This research was supported by the National Science Foundation (Awards CMMI-1437050 and DMR-1207342), the Office of Naval Research (Grant N00014-10-10489), and the Air Force Office of Scientific Research (Grant FA9550-14-1-0090).

1. Preparing Sr and Ti Precursors for ALD Experiments
<ol>
	<li>Load the clean, dry saturators and new precursors into the antechamber of a glove box. Follow the glove box&#39;s loading procedure to ensure proper purging of air and moisture. Transfer the materials into the main chamber. 
	Note: This group uses in-house built saturators (see Figure 3) with components purchased commercially. Details of the saturator assembly can be found in the List of Specific Reagents and Equipment.</li>
	<li>Store the strontium precursor (strontium bis(triisopropylcyclopentadienyl) [Sr(iPr3Cp)2]) and titanium precursor (titanium tetraisopropoxide [Ti(O-iPr)4], TTIP) in an inert environment (e.g., a glove box) after opening the original packaging provided by the manufacturer. 
	Note: This group uses a glovebox with a moisture level no greater than 5 ppm.</li>
	<li>Load the precursor into the saturator such that the precursor occupies approximately 2/3 of the glass part of the saturator (about 5 g).</li>
	<li>Reassemble the saturators and ensure a good leak tight seal is achieved. 
	Note: This group uses metal gasket face seal fittings to achieve leak tight seals.</li>
	<li>Unload the filled saturators from the glove box and connect the filled saturators to the ALD manifold. 
	Note: The loaded precursors can be used multiple times over an extended period. The precursors in this group&#39;s system generally require refilling every six months as they become consumed. Sr(iPr3Cp)2 is a brown liquid at both RT and the operating temperature for this study (130 - 140 &#176;C). TTIP is a clear liquid. When TTIP deteriorates, typically due to moisture and/or air contamination, the precursor will turn into a white solid. There has been no visible indicator of precursor deterioration for the Sr(iPr3Cp)2 observed by this group. Sr precursor deterioration is generally detected by a significant decrease (greater than 10%) of Sr content in a repeatable ALD growth that utilizes Sr(iPr3Cp)2.</li>
</ol>
2. Cleaning the Ge (001) Substrate
<ol>
	<li>Place a Ge (001) substrate (18 mm &#215; 20 mm), polished side facing upwards, into a small beaker (25-50 ml). Fill the beaker to about 1 cm height with acetone. Place the beaker in a bath sonicator and sonicate for 10 min. 
	Note: This group uses single-side polished 4-in Ge wafers, cut into 18 &#215; 20 mm2 pieces using a dicing saw. Use heavily doped n-type Ge if electrical measurements of the film are needed (this study uses Sb-doped Ge wafers with &#961; &#8776; 0.04 &#937;-cm), otherwise all doping level and dopant types are acceptable.</li>
	<li>Decant the majority of the acetone into a waste container, taking care not to pour out or flip the Ge substrate. Rinse the walls of the beaker with isopropyl alcohol (IPA) and fill to approximately 1 cm height. Pour the majority of the IPA into a waste container, refill beaker to 1 cm with IPA, and sonicate for another 10 min.</li>
	<li>Repeat step 2.2, but replace IPA with deionized water.</li>
	<li>Remove the substrate from the beaker with tweezers. Dry the substrate with a nitrogen gun or other dry inert gas flow.</li>
	<li>Place the substrate in the UV-ozone cleaner and run the cleaner for 30 min.</li>
	<li>After UV-ozone cleaning, immediately load the substrate into the vacuum system.</li>
</ol>
3. Loading the Ge Substrate
<ol>
	<li>Move the transfer line sample carrier-cart into the load lock. Close the gate-valve to isolate the load lock.</li>
	<li>Turn off the load lock turbomolecular pump and open the nitrogen line to vent the load lock. Complete Step 3.3 while waiting for the load lock to completely vent.</li>
	<li>Place the substrate, polished side facing downward, into a 20 mm &#215; 20 mm sample holder. 
	Note: All depositions are performed with the sample facing downward. Ensure the substrate is flush with the bottom of the holder; otherwise RHEED experiments may experience difficulty and films may not deposit uniformly. A sample holder this group uses is shown in Figure 4.</li>
	<li>Open the load lock after it has completely vented. Place the sample holder into an open carrier-cart position by aligning the tabs of the sample holder with the channels of the open cart position and lowering it into place.</li>
	<li>Close the load lock and turn on the load lock turbomolecular pump. Close the nitrogen line.</li>
	<li>Wait until the pressure in the load lock is approximately 5.0&#215;10-7 Torr before opening the load lock gate valve and moving the cart through the transfer line.</li>
</ol>
4. Ge Deoxidization
<ol>
	<li>Transfer the Ge substrate into the MBE chamber.</li>
	<li>Ramp the Ge substrate temperature to 550 &#176;C at 20 &#176;C&#8226;min-1 and then to 700 &#176;C at 10 &#176;C&#8226;min-1. After holding the sample at 700 &#176;C for 1 hr, cool the sample to 200 &#176;C with a 30 &#176;C&#8226;min-1 ramp rate.</li>
	<li>Use RHEED to confirm the 2&#215;1 reconstructed surface as described in Representative Results section.26,39</li>
	<li>Optional: Use XPS to ensure that the Ge (001) substrate is free of oxides (described in Section 8).</li>
</ol>
5. Thin Film ALD Growth of STO on Ge Substrate
<ol>
	<li>Adjust the ALD reactor temperature to 225 &#186;C.</li>
	<li>Heat Sr(iPr3Cp)2 to 130 &#176;C and TTIP to 40 &#176;C. Maintain water at RT (between 20 and 25 &#176;C). Regulate the water vapor flow into the ALD system via the needle valve attached to the saturator such that the dosing pressure of water is around 1 Torr. Maintain constant precursor temperatures throughout the deposition process.</li>
	<li>Transfer the sample in vacuo to the ALD reactor that has been preheated to 225 &#176;C and wait for 15 min for the sample to reach thermal equilibrium.</li>
	<li>Switch the exhaust port of the ALD reactor from the turbomolecular pump to the mechanical pump.</li>
	<li>Turn on the flow controller to allow the flow of inert gas (this group uses argon). Maintain an operating pressure of 1 Torr during the entire growth process.</li>
	<li>Set the unit cycle ratio of Sr to Ti to be 2:1. Set the unit cycles of Sr and Ti to a 2-sec dose of the Sr or Ti precursor, followed by a 15-sec argon purge, and then a 1-sec dose of water, followed by another 15-sec argon purge.</li>
	<li>Adjust the number of unit cycles to achieve the desirable thickness. Ensure that the ALD cycling sequence contains as little repetition of individual Sr or Ti unit cycles as possible. For example, a 2:3 Sr-to-Ti cycling sequence will achieve better results when executed as 1-Sr, 1-Ti, followed by 1-Sr, 2-Ti, rather than 2-Sr followed by 3-Ti. 
	Note: This group used 36 unit cycles to deposit a 2-nm thick STO film on Ge.</li>
	<li>Optional: Use XPS to verify the film composition (described in Section 8).</li>
</ol>
6. Annealing of STO Film
<ol>
	<li>Transfer the deposited sample in vacuo into the annealing chamber.</li>
	<li>Heat the sample to 650 &#176;C at a rate of 20 &#176;C&#8226;min-1 under UHV conditions (10-9- 10-8 Torr). Hold the temperature at 650 &#186;C for 5 min, and then cool the sample to 200 &#176;C at the same rate. 
	Note: Use RHEED to evaluate the annealing result, as described in the Representative Results section.26,39</li>
</ol>
7. Further Growth of STO
<ol>
	<li>Repeat Section 5.1 - 5.5.</li>
	<li>Set the unit cycle ratio to between 1:1 and 4:3. Maintain the same dosing/purging component within each unit cycle. Set the sequence according to the principles mentioned in Step 5.6.</li>
	<li>Adjust the number of unit cycles to achieve the intended thickness.</li>
	<li>Anneal the deposited film according to Section 6 of the Protocol.</li>
</ol>
8. XPS Measurements
<ol>
	<li>Load the sample into the XPS analytical chamber and turn on the X-ray source. Ensure all appropriate gates/doors are closed to prevent accidental X-ray exposure.</li>
	<li>Create a new scan by selecting the elements (binding energy ranges) desired for analysis, or select a pre-existing scan program. 
	Note: Binding energy ranges can be manually changed, if needed. Set other settings, such as pass energy, excitation energy, step energy, and step time to optimize the signal-to-noise ratio, but remain constant across all elemental scans to maintain comparability between elemental spectra. Table 1 shows the scan settings used by this group.</li>
	<li>Check if any charging is occurring on the substrate by observing the binding energy of a known element&#39;s peak, such as O 1s at 531 eV. 
	Note: Charging is occurring if the peak has shifted from its known value.</li>
	<li>Insert a flood gun into the XPS chamber and turn on the flood gun if charging is occurring. Adjust the flood gun energy output and distance from the sample so that the chosen peak is shifted back to its correct binding energy.</li>
	<li>Manipulate the stage position to maximize the area observed under a known element&#39;s peak (typically the O 1s peak at 531 eV).</li>
	<li>Run the XPS scan and collect the data.</li>
	<li>Turn off the X-ray source and remove the sample from the XPS.</li>
</ol>

