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Chapter 2: Properties of TiOx thin lms

2.1 Introduction

In this chapter we would like to report about our attempt to make TiOx thin lms, with x varying between 0.71 and 1.28. The aim was to study the modication of the properties due to the lattice mismatch between layer and substrate. Therefore we grew our titanium oxide layers on dierent kinds of substrates, i.e. MgO and MgAl2 O4 , with dierent amounts of oxygen. We analyzed our samples with a number of techniques. RHEED is probably the most important one followed by X-Ray Diraction (XRD). We also performed resistivity measurements and compared them with literature data for bulk samples. We also observed superconductivity in our samples.

2.2

Properties of TiOx single crystals

The titanium oxides, as well as the vanadium oxides, have been under investigation for a long time already. This is mainly because of the rich phase diagram and the accompanying variation in physical properties. Already in the 1940s several detailed studies were performed into the structure of TiOx [1, 2]. At that time a most remarkable property of TiOx was recognized. At temperatures larger than 990 C, a sample near the lower limit of the stoichiometry range, x = 0.70, was stable even though the oxygen lattice had almost 30% vacancies. The titanium lattice, however, was almost perfect. Near the opposite limit of the stoichiometry range, i.e. for a stable sample of TiO1.25 , the oxygen lattice was almost perfect and the titanium lattice had about 25% vacancies. For the ideal stoichiometric case, i.e. x = 1, the amount of vacancies was about 15% for both lattices. For temperatures lower than 990 C it was found that the stoichiometry range is a little smaller, but nevertheless runs from x = 0.90 to 1.25. Although the vacancies are distributed at random in the samples at temperatures above 990 C, at temperatures below this equilibrium temperature some 5

Chapter 2: Properties of TiOx thin lms

vacancy ordered phases exist. Watanabe et al. [4] performed a detailed structure analysis of the low temperature forms of TiOx using electron diraction, electron microscopy and X-Ray powder diraction methods. They propose a vacancy structure for TiOx where in every (110) plane of the original cubic cell half of the titanium and half of the oxygen atoms are missing alternately. They claim this structure to be valid for TiOx , with 0.9 x 1.1, indicating a tolerance for some disorder. They also recognize that this structure is not applicable over the whole stoichiometry range. Denker [3] carefully prepared polycrystalline samples over the stoichiometric range from TiO0.55 to TiO1.30 . While preparing his samples he was very cautious not to introduce impurities into his samples. He used the prepared samples to study the electronic properties of titanium monoxide. He however only presents results for TiOx with x varying between 0.80 and 1.25. His conclusions are, amongst others, that titanium monoxide is metallic, even though TiOx has a high resistivity as compared to conventional metals, and exhibits weak paramagnetism. The high resistivity is attributed to the large concentration of randomly disordered lattice vacancies. Like TiOx , VOx also exists over a wide stoichiometry range with similarly sized vacancy concentrations. The two materials were often mentioned together [6, 7]. Mott [5] tried to explain the conduction properties of VOx by assuming that the electrons form a highly correlated electron gas and that, in addition, the random eld due to the high concentration of vacant lattice sites produces so-called Anderson localization. His theory might also apply to TiOx . Goodenough [7] also studies the eect of vacancies on the properties of the TiOx and VOx transition metal oxides. He concludes that in the case of TiOx the variation of the conductivity with x is compatible with itinerant d electrons and the mobility decreases as the number of cation vacancies increases. Banus et al. [6] performed a range of experiments on prepared ingots of TiOx and VOx and compared their results to the work of others. They present experimental results for the stoichiometric range of 0.71 x 1.28. They nd that the lattice parameter a0 and the density of TiOx decreases linearly with increasing x. They also nd that the resistivity of cubic TiOx is essentially independent of both temperature and composition. A series of pressure annealed samples showed an overall increase in lattice parameter and density and a 12% 22% decrease of vacancies. The series also showed an increase in superconducting transition temperature with increasing x. Through the years there were some other investigations into the band structure of TiOx and some theory with respect to why there are so many vacancies and what are the consequences of this for the electronic structure [8, 9, 11, 12, 15, 20, 34]. The area of thin lms of TiOx is fairly new and the techniques of producing the lms are also very diverse. Oxygen ion assisted physical vapor deposition was used by Martev [28] to grow TiOx

2.3. Experimental

lms with 0.95 x 1.15. After growth, the lms, which usually had very small grain sizes, were annealed to obtain poly-crystalline fcc-TiOx . Typical deposition rates were 60 min1 and MgO was used as a substrate. Suzuki A et al. [26] deposited titanium oxide lms using an electron-beam evaporator at room temperature. The titanium deposition rate was 0.5 min1 and A and 50 . Their lms the thickness of the samples varied between 10 A A were grown in a vacuum chamber with an oxygen background pressure of about 1 106 Pa. After deposition the lms were annealed for 10 minutes at 1000 K in vacuum. In their follow-up paper [29] they found it was also possible to grow TiOx lms without supplying oxygen to the system. The incorporation or diusion of oxygen from the MgO substrate into the Ti lm during the annealing at 1000 K took care of the oxidation. They also report a MgO-(2 2)-TiO superstructure found after a heat treatment of the lm and substrate of 1270 K. We have employed the Molecular Beam Epitaxy technique with typical deposition rates of 1 min1 and MgO and MgAl2 O4 as substrates. A We would like to refer to the work of D. Rata on VOx who used the same system and technique [36, 37] in her work. The reason for growing thin lms of TiOx on dierent kinds of substrates is a simple one. The lattice mismatch between the lattice of the substrate and the lattice of the lm imposes strain on the lm. This strain will modify the properties of the lm, since atoms will lie closer to or further apart from each other and electronic bands might or might not start to overlap. We expect the strain to modify the number of vacancies present in the lm, because in order to get TiOx with x = 1 and a small amount of vacancies, people have grown titanium oxide crystals under high pressure [6]. As we will show, the strain can also modify the structure of the lm and be responsible for vacancy ordering.

