WO2013011297A1 - Procédé - Google Patents

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Publication number
WO2013011297A1
WO2013011297A1 PCT/GB2012/051697 GB2012051697W WO2013011297A1 WO 2013011297 A1 WO2013011297 A1 WO 2013011297A1 GB 2012051697 W GB2012051697 W GB 2012051697W WO 2013011297 A1 WO2013011297 A1 WO 2013011297A1
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Prior art keywords
precursor
lithium
reaction chamber
substrate
layer
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PCT/GB2012/051697
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English (en)
Inventor
Erik ØSTRENG
Ola Nilsen
Helmer FJELLVÅG
Original Assignee
Universitetet I Oslo
Golding, Louise
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Priority claimed from GBGB1112210.8A external-priority patent/GB201112210D0/en
Priority claimed from GBGB1204600.9A external-priority patent/GB201204600D0/en
Application filed by Universitetet I Oslo, Golding, Louise filed Critical Universitetet I Oslo
Publication of WO2013011297A1 publication Critical patent/WO2013011297A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0407—Methods of deposition of the material by coating on an electrolyte layer
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0428—Chemical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a method for the formation of a lithium-containing surface layer on a substrate.
  • WO 2009/084966 describes one such method in which atomic layer deposition (ALD) is used to deposit a thin film containing lithium.
  • ALD atomic layer deposition
  • Li(thd) lithium 2,2,6,6- tetramethylheptane-3,5-dionate
  • Li(thd) lithium 2,2,6,6- tetramethylheptane-3,5-dionate
  • ALD also known as atomic layer chemical vapour deposition, ALCVD, or atomic layer epitaxy, ALE
  • ALCVD atomic layer chemical vapour deposition
  • ALE atomic layer epitaxy
  • the present inventors have now developed an improved method for the deposition of thin films containing lithium which involves the use of a novel lithium precursor.
  • This method enables the formation of lithium-containing materials at higher growth rates than previously observed, e.g. when carrying out the method described in WO 2009/084966.
  • the novel lithium precursor has also been found to be capable of forming Li-N materials. Such materials have previously not been observed.
  • the invention thus provides a method for the formation of a lithium-containing layer on a substrate by atomic layer deposition, said method comprising the following steps:
  • lithium precursor is a compound of general formula (I):
  • R a and R b are independently selected from H, Ci -6 alkyl (preferably d -3 alkyl, e.g. methyl) and -SiR c 3 ; and
  • each R c is independently selected from H and Ci -6 alkyl (preferably Ci -3 alkyl, e.g. methyl);
  • R a and R b is a group -SiR c 3 ).
  • steps b) to e) may independently be repeated a desired number of times, e.g. until the desired film thickness is obtained.
  • steps b) and c) may be repeated as required in order to produce the desired layer of lithium-containing material.
  • steps d) and e) of the method may be repeated using the same or different additional precursors. Where two or more additional precursors are pulsed through the reaction chamber, it is generally preferred that these are not identical.
  • additional precursors When two or more additional precursors are used in the method, these may be pulsed simultaneously or separately from one another. In the case where these are pulsed separately, additional purging steps will generally be employed after each pulse.
  • lithium precursors for use in the method of the invention are those compounds of formula (I) in which both R a and R b are groups -SiR c 3 , preferably those in which at least one R c is methyl.
  • a particularly preferred lithium precursor for use in the invention is LiN(SiMe 3 ) 2 (where Me is methyl).
  • lithium precursor materials examples include:
  • LiN(SiEt 3 ) 2 (where Et is ethyl), LiNH(SiMe 3 ) and LiNH(SiEt 3 ) 2 .
  • an inert purge gas is pulsed through the reaction chamber after each pulse of lithium precursor, or after each sequence of lithium precursor pulses, or even concurrently with the lithium precursor.
  • several purge pulses may be performed between each lithium precursor pulse. Similar purging steps may also be performed after pulsing of the additional precursor (or additional precursors where more than one is used). The purging steps are intended to remove any unreacted reactants thereby ensuring that growth proceeds according to self-limiting gas-to-surface reactions.
  • Purging of the reaction chamber may be performed by flowing a purge gas through the chamber or, alternatively, by evacuating the chamber by reducing the pressure.
