Effective control of nanostructured phases in rapid, room-temperature synthesis of nanocrystalline Si in high-density plasmas

An innovative and effective approach based on low-pressure, low-frequency, thermally nonequilibrium, high-density inductively coupled plasmas is proposed to synthesize device-quality nanocrystalline silicon (nc-Si) thin films at room temperature and with very competitive growth rates. The crystallinity and microstructure properties (including crystal structure, crystal volume fraction, surface morphology, etc.) of this nanostructured phase of Si can be effectively tailored in broad ranges for different device applications by simply varying the inductive rf power density from 25.0 to 41.7 mW/cm3. In particular, at a moderate rf power density of 41.7 mW/cm3, the nc-Si films feature a very high growth rate of 2.37 nm/s, a high crystalline fraction of 86%, a vertically aligned columnar structure with the preferential (111) growth orientation and embedded Si quantum dots, as well as a clean, smooth and defect-free interface. We also propose the formation mechanism of nc-Si thin films which relates the high electron density and other unique properties of the inductively coupled plasmas and the formation of the nanocrystalline phase on the Si surface.

How to achieve high mobility thin film transistors by direct deposition of silicon using 13.56 MHz RF PECVD?

CMOS nanocrystalline silicon thin film transistors with high field effect mobility are reported. The transistors were directly deposited by radio-frequency plasma enhanced chemical vapor deposition at 150°C The transistors show maximum field effect mobility of 450 cm2/V-s for electrons and 100 cm2/V-s for holes at room temperature. We attribute the high mobilities to a reduction of the oxygen content, which acts as an accidental donor. Indeed, secondary ion mass spectrometry measurements show that the impurity concentration in the nanocrystalline Si layer is comparable to, or lower than, the defect density in the material, which is already low thanks to hydrogen passivation.

Nanostructure in the p-layer and its impacts on amorphous silicon solar cells

The open circuit voltage (V-oc) of n-i-p type hydrogenated amorphous silicon (a-Si:H) solar cells has been examined by means of experimental and numerical modeling. The i- and p-layer limitations on V-oc are separated and the emphasis is to identify the impact of different kinds of p-layers. Hydrogenated protocrystalline, nanocrystalline and microcrystalline silicon p-layers were prepared and characterized using Raman spectroscopy, high resolution transmission electron microscopy (HRTEM), optical transmittance and activation energy of dark-conductivity. The n-i-p a-Si:H solar cells incorporated with these p-layers were comparatively investigated, which demonstrated a wide variation of V-oc from 1.042 V to 0.369 V, under identical i- and n-layer conditions. It is found that the nanocrystalline silicon (nc-Si:H) p-layer with a certain nanocrystalline volume fraction leads to a higher V-oc. The optimum p-layer material for n-i-p type a-Si:H solar cells is not found at the onset of the transition between the amorphous to mixed phases, nor is it associated with a microcrystalline material with a large grain size and a high volume fraction of crystalline phase. (c) 2006 Elsevier B.V. All rights reserved.

The effect of interposing nanocrystalline Si(B) P plus layer on the photovoltaic properties of a-Si: H tandem solar cells

Tandem amorphous silicon solar cells have attracted extensive interest because of better performance than single junction counterpart. As n/p junctions play an important role in the current transportation of tandem solar cells, it is important to design and fabricate good n/p junctions.The properties of the n/p junction of amorphous silicon (a-Si) were studied. We investigate the effect of interposing a nanocrystalline p(+) layer between n (top cell) and p (bottom cell) layers of a tandem solar cell. The crystalline volume fraction, the band gap, the conductivity and the grain size of the nanocrystalline silicon (nc-Si) p(+) layer could be modulated by changing the deposition parameters.Current transport in a-Si based n/p ("tunnel") junctions was investigated by current-voltage measurements. The voltage dependence on the resistance (V/J) of the tandem cells was examined to see if n/p junction was ohmic contact. To study the affection of different doping concentration to the properties of the nc-Si p(+) layers which varied the properties of the tunnel junctions, three nc-Si p(+) film samples were grown, measured and analyzed.