2.3

Experimental

All the samples mentioned in this chapter were prepared in the UHVsystem described in Appendix B. The substrates we used were polished or cleaved MgO or polished MgAl2 O4 crystals. The MgO crystal was cleaved outside the system and then inserted as quickly as possible through the load-lock into the system. The substrates were mounted on stainless steel or tungsten sample holders by spot-welding stainless steel, tungsten or tantalum strips over the corners of the substrates (gure 2.1 B). This had several advantages over the old way the samples were mounted (gure 2.1 A). Some of the samples still had to have contacts evaporated on top of them for conductivity measurements. By mounting the samples in this way it was

Chapter 2: Properties of TiOx thin lms

Figure 2.1:

Here we show the two dierent ways to mount the substrate on the sample holder. A) Sample xed on the sides B) Sample xed on the corners. Black are the strips used to x the substrate, dotted is the substrate and white is the sample-holder

Figure 2.2: This gure shows A) a RHEED pattern of a lm of TiOx grown on


a MgO substrate at Room Temperature (RT) and B) a RHEED pattern of a lm of TiOx grown on a MgAl2 O4 substrate at RT.

easier to evaporate the contacts in situ in our system. Secondly, in this way the free sample area became larger. This allowed us to make RHEEDrotation movies over a larger range. The substrates were cleaned in situ by heating them to 1000 K in the preparation chamber (see Appendix B. They were not exposed to oxygen or any other type of gas during heating. In the beginning of the cleaning the pressure in the chamber would rise. The heating or cleaning was stopped when the background pressure was at the level of 107 Pa, the same level as before the heating began. No contaminants could be detected on the surface of the substrates using XPS. The substrates always showed good RHEED patterns but we needed to use a ood gun to compensate for the charging of the substrates. 5 MgO has a rocksalt like structure with space group F m3m (Oh ) giving it

2.3. Experimental

the selection rules hkl : h + k, k + l, h + l = 2n. MgAl2 O4 has a spinel 7 type structure and space group F d3m (Oh ) with the same selection rules 5 as for F m3m (Oh ) but with an additional condition for possible reections hkl : h + k, k + l, h + l = 4n if the third index is zero. XRD of the substrates usually showed very sharp peaks, indicating a good quality. The lattice parameter found in these measurements for MgO was a = 4.2110.005 in A good agreement with tabulated values. For MgAl2 O4 this was dierent. One batch of substrates turned out to have slightly dierent lattice parameters. The c-parameter found in this batch was c = 7.986 0.008 instead A of the expected value of 8.082 indicating a slight o-stoichiometric A magnesium-aluminum ratio. The substrates from the other batches did have a comparable c-parameter of c = 8.083 0.006 , but the eects described A in this chapter do not seem to be aected much by this dierence, because all phenomena described here occur on both batches. The samples were usually grown at a substrate temperature of 400 C. We also tried to grow at RT. This was successful for samples grown on MgO substrates (gure 2.2 A), but not on MgAl2 O4 substrates (gure 2.2 B). At 400 C good lms were obtained for both kinds of substrates. The titanium ux used was normally 1 min1 . It was calibrated in situ A using the ux monitor of the e-gun evaporator itself, through the quartzbalance present inside the system and ex situ by XRD (Philips XPert). A more accurate way would be if we had observed RHEED oscillations, but we unfortunately rarely did so. This was probably caused by the fact that the ux monitor of the electron-beam evaporator turned out to be not very reliable. Its readings changed from rod to rod, although we kept the current through the lament, the emission current and the accelerating voltage the same. We also found that at some point it was impossible to increase the ux. This was because the titanium rod in the electron-beam evaporator melted. A droplet of titanium would form at the end of the rod and increasing power or voltage wouldnt result in a ux increase. The quartz-balance was also not a very accurate means to calibrate the ux because the device is meant to measure ux rates much higher than 1 A min1 . However in some cases this method was the only option to get a reasonable direct estimate of the ux. A very accurate indirect method is to use XRR curves to determine the layer thickness. When this thickness is divided by the time it took to grow the sample, a number is obtained which we will call the TiOx ux. This number is equivalent to the deposition rate. Although very precise, a drawback of the XRR method is that it is an ex situ method. If the sample is taken out of the system the sample surface is contaminated and a few nanometers are usually added to the thickness. Another problem is that in this way not the titanium ux is determined but the TiOx ux. To derive the titanium ux, assumptions have to be made about the vacancy concentration. The RHEED oscillations are in our case

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Chapter 2: Properties of TiOx thin lms

the only way to determine the deposition rate directly. See gure 2.3 and accompanying text for an explanation. The distance between the gas-inlet tube, or, in our case, the oxygen inlet tube, to the sample was 8 cm and the diameter of the inlet was 1.0 cm. First we grew the samples with 2 50 mV of baratron pressure, which is equivalent to 0.02 0.50 Pa. During the preparation of the lms we found that titanium was very reactive with oxygen in contrast to vanadium [37, 36]. Even at 0.02 Pa of oxygen baratron pressure it turned out we were still able to grow TiOx , which was later conrmed by Rutherford Backscattering Spectroscopy (RBS) measurements, because we could still nd a relatively strong oxygen peak in these measurements. This indicated that we still had not reached the lower limit of TiO0.71 . At 0.02 Pa it was quite dicult to keep the gas ow constant, so to decrease the baratron pressure in this arrangement was out of the question. The solution was found in changing the diameter of the gas inlet. The amount of particles arriving at the sample (f ) is, in the molecular ow regime, proportional to the diameter of the tube to the power three (d3 ) and the length of the tube (l ) d3 f (2.1) l provided we keep the distance of the end of both tubes to the sample constant. If we now halve the diameter of the delivery tube, i.e. make it 0.5 cm instead of the previous 1.0 cm, it results in an eightfold decrease of particle ux arriving at the surface of the sample. This allowed us to decrease the oxygen ux while keeping it stable at the same time. The samples used for conductivity measurements were capped in situ with a MgO cap-layer after the chromium contacts were deposited. The magnesium, 99.999% purity, was evaporated from a Knudsen-cell with a temperature of 155 C. The oxygen baratron pressure used was 1 Pa, making the background pressure inside the system in the order of 102 Pa. During the evaporation of Mg the substrate was kept at RT.