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Solid-State Lett. 2 (10), 504-506 (1999).</li><li>Vehkam&#228;ki, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Atomic+Layer+Deposition+of+SrTiO3+Thin+Films+from+a+Novel+Strontium+Precursor-Strontium-bis(tri-isopropyl+cyclopentadienyl).">Atomic Layer Deposition of SrTiO3 Thin Films from a Novel Strontium Precursor-Strontium-bis(tri-isopropyl cyclopentadienyl).</a> Chem. Vap. Depos. 7 (2), 75-80 (2001).</li><li>Ritala, M., Leskel&#228;, M., Niinisto, L., Haussalo, P. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Titanium+isopropoxide+as+a+precursor+in+atomic+layer+epitaxy+of+titanium+dioxide+thin+films.">Titanium isopropoxide as a precursor in atomic layer epitaxy of titanium dioxide thin films.</a> Chem. Mater. 5 (8), 1174-1181 (1993).</li><li>Aarik, J., Aidla, A., Uustare, T., Ritala, M., Leskel&#228;, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Titanium+isopropoxide+as+a+precursor+for+atomic+layer+deposition:+characterization+of+titanium+dioxide+growth+process.">Titanium isopropoxide as a precursor for atomic layer deposition: characterization of titanium dioxide growth process.</a> Appl. Surf. Sci. 161 (3-4), 385-395 (2000).</li><li>Premkumar, P. A., Delabie, A., Rodriguez, L. N. J., Moussa, A., Adelmann, C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Roughness+evolution+during+the+atomic+layer+deposition+of+metal+oxides.">Roughness evolution during the atomic layer deposition of metal oxides.</a> J. Vac. Sci. Technol. A. 31 (6), 061501 (2013).</li></ol>

The authors have no competing financial interests to disclose.

