LOW TEMPERATURE PHYSICS VOLUME 31, NUMBER 2 FEBRUARY 2005 SUPERCONDUCTIVITY, INCLUDING HIGH-TEMPERATURE SUPERCONDUCTIVITY Influence of internal stresses on the superconductivity of nanocrystalline vanadium films V. M. Kuz’menko and T. P. Chernyaeva National Research Center ‘‘Kharkov Institute of Physics and Engineering,’’ ul. Akademicheskaya 1, Kharkov 61108, Ukraine* ͑Submitted April 6, 2004; revised July 27, 2004͒ Fiz. Nizk. Temp. 31, 148–154 ͑February 2005͒ Nanocrystalline vanadium films 7–20 nm thick are obtained by crystallization of amorphous condensates of this metal by heating to a temperature TϽ60 K. Immediately after completion of the crystallization the critical temperature of the superconducting transition Tc of these films is 3.1–4.3 K. When the films are heated to room temperature in an ultrahigh vacuum the Ϸ values of Tc decrease by 0.4 K. It is shown that this decrease is due, in particular, to relief of the tensile stresses that arise in the films during crystallization. © 2005 American Institute of Physics. ͓DOI: 10.1063/1.1820544͔ INTRODUCTION The vanadium was evaporated by evaporators made of cleaned tungsten wire. To degas the mounting of vanadium It is known that when vanadium vapor is condensed on a and tungsten a significant part of the mounting was evapo- substrate cooled by liquid helium the films formed up to rated off while the substrate was shielded; the substrate re- Ϸ 1–3 thicknesses d 20– 40 nm have an amorphous structure. mained in continuous contact with the liquid helium, and the When this critical thickness dc is exceeded during condensa- average temperature of the vanadium layer during condensa- tion the whole volume of the film undergoes spontaneous tion was not over 18 K. ͑ ͒ explosive avalanche crystallization with the formation of The electrical conductivity of the films was measured by the usual bcc phase. If the layer thickness is less than dc , its a compensation method using a four-probe scheme with an amorphous structure is stable up to a temperature Ta!c accuracy of 0.01% or better. The critical magnetic field per- Ϸ 40– 60 K, and the value of Ta!c increases with decreasing 2,4 pendicular to the plane of the film was produced by a super- d by an approximately hyperbolic law. We have previously conducting solenoid. The thickness of the films during con- investigated the superconducting properties of the amor- 2 densation was monitored by its conductance, and after the phous phase of vanadium. The critical temperature of the experiment was completed and the was ampoule opened it ͑ ͒ superconducting transition CTST of the crystallized film is was measured by an optical density method.7 approximately 1.5 K higher than the value of Tc in the amor- The microstructure of the crystallized vanadium films phous state. Further heating of the samples from Ta!c to and their surface topography were investigated at room tem- room temperature is usually accompanied by a lowering of 8 3 perature on a JEM-100CX analytical electron microscope. the CTST. This behavior has not yet been explained cor- The microstructure was investigated by photography in rectly in the published literature. The goal of the present transmitted light. Both bright-field and dark-field images study is to attempt an explanation. were obtained. The vanadium films were removed from the substrate by dissolving in water a thin (ϳ20– 30 nm) NaCl layer that had been condensed on the glass substrate prior to TECHNIQUE deposition of the metal. The techniques used to grow the films and to study their EXPERIMENTAL RESULTS electronic properties are described in detail elsewhere.5,6 We used welded-up glass ampoules with a flat polished substrate Figure 1 shows the change of the resistivity of a newly and welded-in leads of platinum wire for making electrical condensed vanadium film Ϸ16 nm thick upon heating to measurements of the metallic film condensed on the sub- room temperature. The practically vertical segment of the strate. After being pumped down to a pressure pϳ10Ϫ4 Pa curve corresponds to the transition of the film from the amor- the ampoules were hermetically sealed with a gas torch and phous to the crystalline state (a!c transition͒. Interesting, ! Ϸ removed from the vacuum apparatus. The ampoules were immediately after the a c transition (Ta!c 40 K) and on mounted in a helium cryostat which was then flooded with up to room temperature the ␳(T) curve becomes practically Ϫ10 ␳ ϭ liquid helium, creating an ultrahigh vacuum (ϳ10 Pa) reversible, i.e., the residual resistivity 0 at T 6 K is prac- ␳Ј with respect to all components of air. The bulk vanadium tically equal to its value 0 for the