  • Suitable purge gases include inert gases such as nitrogen, argon, etc. Preferred for use as a purge gas is nitrogen. Also suitable for use as purge gases are
  • nitrogen/argon mixtures for example a mixture of 1 .5% Ar and 98.5% N 2 , although any suitable gas or gas mixture may be used which will not react with the deposited layer of lithium-containing material or the precursors.
  • additional precursor for use in the method will be a non-lithium precursor.
  • the choice of additional precursor will be dependent on the desired end product and may be selected from any
  • Preferred for use in the invention are additional precursor materials selected from the group consisting of oxygen precursors, metal precursors, nitrogen precursors, phosphorus precursors and halogen precursors.
  • Any suitable oxygen precursor may be used, such as for example, water, 0 3 or any other oxygen comprising gaseous compound such as C0 2 . Combinations of oxygen precursors may also be used, either in separate pulsing steps or
  • Suitable metal precursors include metal organic precursors such as metal silylamides, beta-diketonates, amidinates, halides, carbonyls, alkoxides, alkyls, cyclopentadienyls, etc.
  • Any suitable nitrogen precursor may be used, such as for example, ammonia and ammonia derivatives.
  • Derivatives of ammonia which may be used include hydrazine, e.g. 1 ,1 -dimethyl-hydrazine and other hydrazine derivatives.
  • a preferred nitrogen precursor is NH 3 .
  • the method may further comprise the additional step of providing a capping layer using known deposition techniques. This step is carried out once each of steps b) to e) has been completed such that the capping layer is deposited on top of the final deposited Li-N layer.
  • An additional purging step may be employed after deposition of the capping layer.
  • Suitable for use as a capping layer are any materials which can be deposited without destroying the underlying Li-N layer and which protect against reaction with air, water and C0 2 . Examples of such materials include TiN and Mo 2 N.
  • Suitable phosphorus precursors include trimethyl phosphate, POCI 3 , phosphoric acid and organophosphate esters of H 3 P0 4 .
  • Suitable halogen precursors include metal chlorides, preferably volatile chlorides, e.g. TiCI 4 , NbCIs, or ZrCI 4 .
  • the invention provides a method wherein more than one oxygen precursor is pulsed through the reaction chamber such that the resulting sequence comprises the following steps:
  • the first oxygen precursor is water and the second oxygen precursor is C0 2 .
  • steps b) to g) may independently be repeated a desired number of times in order for the formation of the desired thin film layer, e.g. until the desired film thickness is obtained.
  • any of the groups of steps, for example b) and c), d) and e) and/or f) and g) may be independently repeated a desired number of times before continuing with the remaining steps of the method.
  • the thin film layer will comprise Li 2 C0 3 on said at last one surface of the substrate.
  • the invention provides a method wherein a nitrogen precursor is pulsed through the reaction chamber such that the resulting sequence comprises the following steps:
  • the nitrogen precursor is ammonia.
  • steps b) to e) may independently be repeated a desired number of times in order for the formation of the desired thin film layer, e.g. until the desired film thickness is obtained.
  • any of the groups of steps, for example b) and c) and/or d) and e) may be independently repeated a desired number of times before continuing with the remaining steps of the method.
  • the resulting thin film layer will comprise a Li-N type material on said at last one surface of the substrate.
  • At least one of the precursors is introduced into the reaction chamber in the gas phase.
  • all precursors i.e. the lithium precursor and all additional precursors
  • Precursors which exist in solid or liquid form may be converted to the gaseous form by "direct vaporisation" prior to introduction into the reaction chamber.
  • vaporisation is meant that a substantially pure (e.g. pure) precursor compound in solid or liquid form is converted directly to the gaseous state via sublimation or evaporation, without dispersion or dissolution in a liquid (e.g. a solvent or emulsion).
  • a liquid e.g. a solvent or emulsion
  • an inert gas may be employed (e.g. via a bubbler) to assist in the vaporisation and/or act as a carrier gas.
  • Gaseous precursors may be introduced from a compartment which is separated from the reaction chamber, for example via a physical or inert gas valve. Such gaseous precursors may enter the reaction chamber by way of their own intrinsic vapour pressure or optionally by means of an inert carrier gas.
  • the direct vaporisation technique permits simplification of the reaction system.
  • Direct vaporisation also has the advantage that this minimises any pressure differences between precursor pulses and so eliminates the possibility of competing or interfering reactions between solvents and precursors.