The cleanliness of the Ge substrate is the key to success when growing the epitaxial perovskite using ALD. The amount of time a Ge substrate spends between degreasing and deoxidization, and the amount of time between deoxidization and STO deposition, should be kept at a minimum. Samples are still subject to contaminant exposure even under the UHV environment. Prolonged exposure may lead to redeposition of adventitious carbon or Ge reoxidation, resulting in poor film growth. This group has employed a widely-used degreasin...

Perovskite materials are becoming increasingly attractive due to their highly symmetric cubic or pseudocubic structure and myriad of properties. These materials, with general formula ABO3, consist of A atoms coordinated with 12 oxygen atoms and B atoms coordinated with six oxygen atoms. Owing to their simple structure, yet wide range of potential elements, perovskite materials provide ideal candidates for heterostructure devices. Epitaxial oxide heterostructures boast ferromagnetic,1-3 anti/ferroelectric,4 multiferroic,5-8 superconductive,7-12 and magnetoresistive functionalities.13,14 Many of these desirable electronic properties are interfacial and thus dependent on clean, abrupt transitions between materials. The nearly identical structure and lattice constants shared between members of the perovskite family allow for excellent lattice matching and, therefore, high quality interfaces. Readily lattice-matched to each other as well as some semiconductors, perovskite oxides are now being turned to in next generation metal-oxide-semiconductor electronics.
Monolithic integration of crystalline oxides with silicon, first demonstrated with perovskite strontium titanate, SrTiO3 (STO), by McKee and colleagues,15 was a monumental step towards the realization of electronic devices with perovskite-semiconductor incorporation. Molecular beam epitaxy (MBE) is the primary technique for epitaxial growth of oxides on silicon because of the layer-by-layer growth as well as the tunable oxygen partial pressure necessary to control amorphous, interfacial SiO2 formation.16-19 Typical MBE growth of STO on Si (001) is achieved by Sr-assisted deoxidation of SiO2. Under the ultra-high vacuum (UHV) conditions, SrO is volatile and subject to thermal evaporation. Since SrO is thermodynamically preferred over strontium metal and SiO2, deposition of Sr scavenges oxygen from the SiO2 layer and the resulting SrO evaporates from the surface. During this process the silicon surface experiences a 2&#215;1 reconstruction at the surface that forms rows of dimerized silicon atoms. Conveniently, &#189; monolayer (ML) coverage of Sr atoms on the reconstructed surface fills in the gaps created by these dimer rows.20 The &#189; ML coverage provides a protective layer that, with careful control of oxygen pressure, can prevent or control interfacial SiO2 formation during subsequent oxide growth.21-23 In the case of STO (and perovskites with similar lattice match), the resulting lattice is rotated 45&#176; in-plane such that (001)STO&#8214;(001)Si and (100)STO&#8214;(110)Si, allowing registry between the Si (3.84 &#197; Si-Si distance) and STO (a = 3.905 &#197;) with only slight compressive strain on the STO. This registry is necessary for high quality interfaces and the desired properties they possess.
Silicon became industrially significant due to the high quality of its interfacial oxide, but SiO2 use is being phased out for materials capable of equivalent performance at smaller feature sizes. SiO2 experiences high leakage currents when ultra-thin and this diminishes device performance. The demand for smaller feature sizes could be met by perovskite oxide films with high dielectric constants, k, that provide performance equivalent to SiO2 and are physically thicker than SiO2 by the factor k/3.9. Furthermore, alternative semiconductors, like germanium, offer potential for faster device operation due to higher electron and hole mobilities than silicon.24,25 Germanium also has an interfacial oxide, GeO2, but in contrast to SiO2, it is unstable and subject to thermal deoxidation. Thus, 2&#215;1 reconstruction is achievable by simple thermal annealing under UHV, and a protective Sr layer is unnecessary to prevent interfacial oxide growth during perovskite deposition.26
Despite the apparent ease of growth offered by MBE, atomic layer deposition (ALD) provides a more scalable and cost effective method than MBE for the commercial production of oxide materials.27,28 ALD employs doses of gaseous precursors to the substrate that are self-limiting in their reaction with the substrate surface. Therefore, in an ideal ALD process, up to one atomic layer is deposited for any given precursor dosing cycle and continued dosing of the same precursor will not deposit additional material onto the surface. Reactive functionality is restored with a co-reactant, often an oxidative or reductive precursor (e.g., water or ammonia). Previous work has demonstrated the ALD growth of various perovskite films, such as anatase TiO2, SrTiO3, BaTiO3, and LaAlO3, on Si (001) that had been buffered with four-unit-cell thick STO grown via MBE. 29-34 In purely MBE growth of crystalline oxides, &#189; monolayer coverage of Sr on clean Si (001) is enough to provide a barrier against SiO2 formation under the pressures native to the technique (~10-7 Torr). However, under typical ALD operating pressures of ~1 Torr, previous work has shown that four unit cells of STO is required to avoid oxidizing the Si surface.29
The procedure detailed here utilizes the instability of GeO2 and achieves monolithic integration of STO on germanium via ALD without the need of an MBE-grown buffer layer.26 Furthermore, the Ge-Ge interatomic distance (3.992 &#197;) on its (100) surface allows for an analogous epitaxial registry with STO that is observed with Si (001). Though the procedure presented here is specific to STO on Ge, slight modifications may allow for the monolithic integration of a variety of perovskite films on germanium. Indeed, direct ALD growth of crystalline SrHfO3 and BaTiO3 films have been reported on Ge.35,36 Additional possibilities include the potential gate oxide, SrZrxTi1-xO3.37 Finally, building on previous studies of ALD perovskite growth on a four-unit cell STO film on Si (001)29-34 suggests that any film that could be grown on the STO/Si platform could be grown on an ALD-grown STO buffer film on Ge, such as LaAlO3 and LaCoO3.32,38 The multitude of properties available to oxide heterostructures and remarkable similarity between perovskite oxides suggest this procedure could be utilized to study previously difficult or impossible growth combinations with such an industrially viable technique.
Figure 1 depicts the schematic of the vacuum system, which encompasses ALD, MBE, and analytical chambers connected by a 12-foot transfer line. The samples can be transferred in vacuo between each chamber. The baseline pressure of the transfer line is kept at approximately 1.0&#215;10-9 Torr by three ion pumps. The commercial angle-resolved ultraviolet and X-ray photoelectron spectroscopy (XPS) system is maintained with an ion pump such that the pressure in the analytical chamber is kept at approximately 1.0&#215;10-9 Torr.
The ALD reactor is a rectangular custom-built stainless steel chamber with a volume of 460 cm3 and length of 20 cm. A schematic of the ALD reactor is shown in Figure 2. The reactor is a hot wall, continuous cross-flow type reactor. Samples placed in the reactor have a clearance of 1.7 cm between the top surface of the substrate and the chamber ceiling and 1.9 cm between the bottom of the substrate and the chamber floor. A heating tape, powered by a dedicated power supply, is wrapped around the chamber from the inlet to approximately 2 cm beyond the exhaust port and provides temperature control of the reactor walls. A temperature controller adjusts the power input to the heating tape according to a temperature measurement taken by a thermal couple located between the heating tape and exterior reactor wall. The reactor is then completely wrapped with three additional heating tapes of constant power provided by a variac, and a final layer of fiberglass wool with aluminum foil covering provides insulation to promote uniform heating. The power output of the variac is adjusted such that the idling temperature (when the dedicated power supply is turned off) of the reactor is approximately 175 &#176;C. The reactor is passively cooled via ambient air. The substrate temperature is calculated using the linear-fit equation (1), where Ts (&#176;C) is the temperature of substrate and Tc (&#176;C) is the temperature of the reactor wall, obtained by directly measuring a substrate fitted with a thermocouple. A temperature profile exists along the flow direction of the chamber due to the cold gate valve that connects the reactor to the transfer line; the temperature profile perpendicular to the flow direction is negligible. The temperature profile causes a richer Sr deposition at the leading edge of the sample, but the composition variation along sample is small (less than a 5% difference between the leading and trailing edges of the sample) according to XPS.31 The exhaust of the reactor is connected to a turbomolecular pump and a mechanical pump. During the ALD process, the reactor is pumped by the mechanical pump to maintain the pressure at around 1 Torr. Otherwise, the reactor pressure is maintained below 2.0&#215;10-6 Torr by the turbomolecular pump.
(1) Ts=0.977Tc + 3.4
The MBE chamber is maintained at a baseline pressure of approximately 2.0&#215;10-9 Torr or below by a cryogenic pump. The partial pressure of various species in the MBE chamber is monitored by a residual gas analyzer. The background pressure of H2 is around 1.0&#215;10-9 Torr, while those of O2, CO, N2, CO2, and H2O, are less than 1.0&#215;10-10 Torr. In addition, the MBE chamber is also equipped with six effusion cells, a four-pocket electron beam evaporator, an atomic nitrogen plasma source and an atomic oxygen plasma source with high-precision piezoelectric leak valve, and a reflection high energy electron diffraction (RHEED) system for real-time in situ growth and crystallization observations. The sample manipulator allows the substrate be heated up to 1000 &#176;C using an oxygen-resistant silicon carbide heater.

