Thermal redistribution of boron implants in bulk silicon and SOS type structures

The redistribution of boron profiles in bulk silicon and SOS (silicon-on-sapphire) type structures is investigated in this paper. Experimental data on thermally redistributed profiles are correlated with predictions based on a computer program whose numerical algorithm was described in an earlier paper. Three cases were considered which involved the thermal redistribution of 1) a high dose (2×10¹⁵ and 5×10¹⁴ cm^–2) 80keV boron implant in (111) bulk silicon, in an oxidizing ambient of steam at 1000°, 1100°, and 1200°C, respectively; 2) a high dose (2.3×10¹⁵ cm^–2) 25 keV boron implant in (100) silicon-on-sapphire, in a nonoxidizing ambient of nitrogen at 1000 °C; and 3) a low dose (3.2×10¹² cm^–2) 150 keV boron implant in (100) bulk silicon, in oxidizing and nonoxidizing ambients that make up the fabrication schedule of an-channel enhancement mode device. For all three cases the overall correlation of computer predictions with experimental data was excellent. Correlations with experimental data based on SUPREM predictions are also included.     

Channeling study of boron implanted silicon: Liquid nitrogen temperature implantation

Silicon samples have been boron implanted at 150 keV at liquid nitrogen temperature to a dose of 3.6 × 10¹⁵/cm². This dose rendered the implanted layer amorphous as viewed by helium ion backscattering. Four kinds of room temperature measurements were made on the same set of samples as a function of the isochronal annealing temperature. The measurements made were the determination of the substitutional boron content by the channeling technique using the B¹¹(p, α) nuclear reaction, observation of the disorder by helium ion backscattering, determination of the carrier concentration by van der Pauw Hall measurements, and the sheet resistivity by four point probe measurements. These measurements are compared with results from samples implanted at room temperature. The carrier concentration correlates well with the substitutional boron content for both room temperature and liquid nitrogen temperature implantations. Following annealing temperatures in the 600 to 800°C range, a much larger percentage of the boron lies on substitutional lattice sites, and therefore the carrier concentration is larger, if the implantation is done at liquid nitrogen temperature rather than at room temperature. Following liquid nitrogen temperature implantation, reverse annealing is observed from 600 to 800°C in the substitutional boron content, carrier concentration and sheet resistivity. The boron is more than 90 per cent substitutional after annealing to 1100°C for both the room temperature and liquid nitrogen temperature implantations. The low temperature implantation produced a buried amorphous layer, and this layer was observed to regrow from both the surface and substrate sides at approximately equal rates.     

Low energy boron implantation profiles in silicon from junction depth measurements

Some methods have been recently developed to investigate the distribution of implanted ions in semiconductors, especially into silicon. Generally, these techniques are not valid for boron due to the absence of convenient radioactive isotopes, or to a too small sensitivity when the lower part of the distribution is of interest. This corresponds to our problem, since boron implanted nuclear particle detectors prepared with high resistivity material (up to 50,000 ω.cm) are needed. The properties of these P-N junctions depend in a certain amount on the impurity distribution existing several orders of magnitude below the top of the distribution. Therefore, only the junction location method can be employed. In this method a series of N-type silicon samples, differing each from the other by an increase in resistivity are implanted with boron. The depth of the P-N junction corresponds to the point of the profile where the concentration N_A is equal to that of the substrate N_D (i.e. this latter being well known from the resistivity of the starting material). If the location of the junction can be measured, the profile can then be constructed point by point. The junction location is visualized generally by copper staining. Roosild,⁽¹⁾ Kleinfelder,⁽²⁾ Fairfield⁽³⁾ and D. E. Davies⁽⁴⁾ have used this procedure for boron implantations at energies higher than 50 keV. There is a problem due to the small penetration of the boron ion, and, for high resistivity materials, it is difficult to know the true limits of the zones stained with copper.

In our problem, when heavy particle detectors are desired, it is necessary to implant at lower energies than those indicated previously (< 20 keV). We have developed a new technique derived from the junction depth method, which is useful even at very low implant energy (≈ 10 keV). It consists in measuring the energy loss by 100 keV protons when crossing the entrance window of the P-N junctions used as detectors.

In the first part of this paper the method is described and the possible errors are analyzed and evaluated. In the second part, the distribution of 15 keV boron ions implanted under several experimental conditions is studied. Emphasis is given to the defects resulting from the silicon bombardment.     