same film after heating to used had a resistivity ratio of Ϸ550 between temperatures of room temperature. If the critical temperature was exceeded 300 and 6 K. during the condensation process and explosive crystallization 1063-777X/2005/31(2)/5/$26.00 111 © 2005 American Institute of Physics 112 Low Temp. Phys. 31 (2), February 2005 V. M. Kuz’menko and T. P. Chernyaeva TABLE I. Some characteristics of the crystalline vanadium films investi- gated. Note: The temperature smearing of the superconducting transitions for films ͓ ␳ ␳ ␳ V1 –V5 is 0.10–0.12 K the interval (0.1– 0.9) 0], and 300 is the value of at 300 K. exhibited a noticeable increase in residual resistivity which is due, as we shall show below, to an intensification of the FIG. 1. Temperature dependence of the resistivity of a vanadium film of cracking process. It should be emphasized that the films thickness Ϸ16 nm. V1 –V5 were annealed to room temperature in ultrahigh vacuum (ϳ10Ϫ10 Pa). For this the upper part of the ampoule containing the substrate was heated by a furnace under a hood in the form an inverted Dewar while the lower part of occurred, the ␳(T) curve is reversible from the start and is the ampoule was immersed in liquid helium. This precludes described by the lower part of the curve in Fig. 1 ͑without the possibility of contamination of the annealed film by re- the vertical segment͒. Such behavior of ␳(T) is observed sidual gases, the pressure of which without these precaution- only for vanadium films. For all the other low-temperature ary measures would reach ϳ10Ϫ4 Pa at the higher tempera- condensates of pure metals ͑In, Sn, Al, Tl, etc.͒ known to us, tures ͑see Technique͒. In this case the decrease of the CTST the residual resistivity continually decreases as the film is on heating could be ascribed to impurities falling into the annealed up to room temperature, owing to the annealing of film from the surrounding medium, as it is known that vana- defects and the growth of grains. For example, when an alu- dium is not attacked by air at ordinary temperatures. minum film (dϭ70 nm) is heated from helium to room tem- Figure 2 shows the temperature dependence of the criti- perature, Tc decreases from 3.25 to 1.45 K and the residual cal magnetic induction (B ϵB Ќ ; Ref. 9͒ for the film V . resistivity decreases from 16 to 1.25 ␮⍀ cm.4 Apparently in c2 c 4 • Curve 1 was taken after heating to TϭT ! and corresponds vanadium films the lattice defects that have a substantial in- a c to a value T ϭ4.2 K; curve 2 was taken after heating to fluence on the resistivity are not annealed in the temperature c room temperature and corresponds to a value TЈϭ3.78 K. interval Tϭ40– 300 K. c Near the CTST the value of B varies linearly with tempera- The critical temperature of the superconducting transi- c2 ture, while at lower temperatures the dependence is approxi- tion for the crystallized vanadium films directly after their ϭ mately quadratic: heating to T Ta!c , denoted Tc , is always substantially Ј higher than the value Tc for the same films after annealing to room temperature. The value of the temperature Tc remains practically constant after the films have been annealed to T ϭ190– 200 K. Only after further increase in the annealing Ј temperature does the CTST decrease from Tc to Tc . If the film has crystallized as a result of explosive crystallization ͑ ϭ Ј at d dc) the values of Tc and Tc are equal. Ј Table I gives the values of Tc and Tc for typical low- temperature condensates of vanadium. These values are lower than the CTST for for pure bulk vanadium. The mechanisms causing the decrease of the CTST with decreas- ing thickness of metallic films are discussed in detail in Ref. 4. Some films show signs of cracking ͑a slight growth of the residual resistivity͒ already at room temperature ͑see Table I͒. Sometimes a rather long hold at room temperature leads ͑ FIG. 2. Temperature dependence of the critical magnetic induction for a to a slight decrease in the residual resistivity see the result crystalline vanadium film Ϸ16 nm in diameter after annealing to T ͓K͔:50 ϭ ͑ ͒ ͑ ͒ for film V5). After heating to T 330– 340 K all of the films 1 , 300 2 . Low Temp. Phys. 31 (2), February 2005 V. M. Kuz’menko and T. P. Chernyaeva 113 TABLE II. Parameters for the calculation and the calculated values of N(0) ϭ of the film V4 after annealing to T 50 and 300 K. opened; from that we infer that crack formation is practically absent. The absence of cracks in those films is confirmed by FIG. 3. Dark-field electron micrograph of the nanostructure of a vanadium the studies of their surface topography.8 It was found that the film Ϸ37 nm thick.