  • Vaporisation of precursors should be carried out at an evaporation temperature capable of giving yield to a sufficient amount of precursor for use in the ALD process.
  • Appropriate vaporisation temperatures will depend on the nature of the precursor and the ALD process conditions and may be readily determined by those skilled in the art. Such temperatures are typically from about 60 °C to about 200 °C.
  • a temperature of 65 ' ⁇ or higher, e.g. 75 ' ⁇ or higher may be employed.
  • Suitable substrate materials include any materials which are capable of
  • Preferred substrate materials include electrode or electrolyte materials which may be used in a battery.
  • substrate materials include semiconductors, for example Si (e.g. single crystalline Si(1 1 1 )), Si with native oxide, and Si-H; metallic surfaces, for example Si/Pt, Pt, or Ti; crystalline ceramics, for example Si0 2 and Al 2 0 3 ; and amorphous glasses, for example glass (e.g. soda lime glass).
  • Preferred substrate materials include Si, glass, Si0 2 , Al 2 0 3 and Ti.
  • a substrate surface may be pre-treated in order to provide an adhesion layer of Al 2 0 3 using known deposition techniques.
  • This layer may be up to 1 nm in thickness and, typically, will be deposited in situ.
  • Mo-N type materials e.g. Mo 2 N or MoN x
  • an Mo-N type adhesion layer may be deposited by ALD using a Mo(CO) 6 precursor and a nitrogen precursor.
  • Adhesion layers are particularly preferred where the desired thin film layer comprises an Li-N type material. Without wishing to be bound by theory, it is thought that such a barrier layer may prevent reactions with the substrate or assist in the formation of metal-nitrogen-metal bonds.
  • Deposition temperatures may be varied depending on the nature of the precursor materials used. For example, these may be adjusted to ensure that deposition occurs at an optimum rate. As would be readily understood, the temperature must not be too high that the substrate is damaged or that the precursor is decomposed to any appreciable extent.
  • the methods herein described may be performed at a deposition temperature of up to 380 °C. A temperature of up to about 350 ' ⁇ , e.g. a temperature of between about 89 °C and about 332 ⁇ ⁇ , is particularly preferred.
  • Pulse durations may be varied according to need, however, the pulse duration of each precursor will be such that there is sufficient time for a substantial proportion of the substrate surface (e.g. the entire substrate surface) to react with the precursor. Pulse durations can readily be determined by those skilled in the art; typical precursor pulse durations will be at least 0.1 seconds, preferably from about 0.1 to about 20 seconds. In the case of pulsing the lithium precursor, this will generally have a duration of at least 1 second, e.g. at least 4 seconds. Similarly, the purge pulse durations may be tailored to ensure that the purge is effective; typical purge pulse durations may range from about 0.8 to about 12 seconds, e.g. about 1 to 2 seconds. In the case where the additional precursor is NH 3 , this will generally have a pulse duration of at least 2.5 seconds.
  • At least two additional precursors may be employed. These materials may be selected from any of those herein described.
  • a preferred method may involve separate or simultaneous (preferably separate) pulsing of H 2 0 and C0 2 as hereinbefore described.
  • Particularly preferred pulse sequences include:
  • Such products will comprise a substrate carrying a layer containing lithium and at least one other element, e.g. an element selected from nitrogen, oxygen, phosphorus, silicon and carbon.
  • the layer may further comprise at least one metal, such as one selected from Mo, Nb, Fe, Mn, Co, V, Ni, Ti, La and Al.
  • the obtained thin films will vary in stoichiometry depending on the precursor materials used and the conditions in the reaction chamber, but typically will be characterised by comprising lithium in the form of Li 2 C0 3 or Li-CI, or Li-O(H), Li-N, Li-Si-O, Li-M-O, Li-M-N, Li-M-N-O, Li-P-O, Li-P-O-N, Li-M-P-0 or Li-M-P-O-N type materials (where M is a metal element other than Li).
  • the films produced may have a layered structure or may comprise a monolayer.
  • the products according to the invention will be substantially free from (or contain only a limited number of) pin holes and/or defects.
  • the lithium-containing materials which are deposited on the substrate surface also form a further aspect of the invention.