2.4 Results and Discussion


In this section we will show our results categorized by the technique used. We will start with RHEED, from which especially the so called rotation movies are interesting. To our knowledge the rotation movie technique is not used very often. We believe this is a pity because as we will show, it is in fact a very powerful tool for determining the crystal structure. We then continue with XRD. In the past there have been studies in which the relation between oxygen content of the titanium oxide versus lattice parameters for bulk samples was established [6]. We repeat this research

2.4. Results and Discussion

11

for epitaxial thin lms. Finally, we will present resistivity data obtained using the four point probe method. We wanted to determine whether or not our layers are metallic or semiconducting, and whether their resistivity is comparable to bulk data.

2.4.1

RHEED

During the growth of every sample we recorded a RHEED movie not only for monitoring the growth but also for doing post-growth analysis of the growth of the sample. During growth we would like to see RHEED oscillations and after growth we can analyze the evolution of the recorded RHEED patterns and determine the lattice parameters. Along with the RHEED movie we measured the baratron pressure, the substrate temperature and the titanium ux as displayed by the e-gun evaporator. So, for every frame of the RHEED movie we also have information about these three parameters, giving an accurate account of growth conditions. At the end of the growth we made a RHEED rotation movie, which enabled us to determine the structure of the layer. In Appendix A the dierent uses of RHEED are discussed in more detail.

RHEED oscillations RHEED oscillations are commonly observed during sample growth if the growth is layer-by-layer like. They are a useful tool for determining growth rates, because one oscillation-period is equal to the time needed to grow a single atomic layer. They will also give useful information about the growth conditions. RHEED oscillations do not appear if there is no layer by layer growth. If samples become rough very soon the oscillations will damp out fast. This indicates that the growth conditions are not optimal. If there are only a few oscillations, the determination of the ux rate is evidently more dicult and inaccurate, but it still gives a rough estimate. In gure 2.3 we show the RHEED oscillations obtained from one of our samples. Displayed are the st twelve oscillations. These oscillations are measured in about 315 5 time units. The oscillation period is therefore 3 (315 12) = 78 seconds and is equal to the time it took for one layer to grow. The thickness of one titanium oxide layer is half that of the cubic unit cell, so 4.19 2 = 2.095 , making the TiOx ux 1.62 /min. We A A kept growing this layer for 125 minutes, so we expect the layer to have a thickness of 1.62 125 = 202.5 . From XRD measurements a thickness of A is obtained, which is in very good agreement. From the RHEED 204.9 A we can also see that the oscillations are damping out. This is an indication

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Chapter 2: Properties of TiOx thin lms

Figure 2.3:

Here a plot of RHEED oscillations of the specular spot is shown. In total there are twelve oscillations visible in 315 5 time-units. This means the oscillation has a period of about 26 time-units, each time-unit being three seconds. Every oscillation is equal to 1 ML of TiOx , having a thickness of 2.10 . Our growth rate is therefore (2.10 (3 26)) 60 = 1.62 0.05 /min. A A

of roughening of the sample surface.

RHEED images In RHEED we can distinguish between two general patterns. These two patterns appear for both substrates. We start o with the TiOx samples grown on MgO substrates. In gure 2.4 A) we show the RHEED pattern of a clean MgO substrate and in gure 2.4 B) the RHEED pattern of the deposited TiOx layer. The pattern looks the same and it is the same except for the distance between the RHEED lines, which is directly related to the lattice spacing. In gure 2.5 we show the evolution of the separation of the two outermost RHEED streaks. At t = 0 seconds the distance between the lines is equivalent to the lattice parameter of MgO. When the shutter is opened at t = 60 seconds the distance between the lines rst decreases from 210.4 to 208.6 pixels and then increases to about 211.5 pixels. This is the in-plane lattice parameter of the strained TiOx thin lm with a

2.4. Results and Discussion

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Figure 2.4: Shown are A) the RHEED pattern of a clean MgO substrate and B) the RHEED pattern of the resulting TiOx thin lm on top of the MgO substrate. lattice parameter of (210.4 211.5) 4.212 = 4.190 . When the lm A reaches the critical thickness after t = 1450 seconds, the lattice parameter relaxes to the lms intrinsic value which is not aected by the substrate anymore. We can now calculate the in plane lattice parameters. Its value is (210.4 212.2) 4.212 = 4.176 , which is a reasonable value for TiOx . A The lattice of MgO is larger than that of TiOx , by approximately +0.5%. This means that the titanium oxide will have tensile strain, i.e. the inplane lattice parameters are increased with respect to the bulk value. This is exactly what we see happening in gure 2.5. In gure 2.6 A) we again show a RHEED pattern of a MgO substrate and in gure 2.6 B) the RHEED of the layer grown on this substrate. The sample from gure 2.4 and the sample from gure 2.6 have comparable thicknesses, 205 5 and 226 5 respectively. They were also grown at A A the same temperature of 400 C. The deposition rate was dierent for the two (3.42 0.05 /s and 1.88 0.05 /s) as well as the oxygen baratron A A pressure (0.05 Pa and 0.08 Pa). In other words, the sample from gure 2.6 had more oxygen available per titanium atom. If we now look at the RHEED pattern, it is clear that this image is dierent from the previous sample, and it is the second general TiOx RHEED pattern observed. There now have appeared pairs of lines between the MgO streaks. In gure 2.7 we show a transverse scan through the RHEED pattern, taken at the end of growth (line of intermediate thickness). Also shown are the RHEED intensities of the substrate (thin line) and the dierence between these two (thick line). The peak positions are indicated by arrows. They divide the area between the two outermost peaks in six equal sized parts. Since the two outermost peaks are almost at the same position as the MgO peaks, the titanium oxide unit cell has become about three times that of MgO. We have performed the same analysis on samples grown on MgAl2 O4 . In

