Modulation of drain current by redox-active molecules incorporated in Si MOSFETs

Gowda, Srivardhan; Mathur, Guru; Li, Q.; Surthi, Shyam; Zhao, Qian; Lindsey, Jonathan S.; Bocian, David F.; Misra, Veena

doi:10.1109/iedm.2004.1419267

Cited by 9 publications

(5 citation statements)

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“…Initially, we employed thiols as the surface attachment group so as to attach the molecules to a Au surface. − ,− ,,− ,,,,, The resulting self-assembled monolayers on Au are readily characterized in laboratory studies; however, Au cannot be used inside chips owing to the facile diffusion of Au atoms in Si-based semiconductors under the conditions employed for fabrication. The need for attachment to industry-compatible surfaces such as oxides (e.g., SiO 2 , WO 2 ) was met with phosphonates, ,,,, whereas attachment to Si itself was accommodated first by alcohols, ,,,− ,,,, thiols, ,,, and selenols ,,, and later by all-carbon tethers. ,− ,,− ,, A selection of tethers is shown in Figure . A surprising variety of all-carbon tethers were successfully attached to Si.…”

Section: Tuning Electronic Properties Of Molecules Using Synthetic De...mentioning

confidence: 99%

“…3À8,11À13,15,18À20, 23,30,36,37,45 The resulting self-assembled monolayers on Au are readily characterized in laboratory studies; however, Au cannot be used inside chips owing to the facile diffusion of Au atoms in Si-based semiconductors under the conditions employed for fabrication. The need for attachment to industry-compatible surfaces such as oxides (e.g., SiO 2 , WO 2 ) was met with phosphonates, 17,21,22,28,31 whereas attachment to Si itself was accommodated first by alcohols, 14,16,20,24À27,32,41,46,47 thiols, 20,27,32,45 and selenols 20,27,32,40 and later by all-carbon tethers. 29,33À35,38,41À46,48,49 A selection of tethers is shown in Figure 5.…”

Section: Tuning Electronic Properties Of Molecules Using Synthetic De...mentioning

confidence: 99%

“…A more near-term strategy entails the development of hybrid semiconductor/molecular devices wherein molecules are used to augment the features of traditional, semiconductor-based, photolithographically constructed circuitry, thereby taking advantage of the vast infrastructure of the semiconductor industry. Toward this latter goal, our laboratories have been engaged over the past decade in the development of a molecular-based information-storage medium that can be readily incorporated into existing semiconductor processing technologies. − Our general approach uses a collection of redox-active porphyrin molecules covalently attached to an electroactive surface wherein information is stored in the discrete redox states of the molecules …”

Section: Introductionmentioning

confidence: 99%

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Molecules for Charge-Based Information Storage

2011

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The inexorable drive to miniaturize information storage and processing devices has fueled the dreams of scientists pursuing molecular electronics: researchers in the field envisage exquisitely tailored molecular materials fulfilling the functions now carried out by semiconductors. A bottom-up assembly of such all-molecular devices would complement, if not supplant, the present top-down lithographic procedures of modern semiconductor fabrication. Short of these grand aspirations, a more near-term objective is to construct hybrid architectures wherein molecules are incorporated in semiconductor-based devices. Such a combined approach exploits the advantages of molecules for selected device functions while retaining the well-developed lithographic approaches for fabrication of the overall chip. In this Account, we survey more than a decade of results from our research programs to employ porphyrin molecules as charge-storage elements in hybrid semiconductor-molecular dynamic random access memory. Porphyrins are attractive for a variety of reasons: they meet the stability criteria for use in real-world applications, they are readily prepared and tailored synthetically, they undergo read-write processes at low potential, and they store charge for extended periods (up to minutes) in the absence of applied potential. Porphyrins typically exhibit two cationic redox states. Molecular architectures with greater than two cationic redox states are achieved by combinations of porphyrins in a variety of structures (for example, dyads, wherein the porphyrins have distinct potentials, triple deckers, and dyads of triple deckers). The incorporation of porphyrins in hybrid architectures has also required diverse tethers (alkyl, alkenyl, alkynyl, aryl, and combinations thereof) and attachment groups (alcohol, thiol, selenol, phosphonate, and hydrocarbon) for linkage to a variety of surfaces (Au, Si, SiO(2), TiN, Ge, and so forth). The porphyrins as monolayers exhibit high charge density and are robust to high-temperature excursions (400 °C for 30 min) under inert atmosphere conditions. Even higher charge densities, which are invaluable for device applications, were achieved by in situ formation of porphyrin polymers or by stepwise growth of porphyrin-imide oligomers. The various molecular architectures have been investigated by diverse surface characterization methods, including ellipsometry, atomic force microscopy, FTIR spectroscopy, and X-ray photoelectron spectroscopy, as well as a variety of electrochemical methods. These studies have further revealed that the porphyrin layers are robust under conditions of deposition of a top metal contact. The results to date indicate the superior features of selected molecular architectures for molecular electronics applications. The near-term utilization of such materials depends on further work for appropriate integration in semiconductor-based devices, whereas ultimate adoption may depend on advances that remain far afield, such as the development of fully bottom-up assembly processes.