  • the Li-N type materials produced according to Examples 1 to 3 provided herein are particularly preferred materials and may be characterised by one or more of the following: (i) an X-ray diffraction pattern according to Figure 3 or Figure 15; (ii) a Raman spectrum according to Figure 5 or Figure 16; and (iii) an XPS profile according to Figure 6.
  • the resulting thin films find a variety of uses, including in particular, use in battery technology. These may, for example, be used to produce an electrolyte barrier or in the production of electrode (i.e. cathode or anode) materials suitable for use in a solid state lithium battery.
  • the Li carbonates may be used in SEI (solid electrolyte interface) layers of a battery.
  • the Li nitrides are particularly suitable as electrolyte or electrode materials.
  • Lithium nitride (Li 3 N) may also find use in relation to imide-/amide-based hydrogen storage materials and is a very good lithium ion conductor.
  • Figure 1 shows the growth rate (growth per cycle, in picometres) vs. Li pulse, water pulse and C0 2 pulse duration for an embodiment of the invention
  • Figure 3 shows XRD vs. deposition temperature for an embodiment of the invention
  • Figure 4 shows the reaction of LiNSiMe 3 with NH 3 as measured by Quartz Crystal Microbalance in accordance with an embodiment of the invention
  • Figure 5 shows the Raman spectra of a sample with deposited Li-N on top of Al 2 0 3 capped with MoN in accordance with an embodiment of the invention.
  • Figure 6 shows an XPS spectra of a sample with deposited Li-N on top of Ti capped with MoN in accordance with an embodiment of the invention.
  • Figure 7 shows the growth rate, in A, vs. Li pulse, water pulse and C0 2 pulse duration for an embodiment of the invention
  • Figure 8 shows the growth rate and refractive index vs. temperature for an embodiment of the invention
  • Figure 9 shows XRD vs. deposition temperature for an embodiment of the invention.
  • Figure 10 shows the composition of a sample with deposited Li 2 C0 3 on top of Ti as a function of temperature as determined by XPS in accordance with an embodiment of the invention
  • Figure 1 1 shows AFM images of Li 2 C0 3 deposited in accordance with an embodiment of the invention at two different deposition temperatures
  • Figure 12 shows the growth rate and density of Li-N vs Li pulse for an embodiment of the invention
  • Figure 13 shows the growth rate and density of Li-N vs NH 3 pulse for an embodiment of the invention
  • Figure 14 shows the thickness of Li 3 N as a function of the number of deposition cycles for an embodiment of the invention
  • Figure 15 shows the XRD pattern of a sample with deposited Li-N in accordance with an embodiment of the invention
  • Figure 16 shows the Raman spectra of a sample with deposited Li-N in accordance with an embodiment of the invention.
  • Figure 17 shows an AFM image and representative line scan of a Mo-N adhesion layer deposited by ALD.
  • Lithium-containing thin films were deposited by ALD from lithium
  • ALD/ALE Atomic layer deposition or atomic layer epitaxy
  • the samples were made in a ASM microchemistry F-120 ALD reactor from lithium bis(trimethylsilyl)amide (Aldrich, 97%) evaporated at 75 ⁇ and Dl-water, C0 2 (AGA), or NH 3 (AGA, 99.999%).
  • TGA thermo gravimetric analysis
  • a water pulse was following by pulsing of C0 2 to give the following reactions: LiN(SiMe 3 ) 2 + H 2 0 -» LiOH + HN(SiMe 3 ) 2 (g)
  • Figure 1 shows the growth rate and refractive index vs. temperature (of the instrument). The results show ALD-type growth from 80 °C up to 380 °C. Above 380 °C the precursor decomposes thermally and gives a black film with gradients.
  • Crystallinity vs. temperature was investigated using X-ray diffraction.
  • the XRD shows the evolution of crystallinity with increasing deposition temperature (see attached Figure 3).
  • XPS X-ray photoelectron spectroscopy
  • Li 3 N is a compound notoriously difficult to handle and therefore the films were capped with another layer to avoid oxidation of the sample.
  • TiN and Mo 2 N were used as capping layers.
  • the reaction of LiN(SiMe 3 ) 2 with NH 3 was proven by QCM (quartz crystal microbalance).
  • Figure 4 shows the reaction of LiN(SiMe 3 ) 2 with NH 3 , as measured by QCM.
  • Raman spectroscopy shows evidence of Li 3 N (see Figure 5) and the XPS (see Figure 6) shows that the sample contains lithium and nitrogen.