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Chapter 2: Properties of TiOx thin lms

Figure 2.5: Plot of the evolution of the separation between the two outermost
streaks in the RHEED pattern of gure 2.4. In the beginning we have MgO (as indicated) with a distance between the two streaks of 210.4 pixels. Immediately when the shutter is opened the intensity of the RHEED pattern decreases, and the determination of the peaks positions is more dicult, hence a dip in the plot. When the RHEED stabilizes again we observe an intermediate phase of strained TiOx . After reaching the critical thickness, in the plot after 1350 seconds, we again see a small dip before the rest of the lm grows relaxed. The relaxed TiOx is also indicated and there the separation is 212.2 pixels. If we now divide these two values and multiply with the (in-plane) lattice parameter of MgO we get as in-plane lattice parameter for TiOx , a = b = 4.178 . A

gure 2.8 A) the RHEED pattern of a clean MgAl2 O4 substrate and in gure 2.8 B) the RHEED of TiOx grown on this substrate is shown. MgAl2 O4 has a unit cell which is about twice that of natural TiOx . It is therefore not surprising that the nal TiOx layer has streaks which are separated by twice the amount of the distance between the RHEED lines of the substrate. On MgAl2 O4 also TiOx with a superstructure can be grown (gure 2.9). The pattern is similar to the one of TiOx on MgO. When we look at the RHEED evolution of this lm (gure 2.10) we see that two of the substrate streaks disappear immediately after growth has started. After some time (about 750 seconds) there appear pairs of streaks between the remaining streaks. The RHEED image is now similar to that of TiOx with a superstructure on MgO (gure 2.6). The pattern is also divided into six equally spaced peaks. If we plot the in-plane parameters against oxygen

2.4. Results and Discussion

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Figure 2.6: Figure A) shows the RHEED pattern of the clean MgO substrate
before growth and B) shows the RHEED pattern of the resulting TiOx thin lm. The white line indicates the position where the scans in gure 2.7 were taken.

Figure 2.7: A line taken from both images in gure 2.6. On the x-axis the pixels
are displayed and on the y-axis their intensity. The thin line is the RHEED from the substrate showing the three lines as three peaks. The thicker line is the TiOx lm with the superstructure showing in total 7 peaks. The thickest line is the dierence between the two, the arrows marking the positions of the peaks.

content of the TiOx layer and compare these to the MgO case, we can see they are dierent.

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Chapter 2: Properties of TiOx thin lms

Figure 2.8:

Displayed in A) is the RHEED pattern of the clean MgAl2 O4 substrate and in B) the RHEED pattern of the resulting TiOx thin lm. There is no superstructure visible.

Figure 2.9: Here we present A) the RHEED and transmission pattern of TiOx
with a superstructure grown on a MgAl2 O4 substrate and B) RHEED pattern of a dierent TiOx sample grown on MgAl2 O4 also with a superstructure but with a dierent roughness, so no transmission. Also have a look at Appendix A for an explanation about the patterns.

The results for our TiOx samples on MgO and MgAl2 O4 are displayed in gure 2.11 A) and B). In this graph the black squares and triangles represent the samples on MgO and the white squares and triangles represent those on MgAl2 O4 . For both substrates the squares represent data obtained from the RHEED pattern and the triangles represent data obtained from XRD. In the visualization of our results we make use of the thickness of our samples. Because the ux of titanium was not the same for all the samples and the time we grew was dierent for dierent batches, we use the thickness of the samples, determined by XRD, to scale them. This scaling turned out to be much more fruitful than scaling with oxygen baratron pressure alone.

2.4. Results and Discussion

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Figure 2.10:

The RHEED pattern evolution of a TiOx sample with a superstructure grown on a MgAl2 O4 substrate. Indicated in black at the beginning and the end of the scan are the positions of the peaks of the RHEED lines. Indicated in white is the position from where the superstructure clearly appears.

We are however aware that this scaling need not to be continuous, due to phase transitions of the titanium oxide. In our scaling this will cause some overlap between points, i.e. the titanium oxide phases with and without superstructure coexist for some values. Figure 2.11 A) shows the in plane lattice parameters of TiOx without superstructure for both substrates and gure 2.11 B) shows the same for TiOx with a superstructure. The values are similar for both substrates suggesting that in both cases we are looking at relaxed samples. It was shown in gure 2.5 that the lm relaxes (in that case) after 1450 seconds. We usually grew for more than 1 hour, so the above conclusion is probably correct. The trend seems to be that the in-plane lattice parameter is increasing with oxygen content for the normal titanium oxide and the in-plane lattice parameter is decreasing with increasing oxygen content for the reconstructed titanium oxide. This result is quite surprising, because for bulk samples the lattice parameter always decreases with increasing x. We should mention that determining the lattice parameter from RHEED is error sensitive, because of the varying quality of the RHEED patterns. The area-scans are more accurate, and they show a lattice parameter for TiOx of a = b = 4, 20 0.01 ngstrom, even A though x is dierent for the samples. RHEED rotation We would like to have more information about the two kinds of samples, i.e. the ones with and without a superstructure, in order to nd out what the origin of the superstructure is. RHEED rotation movies are a powerfull tool for determining the crystal structure in situ. Especially the samples that show a transmission and a RHEED pattern are very useful, because that pattern does not only provide us with the in-plane lattice parameter, but also with out of plane information. Furthermore, we can do simulations of this pattern for a specic structure which we can then compare with

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Chapter 2: Properties of TiOx thin lms

Figure 2.11:

Lattice a- and b-parameters for titanium oxide layers on MgO determined from the area-scans (black squares) and RHEED (black triangles), and on MgAl2 O4 from the area-scans (white squares) and RHEED (white triangles). In A) we show the samples without a superstructure and in B) the ones with a superstructure. The scaling we use (mV/(/sec)) is dened in the A text.

our measurement. See Appendix A for an explanation of how we obtain a RHEED rotation movie and how to do the simulations. If we make a rotation movie of a TiOx sample grown on MgO we get gure 2.12. From this gure we can see the lattice is cubic, as it should be for a relaxed rocksalt-like material. The resemblance is striking if we compare this to the same kind of rotation picture from a simulation of the rocksalt

2.4. Results and Discussion

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Figure 2.12:

RHEED rotation image of a TiOx thin lm grown on a MgO substrate. For an explanation about RHEED rotation images have a look at Appendix A. The heights at which these slices are taken are at the bottom and halfway the reciprocal space unit cell.

structure (gure 2.13). The next structure to treat is the TiOx with a superstructure.

