3:Eu nanocrystals in the sub-100 nm size range. These crystals are then compared for both photoluminescence (PL) and cathodoluminescence (CL) efficiency against commercially available Y2O3:Eu bulk material (3.5 lm particle size, supplied by Phosphor Technology, UK). The advantage of using chemical techniques to fabricate phosphor material is shown in Figure 1. Figure 1a is a bright field transmission electron micrograph of a cluster of 70100 nm europium doped yttria crystals. Note that the crystals are structurally perfect, i.e., no defects are found within the crystal structure. Defects tend to migrate to the surface of the crystal during the growth stage. A high-resolution lattice image of the surface of one of the crystals is shown in Figure 1b demonstrating the absence of any surface defect layer, which might degrade the low voltage luminescence efficiency. The lattice planes visible are the 3.06 (222) planes of the cubic (a = 10.604 ) phase of yttrium oxide. The phase of yttrium oxide is confirmed by X-ray diffraction. In Figure 1c a high-resolution electron micrograph of a bulk Y2O3:Eu phosphor surface is shown. An amorphous surface layer, a number of defects and strained phosphor regions are visible. Such a surface-damaged region can be expected to have a detrimental effect on phosphor efficiency at low electron penetration depths. A simple calculation of electron penetration depth at an accelerating voltage of 5 kV gives the minimum crystallite size required for efficient luminescence properties. The electron range in a solid for electron acceleration voltages

Fig. 1. a) Nanocrystalline Y2O3:Eu after firing of precursor material. b) Surface of a phosphor nanocrystal. Note the absence of a damage layer. c) Surface of a conventionally synthesized bulk Y2O3:Eu phosphor. The surface damaged amorphous layer is arrowed.

of 110 kV is given by the following empirical formula,[9] which is related in form to Bethe's expression for stopping power.[10] Range [] = 250(A/r)(E/Z1/2)n (1)

where n = 1.2/(10.29log10Z) and A is the atomic weight, r is the density, Z is the atomic number, and E is the accelerating voltage.

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For Y2O3:Eu at an accelerating voltage of 5 kV the electron penetration depth according to Equation 1 is 56 nm. Europium ions are excited by plasmons generated by incident electrons. They may also be excited by the electronhole pairs generated by plasmons. Such electronhole pairs may migrate out of the generation volume of the incident electron beam before recombination via activator ions can take place.[11] Resonant energy transfer by multipolar interactions may also occur.[3] It is therefore necessary for the crystal to be somewhat larger than the calculated value for optimum cathodoluminescence efficiency. The excitation and emission spectra of bulk and nanocrystalline europium doped yttria are shown in Figure 2. The excitation spectra (left hand side of figure) are taken at an emission

result in only marginal improvements to PL efficiency. In Figure 3 CL data comparing nanocrystalline and bulk material is shown. As the accelerating voltage is lowered and more of the electron scattering occurs within the surface region the improved efficiency of the nanocrystalline material over the

Fig. 3. Comparison of CL efficiencies of bulk and nanocrystalline Y2O3:Eu phosphors.

Fig. 2. Excitation and emission spectra from bulk and nanocrystalline Y2O3:Eu.

wavelength of 611 nm, the emission spectra (right hand side of figure) are taken with an excitation wavelength of 254 nm. Integrating over the emission spectra shows that the nanocrystalline material is 1020 % more efficient then the bulk compound, presumably as a result of the improved crystal quality. A characteristic of rare earth ions is a sharp line output as a result of transitions within the 4f shell, which is shielded from environmental effects by the outer shell electrons.[12] These transitions are, strictly speaking, forbidden, but become allowed due to the surrounding crystal field relaxing the selection rules.[13,14] The peak at 611 nm is due to the forced electric dipole transition (5D0 7F2), which is allowed in this case as the europium does not occupy a center of symmetry in yttria. It is also hypersensitive to environmental effects. This peak is responsible for 66 % of the emission intensity in Y2O3:Eu phosphor.[15,16] The broad band on the excitation spectra is excitation from the ground state of the 4f shell to an EuO charge transfer state.[17] As the only mechanism for absorption of photons is due to the activator sites, which typically comprise 12 % of the material, one would expect that the mean free path for photon absorption to be substantially larger than that for low energy electron scattering. As a consequence of this the advantageous effects of the improved surface microstructure

