Ydintyminen ja mikrorakenteen kehittyminen atomikerroskasvatuksessa

Ohutkalvojen mikrorakenne, joka käsittää esimerkiksi raekoon, tekstuurin ja jännitykset, vaikuttaa ohutkalvojen ominaisuuksiin ja edelleen kalvojen toimivuuteen erilaisissa sovelluksissa. Mikrorakenteen kehityksen ymmärtäminen on siten välttämätöntä kalvojen ominaisuuksien muokkaamiseksi eri sovellusten tarpeisiin. Ohutkalvojen mikrorakenteen kehitys alkaa ydintymisestä eli ensimmäisten kalvomateriaalin ydinten muodostumisesta substraatille. Ydintymisen jälkeen mikrorakenne kehittyy edelleen ydinten kasvu-, yhteensulautumis-, ja kalvon paksuuntumisvaiheiden aikana. Useissa sovelluksissa käytettävien ohutkalvojen paksuudet ovat viime vuosikymmeninä pienentyneet samalla, kun vaatimukset kalvojen luotettavuutta ja ominaisuuksia kohtaan ovat kasvaneet. Tämän vuoksi erityisesti ydintymisvaiheen tutkiminen, ymmärtäminen ja muokkaaminen on ensiarvoisen tärkeää. Kirjallisuusosiossa tarkastellaan mikrorakenteen kehittymisen yleispiirteitä sekä erityisesti ydintymistä ja mikrorakenteen kehitystä atomikerroskasvatuksessa (ALD). ALD-kalvojen ydintymisen ja erilaisten ydintymismallien lisäksi käsitellään aluksi amorfisena kasvavien ALD-kalvojen kiteytymistä kasvatuksen aikana sekä monikiteisten ALD-kalvojen mikrorakenteen kehittymistä paksuuntumisvaiheessa. Yleisluontoisempien havaintojen lisäksi mikrorakenteen kehitystä tarkastellaan yksityiskohtaisesti oksidien (erityisesti alumiinioksidi ja ryhmän 4 oksidit), platinametallien (Ru, Pt, Ir ja Pd) sekä kalkogenidien (erityisesti sinkkisulfidi) osalta ydintymisvaiheeseen keskittyen. Kokeellisessa osiossa tutkittiin Ir- ja IrO2-kalvojen atomikerroskasvatusta. ALD-platinametallikalvojen ydintymisvaihe ymmärretään lukuisista tutkimuksista huolimatta huonosti. Iridium on jäänyt sen hyvistä ominaisuuksistaan huolimatta enemmän tutkittujen platinan ja ruteenin varjoon sekä kalvojen ominaisuuksia että ydintymistä tutkittaessa. Tämän tutkielman kokeellinen osa on jaettu neljään osaan, joissa tarkastellaan iridiumin ja iridiumoksidin (IrO2) kasvatusta Ir(acac)3 (acac = asetyyliasetonaatti) -lähtöaineesta. Aiemmin tutkittujen Ir(acac)3+ilma-, Ir(acac)3+O2- ja Ir(acac)3+O3+H2-prosessien lisäksi iridiumia kasvatettiin uudella Ir(acac)3+O2+H2-prosessilla, jossa pinnalle adsorboitunut happi poistettiin vedyllä. Iridiumoksidia kasvatettiin aiemmin tutkitulla Ir(acac)3+O3-prosessilla. Ensimmäisessä osassa vertailtiin Ir- ja IrO2-prosessien ydintymisvaihetta. Ydintymisen havaittiin olevan nopeinta uudessa Ir(acac)3+O2+H2-prosessissa ja hitainta otsoniprosesseissa. Toisessa osassa uutta O2+H2-prosessia verrattiin eniten käytettyyn O2-prosessiin 200–350 °C lämpötila-alueella. Hapen poistaminen vaikutti selvästi kalvojen kasvunopeuteen, morfologiaan, karkeuteen, resistiivisyyteen, raekokoon ja tekstuuriin. Kolmannessa osassa tutkittiin Ir- ja IrO2-prosessien konformaalisuutta VTT:n kehittämien testinäytteiden avulla. O3+H2-prosessin konformaalisuus osoittautui tutkituista prosesseista selvästi parhaaksi. Tämän konformaalisuus oli erinomainen myös aiemmin kirjallisuudessa tutkittuihin ALD-platinametalliprosesseihin verrattuna. Viimeisessä luvussa tutkittiin otsonin mahdollista iridiumkalvoja etsaavaa vaikutusta. Etsautumista vaikutti tapahtuvan käytettäessä otsonia reaktanttina tai altistamalla kalvo otsonille jokaisen iridiumia kasvattavan ALD-syklin jälkeen. Aiemmin kasvatettujen iridiumkalvojen etsaaminen otsonilla ei kuitenkaan onnistunut

Controlling Atomic Layer Deposition of 2D Semiconductor SnS(2)by the Choice of Substrate