In

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Chapter 2: Properties of TiOx thin lms

Figure 2.13: RHEED rotation image of a simulated MgO substrate. The height
at which this slice is taken is comparable to the bottom slice of the previous gure, gure 2.12.

gure 2.14 we show the rotation movie of a lm grown on MgAl2 O4 . It is clear this rotation movie is dierent from that of gure 2.12, although the basic square lattice is still apparent. When we analyze the RHEED rotation movie at dierent heights with respect to the sample surface, we obtain the threedimensional picture of the reciprocal unit cell. By carefully examining the positions where the intensity of the RHEED spots are a maximum we can conclude that the TiOx is growing in a rocksalt lattice, but one out of three titanium sites is vacant. We will now explain how we come to our conclusion. From the careful examination of the positions of maximum intensity, looking along the c -direction, we were able to distinguish six dierent levels in the reciprocal lattice. It also indicated we were dealing with a body-centered reciprocal unit cell. Using this as a basis, we constructed an orthorhombic unit cell with unit cell parameters |a | = 1 |ac | 2, |b | = |ac | and |c | = |ac | 2. This makes the volume of the 3 reciprocal cell V equal to 2 Vc . 3 The reciprocal lattice just described and the accompanying cell are depicted in gures 2.16 and 2.17. In real space we have a face-centered unit

2.4. Results and Discussion

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Figure 2.14: RHEED rotation image of a TiOx sample with a superstructure grown on a MgAl2 O4 substrate.

Figure 2.15:
superstructure.

RHEED rotation image of a simulated TiOx sample with a

cell with a volume of one and a half times that of the rocksalt unit cell. The total number of atoms and vacancies in the rocksalt unit cell is 4 so for our face-centered cell this is six. Since we are dealing with TiOx the

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Chapter 2: Properties of TiOx thin lms

Figure 2.16: The reciprocal space proposed TiOx structure. Only one domain
is shown.

Figure 2.17: The reciprocal space proposed TiOx structure. Only one domain
is shown.

basis consists of 3(Tin Vac1n O) if x in TiOx is greater than one. If the material is stoichiometric, we can form Ti2 O3 + VacT i or TiO3 +2VacT i . From this Ti2 O3 + VacT i is the most probable one, which was also our previous conclusion. The real space cell is drawn in gures 2.19 and 2.20. The observed complex mix of transmission and RHEED patterns (gure 2.9) are obtained if the lattices of all equivalent domains which may be obtained by a fourfold rotation of the body centered orthorhombic lattice of gure 2.18 are superimposed. When we simulate this structure and make a rotation movie we get gure 2.15. Here we would also like to mention a peculiar eect we saw in some of our samples. In gure 2.21 we show the RHEED rotation movie of a TiOx sample grown on MgAl2 O4 . As can be seen, the resulting gure consists of a square grid of lines. The points where the lines intersect are the positions of the RHEED rods. The lines are caused by the phenomena that the vacancies present in the sample order in a certain direction, but are disordered with

2.4. Results and Discussion

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Two of the four identical unit cells in reciprocal space of the proposed TiOx superstructure indicated in grey in the reciprocal unit cell of rocksalt. All the possible domains are drawn in this gure, that is why it seems the unit cell has more than four atoms in it. Attention should only be paid to the atoms at the corners of the unit cells.

Figure 2.18:

respect to each other in the two perpendicular directions. Because of this, the lattice sum eiQRn is only discrete in one direction. These diuse planes cause lines like we see in gure 2.21. The fact that the lines are at every plane perpendicular to the c -direction also supports this idea. The eect was previously observed in LEED [24]. Our RHEED rotation images are actually comparable to LEED images, only for the latter it is not always possible to obtain an image, especially for rough samples. In the thesis of F.C. Voogt [24] the eect is described for a MgO substrate. There calcium segregation causes (110) planes of diuse intensity. This indicates long range order in one [110] or [1 direction, but disorder in the [1 or 11] 11] [110] direction perpendicular to it, i.e. they correspond to one-dimensional line features. The streaking in LEED was accompanied in RHEED by a splitting of the diraction rods, just like the RHEED pattern of the streaky rotation movie was split up (gure 2.6).
Rn

2.4.2

XRD

A known property of TiOx is the decrease of lattice parameters with decreasing oxygen content [6]. Since the epitaxially grown thin lms are (partially) strained in the in-plane direction, probably the best way to observe the dependency of the lattice parameter on oxygen content of the lm is in the out of plane direction. Through the Poisson-ratio we could also relate this to a volume change of the unit cell. With X-rays we can also determine the critical angle c , i.e. the angle below which there is

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Chapter 2: Properties of TiOx thin lms

Figure 2.19: The real space proposed TiOx structure.