<table><tbody><tr><td>MBE</td><td>DCA</td><td>M600</td><td></td></tr><tr><td>Cryopump for MBE</td><td>Brooks Automation, Inc.</td><td>On-Board 8</td><td></td></tr><tr><td>Residual Gas Analyzer for MBE</td><td>Extorr, Inc.</td><td>XT200M</td><td></td></tr><tr><td>ALD Reaction Chamber</td><td>Huntington Mechanical Laboratories</td><td></td><td>Custom manufactured, hot-wall, stainless steel, rectangular (~20&amp;nbsp;cm long, 460 cm&lt;sup&gt;3&lt;/sup&gt;)</td></tr><tr><td>ALD Saturator</td><td>Swagelok/Larson Electronic Glass</td><td>See comments</td><td>Custom-built from parts supplied by Swagelok and Larson Electronic Glass. The saturator is made out of 316 stainless steel and Pyrex. All parts are connected via butt welding. Swagelok catalog numbers: SS-4-VCR-7-8VCRF, SS-4-VCR-1, SS-8-VCR-1-03816, SS-8-VCR-3-8MTW, 316L-12TB7-6-8, SS-8-VCR-9, SS-4-VCR-3-4MTW, SS-T2-S-028-20. Larson Electronic Glass catalog number: SP-075-T.</td></tr><tr><td>Manual Valves for Saturators</td><td>Swagelok</td><td>SS-DLVCR4-P and 6LVV-DPFR4-P</td><td>Both diaphragm-sealed valves are used interchangably by this group. The specific connectors (VCR male/female/&lt;em&gt;etc.&lt;/em&gt;) to use will depend on the actual system design.</td></tr><tr><td>ALD Valves</td><td>Swagelok</td><td>6LVV-ALD3TC333P-CV</td><td></td></tr><tr><td>ALD System Tubing</td><td>Swagelok</td><td></td><td>316L tubing of various sizes. This group uses inner diameter of 1/4&quot;</td></tr><tr><td>ALD power supply</td><td>AMETEK Programmable Power, Inc.</td><td>Sorensen DCS80-13E</td><td></td></tr><tr><td>ALD Temperature Controller</td><td>Schneider Electric</td><td>Eurotherm 818P4</td><td></td></tr><tr><td>ALD Valve Controller&amp;nbsp;</td><td>National Instruments</td><td>LabView</td><td>Program developed within the group</td></tr><tr><td>XPS</td><td>VG Scienta</td><td></td><td></td></tr><tr><td>RHEED</td><td>Staib Instruments</td><td>CB801420</td><td>18 keV at ~3&amp;deg; incident angle</td></tr><tr><td>RHEED Analysis System</td><td>k-Space Associates</td><td>kSA 400</td><td></td></tr><tr><td>Digital UV Ozone System</td><td>Novascan</td><td>PSD-UV 6</td><td></td></tr><tr><td>Ozone Elimination System</td><td>Novascan</td><td>PSD-UV OES-1000D</td><td></td></tr><tr><td>Titanium tetraisopropoxide (TTIP)</td><td>Sigma-Aldrich</td><td>87560</td><td>Flammable in liquid and vapor phase&lt;br /&gt;&amp;nbsp;&lt;br /&gt;&amp;nbsp;</td></tr><tr><td colspan="4">[header]</td></tr><tr><td>Strontium bis(triisopropylcyclopentadienyl)</td><td>Air Liquide</td><td>HyperSr</td><td>Mildly reactive to air and water. Further information supplied by Air Liquide can be found at https://www.airliquide.de/inc/dokument.php/standard/1148/airliquide-hypersr-datasheet.pdf</td></tr><tr><td>Ge (001) wafer</td><td>MTI Corporation</td><td>GESBA100D05C1</td><td>4&quot;, single-side polished Sb-doped wafer with &amp;rho; &amp;asymp; 0.04 &amp;Omega;-cm</td></tr><tr><td>Argon (UHP)</td><td>Praxair</td><td></td><td></td></tr><tr><td>Deionized Water</td><td></td><td></td><td>18.2 M&amp;Omega;-cm</td></tr></tbody></table>

