Hexacoordinated Gallium(III) Triazenide Precursor for Epitaxial Gallium Nitride by Atomic Layer Deposition

Gallium nitride (GaN) is the main component of modern-day high electron mobility transistors due to its favorable electronic properties. As electronic devices become smaller with more complex surface architecture, the ability to deposit high-quality GaN films at low temperatures is required. Herein, we report a new highly volatile Ga(III) triazenide precursor and demonstrate its ability to deposit high-quality epitaxial GaN by atomic layer deposition (ALD). This new Ga(III) triazenide, the first hexacoordinated Ga-N bonded precursor used in a vapor deposition process, was easily synthesized and purified by either sublimation or recrystallisation. Thermogravimetric analysis showed single-step volatilization with an onset temperature of 155 degrees C and negligible residual mass. Three temperature intervals with self-limiting growth were observed when depositing GaN films. The GaN films grown in the second growth interval at 350 degrees C were epitaxial on 4H-SiC without an AlN seed layer and found to have a near stoichiometric Ga/N ratio with very low levels of impurities. In addition, electron microstructure analysis showed a smooth film surface and a sharp interface between the substrate and film. The band gap of these films was 3.41 eV with the Fermi level at 1.90 eV, showing that the GaN films were unintentionally n-type-doped. This new triazenide precursor enables ALD of GaN for semiconductor applications and provides a new Ga(III) precursor for future deposition processes

Time-resolved CVD of Group 13-Nitrides

Group 13 nitrides (AlN, GaN and InN) and their alloys are semiconductor materials with a wide bandgap span covering from UV down to IR range. Their excellent electronic properties make them extremely attractive materials for light emitting diodes (LEDs) and different kind of transistor structures, especially high electron mobility transistors (HEMTs). These materials are routinely deposited by chemical vapor deposition (CVD) at high temperatures. The most sought-after material among the group 13 nitrides is InN due to its high electron mobility making it extremely useful in transistor structures. InN needs to be deposited at low temperatures as it decomposes at high temperatures. This does not only limit the deposition temperature for InN growth but also for all the other materials that will be deposited on top of InN. In this thesis the deposition of group 13 nitrides is investigated by low temperature atomic layer deposition (ALD) via both a thermal and plasma route. This was conducted by both process development and by improving the deposition chemistry by developing new precursors.  Carbon impurities is one of the greater challenges when using the standard aluminum precursor trimethylaluminum (TMA) in ALD due to the strong Al–C bonds in the molecule. An in-situ removal of carbon impurities was investigated by introducing a cleaning pulse, after the TMA pulse. The cleaning pulse consisted of an H2, N2 or Ar gas pulse perpendicular to the surface. The introduction of the cleaning pulse reduced the carbon impurity in the AlN film from 3 at% down to under 1 at%. This made it possible to deposit AlN at higher temperature to obtain better crystalline quality and on the same time reduce the impurity levels. Kinetic simulations showed that the cleaning pulse cleans the surface from desorbed methyl groups resulting in a suppressed reabsorption pathway.  To further reduce carbon impurities, the strong M–C bonded precursors was replaced with a M–N bonded one. The precursor used were tris(dimethylamido)gallium together with ammonia (NH3) plasma to deposit GaN. The precursor showed ALD behavior and the resulting GaN film possessed significantly lower carbon impurities compared to M-C bonded precursor at low deposition temperatures. This precursor could also produce epitaxial GaN directly on 4H-SiC without a need of a seed layer. To further investigate the precursor impact on deposition chemistry and ultimately the film quality, three indium precursors were evaluated, indium(III)guanidinate, indium(III)amidinate and indium(III)formamidinate. All three precursors have more or less the same structure, only difference being the size of the substituent on the endocyclic carbon position (-NMe2, -Me and -H respectively). Experimental results showed that smaller groups on the endocyclic carbon position improved the InN film quality in terms of crystallinity, morphology, stoichiometry and optical properties. Density functional theory (DFT) calculations showed that smaller moieties on the endocyclic position will lead to less surface and steric repulsion with the exocyclic position. As the size is decreased the exocyclic groups can fold up closer towards the endocyclic position leading to elongated metal-ligand bonds which will result in easier removal of the ligand for the upcoming NH3 plasma pulse.  From these results a new ligand was developed to further improve the deposition chemistry where the endocyclic carbon atom in the ligand backbone of the foramidinate ligand was replaced by a N atom to form a triazenide ligand (iPr–N–N=N–iPr). The triazenide ligand possess no moiety on the endocyclic position compared to the ligands used previously and hence should result in improved material quality if extrapolated from our previous study. The ligand was placed on indium and gallium forming In(III)triazenide and Ga(III)triazenide respectively. Both precursors showed excellent thermal properties making them good ALD precursors. Their use for depositing InN and GaN was investigated with NH3plasma. The resulting films showed excellent quality where no carbon could be detected for either InN nor GaN using XPS and ERDA. Both InN and GaN showed epitaxial growth behavior on 4H-SiC at deposition temperature of 350 °C, a factor of three lower deposition temperature compared to CVD. Interestingly, several linear growth regimes (ALD windows) upon changing the temperature were observed, two and three for InN and GaN respectively. This indicated that the precursors decomposed upon increasing the temperature to form smaller fragments which increased the growth rate but on the same time the smaller precursor fragments saturated the surface. This was further confirmed by DFT calculations.    The In(III)triazenide and Ga(III)triazenide was further used to deposit the ternary InGaN phase. A new method was developed where both precursors were mixed in the bubbler and co-sublimed into the reactor via a single pulse. The composition of the films could be tuned via bubbler temperature, deposition temperature and premixed ratio of the precursors in the bubbler. Near In0.5Ga0.5N could be obtained at low deposition temperatures confirmed by both XPS, ERDA and bandgap measurement. Deposition at 350 °C on 4H-SiC resulted in epitaxial In1-xGaxN without a need of a seed layer.

