Mathias Nyman

Reducing leakage currents in n-channel organic field-effect transistors using molecular dipole monolayers on nanoscale oxides.

Leakage currents through the gate dielectric of thin film transistors remain a roadblock to the fabrication of organic field-effect transistors (OFETs) on ultrathin dielectrics. We report the first investigation of a self-assembled monolayer (SAM) dipole as an electrostatic barrier to reduce leakage currents in n-channel OFETs fabricated on a minimal, leaky ∼10 nm SiO2 dielectric on highly doped Si. The electric field associated with 1H,1H,2H,2H-perfluoro-octyltriethoxysilane (FOTS) and octyltriethoxysilane (OTS) dipolar chains affixed to the oxide surface of n-Si gave an order of magnitude decrease in gate leakage current and subthreshold leakage and a two order-of-magnitude increase in ON/OFF ratio for a naphthalenetetracarboxylic diimide (NTCDI) transistor. Identically fabricated devices on p-Si showed similarly reduced leakage and improved performance for oxides treated with the larger dipole FOTS monolayer, while OTS devices showed poorer transfer characteristics than those on bare oxide. Comparison of OFETs on both substrates revealed that relative device performance from OTS and FOTS treatments was dictated primarily by the organosilane chain and not the underlying siloxane-substrate bond. This conclusion is supported by the similar threshold voltages (VT) extrapolated for SAM-treated devices, which display positive relative VT shifts for FOTS on either substrate but opposite VT shifts for OTS treatment on n-Si and p-Si. Our results highlight the potential of dipolar SAMs as performance-enhancing layers for marginal quality dielectrics, broadening the material spectrum for low power, ultrathin organic electronics.

Voltage dependent displacement current as a tool to measure the vacuum level shift caused by self-assembled monolayers on aluminum oxide

We present charge extraction by a linearly increasing voltage measurements on diodes based on an n-channel naphthalenetetracarboxylic acid diimide semiconductor and an aluminum oxide blocking layer. Results show a large displacement current (roughly 15 times that expected from the geometrical capacitance), which we associate with trap filling in the oxide. The trap density is calculated to be on the order of 1019 cm−3, in agreement with preceding work. We present a way of using the displacement current as a tool for probing the vacuum level shift caused by modifying the oxide surface with self-assembled monolayers in operating devices.

On the validity of MIS-CELIV for mobility determination in organic thin-film devices

The charge extraction (of injected carriers) by linearly increasing voltage in metal-insulator-semiconductor structures, or MIS-CELIV, is based on the theory of space-charge-limited currents. In this work, the validity of MIS-CELIV for mobility determination in organic thin-film devices has been critically examined and clarified by means of drift-diffusion simulations. It is found that depending on the applied transient voltage, the mobility might be overestimated by several orders of magnitude in the case of an ohmic injecting contact. The shortcomings of the MIS-CELIV theory can be traced back to the underlying assumption of a drift-dominated transport. However, the effect of diffusion can be taken into account by introducing a correction factor. In the case of non-ohmic injecting contacts, the extracted mobility becomes strongly dependent on device parameters, possibly leading to large deviations from the actual mobility.

Quantifying loss-mechanisms related to charge carrier collection in thin-film solar cells (Conference Presentation)

Processes taking place at contacts are of particular importance in organic and perovskite solar cells where selective contacts that are able to efficiently collect majority carriers, simultaneously blocking minority carriers are desired. The surface recombination velocity S_R, describing the quality of the contact interface, is a key parameter in obtaining an increased understanding of the kinetics taking place at contacts in thin-film devices [1]. We have extended the analytical framework of the charge extraction by linearly increasing voltage (CELIV) theory taking the effect of built-in voltage, diffusion and band-bending into account [2] and show how we can experimentally quantify loss mechanisms in charge collection [3-4]. We have derived analytical expressions describing the effective reduction of the built-in voltage and the (effective) open-circuit voltage providing means to quantify and distinguish various (loss) mechanisms for contact related effects in thin film solar cells [2-4]. References [1] O. Sandberg, M. Nyman, R. Osterbacka, Physical Review Applied 1, 024003 (2014) [2] O. Sandberg, M. Nyman, R. Osterbacka, Organic Electronics 15, 3413-3420 (2015) [3] A. Sundqvist, M. Nyman, O. Sandberg, S. Sanden, J.-H. Smatt, and R. Osterbacka, Advanced Energy Materials, 1502265 (2016) [4] O.J. Sandberg, et. al, Physical Review Letters, 118, 076601 (2017).

