Synchrotron induced photoelectron spectroscopy on in situ
co-evaporated blends of CuPc and TCNQ and on
TCNQ/CuPc interfaces is applied for monitoring the electronic interaction indicated in systematic shifts of the CuPc and
TCNQ HOMO and core orbitals. These shifts correspond to a movement of the Fermi level within the HOMO LUMO
energy gap. The shifts in CuPc induced by the interaction with TCNQ are similar in the composites and in the interface
model experiment. At the interface an additional induced dipole potential can be measured. The interface-dipole plus the
Fermile level shift add up to the work function difference of pure CuPc and TCNQ. We conclude that TCNQ forms a
separate phase in CuPc rather than single isolated acceptor molecules. Charge transfer at the bulk hetero-junction
induces the Fermi level variations, which may be called doping.
In the present paper a new concept towards O-CMOS technology is presented substantiating the importance of the semiconductor/dielectric interface for charge carrier transport in organic semiconductors. It will be demonstrated that by controlling the interface properties of either SiO<sub>2</sub> or PMMA, unipolar p- and n-type OFETs can be realized using a single organic semiconductor and even a single metal for source and drain contacts. Two dielectric/semiconductor interface modifications are considered for the realization of complementary OFETs on the basis of pentacene, otherwise known for its exclusive hole transporting properties. Selective modification of the SiO<sub>2</sub> dielectric interface with traces of vacuum deposited Ca, allows for electron transport in pentacene and the realization of complementary pentacene OFETs on a single substrate. By this technique electron traps are removed due to a reaction of atomic Ca with oxygen from available hydroxide groups, resulting in the formation of an oxidized Ca layer. In a second approach, it is demonstrated that by selective UV treatment of a PMMA dielectric surface, unipolar n-type pentacene OFETs can be converted to unipolar p-type by the introduction of electron traps in the form of -OH and -COOH groups at the PMMA interface. Both methods allow for the realization of CMOS organic inverter stages with decent electrical properties.
In this study we report on new concepts to generate light emission in organic thin film transistors. The initial physical understanding of light emission from tetracene based field-effect transistors was proposed to be originated from a strong underetching of the drain and source electrodes. This underetched electrodes in combination with the evaporated tetracene is thereby believed to generate a virtual OLED at the drain electrode. Accumulated holes have to leave the gate
oxide interface to reach the drain electrode by crossing the bulk of the organic semiconductor. Light then occurs by injection of electrons in a large electric field in the bulk. Today's transistors do not show the underetching anymore but are still emitting light only at the drain electrode, again supporting the initial interpretation of a defect state at the edge of the drain electrode. In this context the question how electrons can overcome a potential barrier of 2.7 eV is still open. Therefore an investigation of the gold tetracene interface by UPS and XPS techniques has been started and preliminary data indicate the unexpected result that the barrier for electrons is comparable to that for holes. In a further step the generation of an ambipolar transistor by interface doping with calcium was tried and an n-type pentacene transistor could be fabricated but the strategy failed for tetracene. Finally an electrochemical interface doping was performed by the application of Lithium triflate in PEO to a thin interface layer between gate oxide and tetracene. This leads to light emission but unfortunately also to the loss of the gate voltage influence. Based on these results a possible strategy will be presented.