Phosphorus-doped Polycrystalline Silicon Research Articles

22.56% total area efficiency of n-TOPCon solar cell with screen-printed Al paste

Screen-printing Ag paste on the rear side of the Tunnel Oxide Passivated Contact solar cells (TOPCon) is still the mainstream method to form electrodes. However, the high price of precious metals increases the cost of TOPCon cells. Al is a cheap and high-performance conductor, and its work function is compatible with the rear side of TOPCon cells. In this study, we used a UV pulse laser (355 nm, 10 ps) to ablate the rear side SiNx passivation layer of TOPCon cells and then printed Al paste with different weight percentages of silicon (Si-wt.%) on the phosphorus-doped polycrystalline silicon (n+-poly-Si) layer to reduce the cost. We investigated the damage mechanism of laser on SiOx/n+-poly-Si/SiNx passivation structure and the contact mechanism between Al paste and n+-poly-Si layer. The results show that the Voc of SiOx/n+-poly-Si/SiNx passivation structure reduced about 6–7 mV when the laser energy density was 0.431 J/cm2. We got the best electrical performance of TOPCon cells printed with Al paste (25 wt%-29 wt% silicon). The open-circuit voltage (Voc) and the conversion efficiency (Eff), have reached 663.60 mV and 22.56 % respectively. Although the efficiency was 9.40 % relative lower than that of TOPCon cells printed with Ag paste, but the cost of Al paste only accounted for 10 % of Ag paste. In the future, the highest Eff of TOPCon solar cells printed with Al paste on the rear side are expected to reach the commercial TOPCon based on Ag paste, which applies laser doping selective emitter technology (SE) and bifacial poly-Si passivation structure.

Ex-situ phosphorus-doped polycrystalline silicon passivating contacts for high-efficiency solar cells by physical vapour deposition

We present ex-situ phosphorus-doped polycrystalline silicon (poly-Si) passivating contacts fabricated by the physical vapour deposition method, specifically sputtering. This technique is currently of great interest to the photovoltaics (PV) community due to its low deposition temperature, small footprint, high throughput, and use of low-hazard, solid targets and gases. We optimise the performance of the passivating contacts by adjusting various parameters from the sputtering of amorphous Si films to the formation of the poly-Si layers by a high-temperature thermal diffusion (with phosphorus oxychloride – POCl3, or phosphorus spin-on glass as the dopant sources). For the case of POCl3 diffusion, a high iVoc of ∼720 mV together with a low J0 of 2.6 fA/cm2 after a hydrogenation treatment by atomic layer deposition (ALD) AlOx and forming gas annealing (FGA), and a low contact resistivity ρc of less than 10 mΩ cm2 were achieved. Meanwhile, with spin-on doping, a low average iVoc of ∼600 mV was observed. This variation in performance could be explained by the difference in the crystallinity and the diffusion mechanism of the sputtered Si films after different subsequent thermal diffusion processes. Quokka3 simulations show that cell efficiencies as high as 25% are possible using the optimised passivating contacts. The results demonstrate the potential of these PVD poly-Si films as a promising candidate for future industrial solar cells.

Development of Phosphorus-Doped Nanoscale Poly-Si Passivating Contacts via Inkjet Printing for Application in Silicon Solar Cells

Herein, high-quality localized phosphorus-doped polycrystalline silicon (poly-Si) passivating contacts containing nanoscale poly-Si film (∼100 nm) on an ultrathin SiOx layer (∼1.5 nm) were fabricated via an inkjet printing technique. A detailed study of the impacts of inkjet printer settings, dopant concentration, and annealing temperature on the poly-Si passivating contact performance (represented by implied open-circuit voltage iVoc and contact resistivity ρc) was carried out. By applying optimized process conditions on symmetrical industrially processed intrinsic poly-Si/SiOx/n-type crystalline Si (c-Si) substrates, good surface passivation was achieved with an iVoc of 699 mV, together with a low ρc of 6.4 mΩ·cm2, after annealing at 975 °C. After a hydrogenation treatment via the deposition of aluminum oxide (AlOx)/silicon nitride (SiNy) stack and subsequent forming gas annealing (FGA), the optimum annealing temperature shifted to 950 °C and the iVoc was further improved to an excellent value of 729 mV. Optical images reveal that a line width of 75 μm can be realized on a mechanically polished silicon wafer. Moreover, high-resolution micro-photoluminescence (μ-PL) maps clearly demonstrate the localization of the doped regions on the symmetrical substrate after annealing. These results show that inkjet printing is a promising technique for the fabrication of localized poly-Si/SiOx passivating contacts in high-efficiency solar cells with high flexibility and simplicity.