epitaxial growth of perovskite strontium titanate on germanium via atomic layer deposition

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and conformality by taking advantage of self-limiting reactions between vapor-phase precursors and the growing film. Perovskite oxides present potential for next-generation electronic materials, but to-date have mostly been deposited by physical methods. This work outlines a method for depositing SrTiO3 (STO) on germanium using ALD. Germanium has higher carrier mobilities than silicon and therefore offers an alternative semiconductor material with faster device operation. This method takes advantage of the instability of germanium's native oxide by using thermal deoxidation to clean and reconstruct the Ge (001) surface to the 2&#215;1 structure. 2-nm thick, amorphous STO is then deposited by ALD. The STO film is annealed under ultra-high vacuum and crystallizes on the reconstructed Ge surface. Reflection high-energy electron diffraction (RHEED) is used during this annealing step to monitor the STO crystallization. The thin, crystalline layer of STO acts as a template for subsequent growth of STO that is crystalline as-grown, as confirmed by RHEED. In situ X-ray photoelectron spectroscopy is used to verify film stoichiometry before and after the annealing step, as well as after subsequent STO growth. This procedure provides framework for additional perovskite oxides to be deposited on semiconductors via chemical methods in addition to the integration of more sophisticated heterostructures already achievable by physical methods.

Figures 5 and 6 show typical X-ray photoelectron spectra and RHEED images from a cleaned and deoxidized Ge substrate. A successfully-deoxidized Ge substrate is characterized by its &#34;smiley face&#34; 2&#215;1 reconstructed RHEED pattern.26,39 In addition, Kikuchi lines are also observed in the RHEED images, which indicate the cleanliness and long range order of the sample.40 The sharpness and intensity of the diffraction pattern a...

Watch this Scientific Journal Video about Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition at JoVE.com

Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition

This work details the procedures for the growth and characterization of crystalline SrTiO3 directly on germanium substrates by atomic layer deposition. The procedure illustrates the ability of an all-chemical growth method to integrate oxides monolithically onto semiconductors for metal-oxide semiconductor devices.

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and ...

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Chemistry

12.3K Views.  The University of Texas at Austin.  Dit werk beschrijft de procedures voor de groei en de karakterisering van kristallijn SrTiO 3 rechtstreeks op germaniumsubstraten door atomic layer deposition. De procedure illustreert het vermogen van een all-chemische groeimethode oxiden monolithisch geïntegreerd op halfgeleiders voor metaal-oxide halfgeleiderinrichtingen. 