Figure 2.20: The real space proposed TiOx structure.

total reection and above which part of the photons is absorbed. This is a number directly related to the electron density, i.e. the number of electrons per unit cell, of the material. This gives us information about the phase of the material under investigation. Reectivity In analyzing the samples using XRD, the rst measurement we usually performed was a reectivity scan, i.e. a 2 scan near c . Because the obtained curve is mostly a result of kinematical processes, we can accurately simulate these scans. By tting the obtained curve we can in this way determine several important properties of our thin lm. The properties are electronic density, thickness and roughness of interface and surface. From the critical angle c (in radians) we can deduce the electron density e through the relation 2 (2.2) e r e 2 c

2.4. Results and Discussion

25

Figure 2.21: RHEED rotation image of a TiOx sample with a superstructure grown on a MgAl2 O4 substrate, seemingly showing lines connecting the rocksalt lattice points. where is in our case equal to the Cu-K radiation wavelength and re is the classical electron radius. For a typical value for the critical angle of c = 0.31 /180 we get an electron density of e = 1.376 e/3 . A In gure 2.22 we show our results for the electron density of our samples versus the previously dened scaling of oxygen baratron pressure (in mV) divided by the deposition rate. As can be seen there are two separate regions of points for both kinds of substrates. One region with an electron density of about 1.62 1.67 3 corresponds to the calculated electron density of A stoichiometric TiO, which is 1.663 3 . The other region with an electron A density of about 1.30 1.36 3 seems to correspond to the calculated A electron density of Ti2 O3 , which is 1.314 3 . A In the ideal case, the deposition rate would be kept constant and only the oxygen ux would be varied. In our case, however, during growth we had problems keeping the deposition rate constant between dierent samples, although there was no problem keeping the deposition rate constant for one sample. This was caused by problems with the e-gun evaporator described before in section 2.3. Therefore we followed another method. We kept

26

Chapter 2: Properties of TiOx thin lms

Figure 2.22: Electron density versus our scaling, dened in the text, of baratron

pressure in mV divided by the deposition rate in Angstrom per second for MgO (white circles) and MgAl2 O4 (black squares). The lines indicate the error bar of each point. They only point in one direction because the error depends on the observed oxygen baratron pressure, which is an upper limit to the real baratron pressure.

the amount of oxygen, i.e. the baratron pressure, constant and changed the deposition rate. By determining the layer thickness, the eective deposition rate could be determined after growth, and the sample would get its place on our scale. By increasing the deposition rate and keeping the oxygen ux constant, we move towards zero in our scaling. If we have a constant oxygen pressure and a relatively large deposition rate, we grow TiOx . If we have a relatively low deposition rate, we grow titanium oxide with a superstructure. There is some overlap, probably because of a phase transition. This overlap is in the region of our scaling of about 2.5 3.0 mV/(/min). A It is clear that for TiOx the electron density increases with increasing amount of oxygen. This means that the volume of the unit cell is decreasing with an increasing amount of oxygen, in agreement with experimental observations. The electron density of Ti2 O3 seems to be decreasing slightly, implying an increase in unit cell volume with an increasing amount of oxygen.

2.4. Results and Discussion

27

2 scans, also called wide-scans, of TiOx layers on MgO. The normal TiOx , at a 2 value of about 43.0 , has a plane spacing of 2.099 . The TiOx with a superstructure can be found at a 2 value of about A 45.3 , and a plane spacing of 1.991 . A

Figure 2.23: Overlay of two

Figure 2.24: Overlay of two 2 scans, also called wide-scans, of TiOx grown on a MgAl2 O4 substrate. The normal TiOx , at a 2 value of about 41.0 , has a plane spacing of 2.191 . The TiOx with a superstructure can be found at a 2 A value of about 42.5 , and a plane spacing of 2.120 . A Wide-scans Wide-scans are 2 scans like reectivity scans but far away from c . They typically run over about 100 in 2. From these scans the distance between crystallographic planes can be determined through the Bragg relation 2dhkl sin = n. For our samples grown on MgO and MgAl2 O4

28

Chapter 2: Properties of TiOx thin lms

Figure 2.25: Lattice parameter versus x in TiOx for bulk crystals, taken from
reference [6].

we used this type of scan to determine the lattice c-parameter. In gure 2.23 an overlay of wide-scans of the two dierent types of TiOx grown on MgO is shown. In gure 2.24 we show the same for MgAl2 O4 as a substrate. As can be seen, it is easier to distinguish between the two dierent types in the case of MgAl2 O4 as a substrate. In gure 2.25 we show a plot of the lattice parameter versus x in TiOx for bulk samples, taken from reference [6]. The lattice parameter and therefore also the unit cell volume linearly decreases with increasing oxygen content. Since we can determine from the RHEED patterns if there is a superstructure present or not we can already divide our data into two sets. In gure 2.26 A) and B) we show the data collected for the cparameters of our lms on both MgO (black points) and MgAl2 O4 (white points) substrates plotted against the previously dened scaling. For both substrates the squares represent data obtained from the wide-scans and the triangles represent out of plane data obtained from area-scans. The in-plane data obtained from area-scans was already shown in gure 2.11. Figure 2.26 A) shows the out-of-plane lattice parameters of TiOx without superstructure for both substrates and gure 2.26 B) shows the same for TiOx with a superstructure. As can be seen, the c-parameter for both substrates decreases with increasing oxygen content, as expected. However, the values for titanium oxide on MgAl2 O4 are larger than those on MgO. For MgO the tensile strain

2.4. Results and Discussion

29

Figure 2.26: Lattice c-parameters for titanium oxide layers on MgO from the
wide-scans (black squares) and the area-scans (black triangles), and on MgAl2 O4 from the wide-scans (white squares) and area-scans (black triangles).

imposed by the lattice mismatch does not modify the lattice parameters too much, but for MgAl2 O4 this is dierent. The compressive strain seems to increase the out of plane lattice parameter by about 4% with respect to the bulk. When we compare our scale with the one from gure 2.25, we can see that our scale runs from about 1 mV/(/min)to about 5 mV/(/min) compared A A to an x that runs from 0.72 to 1.28. Since the c-parameter changes from 4.20 to 4.17 in our measurements and from 4.20 to 4.17 in reference A A A A

30

Chapter 2: Properties of TiOx thin lms

Figure 2.27: Area-scan of the reciprocal plane spanned by the MgO(004) and
the (202) reection, also showing the TiOx (002) and (202) reections.

[6], we believe the two scales are comparable, i.e. they illustrate the same phenomena. For the titanium oxide with a superstructure the magnitude and behavior are also dierent for both kinds of substrates. For the samples on a magnesium oxide substrate the lattice parameter decreases with increasing oxygen content, just like the titanium oxide without superstructure. For the samples on MgAl2 O4 however, the lattice parameter seems to stay more or less constant. The c-parameter is larger than that of samples on MgO.