Boron electrical activation in dual B+ + N+ + and B+ + Ar+ ion-implanted silicon

Silicon wafers were implanted with 40 keV B⁺ ions and then with 50 keV N⁺ or 100 keV Ar+ ions to doses from 1.2 x 1014 to 1.2 x 1015 cm^–2. The implanted samples were studied using the Hall effect and standard van der Pauw methods. The dependences of the sheet resistivity and the sheet concentration of charge carriers on the annealing temperature in the range from 700 to 1300 K were obtained. Models describing the influence of additional implantation of nitrogen and argon ions on the process of boron electrical activation during annealing are proposed.     

Lattice location and dopant behavior of group II and VI elements implanted in silicon

Outdiffusion, lattice location and electrical behavior of Zn, Cd, Hg and Se, Te implanted into silicon at 50 keV were investigated by backscattering and channeling effect of 1 MeV He⁺ ions and by Hall effect and sheet resistivity measurements. All the species exhibited outdiffusion with thermal processing. A significant fraction of Zn, Cd and Hg, when implanted into a substrate of 350°C, occupied regular interstitial lattice sites, while 50–60 per cent of the Se and Te atoms were on substitutional lattice sites. Selenium implanted at room temperature and mercury implanted into a substrate of 350°C exhibited depth dependent lattice location. The implanted layers showed n-type behavior: the maximum value of number of carriers/cm² was less than the number of implanted ions/cm² in all cases. The highest electrical activity was observed for Se corresponding to 25 per cent of the substitutional component.     

Particle track etch method for analysis op boron in silicon using 10B(n,∝)7L1 reaction

Abstract

Boron bulk doped p-type (111) silicon thin wafers or different resistivities (1 ? 100 ohm-cm ± 20%) have been analysed for boron using cellulose nitrate- Daicel and red dyed LR-115 tvpe II films as detectors of alpha particles from 10B(n,α)⁷Li reaction. The two detectors measure the same value of boron (～0.1 ppm) in 1 ohm-cm silicon samples and agree closely with the four-point probe electrical resistivity measurement results whereas large discrepancies are observed in case of samples with resistivity >1 ohm-cm (B concent rat ion <0.1ppm) between the electrical measurements and the results obtained from the present technique. Also the results shown by the two types of detectors differ very much in case of samples with resistlvity>1 ohm-cm.     

Thermoelectric effect in laser annealed printed nanocrystalline silicon layers

Nanocrystalline boron and phosphorus doped silicon particles were produced in a microwave reactor, collected, and dispersed in ethanol. Pulsed laser annealing of spin‐coated films of these particles resulted in p‐ and n‐type conductive layers on flexible substrates if a threshold laser energy density of 60 mJ/cm² was exceeded. The thermopower of the laser sintered layers exhibits a distinct maximum at a doping concen‐ tration around 10¹⁹ cm^–3 for both boron and phosphorus doping with an absolute value of the Seebeck coefficient of about 300 µV/K. Since the thermal conductivity of the layers is reduced by nearly the same factor compared to bulk crystalline silicon as the electrical conductivity, these results are promising for the application of such nanocrystalline layers in thin film thermoelectric devices. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The electrical properties of doped silicon,grown by Molecular-Beam-Epitaxy (MBE)

Measurements of the Hall coefficients and of the resistivity of MBE-grown Si, doped with P, As, Sb, B, and Ga in the concentration range 10¹⁴ to 10²⁰ cm^–3, were carried out at 77 K and at 300 K. With the exception of Ga-doped Si, the measured mobilities were close to or higher than those of bulk materials at both temperatures. The Mott metal/non-metal transition has been observed in the present epitaxial materials and the measured values for the critical impurity concentration at which the transition occurs, agree with values reported by other workers for bulk silicon.     

Defect removal after low temperature annealing of boron implantations by emitter etch‐back for silicon solar cells

Ion implantation offers new possibilities for silicon solar cell production, e.g. single side doping that can be structured in‐situ with shadow masks. While phosphorus implantations can easily be annealed at low temperature, the annealing of boron implantations is challenging. In this study, we use low energy implantations of boron (1 keV and 5 keV) with a projected range of 5.6 nm and 21.2 nm that form defects causing charge carrier recombination after a low temperature anneal (950 °C, 30 min). An ozone‐based wet chemical etching step is applied to remove this near surface damage. With increasing chemical etch‐back the electrical quality (i.e. emitter saturation current density, J_0e) improves continuously. The calculated limit for J_0e was reached with an abrasion of 35 nm for 1 keV and 85 nm for 5 keV implantations, showing that the relevant defects causing charge carrier recombination are located very close to the surface, corresponding to the as‐implanted profile depth. This emitter etch‐back allows for the fabrication of defect free boron doping profiles with good sheet resistance uniformity (standard deviation <2%). With the resulting characteristics (sheet resistance <100 Ω/sq, surface doping concentration >5 × 10¹⁹ cm^–3, J_0e < 30 fA/cm²), these boron profiles are well suited for silicon solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Polycrystalline silicon S-diode fabricated using phosphorus thermal diffusion along grain boundaries

