Name: plasma-assisted molecular beam epitaxy growth of mg3n2 and zn3n2 thin films
Uploaded: 2019-05-11T13:00:00
Description: Watch this Scientific Journal Video about Plasma-Assisted Molecular Beam Epitaxy Growth of Mg3N2 and Zn3N2 Thin Films at JoVE.com

This work was supported by the Natural Sciences and Engineering Research Council of Canada.

1. MgO substrate preparation
NOTE: Commercial one-side epi-polished (100) oriented single crystal MgO square substrates (1 cm x 1 cm) were employed for the X3N2 (X = Zn and Mg) thin film growth.
<ol>
	<li>High temperature annealing
	<ol>
		<li>Place the MgO on a clean sapphire wafer sample carrier with the polished side facing upwards in a furnace and anneal for 9 h at 1,000 &#176;C. Raise the temperature to 1000 &#176;C over a 10 min period. 
		NOTE: H...

<ol>
	<li>Suda, T., Kakishita, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Band-gap+energy+and+electron+effective+mass+of+polycrystalline+Zn3N2.">Band-gap energy and electron effective mass of polycrystalline Zn3N2.</a> Journal of Applied Physics. 99 (7), 076101.1-076101.3 (2006).</li><li>Hu, J., Bando, Y., Zhan, J., Zhi, C., Golberg, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Carbon+nanotubes+as+nanoreactors+for+fabrication+of+single-crystalline+Mg3N2+nanowires.">Carbon nanotubes as nanoreactors for fabrication of single-crystalline Mg3N2 nanowires.</a> Nano Letters. 6 (6), 1136-1140 (2006).</li><li>Fang, C. M., Groot, R. A., Bruls, R. J., Hintzen, H. T., With, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ab+initio+band+structure+calculations+of+Mg3N2+and+MgSiN2.">Ab initio band structure calculations of Mg3N2 and MgSiN2.</a> Journal of Physics: Condensed Matter. 11 (25), 4833-4842 (1999).</li><li>Yoo, S. H., Walsh, A., Scanlonc, D. O., Soon, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electronic+structure+and+band+alignment+of+zinc+nitride,+Zn3N2.">Electronic structure and band alignment of zinc nitride, Zn3N2.</a> RSC Advances. 4 (7), 3306-3311 (2014).</li><li>Partin, D. E., Williams, D. J., O'Keeffe, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+crystal+structures+of+Mg3N2+and+Zn3N2.">The crystal structures of Mg3N2 and Zn3N2.</a> Journal of Solid-State Chemistry. 132 (1), 56-59 (1997).</li><li>Ullah, M., Murtaza, G., Ramay, S. M., Mahmood, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Structural,+electronic,+optical+and+thermoelectric+properties+of+Mg3X2+(X+=+N,+P,+As,+Sb,+Bi)+compounds.">Structural, electronic, optical and thermoelectric properties of Mg3X2 (X = N, P, As, Sb, Bi) compounds.</a> Materials Research Bulletin. 91, 22-30 (2017).</li><li>Li, C. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electrocatalytic+zinc+composites+as+the+efficient+counter+electrodes+of+dye-sensitized+solar+cells:+study+on+the+electrochemical+performance+and+density+functional+theory+Calculations.">Electrocatalytic zinc composites as the efficient counter electrodes of dye-sensitized solar cells: study on the electrochemical performance and density functional theory Calculations.</a> ACS Applied Materials &amp; Interfaces. 7 (51), 28254-28263 (2015).</li><li>Sinha, S., Choudhury, D., Rajaraman, G., Sarkar, S. <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+Zn3N2+thin+films:+growth+mechanism+and+application+in+thin+film+transistor.">Atomic layer deposition of Zn3N2 thin films: growth mechanism and application in thin film transistor.</a> RSC Advances. 5 (29), 22712-22717 (2015).</li><li>Bhattacharyya, S. R., Ayouchi, R., Pinnisch, M., Schwarz, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Transfer+characteristic+of+zinc+nitride+based+thin+film+transistors.">Transfer characteristic of zinc nitride based thin film transistors.</a> Physica Status Solidi C. 9 (3-4), 469-472 (2012).</li><li>Wu, P., Tiedje, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Molecular+beam+epitaxy+growth+and+optical+properties+of+Mg3N2+films.">Molecular beam epitaxy growth and optical properties of Mg3N2 films.</a> Applied Physics Letters. 113 (8), 082101.1-082101.4 (2018).</li><li>Wu, P., 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=Molecular+beam+epitaxy+growth+and+optical+properties+of+single+crystal+Zn3N2+films.">Molecular beam epitaxy growth and optical properties of single crystal Zn3N2 films.</a> Semiconductor Science and Technology. 31 (10), 10LT01.1-10LT01.4 (2016).</li><li>Jiang, N., Georgiev, D. G., Jayatissa, A. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+effects+of+the+pressure+and+the+oxygen+content+of+the+sputtering+gas+on+the+structure+and+the+properties+of+zinc+oxy-nitride+thin+films+deposited+by+reactive+sputtering+of+zinc.">The effects of the pressure and the oxygen content of the sputtering gas on the structure and the properties of zinc oxy-nitride thin films deposited by reactive sputtering of zinc.</a> Semiconductor Science and Technology. 28 (2), 025009 (2013).</li><li>Nakano, Y., Morikawa, T., Ohwaki, T., Taga, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Electrical+characterization+of+p-type+N-doped+ZnO+films+prepared+by+thermal+oxidation+of+sputtered+Zn3N2+films.">Electrical characterization of p-type N-doped ZnO films prepared by thermal oxidation of sputtered Zn3N2 films.</a> Applied Physics Letters. 88 (17), 172103.1-172103.3 (2006).</li><li>Cao, X., Yamaguchi, Y., Ninomiya, Y., Yamada, N. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Comparative+study+of+electron+transport+mechanisms+in+epitaxial+and+polycrystalline+zinc+nitride+films.">Comparative study of electron transport mechanisms in epitaxial and polycrystalline zinc nitride films.</a> Journal of Applied Physics. 119 (2), 025104.1-025104.10 (2016).</li><li>Jia, J., Kamijo, H., Nakamura, S., Shigesato, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=How+the+sputtering+process+influence+structural,+optical,+and+electrical+properties+of+Zn3N2+films.">How the sputtering process influence structural, optical, and electrical properties of Zn3N2 films.</a> MRS Communications. 8 (2), 314-321 (2018).</li><li>Trapalis, A., Hefferman, J., Farrer, I., Sherman, J., Kean, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Structural,+electrical+and+optical+characterization+of+as-grown+and+oxidized+zinc+nitride+films.">Structural, electrical and optical characterization of as-grown and oxidized zinc nitride films.</a> Journal of Applied Physics. 120 (20), 205102.1-205102.9 (2016).</li><li>N&#250;&#241;ez, C. G., 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=On+the+zinc+nitride+properties+and+the+unintentional+incorporation+of+oxygen.">On the zinc nitride properties and the unintentional incorporation of oxygen.</a> Thin Solid Films. 520 (6), 1924-1929 (2012).</li><li>Oshima, T., Fujita, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=(111)-oriented+Zn3N2+growth+on+a-plane+sapphire+substrates+by+molecular+beam+epitaxy.">(111)-oriented Zn3N2 growth on a-plane sapphire substrates by molecular beam epitaxy.</a> Japanese Journal of Applied Physics. 45 (111), 8653-8655 (2006).</li><li>Heavens, O. S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Optical properties of thin solid films. , 46-48 (1955).</li><li>Heyns, A. H., Prinsloo, L. C., Range, K. J., Stassen, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+vibrational+spectra+and+decomposition+of+&#945;-calcium+nitride+(&#945;-Ca3N2)+and+magnesium+nitride+(Mg3N2).">The vibrational spectra and decomposition of &#945;-calcium nitride (&#945;-Ca3N2) and magnesium nitride (Mg3N2).</a> Journal of Solid-State Chemistry. 137, 33-41 (1998).</li><li>Lewis, R. B., Bahrami-Yekta, V., Patel, M. J., Tiedje, T., Masnadi-Shirazi, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Closed-cycle+cooling+of+cryopanels+in+molecular+beam+epitaxy.">Closed-cycle cooling of cryopanels in molecular beam epitaxy.</a> Journal of Vacuum Science Technology B. 32 (2), 02C102.1-02C102.7 (2014).</li></ol>