Semiconducting 2D materials, such as SnS2, hold great promise in a variety of applications including electronics, optoelectronics, and catalysis. However, their use is hindered by the scarcity of deposition methods offering necessary levels of thickness control and large-area uniformity. Herein, a low-temperature atomic layer deposition (ALD) process is used to synthesize up to 5x5 cm(2)continuous, few-layer SnS(2)films on a variety of substrates, including SiO2/Si, Si-H, different ALD-grown films (Al2O3, TiO2, and Ir), sapphire, and muscovite mica. As a part of comprehensive film characterization, the use of low energy ion scattering (LEIS) is showcased to determine film continuity, coverage of monolayer and multilayer areas, and film thickness. It is found that on sapphire substrate, continuous films are achieved at lower thicknesses compared to the other substrates, down to two monolayers or even less. On muscovite mica, van der Waals epitaxial growth is realized after the post-deposition annealing, or even in the as-deposited films when the growth is performed at 175 to 200 degrees C. This work highlights the importance of the substrate choice for 2D materials and presents a practical low-temperature method for the deposition of high-quality SnS(2)films that may be further evaluated for a range of applications.Peer reviewe

Atomic Layer Deposition of Insulating AlF3/Polyimide Nanolaminate Films

This article describes the deposition of AlF3/polyimide nanolaminate film by inorganic-organic atomic layer deposition (ALD) at 170 °C. AlCl3 and TiF4 were used as precursors for AlF3. Polyimide layers were deposited from PMDA (pyromellitic dianhydride, 1,2,3,5-benzenetetracarboxylic anhydride) and DAH (1,6-diaminohexane). With field-emission scanning electron microscopy (FESEM) and X-ray reflection (XRR) analysis, it was found that the topmost layer (nominally 10 nm in thickness) of the nanolaminate film (100 nm total thickness) changed when exposed to the atmosphere. After all, the effect on roughness was minimal. The length of a delay time between the AlF3 and polyimide depositions was found to affect the sharpness of the nanolaminate structure. Electrical properties of AlF3/polyimide nanolaminate films were measured, indicating an increase in dielectric constant compared to single AlF3 and a decrease in leakage current compared to polyimide films, respectively

Atomic layer deposition of GdF3 thin films

doi: 10.1116/6.0001629Gadolinium fluoride is an attractive optical material with applications in, e.g., deep-UV lithography, solar cells, and medical imaging. Despite the interest toward this material, no atomic layer deposition (ALD) process has been published. In this article, an ALD process for GdF3 using Gd(thd)(3) and NH4F as precursors is presented. The deposition was studied at temperatures 275-375 & DEG;C, but 285-375 & DEG;C produce the purest films. The saturation of the growth per cycle (GPC) with respect to precursor pulses and purges was proved at 300 & DEG;C. The GPC value at this temperature is & SIM;0.26 & ANGS;, and the deposition temperature has very little effect on the GPC. According to x-ray diffraction, all the films consist of orthorhombic GdF3. The impurity contents, evaluated by time-of-flight elastic recoil detection analysis, is low, and the films are close to stoichiometric. The nitrogen content is less than < 0.04 at. %. The antireflection properties were qualitatively evaluated by UV-vis spectrometry in a transmission mode at a 190-1100 nm range: on sapphire substrates, GdF3 serves as an antireflective coating. Dielectric properties of the films were studied, and for example, a permittivity value of 9.3 was measured for a & SIM;64 nm film deposited at 300 & DEG;C.Peer reviewe

Rhenium Metal and Rhenium Nitride Thin Films Grown by Atomic Layer Deposition

Abstract Rhenium is both a refractory metal and a noble metal that has attractive properties for various applications. Still, synthesis and applications of rhenium thin films have been limited. We introduce herein the growth of both rhenium metal and rhenium nitride thin films by the technologically important atomic layer deposition (ALD) method over a wide deposition temperature range using fast, simple, and robust surface reactions between rhenium pentachloride and ammonia. Films are grown and characterized for compositions, surface morphologies and roughnesses, crystallinities, and resistivities. Conductive rhenium subnitride films of tunable composition are obtained at deposition temperatures between 275 and 375 °C, whereas pure rhenium metal films grow at 400 °C and above. Even a just 3 nm thick rhenium film is continuous and has a low resistivity of about 90 µΩ cm showing potential for applications for which also other noble metals and refractory metals have been considered.Peer reviewe

Van der Waals epitaxy of continuous thin films of 2D materials using atomic layer deposition in low temperature and low vacuum conditions

Van der Waals epitaxy holds great promise in producing high-quality films of 2D materials. However, scalable van der Waals epitaxy processes operating at low temperatures and low vacuum conditions are lacking. Herein, atomic layer deposition is used for van der Waals epitaxy of continuous multilayer films of 2D materials HfS2, MoS2, SnS2, and ZrS2 on muscovite mica and PbI2 on sapphire at temperatures between 75 degrees C and 400 degrees C. For the metal sulfides on mica, the main epitaxial relation is MS2 mica. Some domains rotated by 30 degrees are also observed corresponding to the MS2 mica alignment. In both cases, the presence of domains rotated by 60 degrees (mirror twins) is also expected. For PbI2 on sapphire, the epitaxial relation is PbI2 Al2O3 with no evidence of 30 degrees domains. For all of the studied systems there is relatively large in-plane mosaicity and in the PbI2/Al2O3 system some non-epitaxial domains are also observed. The study presents first steps of an approach towards a scalable and semiconductor industry compatible van der Waals epitaxy method.Peer reviewe