Video: Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition

Fabrication of Spatially Confined Complex Oxides

Complex materials such as high Tc superconductors, multiferroics, and colossal magnetoresistors have electronic and magnetic properties that arise from the inherent strong electron correlations that reside within them. These materials can also possess electronic phase separation in which regions of vastly different resistive and magnetic behavior can coexist within a single crystal alloy material. By reducing the scale of these materials to length scales at and below the inherent size of the electronic domains, novel behaviors can be exposed. Because of this and the fact that spin-charge-lattice-orbital order parameters each involve correlation lengths, spatially reducing these materials for transport measurements is a critical step in understanding the fundamental physics that drives complex behaviors. These materials also offer great potential to become the next generation of electronic devices 1-3. Thus, the fabrication of low dimensional nano- or micro-structures is extremely important to achieve new functionality. This involves multiple controllable processes from high quality thin film growth to accurate electronic property characterization. Here, we present fabrication protocols of high quality microstructures for complex oxide manganite devices. Detailed descriptions and required equipment of thin film growth, photo-lithography, and wire-bonding are presented.

We describe the use of pulsed laser deposition (PLD), photolithography and wire-bonding techniques to create micrometer scale complex oxides devices. The PLD is utilized to grow epitaxial thin films. Photolithography and wire-bonding techniques are introduced to create practical devices for measurement purposes.

Complex materials such as high Tc superconductors, multiferroics, and colossal magnetoresistors have electronic and magnetic properties that arise from ...

Engineering

Atomically Defined Templates for Epitaxial Growth of Complex Oxide Thin Films

Atomically defined substrate surfaces are prerequisite for the epitaxial growth of complex oxide thin films. In this protocol, two approaches to obtain such surfaces are described. The first approach is the preparation of single terminated perovskite SrTiO3 (001) and DyScO3 (110) substrates. Wet etching was used to selectively remove one of the two possible surface terminations, while an annealing step was used to increase the smoothness of the surface. The resulting single terminated surfaces allow for the heteroepitaxial growth of perovskite oxide thin films with high crystalline quality and well-defined interfaces between substrate and film. In the second approach, seed layers for epitaxial film growth on arbitrary substrates were created by Langmuir-Blodgett (LB) deposition of nanosheets. As model system Ca2Nb3O10- nanosheets were used, prepared by delamination of their layered parent compound HCa2Nb3O10. A key advantage of creating seed layers with nanosheets is that relatively expensive and size-limited single crystalline substrates can be replaced by virtually any substrate material.

Various procedures are outlined to prepare atomically defined templates for epitaxial growth of complex oxide thin films. Chemical treatments of single crystalline SrTiO3 (001) and DyScO3 (110) substrates were performed to obtain atomically smooth, single terminated surfaces. Ca2 Nb3 O10- nanosheets were used to create atomically defined templates on arbitrary substrates.

Atomically defined substrate surfaces are prerequisite for the epitaxial growth of complex oxide thin films. In this protocol, two approaches to obtain ...

Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells

Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical properties. The possibility of doping was investigated by adding monovalent cation halides with similar ionic radii to Pb2+, including Cu+, Na+, and Ag+. A shift in the Fermi level and a remarkable decrease of sub-bandgap optical absorption, along with a lower energetic disorder in the perovskite, was achieved. An order-of-magnitude enhancement in the bulk hole mobility and a significant reduction of transport activation energy within an additive-based perovskite device was attained. The confluence of the aforementioned improved properties in the presence of these cations led to an enhancement in the photovoltaic parameters of the perovskite solar cell. An increase of 70 mV in open circuit voltage for AgI and a 2 mA/cm2 improvement in photocurrent density for NaI- and CuBr-based solar cells were achieved compared to the pristine device. Our work paves the way for further improvements in the optoelectronic quality of CH3NH3PbI3 perovskite and subsequent devices. It highlights a new avenue for investigations on the role of dopant impurities in crystallization and controls the electronic defect density in perovskite structures.

Monovalent Cation Doping of CH3NH3PbI3 for Efficient Perovskite Solar Cells

Here, we present a protocol to adjust the properties of solution-processed CH3NH3PbI3 through the incorporation of monovalent cation additives in order to achieve highly efficient perovskite solar cells.

Here, we demonstrate the incorporation of monovalent cation additives into CH3NH3PbI3 perovskite in order to adjust the optical, excitonic, and electrical ...

Growth and Electrostatic/chemical Properties of Metal/LaAlO3/SrTiO3 Heterostructures

The quasi 2D electron system (q2DES) that forms at the interface between LaAlO3 (LAO) and SrTiO3 (STO) has attracted much attention from the oxide electronics community. One of its hallmark features is the existence of a critical LAO thickness of 4 unit-cells (uc) for interfacial conductivity to emerge. Although electrostatic mechanisms have been proposed in the past to describe the existence of this critical thickness, the importance of chemical defects has been recently accentuated. Here, we describe the growth of metal/LAO/STO heterostructures in an ultra-high vacuum (UHV) cluster system combining pulsed laser deposition (to grow the LAO), magnetron sputtering (to grow the metal) and X-ray photoelectron spectroscopy (XPS). We study step by step the formation and evolution of the q2DES and the chemical interactions that occur between the metal and the LAO/STO. Additionally, magnetotransport experiments elucidate on the transport and electronic properties of the q2DES. This systematic work not only demonstrates a way to study the electrostatic and chemical interplay between the q2DES and its environment, but also unlocks the possibility to couple multifunctional capping layers with the rich physics observed in two-dimensional electron systems, allowing the fabrication of new types of devices.