bulk becomes more pronounced. At voltages above 4 kV the nanocrystalline and bulk materials have approximately equal efficiency. Below this the nanocrystalline material shows superior performance, at 1 kV it is over 50 % more efficient than the bulk. As the accelerating voltage is lowered further, it is expected that the performance advantage of the nanocrystalline material will become greater. However, it is also necessary to consider the conductivity of the screen at low voltages. Experiments to determine the properties of nanocrystalline phosphors between 50 and 1000 V are underway. We are also working on the synthesis of green and blue emitting nanocrystals for use in this application. In conclusion, we have synthesized Y2O3:Eu nanocrystals in the size range 70100 nm. The crystals show a photoluminescence efficiency 1020 % higher than commercial bulk material. Under electron excitation the nanocrystalline material is 50 % more efficient than the bulk at 1 kV accelerating voltage. It is expected that such material will prove useful in improving the properties of low voltage field emission displays.

Experimental
Nanocrystal Synthesis: Nanocrystalline Y2O3:Eu is synthesized by precipitation of amorphous spherical precursor material, which is then fired to form nanocrystalline material [18]. Salts, typically chlorides, of yttrium and europium in water are adjusted to pH 1 with hydrochloric acid or potassium hydroxide. The concentration of europium is 3 mol-%. An excess of urea, typically 15, is dissolved in the cell. The temperature is then raised to >80 C for 2 h. The urea decomposes slowly and there is a burst of particle nucleation when a certain pH (typically pH 45) is reached. After this the particles continue to grow uniformly until the cation supply is exhausted. The precipitate is then flocculated, washed thoroughly, and dried. It is then fired in air for 3 h, typically at >1000 C. The material formed consists of agglomerations of nanocrystals, the size of the agglomerates being defined by the drying stage. The luminescence

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efficiency is controlled by the size of the nanocrystals rather than the size of the agglomerates. There is no growth of the agglomerates during firing. Nanocrystal Characterization: The nanocrystals were characterized structurally on a JEOL4000EX high-resolution transmission electron microscope and on an X-ray diffractometer. PL spectra were obtained on an Hitachi F-4500 fluorescence spectrophotometer. In order to obtain comparative phosphor performance data samples were prepared with an identical loading of 0.1 g/cm3 of phosphor in a silicone binder. Measurements were taken in reflection mode. Therefore, the amount of phosphor material excited is the same in both cases. CL measurements were undertaken on screens of bulk and nanocrystalline Y2O3:Eu in transmission with a 50 V specimen voltage applied to recover any secondary electrons generated. Screens were fabricated by electrophoretic deposition [19] with an electrolyte composition as follows. In 400 mL of isopropyl alcohol, 1.6 g of phosphor, and 103 M of MgNO3 are mixed for 3 h. The phosphor is deposited on indium tin oxide (ITO) glass by application of a voltage of 200 V for 50300 s. A series of screens of various loadings are prepared of both the bulk and nanocrystalline yttria. The screens with maximum efficiency for each voltage are then compared. In this way the screens remain at an optimal loading for each phosphor at each voltage. The optimum loading is about 1.8 mg cm2. The electron source for CL assessment is a 110 kV Kimball Physics electron gun running in continuous mode at 200 nA. Received: January 22, 2001 Final version: June 26, 2001 [1] T. Guo, Z. Huang, X. Wu, J. Lin, Z. Lin, Y. Zeng, Z. Liu, D. Zhang, Society for Information Display, International Symposium Digest of Technical Papers 2000, 31, 416. [2] Q. Weng, J. Cheng, Z. Lin, G. Yang, J. SID 1999, 7, 183. [3] S. Shigeo, W. M. Yen, Phosphor Handbook, CRC Press, Boca Raton, FL 1999. [4] T. Hase, T. Kano, E. Nakazawa, H. Yamamoto, Adv. Electron. Electron Phys. 1990, 79, 271. [5] N. C. Chang, J. Appl. Phys. 1963, 34, 3500. [6] J. McKittrick, C. F. Bacalski, G. A. Hirata, K. M. Hubbard, S. G. Pattillo, K. V. Salazar, M. Trkula, J. Am. Ceram. Soc. 2000, 83, 1241. [7] T. Ye, G. W. Zhao, W. P. Zhang, S. D. Xia, Mater. Res. Bull. 1997, 32, 501. [8] M. H. Lee, S. G. Oh, S. C. Yi, J. Colloid Interface Sci. 2000, 226, 65. [9] C. Feldman, Phys. Rev. 1960, 117, 455. [10] H. A. Bethe, Ann. Phys. (Leipzig) 1930, 5, 325. [11] L. Ozawa, Cathodoluminescence: Theory and Applications, VCH, Weinheim 1990, p. 7. [12] G. Blasse, in Handbook on the Physics and Chemistry of Rare Earths, Vol. 4 (Ed: K. Gschneider), North Holland, Amsterdam 1979, p. 237. [13] B. R. Judd, Phys. Rev, 1962, 127, 750 [14] G. S. Ofelt, J. Chem. Phys, 1962, 37, 511 [15] W. T. Carnell, in Handbook on the Physics and Chemistry of Rare Earths, Vol. 3 (Ed: K. Gschneider), North Holland, Amsterdam 1979, p. 171. [16] G. Cheng, N. A. Stump, R. G. Haire, J. R. Peterson, J. Alloys Compd. 1992, 181, 503. [17] M. Yin, W. Zhang, S. Xia, J.-C. Krupa, J. Lumin. 1996, 68, 335. [18] B. Aiken, W. P. Hsu, E. Matijevic, J. Am. Ceram. Soc. 1988, 71, 845. [19] B. E. Russ, J. B. Talbot, J. Electrochem. Soc. 1998, 145, 1245.

