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.     

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.     

High-conductive nanocrystalline silicon with phosphorous and boron doping

Intrinsic, P- and B-doped hydrogenated amorphous silicon thin films were prepared by plasma-enhanced chemical vapor deposition technique. As-deposited samples were thermally annealed at the temperature of 800 °C to obtain the doped nanocrystalline silicon (nc-Si) films. The microstructures, optical and electronic properties have been evaluated for the undoped and doped nanocrystalline films. X-ray photoelectron spectroscopy (XPS) measurements demonstrated the presence of the substitutional boron and phosphorous in the doped films. It was found that thermal annealing can efficiently activate the dopants in films accompanying with formation of nc-Si grains. Based on the temperature-dependent conductivity measurements, it was shown that the activation of dopant by annealing increased the room temperature dark conductivity from 3.4 × 10⁻⁴ S cm⁻¹ to 5.3 S cm⁻¹ for the P-doped films and from 1.28 × 10⁻³ S cm⁻¹ to 130 S cm⁻¹ for the B-doped films. Meanwhile, the corresponding value of conductivity activation energies was decreased from 0.29 eV to 0.03 eV for the P-doped films and from 0.3 eV to 5.6 × 10⁻⁵ eV for the B-doped films, which indicated the doped nc-Si films with high conductivity can be achieved with the present approach.     

Understanding ultrahigh doping: the case of boron in silicon

Using first-principles calculations, we develop a theory for ultrahigh impurity doping in semiconductors. Our study of B in Si explains why boron solubility in epitaxial growth could exceed the solid solubility to reach the kinetic solubility, and, with adequate surface passivation, to reach even higher values. We further show that the partial ionization at high B concentration, C(B), observed by experiment is predominantly an electron chemical potential effect, not a boron clustering effect. Our calculated hole concentration over a wide C(B) range is in reasonable agreement with experiments.     

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.     

Exchange-correlation energy in the subbands of silicon doping superlattices

The energy subbands in three types (pn⁺p, pnpn, nipi) of Si and GaAs doping superlattices are calculated self-consistently including the exchange-correlation energy given by the density functional method. The results show that the exchange-correlation term is more important in Si than in GaAs in all three cases. For the same doping levels, layer thicknesses and electron concentrations, the shift in the lowest subband energy from the value given by the Hartree Approximation is 20–50% greater in Si than in GaAs.     

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     

Damage anneal of antimony/phosphorus double implants in silicon

A method is presented for avoiding the dislocation generation in (100) silicon implanted with phosphorus doses up to 5×10¹⁵ ions/cm² at 50 keV. The residual defects after the damage anneal are considerably reduced if the phosphorus implant is combined with a low dose, e.g. 1×10¹⁴ ions/cm², antimony implant which produces a deeper surface layer of amorphous silicon. It is essential that the phosphorus ions are implanted shallower than the antimony ions, and come to rest within the amorphous layer. Subsequent thermal annealing proceeds by a solid phase epitaxial regrowth mechanism.     

Electron irradiation assisted annealing of boron and phosphorus implanted silicon layers

Radíatíon annealing due to a 1.0 MeV election beam of intensity 25 μA/cm² was studied in silicon samples implanted with phosphorus and boron ions and annealed at 350–500°C. A significant annealing enhancement as compared to thermal annealing has been observed in phosphorus-implanted samples. In boron-implanted samples, a fast initial rise of electrical activity is followed by a continuous decrease of carrier concentration. The results are interpreted in terms of two competing processes: electron irradiation induced removal of post-implantation defects and introduction of simple electrically active defects.     

High-resolution depth profiling of ultrashallow boron implants in silicon using high-resolution RBS

Depth profiles of ultralow energy (0.2–0.5 keV) B ion implants in Si(0 0 1) samples are measured by high-resolution Rutherford backscattering spectroscopy. The boron profile does not show a narrow surface concentration peak which is usually observed in the measurement of secondary ion mass spectroscopy. The obtained boron profiles roughly agree with TRIM simulation even at 0.2-keV B ion implantation.     

Influence of annealing on the concentration profiles of boron implantations in silicon

The influence of annealing on the concentration profiles of boron implanted into silicon with does of 10¹⁴ ions/cm² up to 10¹⁶ ions/cm² and an energy of 70 keV was studied. The concentration profiles were measured with Secondary Ion Mass Spectrometry (SIMS). The broadening of the concentration profiles during annealing can be described as a superposition of effects resulting from a relatively immobile and a mobile boron fraction. The properties of the immobile boron fraction were studied by measuring the influence of a boron implantation on the distribution of a homogeneous boron background dope. From these experiments it was concluded that the immobile boron fraction consists of boron precipitates. The properties of the mobile fraction were studied from concentration profiles that were obtained after annealing during different periods at the same temperature. It was found that during the initial stage of the annealing process a fast broadening of the profile occurs; this was assumed to be due to an interstitial type boron diffusion. After prolonged annealing the much slower substitutional type diffusion prevails, due to trapping of the interstitial boron atoms by vacancies. The reliability of the SIMS method, as applied to profile measurements, was checked for the high boron doses used in this investigation. Excessive boron precipitates, obtained after annealing of a high dose, such as 10¹⁶ ions/cm² at about 1000°C, appear to give some increase of the ion yield.     