Growth and Electrostatic/chemical Properties of Metal/LaAlO3/SrTiO3 Heterostructures

We fabricate metal/LaAlO3/SrTiO3 heterostructures using a combination of pulsed laser deposition and in situ magnetron sputtering. Through magnetotransport and in situ X-ray photoelectron spectroscopy experiments, we investigate the interplay between electrostatic and chemical phenomena of the quasi two-dimensional electron gas formed in this system.

The quasi 2D electron system (q2DES) that forms at the interface between LaAlO3 (LAO) and SrTiO3 (STO) has attracted much attention from the oxide ...

Chemical Synthesis of Porous Barium Titanate Thin Film and Thermal Stabilization of Ferroelectric Phase by Porosity-Induced Strain

Barium titanate (BaTiO3, hereafter BT) is an established ferroelectric material first discovered in the 1940s and still widely used because of its well-balanced ferroelectricity, piezoelectricity, and dielectric constant. In addition, BT does not contain any toxic elements. Therefore, it is considered to be an eco-friendly material, which has attracted considerable interest as a replacement for lead zirconate titanate (PZT). However, bulk BT loses its ferroelectricity at approximately 130 &#176;C, thus, it cannot be used at high temperatures. Because of the growing demand for high-temperature ferroelectric materials, it is important to enhance the thermal stability of ferroelectricity in BT. In previous studies, strain originating from the lattice mismatch at hetero-interfaces has been used. However, the sample preparation in this approach requires complicated and expensive physical processes, which are undesirable for practical applications.
In this study, we propose a chemical synthesis of a porous material as an alternative means of introducing strain. We synthesized a porous BT thin film using a surfactant-assisted sol-gel method, in which self-assembled amphipathic surfactant micelles were used as an organic template. Through a series of studies, we clarified that the introduction of pores had a similar effect on distorting the BT crystal lattice, to that of a hetero-interface, leading to the enhancement and stabilization of ferroelectricity. Owing to its simplicity and cost effectiveness, this fabrication process has considerable advantages over conventional methods.

Here, we present a protocol for the synthesis of porous barium titanate (BaTiO3) thin film by a surfactant-assisted sol-gel method, in which self-assembled amphipathic surfactant micelles are used as an organic template.

Barium titanate (BaTiO3, hereafter BT) is an established ferroelectric material first discovered in the 1940s and still widely used because of its ...

A Fabrication and Measurement Method for a Flexible Ferroelectric Element Based on Van Der Waals Heteroepitaxy

Flexible non-volatile memories have received much attention as they are applicable for portable smart electronic device in the future, relying on high-density data storage and low-power consumption capabilities. However, the high-quality oxide based nonvolatile memory on flexible substrates is often constrained by the material characteristics and the inevitable high-temperature fabrication process. In this paper, a protocol is proposed to directly grow an epitaxial yet flexible lead zirconium titanate memory element on muscovite mica. The versatile deposition technique and measurement method enable the fabrication of flexible yet single-crystalline non-volatile memory elements necessary for the next generation of smart devices.

In this paper, we present a protocol to directly grow an epitaxial yet flexible lead zirconium titanate memory element on muscovite mica.

Flexible non-volatile memories have received much attention as they are applicable for portable smart electronic device in the future, relying on ...

Fabrication of Schottky Diodes on Zn-polar BeMgZnO/ZnO Heterostructure Grown by Plasma-assisted Molecular Beam Epitaxy

Heterostructure field effect transistors (HFETs) utilizing a two dimensional electron gas (2DEG) channel have a great potential for high speed device applications. Zinc oxide (ZnO), a semiconductor with a wide bandgap (3.4 eV) and high electron saturation velocity has gained a great deal of attention as an attractive material for high speed devices. Efficient gate modulation, however, requires high-quality Schottky contacts on the barrier layer. In this article, we present our Schottky diode fabrication procedure on Zn-polar BeMgZnO/ZnO heterostructure with high density 2DEG which is achieved through strain modulation and incorporation of a few percent Be into the MgZnO-based barrier during growth by molecular beam epitaxy (MBE). To achieve high crystalline quality, nearly lattice-matched high-resistivity GaN templates grown by metal-organic chemical vapor deposition (MOCVD) are used as the substrate for the subsequent MBE growth of the oxide layers. To obtain the requisite Zn-polarity, careful surface treatment of GaN templates and control over the VI/II ratio during the growth of low temperature ZnO nucleation layer are utilized. Ti/Au electrodes serve as Ohmic contacts, and Ag electrodes deposited on the O2 plasma pretreated BeMgZnO surface are used for Schottky contacts.

Attainment of high-quality Schottky contacts is imperative for achieving efficient gate modulation in heterostructure field effect transistors (HFETs). We present the fabrication methodology and characteristics of Schottky diodes on Zn-polar BeMgZnO/ZnO heterostructures with high-density two dimensional electron gas (2DEG), grown by plasma-assisted molecular beam epitaxy on GaN templates.

Heterostructure field effect transistors (HFETs) utilizing a two dimensional electron gas (2DEG) channel have a great potential for high speed device ...