Atomic layer deposition of lanthanum oxide with heteroleptic cyclopentadienyl-amidinate lanthanum precursor - Effect of the oxygen source on the film growth and properties

La2O3 thin films were deposited by atomic layer deposition from a liquid heteroleptic La precursor, La(iPrCp)2(iPr-amd), with either water, ozone, ethanol, or both water and ozone (separated by a purge) as the oxygen source. The effect of the oxygen source on the film growth rate and properties such as crystallinity and impurities was studied. Saturation of the growth rate was achieved at 225 °C with O3 as the oxygen source. With water, very long purge times were used due to the hygroscopicity of La2O3 but saturation of the growth rate was not achieved. Interestingly, when an O3 pulse was added after the water pulse with a purge in between, the growth rate decreased and the growth saturated at 200 °C. With ethanol lanthanum hydroxide was formed instead of La2O3 at 200–275 °C whereas hexagonal La2O3 films were obtained at 300 °C but the growth was not saturative. Using the separate pulses of water and ozone in the same deposition provided the best results from the four studied deposition processes. After annealing the films deposited with the La(iPrCp)2(iPrAMD)/H2O/O3 process showed pure hexagonal phase in all the films regardless of the deposition temperature, whereas mixtures of cubic and hexagonal La2O3 were seen with the other processes.Peer reviewe

Atomic layer deposition of TbF3 thin films

Lanthanide fluoride thin films have gained interest as materials for various optical applications, including electroluminescent displays and mid-IR lasers. However, the number of atomic layer deposition (ALD) processes for lanthanide fluorides has remained low. In this work, we present an ALD process for TbF3 using tris(2,2,6,6-tetramethyl-3,5-heptanedionato)terbium and TiF4 as precursors. The films were grown at 175-350 degrees C. The process yields weakly crystalline films at the lowest deposition temperature, whereas strongly crystalline, orthorhombic TbF3 films are obtained at higher temperatures. The films deposited at 275-350 degrees C are exceptionally pure, with low contents of C, O, and H, and the content of titanium is below the detection limit (Peer reviewe

Toolbox of Advanced Atomic Layer Deposition Processes for Tailoring Large-Area MoS2 Thin Films at 150 °C

Two-dimensional MoS2 is a promising material for applications, including electronics and electrocatalysis. However, scalable methods capable of depositing MoS2 at low temperatures are scarce. Herein, we present a toolbox of advanced plasma-enhanced atomic layer deposition (ALD) processes, producing wafer-scale polycrystalline MoS2 films of accurately controlled thickness. Our ALD processes are based on two individually controlled plasma exposures, one optimized for deposition and the other for modification. In this way, film properties can be tailored toward different applications at a very low deposition temperature of 150 °C. For the modification step, either H2 or Ar plasma can be used to combat excess sulfur incorporation and crystallize the films. Using H2 plasma, a higher degree of crystallinity compared with other reported low-temperature processes is achieved. Applying H2 plasma steps periodically instead of every ALD cycle allows for control of the morphology and enables deposition of smooth, polycrystalline MoS2 films. Using an Ar plasma instead, more disordered MoS2 films are deposited, which show promise for the electrochemical hydrogen evolution reaction. For electronics, our processes enable control of the carrier density from 6 × 1016 to 2 × 1021 cm–3 with Hall mobilities up to 0.3 cm2 V–1 s–1. The process toolbox forms a basis for rational design of low-temperature transition metal dichalcogenide deposition processes compatible with a range of substrates and applications

Atomic Layer Deposition of PbI₂ Thin Films

Atomic layer deposition (ALD) enables the deposition of numerous materials in thin film form, yet there are no ALD processes for metal iodides. Herein, we demonstrate an ALD process for PbI2, a metal iodide with a two-dimensional (2D) structure that has applications in areas such as photo-detection and photovoltaics. This process uses lead silylamide Pb(btsa)(2) and SnI4 as precursors and works at temperatures below 90 degrees C, on a variety of starting surfaces and substrates such as polymers, metals, metal sulfides, and oxides. The starting surface defines the crystalline texture and morphology of the PbI2 films. Rough substrates yield porous PbI2 films with randomly oriented 2D layers, whereas smooth substrates yield dense films with 2D layers parallel to the substrate surface. Exposure to light increases conductivity of the ALD PbI2 films which enables their use in photodetectors. The films can be converted into a CH3NH3PbI3 halide perovskite, an important solar cell absorber material. For various applications, ALD offers advantages such as ability to uniformly coat large areas and simple means to control film thickness. We anticipate that the chemistry exploited in the PbI2 ALD process is also applicable for ALD of other metal halides.Peer reviewe