Area-scans Area-scans made with XRD are very helpful if the crystal structure of the thin lm is more or less known. There are dierent kinds of area-scans that we can perform with our XRD apparatus. One of them, the one where a range in 2 is divided into discrete steps and at every step a -scan is measured, is the most used area-scan. These scans produce an image like gure 2.27. We are growing TiOx in the rocksalt structure, so we expect the same reections as for MgO. In gure 2.27 we show an image of the reciprocal plane spanned by the (004) and the (202) reections of MgO and in gure 2.28 we show the reciprocal plane spanned by the (004) and the (222) reections of MgO. These reections are indexed in bold

2.4. Results and Discussion

31

Figure 2.28: Area-scan of the reciprocal plane spanned by the MgO(004) and
the (222) reection, also showing the TiOx (002), (004) and (113) reections.

Figure 2.29: Area-scan of the reciprocal plane spanned by the MgAl2 O4 (008) and the (404) reection, also showing the TiOx (002) and (202) reections.

32

Chapter 2: Properties of TiOx thin lms

Figure 2.30:

Area-scan of the MgO(113) reection, also showing the strained TiOx (113) reection.

Figure 2.31: Area-scan of the MgAl2 O4 (226) and the TiOx (113) reciprocal lattice points. There is also a powder line visible, originating from the aluminum sample holder. in the gures. Since MgO also has a NaCl type of structure all the MgO reections are accompanied by TiOx reections, indicated in italic in both gures. In gure 2.29 we show the reciprocal plane spanned by the (008) and the (404) reections of MgAl2 O4 . It also shows the TiOx (002), (004) and (202) reections. The substrate reections are again indexed in bold and the ones from the lm in italic. If we zoom in on certain reections, the area-scans provide us with information about the strain or relaxation of the thin lm. In gure 2.30 we have zoomed in on the (113) reection of MgO. Also visible is the (113)

2.4. Results and Discussion

33

A
Figure 2.32:

A) a side-view of a sample with contacts evaporated before lm deposition B) a side-view of a sample with contacts evaporated after lm deposition. In black are the contacts, striped is the substrate and dotted is the lm.

reection of TiOx . It appears as a streak right above the MgO reection. This means the lm is fully strained, i.e. it did not take on its own aand b- lattice parameters. The strain is caused by the lattice mismatch, which in the case of MgO is +0.5% and in the case of MgAl2 O4 is 3.5%. Measuring area-scans of o-specular reections will thus provide us with a- and b- lattice parameters as well as the out of plane c-parameter. The c-parameters obtained in this way were already shown in gure 2.26 and in gure 2.11 we show a plot of the in plane lattice parameters versus our scaling. For MgAl2 O4 we expect the TiOx (113) reection to lie next to the substrates (226) reection. In gure 2.31 we show this is indeed observed. What is immediately clear from this picture is that it is completely dierent from that of the TiOx (113) reection on MgO. The titanium oxide layer of this sample is completely relaxed, hence there is no streak visible.

2.4.3

Resistivity

In order to perform conductivity measurements on our samples there had to be contacts on the samples. These contacts can either be deposited ex situ on the dirty substrate after which it is introduced into vacuum and cleaned by heat treatment or in situ on top of the freshly grown sample. We chose to follow the latter procedure after experiencing problems with the rst one. We used chromium for contact material. One of the problems we encountered with evaporating contacts before cleaning the substrate is that they would oxidize to Cr2 O3 during the substrate cleaning process or the sample growth process. We conclude this from the drastic decrease of conductivity and the change of color from silvery to transparent of the contacts. By evaporating the contacts after the cleaning process and after the lm was grown, the contacts will not oxidize by these steps. Another reason for putting on the contacts in situ is illustrated by gure 2.32. The contacts evaporated on the substrate ex situ are much thicker than our lm. This will result in macro-steps in our lm (gure 2.32 A). Shadowing will

34

Chapter 2: Properties of TiOx thin lms

Figure 2.33:

Resistivity versus 1000/T curves of dierent samples on MgO (white) and MgAl2 O4 (black). On top or on the left the curves ar shown for normal samples. In the middle picture we show the digitized curves from reference [6], i.e. resistivity curves for bulk samples. In the gure on the bottom or on the right we show the resistivity curves for the samples with a superstructure.

2.4. Results and Discussion

35

make the contact of our lm with the metal strips poor. The interface between the contacts and the lm is not well dened and dislocations and defects are present at the boundary. The resistivity measurements may therefore give unrealistic results. In the case where we evaporate the contacts after lm growth (gure 2.32 B) most of these problems are circumvented. In some cases we were even able to grow epitaxial Crcontacts on the lm. This means the interface is well dened and resistivity measurements are much more reliable. For these reasons we preferred method B over method A. We performed resistance measurements from 5 K - 300 K on our samples. We did this to be able to compare available bulk data with our samples. But, to be able to compare these resistance measurements, we have to convert the resistance into the resistivity. For this we need four ingredients, namely the measured resistance (R), the distance between the contacts (d), the length of the contacts (l) and the thickness of the lm (t). Since we used the four point probe contact method for measuring the resistance we dont have to worry about contact resistances or interface resistance. Now, through the relation d = (t )R l (2.3)

we can calculate the resistivity. We note that the thickness of the lm has the largest uncertainty of the measured parameters. This is because the contacts and MgO cap-layer complicate the determination of the thickness with XRD. With typical measured values for R = 30 , d = 1, 25 mm, l = 10 mm and t = 100 we get a resistivity of = 3 105 cm, which A is about the same as for bulk titanium oxide. The bulk data is displayed in the center pane of gure 2.33 using the same scaling, log() vs. 1000/T, as the other two panes. In our resistivity measurements we observe two types of behavior. In one case the resistance varies only a little with temperature, not even one order of magnitude. In the other case it changes considerably, more than two orders of magnitude. These two cases are shown in the left and in the right panel of gure 2.33, respectively. We attribute these dierent behaviors to two dierent structures. The points measured in the left pane of gure 2.33 were obtained from TiOx samples without a superstructure, like the one from gure 2.4. They are quite similar to the resistivity measurements of bulk samples. The measured points from the right panel were obtained from titanium oxide with a superstructure, like in gure 2.9. This behavior is quite dierent from that of the bulk, again showing we are dealing with another phase of TiOx .

