Matthias Fehr

Influence of deep defects on device performance of thin-film polycrystalline silicon solar cells

Employing quantitative electron-paramagnetic resonance analysis and numerical simulations, we investigate the performance of thin-film polycrystalline silicon solar cells as a function of defect density. We find that the open-circuit voltage is correlated to the density of defects, which we assign to coordination defects at grain boundaries and in dislocation cores. Numerical device simulations confirm the observed correlation and indicate that the device performance is limited by deep defects in the absorber bulk. Analyzing the defect density as a function of grain size indicates a high concentration of intra-grain defects. For large grains (>2 μm), we find that intra-grain defects dominate over grain boundary defects and limit the solar cell performance.

Pulsed electrically detected magnetic resonance for thin film silicon and organic solar cells

In thin film solar cells based on non-crystalline thin film silicon or organic semiconductors structural disorder leads to localized states that induce device limiting charge recombination and trapping. Both processes frequently involve paramagnetic states and become spin-dependent. In the present perspectives article we report on advanced pulsed electrically detected magnetic resonance (pEDMR) experiments for the study of spin dependent transport processes in fully processed thin film solar cells. We reflect on recent advances in pEDMR spectroscopy and demonstrate its capabilities on two different state of the art thin film solar cell concepts based on microcrystalline silicon and organic MEH-PPV:PCBM blends, recently studied at HZB. Benefiting from the increased capabilities of novel pEDMR detection schemes we were able to ascertain spin-dependent transport processes and microscopically identify paramagnetic states and their role in the charge collection mechanism of solar cells.

Lock-in detection for pulsed electrically detected magnetic resonance

We show that in pulsed electrically detected magnetic resonance (pEDMR) signal modulation in combination with a lock-in detection scheme can reduce the low-frequency noise level by one order of magnitude and in addition removes the microwave-induced non-resonant background. This is exemplarily demonstrated for spin-echo measurements in phosphorus-doped silicon. The modulation of the signal is achieved by cycling the phase of the projection pulse used in pEDMR for the readout of the spin state.

Electrical detection of electron spin resonance in microcrystalline silicon pin solar cells

Pulsed electrically detected magnetic resonance (pEDMR) was employed to study spin-dependent processes that influence charge transport in microcrystalline silicon (µc-Si:H) pin solar cells. Special emphasis was put on the identification of the signals with respect to the individual layers of the cell structure. To do this, we systematically modulated the morphology of the highly doped n- and p-layers from amorphous to microcrystalline. By combining the information obtained from low-temperature (T = 10 K) pEDMR spectra and from the deconvoluted time evolution of spectrally overlapping resonances, we found signals from conduction band tail states as well as phosphorus donor states in samples containing an amorphous n-type layer and a resonance associated with valence band tail states in samples with an amorphous p-layer. Moreover, several signals from the intrinsic microcrystalline absorber layers could be identified. An additional resonance at g = 1.9675(5), which has not been observed in EDMR before, was found. We assign this signal to shallow donors in the Al-doped ZnO layer, which is commonly used as transparent conducting oxide in thin-film solar cells. The experimental findings are discussed in the light of various spin-dependent transport mechanisms known to occur in the respective layers of the pin structure.

Electronic structure of positive and negative polarons in functionalized dithienylthiazolo[5,4-d]thiazoles: a combined EPR and DFT study

2,5-Dithienylthiazolo[5,4-d]thiazole (DTTzTz) derivatives have high potential for solution-processed organic field-effect transistors and solar cells, both as electron acceptors and donors. Here, the electronic structure of positive and negative radicals (polarons) of two functionalized DTTzTz materials is studied using multi-frequency and multi-resonance electron paramagnetic resonance (EPR) in combination with density functional theory (DFT). It is shown that the negative and positive DTTzTz polarons can be distinguished on the basis of their characteristic EPR parameters. The chemically induced polarons are compared to light-generated states observed in a blend of one of the DTTzTz derivatives with a donor polymer. The study gives in-depth information about the spread of the electron or hole in the DTTzTz molecules.

CW and pulsed electrically detected magnetic resonance spectroscopy at 263 GHz/12 T on operating amorphous silicon solar cells

Here we describe a new high frequency/high field continuous wave and pulsed electrically detected magnetic resonance (CW EDMR and pEDMR) setup, operating at 263GHz and resonance fields between 0 and 12T. Spin dependent transport in illuminated hydrogenated amorphous silicon p-i-n solar cells at 5K and 90K was studied by in operando 263GHz CW and pEDMR alongside complementary X-band CW EDMR. Benefiting from the superior resolution at 263GHz, we were able to better resolve EDMR signals originating from spin dependent hopping and recombination processes. 5K EDMR spectra were found to be dominated by conduction and valence band tail states involved in spin dependent hopping, with additional contributions from triplet exciton states. 90K EDMR spectra could be assigned to spin pair recombination involving conduction band tail states and dangling bonds as the dominating spin dependent transport process, with additional contributions from valence band tail and triplet exciton states.

High resolution in-operando microimaging of solar cells with pulsed electrically-detected magnetic resonance

The in-operando detection and high resolution spatial imaging of paramagnetic defects, impurities, and states becomes increasingly important for understanding loss mechanisms in solid-state electronic devices. Electron spin resonance (ESR), commonly employed for observing these species, cannot meet this challenge since it suffers from limited sensitivity and spatial resolution. An alternative and much more sensitive method, called electrically-detected magnetic resonance (EDMR), detects the species through their magnetic fingerprint, which can be traced in the devices electrical current. However, until now it could not obtain high resolution images in operating electronic devices. In this work, the first spatially-resolved electrically-detected magnetic resonance images (EDMRI) of paramagnetic states in an operating real-world electronic device are provided. The presented method is based on a novel microwave pulse sequence allowing for the coherent electrical detection of spin echoes in combination with powerful pulsed magnetic-field gradients. The applicability of the method is demonstrated on a device-grade 1-μm-thick amorphous silicon (a-Si:H) solar cell and an identical device that was degraded locally by an electron beam. The degraded areas with increased concentrations of paramagnetic defects lead to a local increase in recombination that is mapped by EDMRI with ∼20-μm-scale pixel resolution. The novel approach presented here can be widely used in the nondestructive in-operando three-dimensional characterization of solid-state electronic devices with a resolution potential of less than 100 nm.