A variety of considerations is involved in the choice of substrates and establishing the growth conditions that optimize the structural and electronic properties of the films. The MgO substrates are heated at high temperature in air (1000 &#176;C) to remove carbon contamination from the surface and improve the crystalline order in the substrate surface. Ultrasonic cleaning in acetone is a good alternative method to clean the MgO substrates.
The (400) X-ray diffraction peak for the Zn3</su...

The II3-V2 materials are a class of semiconductors that have received relatively little attention from the semiconductor research community compared to III-V and II-VI semiconductors1. The Mg and Zn nitrides, Mg3N2 and Zn3N2, are attractive for consumer applications because they are composed of abundant and non-toxic elements, making them inexpensive and easy to recycle unlike most III-V and II-VI compound semiconductors. They display an anti-bixbyite crystal structure similar to the CaF2 structure, with one of the interpenetrating fcc F-sublattices being half-occupied2,3,4,5. They are both direct band gap materials6, making them suitable for optical applications7,8,9. The band gap of Mg3N2 is in the visible spectrum (2.5 eV)10, and the band gap of Zn3N2 is in the near-infrared (1.25 eV)11. To explore the physical properties of these materials and their potential for electronic and optical device applications, it is critical to obtain high quality, single crystal films. Most work on these materials to date has been carried out on powders or polycrystalline films made by reactive sputtering12,13,14,15,16,17.
Molecular beam epitaxy (MBE) is a well-developed and versatile method for growing single-crystal compound semiconductor films18 that has the potential to yield high quality materials using a clean environment and high-purity elemental sources. Meanwhile, MBE rapid shutter action enables changes to a film at the atomic layer scale and allows for precise thickness control. This paper reports on the growth of Mg3N2 and Zn3N2 epitaxial films on MgO substrates by plasma-assisted MBE, using high purity Zn and Mg as vapor sources and N2 gas as the nitrogen source.