  • Example 2
  • Lithium-containing thin films were deposited by ALD from lithium
  • Thin films were deposited in a F-120 Sat ALD-reactor (ASM Microchemistry Ltd.) using LiN(SiMe 3 ) 2 (Aldrich 98%), Mo(CO) 6 (Aldrich 98%), deionised H 2 0, C0 2 (95%, AGA) and NH 3 (Linde, anhydrous 99,999%) as precursors.
  • LiN(SiMe 3 ) 2 was sublimated inside the reactor at 75 ' ⁇ .
  • Nitrogen was used as a carrier gas in all experiments and supplied at 500 cm 3 /min. Nitrogen was generated with a Schmidlin UHPN3001 N 2 purifier which provided better than 99.999% N 2 +Ar in the carrier gas. The carrier gas was further dried by P 2 0 5 and purified of remaining 0 2 by a Mykrolis gas purifier.
  • Thin films were deposited on soda-lime glass, polished titanium plates and 2.5 x 2.5 cm 2 single crystal Si(100) wafers.
  • the soda-lime glass substrates were cleaned with ethanol.
  • the single crystals were blown dry with pressurized air, and otherwise used as supplied.
  • LiN(SiMe 3 ) 2 compound being orange to yellow-brown and sticky, reacts slowly with air and moisture.
  • the compound must nevertheless be stored and handled under inert conditions to assure sufficient reproducibility of experiments. Fresh precursor was therefore transferred directly from a glovebox prior to each experiment.
  • TGA experiments were done using a Perkin Elmer TGA 7 at a heating rate of 2 ⁇ C in N 2 .
  • Thermal decomposition studies of the precursor were done using the equipment described by Nilsen et al. (Thermochimica Acta, 404:187-192, 2003).
  • the precursor was heated inside 8 mm sealed quartz tubes at 1 15°C for five days.
  • TGA was used to determine a suitable sublimation temperature of 75 °C, at which the residue was about 1 wt%.
  • the precursor decomposition test resulted in a white ring of decomposed precursor in the quartz tube at 375°C suggesting a potential maximum in the ALD-window around 375°C.
  • the pulse and purge parameters were optimised at a deposition temperature of 186°C, as shown in Figure 7, resulting in a LiN(SiMe 3 ) 2 pulse of 4 s and a H 2 0 pulse of 0.25 s in order to obtain surface limited growth.
  • Spectroscopic ellipsometry data were collected with a Woollam Alpha SE ellipsometer between 380 and 900 nm and analyzed by fitting a Cauchy model to the whole dataset. Ellipsometry was used to determine refractive index and thickness of all Li 2 C0 3 samples. A wide ALD window was observed experimentally, in line with the results of the thermal decomposition experiments described above. This is shown in Figure 8. Samples were deposited using 4 s Li pulse, 0.5 s water pulse and 7.5 s C0 2 pulse at temperatures between 89 ' ⁇ and 429 ⁇ ⁇ . Uniform films with low silicon contents were achieved up to 380 °C. At 429 °C the resulting film was black, showed gradients and extraction of growth rate data were cumbersome. X-ray diffraction and reflectometry measurements
  • XRD X-ray diffraction
  • ⁇ -29-mode Characterization by X-ray diffraction (XRD) in ⁇ -29-mode was performed with a Bruker AXS powder diffractometer equipped with a Ge(1 1 1 ) monochromator providing Cu- ⁇ radiation and using a LynxEye detector.
  • X-ray reflectometry (XRR) and ⁇ -scans were performed using a Bruker AXS D8 diffractometer with a thin film stage and an asymmetric double bounce Ge(220) monochromator and 0.2 mm slits to provide Cu- ⁇ radiation.
  • the XRR-data were fitted using the GENX software package.
  • Li 2 C0 3 films was further supported by the density as measured by XRR (not shown) of 2.01 g/cm 3 compared to a theoretical density of 2.10 g/cm 3 .