Electrical activity of grain boundaries (GB) in polycrystalline silicon films can stand duty as an additional factor of action on its properties. At present paper it has been studied polycrystalline silicon epitaxial films grown by CVD-method at low-resistivity n ⁺-type poly-Si substrates. A p ⁺-n junction of 0,5 m deep was formed by ion implantation of boron. The effect of thermal annealing (TA) on I-V characteristics of the p ⁺-n-n ⁺ structures was studied. It was founded that the region with negative resistivity is appeared in I-V characteristic after TA in vacuum at 800°C for 1 hour. Investigations by means of C-V and temperature characteristics of samples show that the S-image of the I-V characteristics is caused by phosphorus diffusion along GB that give rise to conduction of the charge carriers along GB. For the first time it was shown the opportunity of the creation of low-cost poly-Si S-diode by TA.     

High concentration effects of ion implanted boron in silicon

The diffusion behaviour of implanted boron in silicon was investigated using the¹⁰B(n,α)⁷ Li nuclear reaction. An anomalous behavior with a strong reduction of the diffusivity above an effective solubility limit at 1.5×10¹⁹, 6×10¹⁹, and 1.1×10²⁰ cm⁻³ was found for annealing temperatures of 800, 900, and 1,000°C, respectively.     

Range parameters of boron implanted into silicon

The range parameters of boron in silicon have been measured using the¹⁰B(n,α)⁷ Li-nuclear reaction. The results indicate that the distributions can be perfectly modeled using Pearson IV distributions with 4 moments. The range is very well described by theoretical calculations, whereas the higher moments show a strong deviation from theory.     

Measurement of boron and phosphorus concentration in silicon by low-temperature FTIR spectroscopy

The calibration factors for the determination of boron and phosphorus concentration in single crystal silicon by low temperature Fourier transform infrared spectroscopy are examined, with the aim of comparing the behaviour of float-zone and Czochralski samples. It is shown that common calibration factors, derived from a correlation with four-point probe resistivity measurement, can be applied to both material types. Moreover, no significant difference in carrier mobility is observed between FZ and CZ, as determined by Hall effect measurements, in a wide oxygen range: 2–9×10¹⁷ cm^-3, confirming that the same conversion algorithm to deduce the carrier concentration from the resistivity measurement can be applied. PACS 72.80; 78.30; 81.05     

Some studies of BF2 and B+F implanted Silicon

Ion-implanted shallow junctions have been investigated using BE₂ (molecular ions) by the anodic oxidation method coupled with a four-point probe technique. BF₂ ions were implanted through screen oxide at doses of 3–5 × 10¹⁵ ions/cm² and energies of 25 and 45 keV which is equivalent to 5.6 keV and 10 keV of boron ions. The effect of energy, dose and annealing temperature on shallow junctions is presented in this paper. The shallow junctions in the range of 0.19 μm to 0.47 μm were fabricated.

The effect of fluorine on sheet resistivity of boron implanted silicon at various doses, treated with two-step and three-step annealing, is also presented for comparison in the paper.     

Optimising dislocation-engineered silicon light-emitting diodes

This article presents a study of the possibilities of optimising the electroluminescence (EL) efficiency of dislocation-engineered silicon light-emitting diodes (DELEDs). The diodes were produced by implantation of boron in n-type (100)Si wafers, at a constant ion energy and fluence, of 30 keV and 1×10¹⁵ ions/cm², respectively. The density and the areal coverage by dislocation loops were varied by applying different annealing times in a rapid thermal processing, from 30 s to 60 min. It is shown that the EL efficiency is directly correlated to the number and areal coverage by the loops. The highest population of loops, ∼5×10⁹ /cm², and an areal coverage of around 50% were achieved for 1–5 min annealing. This loop distribution results in optimal DELEDs, having the highest EL response and the largest increase of EL intensity with operating temperature (80–300 K). The results of this work confirm a previously introduced model of charge-carrier spatial confinement by a local stress induced by the edge of the dislocation loops, preventing carrier diffusion to non-radiative recombination centres and enhancing radiative transitions at the silicon band edge. PACS 85.60.Jb; 78.60.Fi; 61.72.Tt     

21.0%‐efficient co‐diffused screen printed n‐type silicon solar cell with rear‐side boron emitter

