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Laser Implantation of Impurities in Cadmium Telluride Crystals N

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Laser Implantation of Impurities in Cadmium Telluride Crystals N TECHNICAL PHYSICS LETTERS VOLUME 24, NUMBER 6 JUNE 1998 Laser implantation of impurities in cadmium telluride crystals N. K. Zelenina and O. A. Matveev A. F. Ioffe Physicotechnical Institute, Russian Academy of Sciences, St. Petersburg ~Submitted December 26, 1997! Pis’ma Zh. Tekh. Fiz. 24, 1–6 ~June 12, 1998! Processes of laser implantation of shallow donors ~aluminum and indium! and an acceptor ~antimony! in CdTe crystals (n,p;1015 cm23) are investigated. Thin dopant films vacuum deposited on the etched surface of the crystals are irradiated by ruby (l50.694 mm! and Nd:YAG (l51.06 mm! laser pulses ~pulse duration 20 ns! over a wide energy interval ~0.1–1.8 J/cm2). The irradiated surfaces are studied by x-ray microanalysis, Auger spectroscopy, and the thermopower method. It is it is shown that irradiation by a Nd:YAG laser produces a uniform doping of a subsurface layer of the crystal by aluminum. The implantation of indium leads to the formation of a precipitate. The concentration of implanted impurities reaches 1019–1021 cm23.©1998 American Institute of Physics. @S1063-7850~98!00106-2# The laser implantation of impurities in silicon and gal- interval 0.4–1.8 J/cm2. The thermopower measurements lium arsenide crystals is now widely used to make Ohmic showed that n-type samples irradiated at energies above 0.6 1,2 and rectifying contacts. In the case of cadmium telluride J/cm2 had a layer of p-type conductivity formed on the sur- 3 ~CdTe!, which is especially sensitive to heating, this method face. The surface of the p-type samples did not have a may be extremely promising, since doping can be accom- change in the type of conductivity. The observed effect can plished without subjecting the bulk of the crystal to heating, be explained by an enrichment of the surface layer as a result which is confined to a thin subsurface region. of the predominant evaporation of the more volatile cad- In this paper we investigate shallow donors ~Al and In! mium component, since cadmium vacancies are acceptors. and an acceptor ~Sb! in a CdTe crystal under pulsed laser Under irradiation at energies below 0.6 J/cm2 the change in irradiation. sign of the thermopower of the n-type samples did not occur, In this study we used an OGM-40 pulsed laser with ruby and therefore the change of state of the surface layer at these (l50.694 mm! and neodymium ~Nd:YAG, l51.06 mm! energies must not have a governing influence on the implan- heads. The pulse duration of 20 ns ensured an adiabatic re- tation of a dopant from a film deposited on the sample. We gime of energy transfer, i.e., one in which only the region of have previously established5 that the energy interval 0.2–0.5 the sample which directly absorbs the radiation is heated, J/cm2 is also of interest in that the real structure of CdTe and not the entire volume of the crystal. The ruby laser ra- crystals is globally improved at these energies. diation ~absorption coefficient a563104 cm21; Ref. 4! is The laser implantation of aluminum was done on p-type absorbed in and heats up the dopant film deposited on the crystals (p;1015 cm23) under irradiation by both the ruby crystal and a subsurface region of the crystal itself. The and Nd:YAG lasers. The aluminum remaining after the irra- Nd:YAG laser radiation, which is hardly absorbed in CdTe diation was removed from the surface of the samples in a crystals (a51–3 cm21; Ref. 4!, can act directly only on the KOH solution, and then the sample was freshened in butyl dopant film. For focusing and distributing the intensity of the radia- alcohol containing bromine. On these samples the amount of tion over the cross section of the beam we used a focon — a aluminum implanted in the crystal and its distribution over truncated quartz cone with a ground-finished entrance end the laser-irradiated area were determined by a Cameca x-ray and with an exit end 0.7 cm in diameter. The sample was microprobe. The depth profile of the implanted aluminum by mounted practically up against the exit end of the focon. was determined by Auger spectroscopy. Studies were carried out on CdTe crystals with both n- When samples with a semitransparent aluminum film and p-type conductivity (n,p;1015 cm23), grown by hori- ~3000 Å! were irradiated by the ruby laser (E50.5–1.8 2 zontal directed crystallization. Films of the doping impurities J/cm ), it was found that the concentration of the implanted 18 20 23 ~Al, In, or Sb! with a thickness of 2000–4000 Å were depos- aluminum lay in a range from 1310 to 1310 cm and ited on the crystals by vacuum