How to Prepare Tunable Planar Molecular Chemical Gradients**

By Kirill Efimenko and Jan Genzer* Deposition of self-assembled monolayers (SAMs) made of either mercapto-terminated molecules attached to gold (or other noble metals) or chlorosilane-terminated moieties anchored to hydroxyl-terminated substrates, offers one of
[*] Prof. J. Genzer, Dr. K. Efimenko Department of Chemical Engineering, North Carolina State University Raleigh, NC 27695-7905 (USA) E-mail: jan_genzer@ncsu.edu

the highest quality routes of systematically and reproducibly tuning the surface properties of materials.[1] By controlling the chemical composition of the terminal group, the length, and microstructure of the SAM molecule, the chemical and physical properties, including wetting, adhesion, friction, and biosensing, can be successfully tailored. While early studies concentrated mainly on preparing substrates with laterally homogeneous SAMs, recent advances in the field allowed for creating SAMs with two-dimensional chemical patterns.[2] In particular, the microcontact printing (lCP) technique has proven to be a convenient method for preparing chemically patterned substrates.[3] While lCP is a useful method for decorating materials substrates with a variety of motif shapes and dimensions, it always produces sharp boundaries between the distinct chemical substrate regions. However, for some applications, it is required that the wetting properties of the substrate change gradually over a certain region in space. This situation can be accomplished by producing surfaces with a gradually varying chemistry along their length. In these so-called gradient surfaces, the gradient in surface energy is responsible for a position-bound variation in physical properties, most notably the wettability. For example, gradient surfaces can be particularly useful to study interactions in biological systems, as the influence of the entire wettability spectrum upon protein adsorption or cellular interactions can be obtained in one single experiment. While methods to prepare such gradient substrates have been described previously,[4] none of the currently used techniques provides a complete control over all gradient parameters, including the wettability of the two opposite gradient sides and the steepness of the gradient region in between. In this paper we present a novel technique that removes the above-mentioned limitations and demonstrate that gradients with tailorable surface properties can be successfully fabricated. Recently, we have demonstrated that one can fine-tune the grafting density of molecules on surfaces by fabricating mechanically assembled monolayers (MAMs), structures that are based on the combination of self-assembly and mechanical manipulation of the grafted molecules on surfaces.[5] In this work we utilize the MAMs to adjust the surface density of the initiators and consequently that of molecular gradients prepared on flexible supports. The technique is based on the combination of i) the well-known grafting reaction between x-(CH2)nSiCl3 molecules[6] and OH functionalities present on silicon-based surfaces, [Si]substrate (Scheme 1),

[**] Supported by the NSF CAREER award (Grant No. DMR98-75256), The Camille & Henry Dreyfus Foundation, and a grant from NACE International.

Scheme 1.

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