J. Stuchlík

Local characterization of electronic transport in microcrystalline silicon thin films with submicron resolution

Two-dimensional maps of dark conductivity with submicron resolution have been obtained on in situ prepared hydrogenated microcrystalline silicon (μc-Si:H) layers used for solar cells by atomic force microscopy with conductive cantilever. Comparison of the morphology and current image allows clear identification of Si crystallites. Pronounced current decrease has been detected at the grain boundaries. The technique was used to study initial stages of μc-Si:H growth, and we show how the incubation layer, detrimental for solar cells efficiency, can be minimized by pulsed excimer laser crystallization of the initial amorphous layer.

Basic features of transport in microcrystalline silicon

Charge transport in microcrystalline silicon is strongly influenced by its heterogeneous microstructure composed of crystalline grains and amorphous tissue. An even bigger effect on transport is their arrangement in grain aggregates or possibly columns, separated by grain boundaries, causing transport anisotropy and/or depth profile of transport properties. We review special experimental methods developed to study the resulting transport features: local electronic studies by combined atomic force microscopy, anisotropy of conductivity and diffusion length and also their thickness dependence. A simple model based on the concept of changes of transport path for description of the observed phenomena is reviewed and its consequences for charge collection in microcrystalline based solar cells are discussed.

Microcrystalline silicon thin films studied by atomic force microscopy with electrical current detection

Hydrogenated microcrystalline silicon (μc-Si:H) layers with thickness from 100 to 540 nm were prepared in situ by plasma enhanced chemical vapor deposition. The growth of μc-Si:H on various substrates [NiCr, device quality, and laser annealed amorphous silicon (a-Si:H)] was studied in ultrahigh vacuum by atomic force microscope using a conductive cantilever which enabled simultaneous measurement of morphology and local current with lateral resolution below 5 nm. The effect of barriers, voltage, and time on contrast in local current map is discussed in detail. Coexistent amorphous and microcrystalline regions are clearly identified due to their different conductivity. Laser annealing of the a-Si:H substrate significantly increases the crystalline fraction at the same layer thickness. Grains as small as 10–30 nm separated by less conductive grain boundaries were revealed in microcrystalline regions.

Model of transport in microcrystalline silicon

Abstract Large complexity of microstructure in hydrogenated microcrystalline silicon and existence of at least two different sizes of crystallites is demonstrated by combined atomic force microscope topography/local current map. We correlate activation energy and prefactor of the simplest transport property – dark conductivity, measured parallel to the substrate – with the crystallinity and roughness in wide range of microcrystalline silicon samples. This allowed us to formulate a simple model of transport based on the idea that, contrary to small grains, the formation of their aggregates (large grains/columns) dramatically changes the mechanism of transport from band like to hopping.

Transport anisotropy in microcrystalline silicon studied by measurement of ambipolar diffusion length

We have studied charge transport anisotropy in microcrystalline silicon (μc-Si:H) by comparing diffusion length measured parallel to the substrate by steady stage photocarrier grating and perpendicular to the substrate by surface photovoltage method (SPV). We have developed a SPV evaluation procedure which allowed us to exclude the effect of light scattering at the naturally rough surface of the μc-Si:H. The procedure allows us to deduce not only the diffusion length, but also the depth of the depletion layer at the surface and recombination coefficients at both top and bottom interfaces of the film. With growing μc-Si:H film thickness the size of the crystallites increases, leading to higher roughness and thus also light scattering. At the same time density of grain boundaries decreases, resulting in an increase of the diffusion length and of the surface depletion layer depth. For all samples the diffusion length perpendicular to the substrate was several times higher than the diffusion length parallel to it, clearly confirming previous indication of the transport anisotropy resulting from the measurements of coplanar and sandwich conductivity.