Nanostructure in the p-layer and its impacts on amorphous silicon solar cells

The open circuit voltage (V-oc) of n-i-p type hydrogenated amorphous silicon (a-Si:H) solar cells has been examined by means of experimental and numerical modeling. The i- and p-layer limitations on V-oc are separated and the emphasis is to identify the impact of different kinds of p-layers. Hydrogenated protocrystalline, nanocrystalline and microcrystalline silicon p-layers were prepared and characterized using Raman spectroscopy, high resolution transmission electron microscopy (HRTEM), optical transmittance and activation energy of dark-conductivity. The n-i-p a-Si:H solar cells incorporated with these p-layers were comparatively investigated, which demonstrated a wide variation of V-oc from 1.042 V to 0.369 V, under identical i- and n-layer conditions. It is found that the nanocrystalline silicon (nc-Si:H) p-layer with a certain nanocrystalline volume fraction leads to a higher V-oc. The optimum p-layer material for n-i-p type a-Si:H solar cells is not found at the onset of the transition between the amorphous to mixed phases, nor is it associated with a microcrystalline material with a large grain size and a high volume fraction of crystalline phase. (c) 2006 Elsevier B.V. All rights reserved.

Comparative study of the surface passivation on crystalline silicon by silicon thin films with different structures

Si thin films with different structures were deposited by plasma enhanced chemical vapor deposition (PECVD), and characterized via Raman spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The passivation effect of such different Si thin films on crystalline Si surface was investigated by minority carrier lifetime measurement via a method, called microwave photoconductive decay (mu PCD), for the application in HIT (heterojunction with intrinsic thin-layer) solar cells. The results show that amorphous silicon (a-Si:H) has a better passivation effect due to its relative higher H content, compared with microcrystalline (mu c-Si) silicon and nanocrystalline silicon (nc-Si). Further, it was found that H atoms in the form of Si-H bonds are more preferred than those in the form of Si-H-2 bonds to passivate the crystalline Si surface. (C) 2009 Elsevier B.V. All rights reserved.

Raman scattering and infrared absorption of silicon nanocrystals in silicon oxide matrix

Structural dependence on annealing of a-SiOx:H was studied by using infrared absorption and Raman scattering. The appearance of Raman peaks in the range of 513-519cm(-1) after 1170 degreesC annealing was interpreted as the formation nanocrystalline silicon with the sizes from 3-10nm. The Raman spectra also show the existence of amorphous-like silicon phase, which is associated with Si-Si bond re-construction at boundaries of silicon nanocrystallites. The presence of the shoulder at 980cm(-1) of Si-O-Si stretching vibration at 1085cm(-1) in infrared spectra imply that except that SiO2 phase, there is silicon sub-oxide phase in the films annealed at 1170 degreesC. This sub-oxide phase is located at the interface between Si crystallites and SiO2, and thus support the shell model for the mixed structures of Si grains and SiO2 matrix.

Temperature-dependent properties of nc-Si thin films synthesized in low-pressure, thermally nonequilibrium, high-density inductively coupled plasmas

Silicon thin films were synthesized simultaneously on single-crystal silicon and glass substrates by lowpressure, thermally nonequilibrium, high-density inductively coupled plasma-assisted chemical vapor deposition from the silane precursor gas without any additional hydrogen dilution in a broad range of substrate temperatures from 100 to 500 °C. The effect of the substrate temperature on the morphological, structural and optical properties of the synthesized silicon thin films is systematically studied by X-ray diffractometry, Raman spectroscopy, UV-vis spectroscopy, and scanning electron microscopy. It is shown that the formation of nanocrystalline silicon (nc-Si) occurs when the substrate temperature is higher than 200 °C and that all the deposited nc-Si films have a preferential growth along the (111) direction. However, the mean grain size of the (111) orientation slightly and gradually decreases while the mean grain size of the (220) orientation shows a monotonous increase with the increased substrate temperature from 200 to 500 °C. It is also found that the crystal volume fraction of the synthesized nc-Si thin films has a maximum value of ∼69.1% at a substrate temperature of 300 rather than 500 °C. This rather unexpected result is interpreted through the interplay of thermokinetic surface diffusion and hydrogen termination effects. Furthermore, we have also shown that with the increased substrate temperature from 100 to 500 °C, the optical bandgap is reduced while the growth rates tend to increase. The maximum rates of change of the optical bandgap and the growth rates occur when the substrate temperature is increased from 400 to 500 °C. These results are highly relevant to the development of photovoltaic thin-film solar cells, thin-film transistors, and flat-panel displays.