Hole Transport in Low-Donor-Content Organic Solar Cells

Organic solar cells with an electron donor diluted in a fullerene matrix have a reduced density of donor-fullerene contacts, resulting in decreased free-carrier recombination and increased open-circuit voltages. However, the low donor concentration prevents the formation of percolation pathways for holes. Notwithstanding, high (>75%) external quantum efficiencies can be reached, suggesting an effective hole-transport mechanism. Here, we perform a systematic study of the hole mobilities of 18 donors, diluted at ∼6 mol % in C60, with varying frontier energy level offsets and relaxation energies. We find that hole transport between isolated donor molecules occurs by long-range tunneling through several fullerene molecules, with the hole mobilities being correlated to the relaxation energy of the donor. The transport mechanism presented in this study is of general relevance to bulk heterojunction organic solar cells where mixed phases of fullerene containing a small fraction of a donor material or vice versa are present as well.

Doping-induced carrier profiles in organic semiconductors determined from capacitive extraction-current transients

A method to determine the doping induced charge carrier profiles in lightly and moderately doped organic semiconductor thin films is presented. The theory of the method of Charge Extraction by a Linearly Increasing Voltage technique in the doping-induced capacitive regime (doping-CELIV) is extended to the case with non-uniform doping profiles and the analytical description is verified with drift-diffusion simulations. The method is demonstrated experimentally on evaporated organic small-molecule thin films with a controlled doping profile, and solution-processed thin films where the non-uniform doping profile is unintentional, probably induced during the deposition process, and a priori unknown. Furthermore, the method offers a possibility of directly probing charge-density distributions at interfaces between highly doped and lightly doped or undoped layers.

Estimating the surface recombination velocity at contacts in organic devices using charge extraction by linearly increasing voltage (Conference Presentation)

The kinetics at contacts plays a crucial role in sandwich-type thin-film devices based on organic semiconductors. This is of particular importance in organic and perovskite solar cells where selective contacts that are able to efficiently collect majority carriers, simultaneously blocking minority carriers, are desired. Despite the vast progress made, a comprehensive understanding, needed for developing new electrode materials to improve and optimize device performance is still lacking. A key parameter for obtaining information about processes taking place at the contacts is the effective surface recombination velocity.[1] However, means to quantitatively measure surface recombination velocities at contact interfaces in sandwich-type thin-film devices based on organic semiconductors are lacking. The Charge Extraction by a Linearly Increasing Voltage (CELIV) technique is one of the most common methods to measure the charge transport properties in organic semiconductor devices. In this work, we show how CELIV can be used to determine surface recombination velocities at selective and/or blocking contacts in thin-film devices. The analytical framework behind the method is presented, and confirmed by numerical drift-diffusion simulations. We furthermore demonstrate the method on organic semiconductor devices, employing TiO2 and SiO2 as cathode buffer layers. The method allows for an increased understanding of contact properties in sandwich-type thin-film devices based on organic semiconductors. [1] O. J. Sandberg, A. Sundqvist, M. Nyman, and R. Osterbacka, Phys. Rev. Appl. 5, 044005 (2016).

Effect of two-dimensional-Langevin and trap-assisted recombination on the device performance of organic solar cells

Abstract. Using drift-diffusion simulations, we have clarified the effect of two-dimensional lamellar ordering on the device performance and, in particular, the open circuit voltage in donor–acceptor type organic solar cells. The simulations are performed both in systems where direct (band-to-band) recombination dominates and in systems where trap-assisted recombination dominates. Results show that lamellar ordering reduces both the amount of direct and trap-assisted recombination, which is beneficial for device performance. The effect is particularly prominent for small lamellar thicknesses (∼1  nm). It is furthermore shown that in the case of s-shaped current–voltage characteristics due to electrostatic injection barriers the s-shape becomes less prominent for thinner lamellar thicknesses.

The effect of 2D-Langevin and trap-assisted recombination on the open circuit voltage in organic solar cells

Using drift-diffusion simulations we have clarified the effect of 2-dimensional (2D) lamellar ordering on the device performance and, in particular, the open circuit voltage in donor-acceptor type organic solar cells. The simulations are performed both in systems where direct (band-to-band) recombination dominates and in systems where trap-assisted recombination dominates. Results show that lamellar ordering reduces both the amount of direct and trap-assisted recombination, which is beneficial for device performance. The effect is particularly prominent for small lamellar thicknesses (~ 1 nm). It is furthermore shown that in the case of s-shaped current-voltage characteristics due to electrostatic injection barriers the s-shape becomes less prominent for thinner lamellar thicknesses.