The structure and growth mechanism of Si nanoneedles prepared by plasma-enhanced chemical vapor deposition

Silicon nanowires and nanoneedles show promise for many device applications in nanoelectronics and nanophotonics, but the remaining challenge is to grow them at low temperatures on low-cost materials. Here we present plasma-enhanced chemical vapor deposition of crystalline/amorphous Si nanoneedles on glass at temperatures as low as 250 °C. High resolution electron microscopy and micro-Raman spectroscopy have been used to study the crystal structure and the growth mechanism of individual Si nanoneedles. The H(2) dilution of the SiH(4) plasma working gas has caused the formation of extremely sharp nanoneedle tips that in some cases do not contain a catalytic particle at the end.

Dynamics of the excimer laser annealing of hydrogenated amorphous silicon thin films

Time-resolved reflectivity and time-resolved conductivity spectroscopies have been used to monitor phase changes as a function of pulse-energy density during the recrystallization of amorphous hydrogenated Si by an ArF excimer laser. The simultaneous application of both spectroscopies allowed clear identification of the melting threshold and time of melting. The dc conductivity of irradiated Si was measured as a function of pulse energy and number of pulses. These results, together with Raman spectroscopy, revealed that single-pulse annealing gives a conductive, but still amorphous and rather defective layer. At least two consecutive pulses are necessary for obtaining of the substantial crystalline fraction.

Amorphous/microcrystalline silicon superlattices—the chance to control isotropy and other transport properties

Preparation of amorphous silicon/microcrystalline silicon superlattices allowed us a systematic study of transition from isotropic amorphous silicon to microcrystalline silicon with anisotropic (columnar) microstructure. The fact that just a few nm of amorphous interlayers are sufficient to interrupt columnar growth of crystallites is reflected in a clearly demonstrated isotropy of transport properties of all superlattice samples. Values of dark conductivity and diffusion length as well as grain size vary with changing crystallinity and so we can tailor the properties of the resulting material by adjusting thicknesses of amorphous and microcrystalline layers repeated to achieve a total desired thickness. Properly selected design of superlattice can lead to transport properties more suitable for solar cells than with pure microcrystalline silicon.

Rapid crystallization of amorphous silicon at room temperature

Abstract A way in which thin films of hydrogenated amorphous silicon (a-Si: H) can be instantaneously crystallized at room temperature is reported. The metal-induced solid-phase crystallization (MISPC) method with nickel surface coverage is used. In comparison with previous reports on the MISPC of a-Si: H, the crystallization temperature is reduced by more than 350°C. This is achieved by introducing two novel technological steps: firstly, we use hydrogen-rich a-Si: H films (hydrogen content between 20 and 45at.% H) and, secondly, we apply a high transverse electric field. Polycrystalline silicon islands as large as 3 mm across appear instantaneously after having reached a threshold electric field of about 105Vcm−1. We report macroscopic visualization of the crystallization process as well as microscopic investigation (micro-Raman measurements and scanning electron microphotography) of the crystallized films. We have found that appropriate patterning of the nickel electrode helps to increase homogeneity of the resulting polycrystalline silicon.

Microcrystalline silicon -- Relation of transport properties and microstructure

Understanding of transport in hydrogenated microcrystalline silicon ({micro}c-Si:H) is difficult due to its complicated microstructure (grains, grain boundaries, amorphous tissue). {micro}c-Si:H layers often exhibit preferential orientation leading to transport anisotropy. Furthermore, specific {micro}c-Si:H growth features lead to the thickness dependence of the structure and properties. {micro}c-Si:H incubation layer was studied by AFM with conductive cantilever measuring simultaneously morphology and local conductivity maps with submicron resolution. Clear identification of Si crystallites (with size of few tens of nanometers) is demonstrated. The crystalline fraction at the surface may be easily evaluated. For the charge collection in solar cells they need to study transport perpendicular to the substrate. Measurement of frequency spectra of A.C. conductivity is introduced as a new tool which can exclude the influence of contact barriers in sandwich geometry and can be used for finding the true conductivity perpendicular to the substrate. Using this technique transport anisotropy in some {micro}c-Si:H samples was clearly demonstrated. Finally, it is shown how the transport properties change with growing {micro}c-Si:H thickness and how these changes correlate with the structure observed by AFM.