  • XPS spectra were collected with a Kratos Axis UltraDLD instrument using monochromatic Al Ka X-ray radiation. The resolution was 0.54 eV as determined by the full width at half maximum of the Ag 3d 5/2 peak. Low energy electrons were used to compensate for surface charging on the Li 2 C0 3 reference sample. Energy referencing was based on the C 1 s peak of adventitious carbon set to 285.0 eV binding energy (BE). Peak fitting was performed using Voight functions after subtraction of a Shirley type background in CASA XPS. Instrument manufacturer's sensitivity factors were employed for quantification. XPS analysis was undertaken in order to clarify the impurity level of silicon as a function of deposition temperature. 70 nm thick films of Li 2 C0 3 were obtained on polished titanium substrates after 2000 deposition cycles, as shown in Figure 10.
  • Li 3 N Deposition of Li 3 N was achieved on soda lime glass, silicon and titanium substrates by alternating pulses of LiN(SiMe 3 ) 2 and NH 3 .
  • the deposition was facilitated by first growing a 5 nm adhesion layer of MoN x prior to the Li-N growth.
  • the final Li 3 N product was capped with a 20 nm layer of MoN x in order to prevent reactions with the ambient air and to allow ex-situ characterization.
  • the pulse parameters were optimised at 167°C using 200 cycles of 5s LiN(SiMe 3 ) 2 pulse and a 5s NH 3 pulse and modifying one parameter at a time ( Figures 12 and
  • ammonia pulse could be as low as 1 s, however, then yielding products with reduced uniformity. For a 2.5s ammonia pulse, the uniformity was optimal throughout the whole reactor chamber. For longer ammonia pulses, a decrease in density was observed.
  • Raman spectroscopy was used as an additional tool for proving the chemical state of amorphous samples of lithium nitride.
  • Raman spectroscopy was performed with a Spectra- Physics Millennia Pro 12sJS Nd:YV0 4 solid state laser using 532 nm wavelength operating at 200 mW.
  • DFPT Density functional perturbation theory
  • the silicon content of a sample of Li 3 N deposited at 186 ⁇ on MoN x -buffered titanium was analyzed with XPS (not shown). The sample was deposited without a capping layer and allowed to oxidize before the analysis to avoid effects from sputtering through the capping layer. The silicon content was found to be ca. 6 atomic percent when assuming a film composition of Li 3 N.
  • Li 3 N was achieved on silicon with native oxide, Si-H, Si/Pt, titanium and glass substrates by alternating pulses of LiN(SiMe 3 ) 2 and NH 3 using the ALD techniques described in Examples 1 and 2. Deposition was achieved without the need to provide a MoN x adhesion layer prior to Li film growth.
  • the resulting Li-N layer was determined to have a uniform thickness of 48 nm ⁇ 2 nm over the whole sample, independent of substrate.
  • Molybdenum-containing thin films were deposited by ALD from Mo(CO) 6 . Reaction with NH 3 was carried out in order to deposit Mo-N type compounds.
  • Attached Figure 17 shows an AFM image of a Mo(CO) 6 adhesion layer deposited on Si at 167°C using 1 100 cycles of 0.5s Mo(CO) 6 and 2.5s of NH 3 and 2s purges. The samples were made in a ASM microchemistry F-120 Sat ALD reactor from molybdenum hexacarbonyl, Mo(CO) 6 (Strem, 98%) and NH 3 (Linde, 5.0). Mo(CO) 6 was delivered into the reactor from an external bubbler as described by Diskus et al.
  • Nitrogen was used as a carrier gas and supplied at an overall flow rate of 500 cm 3 /min.
  • the carrier gas was generated with a Schmidlin UHPN3001 N 2 purifier providing a mixture of N 2 +Ar with a purity of 99.999% before being further purified by passing through P 2 0 5 and a Mykrolis gas purifier.
  • ALD-type growth was observed from 1 14 ⁇ C up to 167 ⁇ ⁇ .
  • the process proved to be self-limiting at 0.5 s per Mo(CO) 6 pulse.
  • 2.5 s was found to be sufficient for NH 3 pulses.
  • the growth rate increased slightly with longer NH 3 pulses but the difference was small.
  • the pulse durations were therefore optimised at 0.5 s per Mo(CO) 6 pulse, 2.5 s per NH 3 pulse and 2.5 s per purge pulse.
  • the growth rate was found to increase along the flow direction by about 0.02 A per cycle throughout all experiments.
  • the resulting Mo-N type films may be used as an adhesion layer prior to deposition of a Li-containing thin film in accordance with any of the methods herein described.