Emitter formation with boron diffusion from PECVD deposited boron-doped silicon oxide for high-efficiency TOPCon solar cells

We present a systematic study of emitter formation with dopant diffusion from boron (B)-doped hydrogenated silicon oxide (a-SiOx:H) deposited on textured n-type monocrystalline silicon (n-c-Si) wafers using a 13.56 MHz plasma-enhanced chemical vapor deposition (PECVD) system. The B atoms in the a-SiOx:H are activated and diffused into the n-c-Si wafer during a high-temperature annealing to form a p/n junction for solar cell application. Afterward, the B-doped SiOx layer is removed by hydrofluoric acid selective etching to obtain a clean surface for the deposition of AlOx passivation and SiNx antireflection layers. With the optimization of the PECVD deposition and the following annealing/etching processes, the B diffused region with a sheet resistance of 60–100 Ω/sq and a junction depth of 1.2–1.5 μm is obtained. A champion implied open-circuit voltage (iVoc) of 705 mV and a single-side saturated recombination current density (J0,s) of 17.6 fA/cm2 are obtained from a double-sided B diffused sample after the passivation with an atomic-layer-deposition (ALD) AlOx. In addition, the contact resistivity (ρc) at the metal/emitter interface is lower than 5 mΩcm2, where the metal contact is a Ti/Pd/Ag tri-layer structure. All of the material properties meet the requirements of high-efficiency solar cell. With the optimized emitter in the front, we made a SiOx and heavily phosphorus-doped polycrystalline silicon carbide (n-poly-SiCx) stack on the rear surface to form tunnel oxide passivated contact (TOPCon) solar cells. The results show that the iVoc of semi-finished TOPCon solar cell before metallization is more than 725 mV. Finally, a TOPCon solar cell with an efficiency of 24.24% is obtained, which is comparable with the TOPCon solar cells with the industrial thermally diffused emitter.

Trench filling with phosphorus-doped monocrystalline and polycrystalline silicon

Optimized epitaxial processes for the filling of deep trenches are mandatory for the fabrication of advanced devices in the microelectronic industry. The use of Selective Epitaxial Growth (SEG) in deep cavities faces multiple issues such as inhomogeneities along the growth direction or defect formation. In this work, the main objective was to develop void-free processes to fill 1:6 up to 1:16 aspect ratio trenches with monocrystalline and polycrystalline Si:P respectively, in a Reduced Pressure – Chemical Vapour Deposition (RP-CVD) reactor. Previous studies suggested the use of a SiH2Cl2 (DCS) + PH3 + HCl chemistry, with an optimization of the DCS/HCl mass-flow ratio (MFR) to conformally fill large and high aspect ratio trenches with monocrystalline Si:P (c-Si:P) while preventing overgrowth at the trench entrance and voids at the bottom. Current studies were first of all conducted on blanket wafers at T = 950 °C and P = 10 Torr, in order to choose the best strategy for varying DCS/HCl MFRs. The P+ ions concentration was quantified and two trends were highlighted depending on the PH3 partial pressure (P(PH3)). For P(PH3) lower than 10-5 Torr, the dopant concentration (in the 1017 - 1018 cm-3 range) increased solely with the phosphine flow and did not depend on the HCl flow. Meanwhile, for PH3 partial pressures higher than 10-5 Torr and thus higher doping levels (between 3x1018 and 2x1019 cm-3), the P+ ions concentration increased with the PH3 flow and decreased as the HCl flow increased. The filling of 1:6 aspect ratio trenches by monocrystalline Si:P was then achieved thanks to a three steps process with various DCS/HCl MFRs. Characterizations showed good crystalline quality together with a steady doping level of 1.3x1018 at cm-3. Further optimizations will however be required to completely suppress voids. Meanwhile, the filling of 1:16 aspect ratio trenches or needles by poly-Si:P was successfully achieved at 10 Torr with a SiH4 + PH3 chemistry, provided that the deposition temperature, 750°C, was low enough to avoid the formation of large poly-Si:P grains, notably at the entrance of such cavities.