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	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:222px;">(100) MgO</td>
			<td style="width:123px;">University Wafer</td>
			<td style="width:123px;">214018</td>
			<td style="width:276px;">one side epi-polished</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:222px;">Acetone</td>
			<td style="width:123px;">Fisher Chemical&#160;</td>
			<td style="width:123px;">170239</td>
			<td style="width:276px;">99.8%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:222px;">Argon laser</td>
			<td style="width:123px;">Lexel Laser</td>
			<td style="width:123px;">00-137-124</td>
			<td>488 nm visible wavelength, 350 mW output power</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:222px;">Chopper&#160;</td>
			<td style="width:123px;">Stanford Research system&#160;</td>
			<td style="width:123px;">SR540</td>
			<td style="width:276px;">&#160;Max. Frequency: 3.7 kHz&#160;</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:222px;">Lock-in amplifier&#160;</td>
			<td style="width:123px;">Stanford Research system&#160;</td>
			<td style="width:123px;">37909</td>
			<td style="width:276px;">DSP SR810, Max. Frequency: 100 kHz&#160;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:222px;">Magnesium&#160;</td>
			<td style="width:123px;">UMC</td>
			<td style="width:123px;">MG6P5</td>
			<td style="width:276px;">99.9999%</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:222px;">MBE system</td>
			<td style="width:123px;">VG Semicon</td>
			<td style="width:123px;">V80H0016-2 SHT 1</td>
			<td style="width:276px;">V80H-10</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:222px;">Methanol&#160;</td>
			<td style="width:123px;">Alfa Aesar</td>
			<td style="width:123px;">L30U027</td>
			<td style="width:276px;">Semi-grade 99.9%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:222px;">Nitrogen</td>
			<td style="width:123px;">Praxair</td>
			<td style="width:123px;">402219501</td>
			<td style="width:276px;">99.998%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:222px;">Oxygen&#160;</td>
			<td style="width:123px;">Linde Gas</td>
			<td style="width:123px;">200-14-00067</td>
			<td style="width:276px;">&#62; 99.9999%</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:222px;">Plasma source</td>
			<td style="width:123px;">SVT Associates</td>
			<td style="width:123px;">SVTA-RF-4.5PBN</td>
			<td>PBN, 0.11&#34; Aperture, Specify Length: 12&#34; &#8211; 20&#34;</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:222px;">Si photodiode&#160;</td>
			<td style="width:123px;">Newport</td>
			<td style="width:123px;">2718</td>
			<td style="width:276px;">818-UV Enhanced, 200 - 1100 nm</td>
		</tr>
		<tr height="22">
			<td height="22" style="height:22px;width:222px;">Zinc&#160;</td>
			<td style="width:123px;">Alfa Aesar</td>
			<td style="width:123px;">7440-66-6</td>
			<td style="width:276px;">99.9999%</td>
		</tr>
	</tbody>
</table>

plasma-assisted molecular beam epitaxy growth of mg3n2 and zn3n2 thin films

This article describes a procedure for growing Mg3N2 and Zn3N2 films by plasma-assisted molecular beam epitaxy (MBE). The films are grown on 100 oriented MgO substrates with N2 gas as the nitrogen source. The method for preparing the substrates and the MBE growth process are described. The orientation and crystalline order of the substrate and film surface are monitored by the reflection high energy electron diffraction (RHEED) before and during growth. The specular reflectivity of the sample surface is measured during growth with an Ar-ion laser with a wavelength of 488 nm. By fitting the time dependence of the reflectivity to a mathematical model, the refractive index, optical extinction coefficient, and growth rate of the film are determined. The metal fluxes are measured independently as a function of the effusion cell temperatures using a quartz crystal monitor. Typical growth rates are 0.028 nm/s at growth temperatures of 150 &#176;C and 330 &#176;C for Mg3N2 and Zn3N2 films, respectively.

The black object in the inset in Figure 5B is a photograph of an as-grown 200 nm Zn3N2 thin film. Similarly, the yellow object in the inset in Figure 5C is an as-grown 220 nm Mg3N2 thin film. The yellow film is transparent to the extent that it is easy-to-read text placed behind the film10.
The surface ...

Watch this Scientific Journal Video about Plasma-Assisted Molecular Beam Epitaxy Growth of Mg3N2 and Zn3N2 Thin Films at JoVE.com

Plasma-Assisted Molecular Beam Epitaxy Growth of Mg3N2 and Zn3N2 Thin Films

This article describes the growth of epitaxial films of Mg3N2 and Zn3N2 on MgO substrates by plasma-assisted molecular beam epitaxy with N2 gas as the nitrogen source and optical growth monitoring.

Plasma-Assisted Molecular Beam Epitaxy Growth of Mg3N2 and Zn3N2 Thin Films

This article describes a procedure for growing Mg3N2 and Zn3N2 films by plasma-assisted molecular beam epitaxy (MBE). The films are grown on 100 oriented ...

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