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Section: Tuning Electronic Properties Of Molecules Using Synthetic De...mentioning

confidence: 99%

Section: Tuning Electronic Properties Of Molecules Using Synthetic De...mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Molecules for Charge-Based Information Storage

2011

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“…In the memory field, most recent works have shown promising device results [3]- [5]. Capacitive-based devices, in particular, seem to be the good approach for studies dedicated to understanding physical phenomena underneath molecular/Si systems.…”

Section: Introductionmentioning

confidence: 99%

From Atomistic to Device Level Investigation of Hybrid Redox Molecular/Silicon Field-Effect Memory Devices

Pro

Buckley

Barattin

et al. 2011

IEEE Trans. Nanotechnology

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In this paper, an extensive investigation of hybrid molecular/Si field-effect memories is presented, where redox ferrocene (Fc) molecules play the role of the memory charge storage nodes. Engineering of the organic linkers between Fc and Si is achieved by grafting Fc with different linker lengths. The study shows a clear correlation between results from atomistic computational density functional theory, electrochemical measurements (cyclic voltammetry) and electrical data obtained by a detailed study on capacitors and pseudo-MOS devices. Physical-chemical analyses (atomic force microscopy, high-resolution transmission electron microscopy, and X-ray photoelectron spectroscopy), corroborate the quality of molecular layers on devices.

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“…Lieber et al have demonstrated a design that integrates redox molecules [15] by exploring the combination of bistable nanoscale switches assembled using semiconductor nanowires and cobalt phthalocyanines redox active molecules as building blocks. Another approach, consisting of using molecules within capacitive and transistor structures, uses electrochemical capacitors with ferrocene and porphyrin redox molecules [16][17][18]. Charge stocking effects were observed even for mixed ferrocene and porphyrin layers.…”

Section: Introductionmentioning

confidence: 99%

DFT charge transfer of hybrid molecular ferrocene/Si structures

Calboréan¹,

Buimaga-Iarinca²,

Graur³

2015

Phys. Scr.

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The electrochemical behavior and electronic properties of redox-active ferrocenes grafted onto semiconductor Si(100) substrate were investigated theoretically by first-principles calculations. Organic molecules were attached via the formation of Si-C covalent bonds through two different linkers: vinyl (direct grafting), and N 3 (CH 2 ) 11 (indirect grafting). Redox energies and the electronic properties relating to different spacers in hybrid ferrocene Fc/Si and ferrocenium Fc + / Si structures were theoretically extracted and compared with experimental cyclic voltametry data. Electronic charge transfers are discussed through the alignment positions of the frontier orbitals of the molecule with respect to the Si substrate gap. Periodic boundary conditions were used to investigate the Si(100) as a slab surface and hybrid Fc/Si structures. The resulting projected density of states (PDOS) were compared with molecular results and discussed in the light of experimental data.

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Modulation of drain current by redox-active molecules incorporated in Si MOSFETs

Cited by 9 publications

References 9 publications

Molecules for Charge-Based Information Storage

Molecules for Charge-Based Information Storage

From Atomistic to Device Level Investigation of Hybrid Redox Molecular/Silicon Field-Effect Memory Devices

DFT charge transfer of hybrid molecular ferrocene/Si structures

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