In situ phosphorus-doped polycrystalline silicon films by low pressure chemical vapor deposition for contact passivation of silicon solar cells

In situ phosphorus (P)-doped polycrystalline silicon (poly-Si) films by low pressure chemical vapor deposition (LPCVD) were studied in this work for the fabrication of poly-Si passivating contacts. In situ doping was targeted for enabling the full potential of the high-throughput LPCVD technique, as it could allow leaner fabrication of industrial solar cells featuring poly-Si passivating contacts than the more common ex situ doping routes. By careful optimization of the deposition temperature and the flows of the carrier gas (H2) and the dopant precursor (PH3), high doping in the poly-Si layers was achieved with active P concentrations up to 1.3⋅1020 cm−3. While reduction in the deposition rate (rdep) and thus in the throughput is a known problem when growing in situ P-doped films by LPCVD, this reduction could be limited, and the resulting rdep was equal to 0.078 nm/s. The developed poly-Si films were characterized both structurally and in terms of their passivation potential in poly-Si contacts. The latter yielded recombination current densities down to 1.5 fA/cm2 in passivated (J0,p) and 25.6 fA/cm2 in screen-printing metallized (J0,m) regions on saw-damage removed (SDR) Cz-Si surfaces, accompanied by a contact resistivity (ρc,m) of 4.9 mΩ⋅cm2. On textured Cz-Si surfaces, the corresponding values were J0,p = 3.5 fA/cm2, J0,m = 56.7 fA/cm2, and ρc,m = 1.8 mΩ⋅cm2. Optical impact of the developed poly-Si films was also assessed and a short circuit density loss of 0.41 mA/cm2 is predicted per each 100 nm of poly-Si applied at the rear side of solar cells.

Optimum Hydrogen Injection in Phosphorus-Doped Polysilicon Passivating Contacts.

It has previously been shown that ex situ phosphorus-doped polycrystalline silicon on silicon oxide (poly-Si/SiOx) passivating contacts can suffer a pronounced surface passivation degradation when subjected to a firing treatment at 800 °C or above. The degradation behavior depends strongly on the processing conditions, such as the dielectric coating layers and the firing temperature. The current work further studies the firing stability of poly-Si contacts and proposes a mechanism for the observed behavior based on the role of hydrogen. Secondary ion mass spectrometry is applied to measure the hydrogen concentration in the poly-Si/SiOx structures after firing at different temperatures and after removing hydrogen by an anneal in nitrogen. While it is known that a certain amount of hydrogen around the interfacial SiOx can be beneficial for passivation, surprisingly, we found that the excess amount of hydrogen can deteriorate the poly-Si passivation and increase the recombination current density parameter J0. The presence of excess hydrogen is evident in selected poly-Si samples fired with silicon nitride (SiNx), where the injection of additional hydrogen to the SiOx interlayer leads to further degradation in the J0, while removing hydrogen fully recovers the surface passivation. In addition, the proposed model explains the dependence of firing stability on the crystallite properties and the doping profile, which determine the effective diffusivity of hydrogen upon firing and hence the amount of hydrogen around the interfacial SiOx after firing.

Phosphorus-doped polysilicon passivating contacts deposited by atmospheric pressure chemical vapor deposition

In this work, we present a high quality tunnel oxide passivating, electron-selective contact that is formed using an in-situ phosphorus-doped polycrystalline silicon (poly-Si) layer deposited using an in-line atmospheric pressure chemical vapor deposition (APCVD) process. In-line APCVD is a single-sided deposition process that does not require vacuum systems and is well suited for high volume manufacturing. To fabricate this tunnel oxide passivating contact (TOPCon), we deposit an amorphous silicon (a-Si) layer on silicon oxide (SiO) passivated n-type crystalline silicon (c-Si) followed by an annealing step at around 910 ∘C, which provides solid phase crystallization. The contact shows an excellent surface passivation quality with an effective minority carrier lifetime of ≈4.2 ms and an implied open circuit voltage (iV ) of ≈717 mV after annealing without any additional hydrogenation process. Saturation current density (J ) of ≈18 fA cm−2 is recorded for this contact. Contact resistivity () of ≈50 mΩ·cm−2 and junction resistivity of ≈0.24 Ω·cm−2 are realized with e-beam evaporated aluminium (Al) metal contact.