Reduction of Carbon Impurities in Aluminum Nitride from Time-Resolved Chemical Vapor Deposition Using Trimethylaluminum

Aluminum nitride (AlN) is a semiconductor with a wide range of applications from light-emitting diodes to high-frequency transistors. Electronic grade AlN is routinely deposited at 1000 degrees C by chemical vapor deposition (CVD) using trimethylaluminum (TMA) and NH3, while low-temperature CVD routes to high-quality AlN are scarce and suffer from high levels of carbon impurities in the film. We report on an atomic layer deposition-like CVD approach with time-resolved precursor supply where readsorption of methyl groups from the AlN surface is suppressed by the addition of an extra pulse, H-2, N-2, or Ar, between the TMA and NH3 pulses. The suppressed readsorption allowed deposition of AlN films with a carbon content of 1 at. % at 480 degrees C. Kinetic and quantum-chemical modeling suggests that the extra pulse between TMA and NH3 prevents readsorption of desorbing methyl groups terminating the AlN surface after the TMA pulse.Funding Agencies|Swedish Foundation for Strategic Research (SSF) through the project "time-resolved low temperature CVD for III-nitrides" [SSF-RMA 15-0018]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty grant SFO Mat LiU) [2009 00971]; Swedish Research Council (VR)Swedish Research Council</p

Reduction of carbon impurities in aluminium nitride from time-resolved chemical vapour deposition using trimethylaluminum

Aluminium nitride (AlN) is a semiconductor with a wide range of applications from light emitting diodes to high frequency transistors. Electronic grade AlN is routinely deposited at 1000 °C by chemical vapour deposition (CVD) using trimethylaluminium (TMA) and NH3 while low temperature CVD routes to high quality AlN are scarce and suffer from high levels of carbon impurities in the film. We report on an ALD-like CVD approach with time-resolved precursor supply where thermally induced desorption of methyl groups from the AlN surface is enhanced by the addition of an extra pulse, H2, N2 or Ar between the TMA and NH3 pulses. The enhanced desorption allowed deposition of AlN films with carbon content of 1 at. % at 480 °C. Kinetic- and quantum chemical modelling suggest that the extra pulse between TMA and NH3 prevents re-adsorption of desorbing methyl groups terminating the AlN surface after the TMA pulse. </p

Chemical vapor deposition of metallic films using plasma electrons as reducing agents

Metallic thin films are key components in electronic devices and catalytic applications. Deposition of a conformal metallic thin film requires using volatile precursor molecules in a chemical vapor deposition (CVD) process. The metal centers in such molecules typically have a positive valence, meaning that reduction of the metal centers is required on the film surface. Powerful molecular reducing agents for electropositive metals are scarce and hamper the exploration of CVD of electropositive metals. The authors present a new CVD method for depositing metallic films where free electrons in a plasma discharge are utilized to reduce the metal centers of chemisorbed precursor molecules. They demonstrate this method by depositing Fe, Co, and Ni from their corresponding metallocenes using electrons from an argon plasma as a reducing agent.Funding Agencies|Swedish Research Council (VR)Swedish Research Council [2015-03803]</p