High-temperature diffusion of phosphorus and boron in silicon via vacancies or via self-interstitials?

The paper re-examines the effect of oxidation on the diffusion of phosphorus and boron in silicon as well as recent results on redistribution phenomena of these dopants under irradiation and on the emitter-push effect. It is shown that at high temperatures phosphorus and boron diffuse via a defect mechanism involving silicon self-interstitials. These results support the view-point that self-interstitials are the dominating point defects in silicon under thermal equilibrium conditions. Possible generation mechanisms for the self-interstitial supersaturation causing the emitter-push effect are suggested.     

Boron implantations in silicon: A comparison of charge carrier and boron concentration profiles

The concentration profiles of boron implanted in silicon were measured using secondary ion mass spectrometry. The accompanying charge carrier profiles were determined by Hall-effect sheet-resistivity measurements combined with layer removal by anodic oxidation and etching. From a mutual comparison of these profiles an electrically inactive boron fraction was found to exist in the region of maximum boron concentration. This fraction can be correlated with boron precipitates. In high dose implantations the precipitates still exist after annealing at 1000°C. In the tail of the profile a small electrically inactive boron fraction was observed. This fraction was correlated with fast diffusing non-substitutional boron. Near the surface a charge carrier peak was found that can be correlated with the damage caused by implantation. The interpretation of the observed electrical effects was facilitated by investigations on boron concentration profiles of layers implanted with different doses and annealed in accordance with different time-temperature schedules.     

Delta doping in silicon

Two-dimensional doping sheets (“δ-doping”) are integral parts of many novel semiconductor device concepts. Their practical realization in silicon (Si), however, was long delayed by the difficulty to introduce dopants into Si in a well-controlled way during epitaxial growth. Recent advances in the understanding of epitaxial growth and the incorporation of dopants in Si have overcome these difficulties and opened a new field in Si materials and device research. In this article, we review the growth, processing, and characterization of epitaxially grown 5-doped Si. Furthermore, we discuss the electronic subband states of such structures. Finally, we give an overview of device concepts that use 5-doping and analyze their properties.     

Differential nonlinear photocarrier radiometry for characterizing ultra-low energy boron implantation in silicon

The measuring of the depth profile and electrical activity of implantation impurity in the top nanometer range of silicon encounters various difficulties and limitations, though it is known to be critical in fabrication of silicon complementary metal-oxide-semiconductor (CMOS) devices. In the present work, SRIM program and photocarrier radiometry (PCR) are employed to monitor the boron implantation in industrial-grade silicon in an ultra-low implantation energy range from 0.5 keV to 5 keV. The differential PCR technique, which is improved by greatly shortening the measurement time through the simplification of reference sample, is used to investigate the effects of implantation energy on the frequency behavior of the PCR signal for ultra-shallow junction. The transport parameters and thickness of shallow junction, extracted via multi-parameter fitting the dependence of differential PCR signal on modulation frequency to the corresponding theoretical model, well explain the energy dependence of PCR signal and further quantitatively characterize the recovery degree of structure damage induced by ion implantation and the electrical activation degree of impurities. The monitoring of nm-level thickness and electronic properties exhibits high sensitivity and apparent monotonicity over the industrially relevant implantation energy range. The depth profiles of implantation boron in silicon with the typical electrical damage threshold (Y_ED) of 5.3×10¹⁵ cm^-3 are evaluated by the SRIM program, and the determined thickness values are consistent well with those extracted by the differential PCR. It is demonstrated that the SRIM and the PCR are both effective tools to characterize ultra-low energy ion implantation in silicon.     

Electrical properties of silicon implanted with boron ions of MeV energy

Abstract

A knowledge of the interaction energy between two atoms as a function of their separation is important in many aspects of radiation damage theory. Recent calculations of this energy from first principles are reviewed in this article, particular attention being paid to calculations based fin the Thomas-Fermi and Thomas-Fermi-Dirac statistical theories of the atom. The advantages and limitations of these theories are discussed from the radiation damage point of view. The energy ranges over which experimental results or theoretical calculations are more useful at present are also discussed.