The impacts of LPCVD wrap-around on the performance of n-type tunnel oxide passivated contact c-Si solar cell

In this paper, Tunnel Oxide Passivated Contact (TOPCon) silicon solar cells with the industrial area (244.32 cm2) are fabricated on N-type silicon substrates. Both the ultra-thin tunnel oxide layer and phosphorus doped polycrystalline silicon (polysilicon) thin film are prepared by the LPCVD system. The wrap-around of polysilicon is observed on the surface of borosilicate glass (BSG). The polysilicon wrap-around can form a leakage current path, thus degrades the shunt resistance of solar cells, and leads to the degradation of solar cell efficiency. Different methods are adopted to treat the polysilicon wrap-around and improve shunt resistance of solar cells. The experimental results indicate that a chemical etching method can effectively solve the problem of polysilicon wrap-around and improve the performance of solar cells. Finally, a conversion efficiency of 22.81% has been achieved by our bifacial TOPCon solar cells, with Voc of 702.6 mV, Jsc of 39.78 mA/cm2 and FF of 81.62%.

Solid phase epitaxial thickening of boron and phosphorus doped polycrystalline silicon thin films formed by aluminium induced crystallization technique on glass substrate

Aluminium induced crystallization (AIC) technique can be used to form the high-quality and large-grained polycrystalline silicon (poly-Si) thin films, which are with the thickness of ~200 nm and used as a seed layer, on silicon nitride coated glass substrate. Thanks to aluminium metal in AIC process, the natural doping of AIC thin films is p+ type (~2 × 1018 cm−3). On the other hand, recombination of carriers can be controlled by partial doping through the defects that may have advantages to improve the thin film quality by the overdoping induced passivation. In this study, boron (B) and phosphorus (P) doped AIC seed layers were thicken to ~2 μm by solid phase epitaxy (SPE) technique at 800 °C for 3 h under nitrogen flow in a tube furnace. During the crystallization annealing, exodiffusion of dopants was formed through the SPE film from the AIC seed layer. Optical microscope and electron back scattering diffraction technique (EBSD) were used to analyse the structural quality of the Si films. The poly-Si layer with an average grain size value of ~32 μm was formed by AIC + SPE technique for P doped samples while EBSD analysis gave no results for B doped samples due to the quite deterioration on the surface of the films. AIC + SPE films were analyzed in terms of structural properties by using micro-Raman Spectroscopy and X-ray diffraction systems. The results showed that the crystallinity of compressive stress formed AIC + SPE films reached up to 98.55%. Additionally, the Raman analysis pointed out that no temperature-induced stress were generated in the AIC + SPE films while compressive stress was induced by increasing the annealing duration for doped AIC film. For all samples, the preferred orientation was 〈100〉, and the crystallite size up to 44.4 nm was formed by phosphorus doping of AIC films. The doping efficiency was determined by time-of-flight secondary ion mass spectroscopy for doped samples. A graded n+n doping profile was obtained by exo-diffusion of phosphorus from the overdoped seed layer during the epitaxial thickening while boron doping of SPE film has failed with exo-diffusion of boron from AIC seed layer into SPE film. Finally, high-quality n+n type poly-Si films were fabricated on glass substrate by using AIC + SPE technique.

Hydrogenation of Phosphorus-Doped Polycrystalline Silicon Films for Passivating Contact Solar Cells.

We characterize and discuss the impact of hydrogenation on the performance of phosphorus-doped polycrystalline silicon (poly-Si) films for passivating contact solar cells. Combining various characterization techniques including transmission electron microscopy, energy-dispersive X-ray spectroscopy, low-temperature photoluminescence spectroscopy, quasi-steady-state photoconductance, and Fourier-transform infrared spectroscopy, we demonstrate that the hydrogen content inside the doped poly-Si layers can be manipulated to improve the quality of the passivating contact structures. After the hydrogenation process of poly-Si layers fabricated under different conditions, the effective lifetime and the implied open circuit voltage are improved for all investigated samples (up to 4.75 ms and 728 mV on 1 Ω cm n-type Si substrates). Notably, samples with very low initial passivation qualities show a dramatic improvement from 350 μs to 2.7 ms and from 668 to 722 mV.