evaporation. An 83831.5 that the distribution over the area of the spot was nonuni- mm area of the samples was prepared beforehand by me- form. The implantation of aluminum by means of the chanical lapping and polishing with a subsequent etching in Nd:YAG laser was carried out by two different methods in butyl alcohol containing bromine. the interval energy 0.14–0.7 J/cm2. In the first method the To determine the effect of laser irradiation on the elec- radiation was introduced through the dopant film, and in the tronic conductivity of a surface layer of the crystal we also second it was introduced from the back side of the sample. investigated n- and p-type samples without the dopant films. As expected, the results were essentially the same, since in The samples were irradiated by a ruby laser in the energy neither case does the radiation interact directly with the crys- 1063-7850/98/24(6)/3/$15.00 411 © 1998 American Institute of Physics 412 Tech. Phys. Lett. 24 (6), June 1998 N. K. Zelenina and O. A. Matveev According to the x-ray microprobe data, the concentration of the implanted indium was ;531020 cm23. According to the sign of the thermopower, the doped layer had n-type conduc- tivity, and the thickness of the doped layer, as determined by a layer-by-layer chemical etching, was 15 mm. Throughout the doped layer were indium inclusions which appeared as spherules ~several microns in diameter! under an optical mi- croscope. Such an extreme inhomogeneity is not surprising, since it is known6 that for equilibrium methods of doping of CdTe by indium, the latter at concentrations above 231018 cm23 segregates into a second phase at grain boundaries and other structural defects. The great of penetration depth of indium in the crystal is due, we believe, to the high solubility of CdTe in liquid indium,7 which, moreover, can have a FIG. 1. Concentration NAl of aluminum implanted in a CdTe crystal versus the energy E of the Nd:YAG laser irradiation. value during laser implantation that is considerably higher than the equilibrium solubility.8 The implantation of antimony was done using the tal but rather is absorbed in the aluminum film, melting it. A Nd:YAG laser (E50.14 J/cm2)inn-type crystals (n51015 layer of CdTe is melted in the liquid aluminum, and upon its cm23). The concentration of the implanted antimony was 5 subsequent recrystallization it is doped with aluminum. The 31020 cm23, and the distribution was uniform over the irra- concentration of the implanted aluminum ranged from 1 diated area. The depth profile of the dopant is shown in Fig. 31019 to 131021 cm23. Figure 1 shows a plot of the con- 2 ~curve 2!: the concentration falls off rapidly at a depth of centration of aluminum implanted in the crystal as a function ;50Å.Anattempt to increase the depth of antimony dop- of the energy of the Nd:YAG laser. It is seen that the curve ing by increasing the energy of the irradiation to 0.2 J/cm2 goes rapidly to saturation at an energy of 0.3 J/cm2 and upon led to an explosive ~accompanied by crater formation! sput- further increase in the energy begins to decline, apparently tering of the antimony film and of a surface layer of CdTe. because of the increasing evaporation of aluminum. From the Experiments on the laser implantation of aluminum and sign of the thermopower the irradiated layer has acquired indium in CdTe crystals shows that doping occurs more uni- n-type conductivity. The distribution of the concentration formly under irradiation by the Nd:YAG laser in the energy over the area of the spot, which is extremely uniform at low interval 0.1–0.4 J/cm2. Doping by melting of an impurity energies, becomes nonuniform at energies above 0.6 J/cm2, film by a Nd:YAG laser with the subsequent dissolution of possibly because of evaporation of aluminum and CdTe. The CdTe in the molten film and recrystallization of the molten concentration profile of the implanted aluminum measured layer seems to us preferable to the use of ruby laser radiation, by means of Auger spectroscopy is shown in Fig. 2 ~curve the strong absorptivity of which in CdTe creates a high con- 1). The slow decline in the concentration with distance from centration of nonequilibrium charge carriers (;1020 cm23), the surface confirms that the doping mechanism is nondiffu- promoting strong defect formation,9 and also causes intense sional. Evidently this character of the decline is maintained evaporation of a surface layer of the crystal. down to the depth at which the molten aluminum dissolved The concentrations of implanted impurities achieved in the CdTe; below that depth one would expect an abrupt drop this study are significantly greater than the equilibrium val- in the aluminum concentration.
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