Atomic layer deposition of InN using trimethylindium and ammonia plasma

Indium nitride (InN) is a low bandgap, high electron mobility semiconductor material of interest to optoelectronics and telecommunication. Such applications require the deposition of uniform crystalline InN thin films on large area substrates, with deposition temperatures compatible with this temperature-sensitive material. As conventional chemical vapor deposition (CVD) struggles with the low temperature tolerated by the InN crystal, the authors hypothesize that a time-resolved, surface-controlled CVD route could offer a way forward for InN thin film deposition. In this work, the authors report atomic layer deposition of crystalline, wurtzite InN thin films using trimethylindium and ammonia plasma on Si(100). They found a narrow atomic layer deposition window of 240-260 degrees C with a deposition rate of 0.36 A/cycle and that the flow of ammonia into the plasma is an important parameter for the crystalline quality of the film. X-ray diffraction measurements further confirmed the polycrystalline nature of InN thin films. X-ray photoelectron spectroscopy measurements show nearly stoichiometric InN with low carbon level (amp;lt;1 at. %) and oxygen level (amp;lt;5 at. %) in the film bulk. The low carbon level is attributed to a favorable surface chemistry enabled by the NH3 plasma. The film bulk oxygen content is attributed to oxidation upon exposure to air via grain boundary diffusion and possibly by formation of oxygen containing species in the plasma discharge. Published by the AVS.Funding Agencies|Swedish Foundation for Strategic Research through the project "Time-resolved low temperature CVD for III-nitrides" [SSF-RMA 15-0018]; Knut and Alice Wallenberg foundation through the project "Bridging the THz gap" [KAW 2013.0049]; VR [VR 2016-05362]; Carl Trygger Foundation</p

Area Selective Deposition of Metals from the Electrical Resistivity of the Substrate

Area selective deposition (ASD) of films only on desired areas of the substrate opens for less complex fabrication of nanoscaled electronics. We show that a newly developed CVD method, where plasma electrons are used as the reducing agent in deposition of metallic thin films, is inherently area selective from the electrical resistivity of the substrate surface. When depositing iron with the new CVD method, no film is deposited on high-resistivity SiO2 surfaces whereas several hundred nm thick iron films are deposited on areas with low resistivity, obtained by adding a thin layer of silver on the SiO2 surface. Based on such a scheme, we show how to use the electric resistivity of the substrate surface as an extension of the ASD toolbox for metal-on-metal deposition. </p

Area Selective Deposition of Metals from the Electrical Resistivity of the Substrate

Area selective deposition (ASD) of films only on desired areas of the substrate opens for less complex fabrication of nanoscaled electronics. We show that a newly developed CVD method, where plasma electrons are used as the reducing agent in deposition of metallic thin films, is inherently area selective from the electrical resistivity of the substrate surface. When depositing iron with the new CVD method, no film is deposited on high-resistivity SiO2 surfaces whereas several hundred nanometers thick iron films are deposited on areas with low resistivity, obtained by adding a thin layer of silver on the SiO2 surface. On the basis of such a scheme, we show how to use the electric resistivity of the substrate surface as an extension of the ASD toolbox for metal-on-metal deposition.Funding: Swedish Research Council (VR)Swedish Research Council [2015-03803, 2019-05055]; Swedish Foundation for Strategic Research (SSF)Swedish Foundation for Strategic Research [SSF-RMA 15-0018]; Lam Research Corporation</p

Area Selective Deposition of Iron Films Using Temperature Sensitive Masking Materials and Plasma Electrons as Reducing Agents

potential of area selective deposition (ASD) with a newly developed chemical vapor deposition method, which utilize plasma electrons as reducing agents for deposition of metal-containing films, is demonstrated using temperature sensitive polymer-based masking materials. The masking materials tested were polydimethylsiloxane (PDMS), polymethylmethacrylate (PMMA), polystyrene (PS), parafilm, Kapton tape, Scotch tape, and office paper. The masking materials were all shown to prevent film growth on the masked area of the substrate without being affected by the film deposition process. X-ray photoelectron spectroscopy analysis confirms that the films deposited consist mainly of iron, whereas no film material is found on the masked areas after mask removal. SEM analysis of films deposited with non-adhesive masking materials show that film growth extended for a small distance underneath the masking material, indicating that the CVD process with plasma electrons as reducing agents is not a line-of-sight deposition technique. The reported methodology introduces an inexpensive and straightforward approach for ASD that opens for exciting new possibilities for robust and less complex area selective metal-on-metal deposition. </p