Growth and electrical properties of in situ phosphorus-doped polycrystalline silicon films using Si3H8 and PH3

In situ phosphorus-doped polycrystalline silicon (polysilicon) films grown on silicon oxide layers using trisilane (Si3H8) and phosphine (PH3) as precursors are investigated as a function of the Si3H8/PH3 gas flow ratio and the growth temperature. At a high flow rate for Si3H8 in the temperature range of 600–700 °C, the deposition process is controlled by the rate of desorption of hydrogen molecules on the surface, which has an activation energy of 1.13 eV. For a low Si3H8 flow rate at growth temperatures >650 °C, however, the deposition is limited by the diffusion of Si3H8 gas to the surface. The presence of phosphorus decreases the crystallization temperature of the polysilicon layers during growth. In addition, the ratio of phosphorus incorporated into the polysilicon decreases with increasing growth temperature because of the increase in the growth rate. The resistivity of the phosphorus-doped polysilicon films decreases with increasing deposition temperature at the same phosphorus concentration, indicating that the use of a high growth temperature results in an enhancement in the activation of phosphorus in the polysilicon films during growth.

Boron- and phosphorus-doped polycrystalline silicon thin films prepared by silver-induced layer exchange

Intentional boron and phosphorus doping of polycrystalline silicon thin films on glass prepared by the silver-induced layer exchange is presented. A silver/(titanium) oxide/amorphous silicon stack is annealed at temperatures below the eutectic temperature of the Ag/Si system, leading to a complete layer exchange and simultaneous crystallization of the amorphous silicon. Intentional doping of the amorphous silicon prior to the exchange process results in boron- or phosphorus-doped polycrystalline silicon. Hall effect measurements show carrier concentrations between 2×1017 cm−3 and 3×1020 cm−3 for phosphorus and 4×1018 cm−3 to 3×1019 cm−3 for boron-doped layers, with carrier mobilities up to 90 cm2/V s.

Optical properties of evaporated poly-Si thin-films on glass

The optical properties of boron- and phosphorus-doped polycrystalline silicon films with light (~ 1 × 10 16 cm −3), moderate (~ 5 × 10 17 cm −3) and heavy doping (~ 1 × 10 19 cm −3) were investigated in this work. The films were prepared by solid-phase crystallization of evaporated amorphous silicon films on borosilicate glass. Tauc–Lorentz models with one or two oscillators were used to model both reflection and transmission data collected by a spectrophotometer over the wavelength range of 400 nm–2000 nm. The results indicate that the crystal quality of the films is improved by phosphorus doping, while boron has a negligible impact on the crystal quality. The poly-Si films exhibit greater absorption than c-Si for visible wavelengths. This enhanced absorption is believed to be associated with defected a-Si material at the grain boundaries and intra-grain defects.

Macroporous Silicon Electrochemical Etching for Gas Diffusion Layers Applications: Effect of Processing Temperature

MEMS technology requires low cost techniques to permit large scale fabrication for production. Porous silicon (PS) can be used in different manner to replace standard expensive etching techniques like DRIE (Deep Reactive Ion Etching). To perform same process quality as the latter, one need to understand how different parameters can influence porous silicon properties. We investigate here local formation of macroporous silicon on 2D and 3D silicon substrates. The blank substrate is a low doped (26–33 Ω cm) n type 6 inches silicon wafer. Then, an in situ phosphorus-doped polycrystalline silicon (N+ Poly-Si) is deposited on a thermal oxide layer to delimit the regions to be etched. Porous silicon is obtained afterwards using electrochemical anodization in a hydrofluoric acid (HF) solution. The effect of the temperature process on Si-HF electrochemical system voltamperometric curves, macropores morphology and electrochemical etch rates is more specifically studied. Moreover, permeation of porous substrates to hydrogen is studied after various anodization post-treatments such as KOH and HF wet etching or after a thin gold layer deposition used as current collector in micro fuel cells.