Plasma enhanced chemical vapor deposition (PECVD) is applied to deposit boron silicate glasses (BSG) acting as boron diffusion source during the fabrication of n‐type silicon solar cells. We characterize the resulting boron‐diffused emitter after boron drive‐in from PECVD BSG by measuring the sheet resistances R_sheet,B and saturation current densities J_0,B. For process optimization, we vary the PECVD deposition parameters such as the gas flows of the precursor gases silane and diborane and the PECVD BSG layer thickness. We find an optimum gas flow ratio of SiH₄/B₂H₆= 8% and layer thickness of 40 nm. After boron drive in from these PECVD BSG diffusion sources, a low J_0,B values of 21 fA/cm² is reached for R_sheet,B = 70 Ω/□. The optimized PECVD BSG layers together with a co‐diffusion process are implemented into the fabrication process of passivated emitter and rear totally diffused (PERT) back junction (BJ) cells on n‐type silicon. An independently confirmed energy conversion efficiency of 21.0% is achieved on 15.6 × 15.6 cm² cell area with a simplified process flow. This is the highest efficiency reported for a co‐diffused n‐type PERT BJ cell using PECVD BSG as diffusion source. A loss analysis shows a small contribution of 0.13 mW/cm² of the boron diffusion to the recombination loss proving the high quality of this diffusion source. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Secondary ion emission from silicon and silicon oxide

The emission of Si⁺, Si²⁺, Si³⁺, Si₂⁺, SiO⁺ and B⁺ from boron doped silicon has been studied at oxygen partial pressures between 2 × 10^?10 and 2 × 10^?5 Torr. Sputtering was done with 2 to 15 keV argon ions at current densities between 3 and $\text{40}\text{μ}\text{A}\text{cm}{}^2$. The relative importance of the different ionization processes could be deduced from a detailed study of the yield variation at varying bombardment conditions. Comparison with secondary ion emission from silicon dioxide allows a rough determination of the composition of oxygen saturated silicon surfaces.     

Neutron damage and annealing studies of copper-doped silicon solar cells

The effects of Cu-doping, oxygen and dopant on the fast neutron radiation damage of silicon solar cells are studied in this paper. The diffusion length damage coefficientK _L is defined as K_L= (1/L _i ² – 1/L _o ² )^–1= (1/L²)^–1. The (1/L²) values of n/p-type cells, measured at 300 and 80K, are smaller by about one order in magnitude than those of p/n-type cells. Characteristic curves of (1/L ²) values versus total neutron flux of p/n, n/p and copper-doped n/p-type cells begin to deviate from a 45° straight line around a total neutron flux of 10¹² to 10¹³ n cm^–2. The effect of copper-doping on the radiation resistant property is observed with high resistivity bulk n/p-type (20 to 40 -cm) cells, but not with low resistivity bulk n/p-type (10 -cm) cells at 300K. Values of (1/L ²) versus neutron flux, measured at 80K, are not affected by copper-doping, bulk dopant and oxygen concentration in the bulk region of n/p-type cells. The isochronal annealing of silicon solar cells depends on the total neutron flux, copper-doping and carrier injection during the annealing process. Namely, copper-doping and carrier injection enhance the annealing process of the neutron-induced defect clusters in n/p-type cells.     

Low energy boron and phosphorus implants in silicon (a) electrical sheet measurements

Silicon wafers were implanted in 〈111〉-direction with boron and phosphorus ions of 7 keV at room temperature. Doses between 10¹² and 10¹⁸ ions/cm² were applied. After successive annealing steps the electrical properties of the implanted layers have been determined by Hall effect and sheet resistivity measurements. The annealing characteristics of the implants depend on ion dose and species. Three annealing stages can be distinguished: (I) the temperature range below 500°C, (II) 500—700°C, (III) 700—900°C.

After annealing at 90°C the apparent electrical yield is proportional to dose for all implants and amounts to approx. 80 per cent for boron and 40 per cent for phosphorus.

Sheet resistivity vs. dose curves were derived for the annealing temperature of 400°C and used for the fabrication of position sensitive detectors. The position characteristics were found to be linear within ～1 per cent for resistive layers as long as 20 cm.     

Implantation site of boron in heavily doped silicon: A β-NMR study

Using β-NMR with¹²B as nuclear probes the temperature dependence of the lattice-site occupation of boron implanted into heavily doped silicon is studied. In p-type material the unperturbed substitutional fraction of¹²B increases from 10% at 300 K to ≃40 % at 950 K. In n-type material this fraction starting from 20% at 300 K approaches the saturation value of ≃80 % at 600 K already. This behaviour suggests that the site of implanted boron in silicon is controlled by the Fermi level.