Theoretical Calculation and Experimental Verification for Dislocation Reduction in Germanium Epitaxial Layers with Semicylindrical Voids on Silicon

Reduction of threading dislocation density (TDD) in epitaxial germanium (Ge) on silicon (Si) has been one of the most important challenges for the realization of monolithically integrated photonics circuits. The present paper describes methods of theoretical calculation and experimental verification of a novel model for the reduction of TDD. The method of theoretical calculation describes the bending of threading dislocations (TDs) based on the interaction of TDs and non-planar growth surfaces of selective epitaxial growth (SEG) in terms of dislocation image force. The calculation reveals that the presence of voids on SiO2 masks help to reduce TDD. Experimental verification is described by germanium (Ge) SEG, using an ultra-high vacuum chemical vapor deposition method and TD observations of the grown Ge via etching and cross-sectional transmission electron microscope (TEM). It is strongly suggested that the TDD reduction would be due to the presence of semicylindrical voids over the SiO2 SEG masks and growth temperature. For experimental verification, epitaxial Ge layers with semicylindrical voids are formed as the result of SEG of Ge layers and their coalescence. The experimentally obtained TDDs reproduce the calculated TDDs based on the theoretical model. Cross-sectional TEM observations reveal that both the termination and generation of TDs occur at semicylindrical voids. Plan-view TEM observations reveal a unique behavior of TDs in Ge with semicylindrical voids (i.e., TDs are bent to be parallel to the SEG masks and the Si substrate).

Theoretical calculation and experimental verification are proposed for a reduction of threading dislocation (TD) density in germanium epitaxial layers with semicylindrical voids on silicon. Calculations based on the interaction of TDs and surface via image force, TD measurements, and transmission electron microscope observations of TDs are presented.

Reduction of threading dislocation density (TDD) in epitaxial germanium (Ge) on silicon (Si) has been one of the most important challenges for the ...

Epitaxial Nanostructured &alpha;-Quartz Films on Silicon: From the Material to New Devices

In this work, we show a detailed engineering route of the first piezoelectric nanostructured epitaxial quartz-based microcantilever. We will explain all the steps in the process starting from the material to the device fabrication. The epitaxial growth of &#945;-quartz film on SOI (100) substrate starts with the preparation of a strontium doped silica sol-gel and continues with the deposition of this gel into the SOI substrate in a thin film form using the dip-coating technique under atmospheric conditions at room temperature. Before crystallization of the gel film, nanostructuration is performed onto the film surface by nanoimprint lithography (NIL). Epitaxial film growth is reached at 1000 &#176;C, inducing a perfect crystallization of the patterned gel film. Fabrication of quartz crystal cantilever devices is a four-step process based on microfabrication techniques. The process starts with shaping the quartz surface, and then metal deposition for electrodes follows it. After removing the silicone, the cantilever is released from SOI substrate eliminating SiO2 between silicon and quartz. The device performance is analyzed by non-contact laser vibrometer (LDV) and atomic force microscopy (AFM). Among the different cantilever&#8217;s dimensions included in the fabricated chip, the nanostructured cantilever analyzed in this work exhibited a dimension of 40 &#181;m large and 100 &#181;m long and was fabricated with a 600 nm thick patterned quartz layer (nanopillar diameter and separation distance of 400 nm and 1 &#181;m, respectively) epitaxially grown on a 2 &#181;m thick Si device layer. The&#160;measured&#160;resonance frequency was&#160;267 kHz and the estimated quality factor, Q, of the whole mechanical structure was Q ~ 398 under low vacuum conditions. We observed the voltage-dependent linear displacement of cantilever with both techniques (i.e., AFM contact measurement and LDV). Therefore, proving that these devices can be activated through the indirect piezoelectric effect.

Epitaxial Nanostructured &#945;-Quartz Films on Silicon: From the Material to New Devices

This work presents a detailed protocol for the microfabrication of nanostructured &#945;-quartz cantilever on a Silicon-On-Insulator(SOI) technology substrate starting from the epitaxial growth of quartz film with the dip coating method and then nanostructuration of the thin film via nanoimprint lithography.

In this work, we show a detailed engineering route of the first piezoelectric nanostructured epitaxial quartz-based microcantilever. We will explain all ...

Tuning Oxide Properties by Oxygen Vacancy Control During Growth and Annealing

Electrical, optical, and magnetic properties of oxide materials can often be controlled by varying the oxygen content. Here we outline two approaches for varying the oxygen content and provide concrete examples for tuning the electrical properties of SrTiO3-based heterostructures. In the first approach, the oxygen content is controlled by varying the deposition parameters during a pulsed laser deposition. In the second approach, the oxygen content is tuned by subjecting the samples to annealing in oxygen at elevated temperatures after the film growth. The approaches can be used for a wide range of oxides and nonoxide materials where the properties are sensitive to a change in the oxidation state.
The approaches differ significantly from electrostatic gating, which is often used to change the electronic properties of confined electronic systems such as those observed in SrTiO3-based heterostructures. By controlling the oxygen vacancy concentration, we are able to control the carrier density over many orders of magnitude, even in nonconfined electronic systems. Moreover, properties can be controlled, which are not sensitive to the density of itinerant electrons.

Oxide materials show many exotic properties that can be controlled by tuning the oxygen content. Here, we demonstrate the tuning of oxygen content in oxides by varying the pulsed laser deposition parameters and by performing postannealing. As an example, electronic properties of SrTiO3-based heterostructures are tuned by growth modifications and annealing.

Electrical, optical, and magnetic properties of oxide materials can often be controlled by varying the oxygen content. Here we outline two approaches for ...

Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition

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