Rapid, low-temperature synthesis of nc-Si in high-density, non-equilibrium plasmas : enabling nanocrystallinity at very low hydrogen dilution

Nanocrystalline silicon thin films were deposited on single-crystal silicon and glass substrates simultaneously by inductively coupled plasma-assisted chemical vapor deposition from the reactive silane reactant gas diluted with hydrogen at a substrate temperature of 200 °C. The effect of hydrogen dilution ratio X (X is defined as the flow rate ratio of hydrogen to silane gas), ranging from 1 to 20, on the structural and optical properties of the deposited films, is extensively investigated by Raman spectroscopy, X-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/VIS spectroscopy, and scanning electron microscopy. Our experimental results reveal that, with the increase of the hydrogen dilution ratio X, the deposition rate Rd and hydrogen content CH are reduced while the crystalline fraction Fc, mean grain size δ and optical bandgap ETauc are increased. In comparison with other plasma enhanced chemical vapor deposition methods of nanocrystalline silicon films where a very high hydrogen dilution ratio X is routinely required (e.g. X > 16), we have achieved nanocrystalline silicon films at a very low hydrogen dilution ratio of 1, featuring a high deposition rate of 1.57 nm/s, a high crystalline fraction of 67.1%, a very low hydrogen content of 4.4 at.%, an optical bandgap of 1.89 eV, and an almost vertically aligned columnar structure with a mean grain size of approximately 19 nm. We have also shown that a sufficient amount of atomic hydrogen on the growth surface essential for the formation of nanocrystalline silicon is obtained through highly-effective dissociation of silane and hydrogen molecules in the high-density inductively coupled plasmas. © 2009 The Royal Society of Chemistry.

Crystallization of amorphous Si films by pulsed laser annealing and their structural characteristics

Nanocrystalline silicon (nc-Si) films were prepared by pulsed laser annealed crystallization of amorphous silicon (alpha-Si) films on SiO2-coated quartz or glass substrates. The effect of laser energy density on structural characteristics of nc-Si films was investigated. The Ni-induced crystallization of the a-Si films was also discussed. The surface morphology and microstructure of these films were characterized by scanning electron microscopy, high-resolution electron microscopy, atomic force microscopy and Raman scattering spectroscopy. The results show that not only can the alpha-Si films be crystallized by the laser annealing technique, but also the size of Si nanocrystallites can be controlled by varying the laser energy density. Their average size is about 4-6 nm. We present a surface tension and interface strain model used for describing the laser annealed crystallization of the alpha-Si films. The doping of Ni atoms may effectively reduce the threshold value of laser energy density to crystallize the alpha-Si films, and the flocculent-like Si nanostructures could be formed by Ni-induced crystallization of the alpha-Si films.

NIP a-Si : H solar cells on stanless steel with p-type nc-Si : H window layer

The successful application of boron-doped hydrogenated nanocrystalline silicon as window layer in a-Si: H nip solar cells on stainless steel foil with a thickness of 0.05 mm is reported. Open circuit voltage and fill factor of the fabricated solar cell were 0.90V and 0.70 respectively. The optical and structural properties of the p-layers have been investigated by using UV-VIS and Raman spectroscopy. It is confirmed that the p-layer is hydrogenated nanocrystalline silicon with a wide optical gap due to quantum size effect.

Study on variable capacitance diode of (p)nc-Si : H/(n)c-Si heterojunction

Hydrogenated nanocrystalline silicon (nc-Si:H) layers of boron-doped increasing step by step was deposited on n-type crystalline silicon substrate using Plasma Enhanced Chemical Vapor Deposition (PECVD) system. After evaporating Ohm contact electrode on the side of substrate and on the side of nc-Si:H film, a structure of electrode/ (p)nc-Si:H/(n)c-Si/electrode was obtained. It is confirmed by electrical measurement such as I-V curve, C-V curve and DLTS that this is a variable capacitance diode. (C) 2003 Elsevier Science Ltd. All rights reserved.