Moletronics involves the study and application of molecular building blocks for the fabrication of electronic components.

Includes
 

conductive polymers single-molecule electronic components

2 most promising conducting molecular species are:

 

Polyphenylene Carbon nanotubes

 

It is useful in the prospect of size reduction. Extends Moore's Law beyond the foreseen limits of smallscale conventional silicon integrated circuits.

Its a conductive polymer It forms chain-like molecules Formed by linking basic molecular unit,C6H4, i.e Phenylene Phenylene is a derivative of Benzene ring and has 2 free binding sites

Fig (a)
Phenylene group

Fig (b)

Polyphenylene

2 binding sites of Phenylene are represented by open circles on ends of the ring

With 2 binding sites,each Phenylene can be bound to 2 others hence forming a chain as shown in fig (b)

These chains are then used for molecular wires Polyphenylene wires are fairly conductive Conduction in these molecules proceeds by electrons moving through extended molecular orbitals that span the entire molecule

Extended molecular orbitals are called -type When atoms come close enough spatially, the wave-function overlaps leading to extended states

These extended states have large energy

Aliphatic molecules are singly bond molecule They do not contain -bonds , but have -bonds -bonds lie along axes of molecule , cannot be extended b/w atoms -bonds cannot be easily extended because at end of each -bond there is a positively charged nucleus and hence its spatial extent is interrupted by the nucleus

Example, chaining together of Methylene,CH2,molecules can form an aliphatic molecule

When these aliphatic molecules are inserted in C6H4 molecules they interrupt the extended states formed by -bonds thus breaking the conductive pathway in poly-phenylene chain.

Its a primary molecular device type 2 different doped regions are rqd:
 

P-type region N-type region

Electron concentraton can be varied by introduction of foreign agents In molecular s/m , molecular groups are added These molecular groups attach themselves at specific places within chains thus altering the electron concentration

Groups that add electron to s/m are called electron donating groups(donors)

Groups that

remove electrons

are called electron withdrawing

groups(acceptors)

A p-n junction is formed by placing a chain of withdrawing group together with donating groups

A potential barrier is formed b/w donor and acceptor group chains by using semi-insulating groups

The potential barrier which is formed by semi-insulating group maintains charge imbalance b/w the 2 sides of the junction

If the potential barrier is removed, then 2 sides of the junction,would equilibrate in terms of electron densities thus removing any diode action

Fig (c)

Semi-insulating group

I Au contact SI I D
chain with donating group,d

Au contact

A
chain with withdrawing group,d

Molecular arrangement for rectifying diode structure Insulating groups ,I , provide potential barriers for tunneling into and out of the diode

SI,semi-insulating group in center of device maintains electron density imbalance in the jn.

Donating group side is at higher energy than the withdrawing group side

 Consider

the energy level diagrams

 Under equilibrium
 

Fermi levels are aligned fig

donating LUMO STATES withdrawing

Ef

SI

Ef

HOMO STATES

Lowest unoccupied molecular orbital(LUMO) levels in donating chain are at higher energy than those in withdrawing chain

This is because, electron density is higher in donating chain which results in increase electron-electron repulsion and hence a higher total electron energy

Similarly, lower electron density in withdrawing chain results in lower total electron energy

Hence there exists an energy difference b/w 2 sides of molecular diode i.e. the levels in donating chain is at higher energy than withdrawing chain energy levels

Molecular diode has 2 bias conditions:

 

Forward Reverse

Current flow is asymmetric and highly non-linear due to the following facts:


The energy difference b/w Fermi level & LUMO levels on acceptor group side is less as compared to energy difference b/w Fermi level & LUMO levels on donating group side

Bias rqd to align Fermi level with LUMO level on acceptor side is less compared to bias rqd on donor side

Therefore for same magnitude of bias , current flow in device will be highly non-linear & asymmetric.

BIAS CONDITIONS:

Insulator groups , I, and semiconductor-insulator-group,SI,act as potential barriers in structure

Donating chains and acceptor chains are conducting with highest occupied molecular orbital(HOMO) and (LUMO) states


Forward bias:

Fig
donating LUMO STATES

Electron flow withdrawing

+V Ef

SI

I Ef

-V

HOMO STATES

Occurs when high potential is applied to left hand contact w.r.t right hand contact +ve potential lowers electron energies Hence, occupied energy levels in left hand contact are lower than those in right hand contact When Fermi level in right hand contact is raised so as to align with LUMO levels in acceptor chain, electrons tunnel from contact into LUMO levels e- then tunnel through SI potential barrier into donator chain LUMO levels Finally, e- travel through last potential barrier into +vely biased left hand contact When levels are not aligned a very small current flows which is called nonresonant current A very low bias is rqd in forward bias condn.

 

 

Reverse bias:

Fig

donating

LUMO STATES

withdrawing

-V Ef

SI

+V Ef

HOMO STATES
High voltage is applied to right hand contact w.r.t left hand contact Fermi level is lowered on right hand contact & raised on left hand contact For same magnitude of bias
  

  

Fermi level is not aligned with LUMO levels No resonant alignment occurs Little current flows in device

Fig
+V R Diode 1 VA Diode 2 VB VC VA & VB are inputs VC is the output

Operation : +ve voltage is  If

applied across resistance R

either VA or VB are low or both are low then

 Diodes 1 &  There is  VC is

2 are forward biased

small or no voltage drop across diode in ideal case

also low

 If both inputs VA
  

& VB are high then

Both diodes 1 & 2 are reverse biased The 2 diodes are open circuited in ideal case VC is high