36

Chapter 2: Properties of TiOx thin lms

Figure 2.34: Resistivity versus temperature curve showing the superconducting


transition of our TiOx thin lm. The apparent hysteresis is caused because the teperature sensor is not measuring the temperature exactly on the position of the sample.

Superconductivity TiOx is also superconducting with a transition temperature varying with x. In literature values have been reported of 0.47 K for a sample under pressure with an x of 0.86 up to 2.07 K for a single crystal under pressure with an x value of 1.22 [6]. We also tried to measure the superconducting transition temperature in one of our samples. We observed a transition at about 0.65 K (g 2.34). The measurement was performed in a He3 refrigerator that could reach a minimum temperature of 0.3 K. The apparent hysteresis loop is caused by the dierence in location of sample and temperature sensor. This caused the sample to, during cooling, reach the superconducting transition temperature before the temperature sensor measured that temperature. During heating, the sample would reach the transition temperature again before the temperature sensor, and in this way the hysterisis loop is formed. Although the resistance of the sample does not entirely drop down to zero, we still believe this is the superconducting transition we observe. This is because the resistance decreases exactly in the range where we would expect it. One of the reasons why the resistance did not become zero could be the layout of the contacts. Under inuence of the chromium contacts, which remained in a normal state, parts of the thin lm remained in the normal

2.5. Discussion

37

instead of the superconducting state. This could make it possible that there is no direct superconducting path between two contacts. For future research the layout of the contacts on the sample should be changed from four contacts next to each other to four contacts on the four corners of the sample.

2.5

Discussion

The goal of this chapter was to show the modications substrates impose on the properties of epitaxially grown thin lms of titanium oxide through their structure and lattice mismatch. The rst major modication we observed is the growth of TiOx with a superstructure. This structure was formed at high oxygen levels and low deposition rates during growth. Surprising was that we could grow the layer epitaxially on MgO as well as MgAl2 O4 . We used RHEED rotation movies to determine that this new phase was chemically equivalent to, but structurally dierent from Ti2 O3 . The structure has a rocksalt like sublattice with one out of three titanium sites vacant, making the possible unit cell three times as large as that of TiOx without a superstructure. The c-parameter for these lms is bigger for samples grown on MgAl2 O4 substrates than for those grown on MgO. The behavior of the c-parameter with increasing amount of oxygen is dierent for samples grown on MgAl2 O4 than for those on MgO. We showed that the behavior of the resistivity versus temperature for these samples with a superstructure is dierent from that of normal TiOx . The TiOx without a superstructure behave as their bulk equivalents. The c-parameter decreases with increasing oxygen content for both substrates. When we analyzed the in-plane lattice parameters we saw that there was no real dierence between the two of them. This might be caused by relaxation of the lm. As we showed for one of our lms, the critical thickness is reached after about 20 minutes, while we grew our layers for at least one hour or more. The resistivity curves are comparable to those of the bulk. Unfortunately we were not able to make a quantitative analysis of the amount of vacancies present in the thin lms. This could have been possible if we would have had RHEED oscillations and RBS for all our samples. By growing all the lms with the same titanium ux, we could compare the time for one ML of our lm to grow with the time of one ML of a reference sample, like TiO2 , which we assume to have no vacancies. The fraction of these two times is a measure for the amount of vacancies in the TiOx thin lm. By growing the thin lms using 18 O it is possible to determine the ratio of titanium and oxygen using RBS. By comparing to a gauge sample for which the stoichiometry is known, it is possible to determine the

38

Chapter 2: Properties of TiOx thin lms

stoichiometry of the TiOx thin lm. With this extra information we can also dier between the number of oxygen and titanium vacancies. A comparison between c-parameters of our thin lms and those of single crystals suggests that we are covering the whole known range of x in TiOx .

2.6 Outlook and Recommendations


For future research we have a few recommendations. We for instance showed why we believe it is favorable to deposit electrical contacts in situ. We recommend this method and suggest to experiment with dierent layouts of the contacts. The superconductivity measurements were a time consuming but interesting thing to do. We believe the Tc of our lms can be increased to higher values than known for bulk crystals. Since bulk crystals obtain a higher transition temperature when pressure is applied upon them, we think that by imposing a pressure up on a lm through lattice mismatch will modify the Tc of the lm. By choosing the right substrate a lm with a higher Tc than that of the bulk can be obtained. We recommend evaporation of titanium from a Knudsen cell instead of from a e-gun evaporator. The ux control is much more stable because the power input is more constant. It also makes the calibration more easy and reproducible. We saw in our experiments with an e-gun evaporator that settings had changed when we had replaced the titanium rod. The only problem we see with the Knudsen cell is the high temperature needed to evaporate titanium. This could cause other materials to start evaporating as well. Good shielding and a tungsten insert in the Al2 O3 cruicible probably overcome this problem. Titanium is very reactive with oxygen. In further research this property has to be recognized. We solved this by decreasing the diameter of the delivery tube. The samples should also be made thinner. For a lot of the samples we passed the critical thickness, where strain eects due to the substrate are already lost or at least much smaller than below dcr . We tried to determine the stoichiometry by growing our lms with 18 O and measure them with RBS. The attempt failed, mainly because of choosing the wrong thickness of the lms, capping of the samples and channelling eects. When we made our calibration samples we were also not aware of the great reactivity of titanium with oxygen. The measurements we performed mainly resulted in an x of about 1.5 in TiOx . We suggest to redo these measurements with the smaller delivery tube and titanium evaporated from a Knudsen cell. Make sure there are no channelling eects in the measured RBS spectra because this makes tting of the spectra impossible.