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  • Chemical Vapour Deposition (AREA)

Abstract

La présente invention concerne des procédés de formation d'une couche contenant du lithium sur un substrat par dépôt d'une couche atomique, lesdits procédés comprenant les étapes suivantes consistant à : a) fournir un substrat dans une chambre de réaction, ladite chambre de réaction étant conçue pour des réactions gazeuses sur une surface ; b) impulser un précurseur de lithium à travers ladite chambre de réaction de manière à amener ledit précurseur de lithium à se déposer sur au moins une surface dudit substrat et/ou à réagir avec celle-ci pour former une couche contenant du lithium sur au moins une partie de ladite surface ; c) purger ladite chambre de réaction ; d) impulser un précurseur additionnel à travers ladite chambre de réaction de manière à amener ledit précurseur additionnel à réagir avec ladite couche contenant du lithium ; et e) purger ladite chambre de réaction ; ledit précurseur de lithium est un composé de la formule générale LiNRaRb (dans laquelle Ra et Rb sont choisis indépendamment dans le groupe constitué par H, alkyle en C1-6 et -SiRc 3 ; et chaque Rc est choisi indépendamment dans le groupe constitué par H et alkyle en C1-6 ; à condition que Ra et/ou Rb soient un groupe -SiRc 3). Des substrats portant une couche contenant du lithium produits par ces procédés sont également fournis par l'invention et sont notamment utilisés dans des batteries, par exemple comme matériaux d'électrode ou comme barrières électrolytiques.
PCT/GB2012/051697 2011-07-15 2012-07-16 Procédé WO2013011297A1 (fr)

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GBGB1204600.9A GB201204600D0 (en) 2012-03-15 2012-03-15 Method
GB1204600.9 2012-03-15

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DE102015121103A1 (de) * 2015-12-03 2017-06-08 Technische Universität Darmstadt Verfahren zur Herstellung einer Beschichtung auf einer Oberfläche eines Substrats
US9755235B2 (en) 2014-07-17 2017-09-05 Ada Technologies, Inc. Extreme long life, high energy density batteries and method of making and using the same
DE102017203910A1 (de) 2017-03-09 2018-09-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren und Vorrichtung zum Abscheiden lithiumhaltiger Mischoxide
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Publication number Priority date Publication date Assignee Title
US9280157B2 (en) 2013-09-04 2016-03-08 Amazon Technologies, Inc. System and method for transporting personnel within an active workspace
WO2015179831A1 (fr) * 2014-05-23 2015-11-26 Battelle Energy Alliance, Llc Solutions d'électrolyte comprenant un composé phosphoranimine, et des dispositifs de stockage d'énergie comprenant celui-ci
US9761910B2 (en) 2014-05-23 2017-09-12 Battelle Energy Alliance, Llc Electrolyte solutions including a phosphoranimine compound, and energy storage devices including same
US9755235B2 (en) 2014-07-17 2017-09-05 Ada Technologies, Inc. Extreme long life, high energy density batteries and method of making and using the same
US11271205B2 (en) 2014-07-17 2022-03-08 Ada Technologies, Inc. Extreme long life, high energy density batteries and method of making and using the same
US10217571B2 (en) 2015-05-21 2019-02-26 Ada Technologies, Inc. High energy density hybrid pseudocapacitors and method of making and using the same
US11996564B2 (en) 2015-06-01 2024-05-28 Forge Nano Inc. Nano-engineered coatings for anode active materials, cathode active materials, and solid-state electrolytes and methods of making batteries containing nano-engineered coatings
US10692659B2 (en) 2015-07-31 2020-06-23 Ada Technologies, Inc. High energy and power electrochemical device and method of making and using same
DE102015121103A1 (de) * 2015-12-03 2017-06-08 Technische Universität Darmstadt Verfahren zur Herstellung einer Beschichtung auf einer Oberfläche eines Substrats
DE102017203910A1 (de) 2017-03-09 2018-09-13 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren und Vorrichtung zum Abscheiden lithiumhaltiger Mischoxide
DE102017203910B4 (de) 2017-03-09 2019-02-21 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zum Abscheiden lithiumhaltiger Mischoxide
US11024846B2 (en) 2017-03-23 2021-06-01 Ada Technologies, Inc. High energy/power density, long cycle life, safe lithium-ion battery capable of long-term deep discharge/storage near zero volt and method of making and using the same

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