Electron transport and band structure in phosphorus-doped polycrystalline silicon films

We study transport mechanisms, effective mass, and band structure by measuring the resistivity, Hall, and Seebeck and Nernst coefficients in heavily phosphorus-doped polycrystalline silicon films made by thermal crystallization of amorphous silicon. We observe a change in transport mechanism which results in an increase in electron mobility from 10% to 80% of the single-crystal silicon mobility as the carrier concentration increases from 1019 to 1020 cm−3. Our measurements of effective mass at the Fermi level indicate that as the carrier concentration increases, there is a shift from impurity-band transport to conduction-band transport, and that the electron effective mass is lower in the impurity band than in the conduction band of Si. The shift to conduction-band transport improves electron mobility with carrier density by improving intragrain carrier mean free path lengths and relaxation times.

The influence of defects and postdeposition treatments on the free carrier density in lightly phosphorus-doped large-grained polycrystalline silicon films

The influence of postdeposition treatments (rapid thermal annealing and hydrogenation) on the doping of large-grained polycrystalline silicon p+nn+ thin-film diodes on glass substrates is investigated using resistivity and impedance analysis measurements. Whereas in the lightly phosphorus-doped base region both treatments are found to cause an increase in the active doping concentration, hydrogenation decreases the active doping concentration of both heavily doped layers (Al and P). The different behavior is attributed to acceptorlike defects which are present in the nonhydrogenated base region in a similar concentration as the atomic phosphorus concentration and which are well passivated by hydrogenation. From posthydrogenation annealing experiments and temperature-dependent impedance analysis measurements, different temperature dependences and activation energies (depending on the posthydrogenation annealing temperature) are found for the lightly doped base region. The temperature dependences are quanti...

As- or P-Doped Si Layers Grown by RPCVD for Emitter Application in SiGeC HBTs

A new module for the emitter formation in a bipolar transistor is presented. Arsenic- or phosphorus-doped polycrystalline silicon layer for the emitter formation is deposited in a reduced pressure chemical vapor deposition reactor using silane as the silicon source gas. Characteristics such as the carrier concentration, conductivity, surface morphology, and thermal stability of the polycrystalline-silicon layer as well as the influence this layer has on a SiGeC transistor structure during the drive-in step area studied. The active carrier concentration of the as-grown sample is strongly dependent on the deposition temperature, especially arsenic doped layers which exhibit more than one order of magnitude difference. However, the carrier concentration for the As- or P-doped layer were comparable to that of a standard in-situ doped poly-crystalline layer after a dopant activation at 925°C for 10s.

Supergain transistors on high-purity float-zone silicon substrate

Since float-zone (FZ) silicon has lower contamination and longer minority carrier lifetime than those in Czochralski silicon and other semiconductor materials, it has potential advantages to fabricate a bipolar junction transistor on the FZ substrate to achieve high gain at very low current levels. In this report, the authors present preliminary experimental results on supergain bipolar junction transistors fabricated on unusual FZ refined high-resistivity silicon substrate and by ion implantation technology. A phosphorus-doped polycrystalline silicon backside gettering layer has been employed to preserve the long carrier lifetime of the high-purity FZ silicon. Bipolar junction transistors have demonstrated high current gain, more than 3300 for ultralow base current levels of 10 pA in this study. Possible applications of high-purity FZ silicon on some advanced semiconductor devices and circuits are discussed in this letter.

Low-Resistivity Phosphorus-Doped Polycrystalline Silicon Thin Films Formed by Catalytic Chemical Vapor Deposition and Successive Rapid Thermal Annealing

Low-resistivity phosphorus (P)-doped polycrystalline silicon (poly-Si) thin films were prepared from amorphous silicon (a-Si) films deposited by catalytic chemical vapor deposition (Cat-CVD) and successive rapid thermal annealing (RTA). RTA was carried out at 1000°C for crystallization of heavily P-doped a-Si prepared by Cat-CVD. The films are suitable for the solid-phase crystallization (SPC) process because of their low hydrogen (H) content. It is revealed that both the crystallization and low resistivity of 0.001 Ω·cm are realized by RTA at 1000°C for only 5 s. Even after high-temperature RTA processes, perfect surface-flatness is maintained and neither peeling nor bubbling due to H atoms in the films is observed.